JP2023142629A - Adhesive set, bonded body, and method for producing bonded body - Google Patents

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

The present disclosure relates to an adhesive set, an adhesive body, and a method for manufacturing the adhesive body.

In order to reduce the weight of automobiles, the use of multi-material exterior parts is progressing, and the joining method is changing from welding to adhesive bonding. An adhesive composition containing an organic borane complex has been disclosed as an adhesive between plastics such as polyethylene and polypropylene (for example, Patent Document 1). The organoborane complex is decomplexed to provide an organoborane by mixing with a decomplexing agent. Organoborane acts as an initiator that generates radicals by reacting with oxygen. The borinic acid radicals generated here act as dormant species for atom transfer radical polymerization (ATRP), which sustains growth reactions including surface grafting while suppressing chain transfer or termination reactions of compounds having radically polymerizable groups.

Special Publication No. 2005-514489

Although it is possible to bond materials that do not have polar groups, such as polypropylene, by using an alkylborane complex, it is difficult to achieve both adhesive strength and flexibility of the adhesive layer.

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

One aspect of the present disclosure relates to adhesive sets. The adhesive set includes a base agent containing a decomplexing agent and a compound having a radically polymerizable group, and an initiator containing an organic borane complex, and at least one of the base agent and the initiator contains a polymerization control agent. Furthermore, the compound containing a radical polymerizable group is a monofunctional polymerizable compound whose homopolymer glass transition temperature is 80°C or higher, a monofunctional polymerizable compound having an aromatic ring, and a weight average molecular weight of 10,000. and the above polyfunctional polymerizable compounds.

Another aspect of the present disclosure relates to an adhesive body. The adhesive body includes 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 containing the base agent and initiator in the adhesive set described above.

Another aspect of the present disclosure relates to a method for manufacturing an adhesive body. The method for manufacturing the adhesive body includes a step of bonding a first adherend and a second adherend together via an adhesive composition containing a base agent and an initiator.

According to the present disclosure, an adhesive set is provided that can form an adhesive layer with sufficient adhesive strength and excellent flexibility. Further, according to the present disclosure, an adhesive body using such an adhesive set and a method for manufacturing the same are provided.

Embodiments of the present disclosure will be described below. However, the present disclosure is not limited to the following embodiments.

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

In this specification, a compound having one radically polymerizable group is referred to as a monofunctional polymerizable compound, and a compound having two or more radically 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. Further, the materials exemplified below may be used alone or in combination of two or more, unless otherwise specified. When a plurality of substances corresponding to each component are present in the composition, the content of each component in the composition means the total amount of the plurality of substances present in the composition, unless otherwise specified.

[Adhesive set]
An adhesive set of one embodiment includes a base agent containing a decomplexing agent and a compound having a radically polymerizable group, and an initiator containing an organoborane complex. In the adhesive set of the present embodiment, an adhesive composition containing a base ingredient and an initiator can be obtained by mixing the base ingredient and an initiator. According to such an adhesive set, by mixing the base agent and the initiator, it is possible to prepare an adhesive composition that has sufficient adhesive strength and can shorten the curing time.

The main agent contains a decomplexing agent and a compound having a radically polymerizable group. Compounds having radically polymerizable groups include monofunctional polymerizable compounds whose homopolymer glass transition temperature is 80°C or higher, monofunctional polymerizable compounds which have an aromatic ring, and polyfunctional polymerizable compounds whose weight average molecular weight is 10,000 or higher. and a functional polymerizable compound. The initiator contains an organoborane complex. At least one of the main ingredient and the initiator further contains a polymerization control agent. At least one of the main ingredient and the initiator may further contain any one of a filler, a peroxide, a plasticizer, a crosslinking agent, and the like. Each component will be explained below.

(Organoborane complex)
The initiator contains an organoborane complex. The organoborane complex means an organoborane-Lewis base complex obtained by coordinating an organoborane with a Lewis base to form a complex. The organoborane-Lewis base complex is a compound that reacts with a decomplexing agent described below to give an organoborane. Organic borane undergoes radical cleavage in an oxygen atmosphere to generate borinic acid radicals, which are dormant species, and therefore can act as an initiator for living radical polymerization. The organoborane may be, for example, an alkylborane (BR ₃ , R: alkyl group). A Lewis base may be, for example, an amine. An amine is, for example, a compound having a plurality of amino groups, or a group containing an amino group constituting the amine and an atom (such as an oxygen atom) capable of coordinating with boron in addition to the nitrogen atom of the amino group. For example, it may be a compound having at least an alkoxy group). These compounds can be called polydentate amines because they act as polydentate ligands for organoboranes.

The organoborane complex may be an alkylborane-amine complex or an alkylborane-polydentate amine complex. Examples of the organic borane complex include triethylborane-1,3-diaminopropane complex, triethylborane-diethylenetriamine complex, tri-n-butylborane-3-methoxy-1-propylamine complex, and 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-diamino Examples include hexane complexes. These may be used alone or in combination of two or more. Among these, the organoborane complex may be a triethylborane-1,3-diaminopropane complex or a tri-n-butylborane-3-methoxy-1-propylamine complex. As the organic borane complex, a commercially available product or a synthetic product may be used.

The content of the organic borane 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 developing adhesive strength. From the viewpoint of storage stability, 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 adhesive strength development, the content of the organoborane complex is 0.01% by mass or more, 0.05% by mass or more, 0.1% by mass or more, or 0.01% by mass or more, based on the total amount of the main agent and initiator. It may be 2% by mass or more. From the viewpoint of the toughness of the adhesive layer, the content of the organoborane complex is 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. It's fine.

From the viewpoint of adhesive strength development, the content of the organoborane complex is 0.01 mol% or more, 0.05 mol% or more, 0.08 mol% or more, or It may be 0.1 mol% or more. From the viewpoint of the toughness of the adhesive layer, the content of the organoborane complex is 10 mol% or less, 5 mol% or less, 2 mol% or less, or 1 mol% or less, based on the total amount of the compound having a radically polymerizable group. It may be.

(Decomplexing agent)
The base agent contains a decomplexing agent. A decomplexing agent is a compound capable of dissociating a Lewis base in an organoborane complex (organoborane-Lewis base complex) to generate an organoborane. Therefore, by mixing and reacting the organoborane complex contained in the initiator with the decomplexing agent contained in the main agent, it is possible to generate an organic borane that can serve as an initiator for living radical polymerization.

Examples of the decomplexing agent include acids, acid anhydrides, aldehydes, β-ketone compounds, and the like. These may be used alone or in combination of two or more. Examples of the acid include Lewis acids such as _SnCl4 and _TiCl4 , 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, and the like. 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, and 2-methacryloyloxyethyl acetoacetate. 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 from the viewpoint of suppressing the amount of the decomplexing agent blended. or succinic anhydride.

The content of the decomplexing agent is 0.01% by mass or more and 0.1% by mass based on the total amount of the main agent, from the viewpoint of shortening the curing time until the adhesive layer hardens and develops adhesive strength. The content may be 0.2% by mass or more, or 0.3% by mass or more. The content of the decomplexing agent is 10% by mass or less and 5% by mass or less based on the total amount of the base agent, from the viewpoint of securing the working time from applying the adhesive composition to the adherend until bonding. , 3% by mass or less, or 2% by mass or less.

The content of the decomplexing agent is 0.01% by mass or more, based on the total amount of the main agent and initiator, from the viewpoint of shortening the curing time until the adhesive layer hardens and develops adhesive strength. .1% by weight or more, 0.2% by weight or more, or 0.3% by weight or more. The content of the decomplexing agent is 10% by mass or less, based on the total amount of the base agent and initiator, from the viewpoint of securing the working time from applying the adhesive composition to the adherend until bonding. It may be 7% by weight or less, 5% by weight or less, or 3% by weight or less.

The molar ratio of the decomplexing agent to the organoborane complex (molar amount of the decomplexing agent/mole amount of the organoborane complex) is, for example, 0.3 or more, 0.5 or more, 0.8 or more, or 1 or more. It may be. When the molar ratio is 1 or more, more sufficient adhesive strength tends to be obtained. The molar ratio of the decomplexing agent to the organoborane complex (molar amount of the decomplexing agent/molar amount of the organoborane complex) is, for example, 50 or less, 30 or less, 10 or less, 7 or less, 5 or less, or 3 or less. It may be. The smaller the molar ratio, the more sufficient the working time from applying the adhesive composition to the adherend to bonding tends to be secured.

(Compound having a radically polymerizable group)
The main ingredient 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 (meth)acryloyl group, vinyl group, allyl group, styryl group, alkenyl group, alkenylene group, and maleimide group.

The compound having a radically polymerizable group is a monofunctional polymerizable compound whose homopolymer has a glass transition temperature of 80°C or higher (hereinafter referred to as "polymerizable compound A"), and a monofunctional polymerizable compound having an aromatic ring. A compound (hereinafter referred to as "polymerizable compound B") and a polyfunctional polymerizable compound (hereinafter referred to as "polymerizable compound C") having a weight average molecular weight of 10,000 or more. Thereby, an adhesive layer having sufficient adhesive strength and excellent flexibility can be formed.

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

The polymerizable compound A may be a monofunctional polymerizable compound that does not have an aromatic ring. Examples of the 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), and isobornyl. Acrylate (Tg: 97°C), Isobornyl methacrylate (Tg: 180°C), Dicyclopentanyl acrylate (Tg: 120°C), Dicyclopentanyl methacrylate (Tg: 175°C), Dimethyl Acrylamide (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).

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

By using a monofunctional polymerizable compound having an aromatic ring as the polymerizable compound B, it is possible to improve adhesion to a material having no polar group such as polypropylene. 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 the 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, phenyl glycidyl 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.

The content of the polymerizable compound B may be 10% by mass or more, 15% by mass or more, or 20% by mass or more based on the total amount of compounds having radically polymerizable groups, from the viewpoint of further improving adhesive properties. Often, it may be 50% by weight or less, 40% by weight or less, or 30% by weight or less.

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

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

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 is preferably -100 to 10°C, -60 to -20°C, or -50 to - The temperature may be 40°C.

Examples of the polymerizable compound C include urethane acrylate, acrylic resin acrylate, polyester acrylate, and epoxy acrylate.

Since the polymerizable compound C has an excellent balance between the adhesive strength and flexibility of the adhesive layer, it preferably contains a bifunctional polymerizable compound having two radically polymerizable groups, and contains a difunctional urethane acrylate. It is more preferable.

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

The compound having a radically polymerizable group may further contain a compound other than the above-mentioned polymerizable compound (hereinafter referred to as "polymerizable compound D"). The polymerizable compound D may be a monofunctional (meth)acrylate or a polyfunctional (meth)acrylate.

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, and 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), isomyristyl Alkyl (meth)acrylates having an alkyl group such as (meth)acrylate, stearyl (meth)acrylate, and isostearyl acrylate; Alkenyl (meth)acrylates having an alkenyl group such as 3-butenyl (meth)acrylate; Methoxytetraethylene glycol ( meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxyoctaethylene glycol (meth)acrylate, methoxynonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptapropylene glycol (meth)acrylate, ethoxytetra Alkoxypolyalkylene glycol (meth)acrylates such as ethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate; (meth)acrylates having an alicyclic group such as cyclohexyl (meth)acrylate; (Meth)acrylates with hydroxyl groups such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; amino acids such as N,N-dimethylaminoethyl (meth)acrylate (meth)acrylate having an isocyanate group such as 2-(2-methacryloyloxyethyloxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate; tetraethylene glycol mono(meth)acrylate, Polyalkylene glycol mono(meth)acrylate such as hexaethylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, octapropylene glycol mono(meth)acrylate, etc. (Meth)acrylate; Examples include (meth)acrylate having a siloxane skeleton. These may be used alone or in combination of two or more.

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, and polyethylene glycol di(meth)acrylate. 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 (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, Aliphatic (meth)acrylate such as 10-decanediol di(meth)acrylate, glycerin di(meth)acrylate, tricyclodecane dimethanol(meth)acrylate, and ethoxylated 2-methyl-1,3-propanediol di(meth)acrylate. ) 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, propoxy bisphenol F-type di(meth)acrylate, ethoxylated propoxylated bisphenol F-type di(meth)acrylate, ethoxylated fluorene-type di(meth)acrylate, propoxylated fluorene-type di(meth)acrylate, ethoxylated propoxylated fluorene-type di(meth)acrylate Aromatic (meth)acrylates such as (meth)acrylates; aromatic epoxy (meth)acrylates such as bisphenol-type epoxy (meth)acrylates, phenol novolac-type epoxy (meth)acrylates, and cresol novolac-type epoxy (meth)acrylates. . These may be used alone or in combination of two or more.

The total amount of the compound having a radically polymerizable group is 40% by mass or more, 50% by mass or more, 60% by mass, 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. or more, or 65% by mass or more. The content of the compound having a radically polymerizable group is 95% by mass or less, based on the total amount of the base agent and initiator, from the viewpoint of suppressing sagging of the applied adhesive composition and suppressing a decrease in toughness of the adhesive layer. It may be 90% by weight or less, 85% by weight or less, or 80% by weight or less.

(Polymerization control agent)
At least one of the main ingredient and the initiator further contains a polymerization control agent. Examples of the polymerization control agent include halogenated metal salts and compounds having a thiocarbonylthio structure. The polymerization control agent may be at least one selected from the group consisting of halogenated metal salts and compounds having a thiocarbonylthio structure.

Examples of halogenated metal salts include copper(II) bromide, copper(II) chloride, iron(III) bromide, vanadium(III) bromide, chromium(III) bromide, ruthenium(III) bromide, Examples include copper(I) bromide, iron(II) bromide, manganese(II) bromide, cobalt(II) bromide, nickel(II) bromide, palladium(II) bromide, and the like. These may be used alone or in combination of two or more. The metal halide salt may be, for example, copper(II) bromide.

The compound having a thiocarbonylthio structure can be used without any particular restriction as long as it has a thiocarbonylthio structure, and for example, a chain transfer agent used in the field of RAFT polymerization (Reversible Addition/Fragmentation Chain Transfer) RAFT agent) can be suitably used.

The polymerization control agent may be contained in at least one of the main ingredient and the initiator. For example, the main ingredient may contain the polymerization control agent.

The content of the polymerization control agent is 0 based on the total amount of the main agent and initiator, from the viewpoint of securing the working time from applying the adhesive composition to the adherend until bonding and improving the adhesive strength. It may be .01% by weight or more, 0.02% by weight or more, 0.03% by weight or more, or 0.05% by weight or more. From the viewpoint of storage stability of the main agent, the content of the polymerization control agent is 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. It may be.

The content of the polymerization control agent is determined based on the total amount of the compound having a radically polymerizable group, from the viewpoint of securing the working time from applying the adhesive composition to the adherend until bonding and improving the adhesive strength. , 0.01 mol% or more, 0.03 mol% or more, 0.05 mol% or more, or 0.08 mol% or more. From the viewpoint of storage stability of the main ingredient, the content of the polymerization control agent is 5 mol% or less, 3 mol% or less, 1 mol% or less, or 0.7 mol, based on the total amount of the compound having a radically polymerizable group. % or less.

(peroxide)
At least one of the base agent and the initiator may further contain a peroxide. The peroxide can be used without particular limitation as long as it has an -O-O- bond, and for example, commercially available products can be used. These may be used alone or in combination of two or more.

Commercially available peroxides include, for example, Perloil L (1 minute half temperature: 116°C, NOF Corporation), Perbutyl O (1 minute half temperature: 134 °C, NOF Corporation), Perbutyl E (1 minute half temperature: 134 °C, NOF Corporation). Half-life temperature: 161°C, NOF Corporation), Percmill H (1-minute half-life temperature: 254°C, NOF Corporation), and the like. Among these, the peroxide may be a peroxide having a 1-minute half-life temperature of 270° C. or less from the viewpoint of shortening curing time and storage stability. The 1-minute half-life temperature of peroxide is, 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 The temperature may be below 120°C or below. The 1-minute half-life temperature of peroxide may be, for example, 80°C or higher, 90°C or higher, or 100°C or higher.

From the viewpoint of shortening the curing time, the peroxide content is 0.01% by mass or more, 0.03% by mass or more, 0.05% by mass or more, or 0.01% by mass or more, based on the total amount of the main agent and initiator. It may be 1% by mass or more. From the viewpoint of storage stability, the content of peroxide 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. .

From the viewpoint of shortening the curing time, the content of peroxide 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 content of peroxide 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.

The peroxide may be contained in at least one of the base agent and the initiator. For example, the base agent may contain the peroxide.

(filler)
The filler may be, for example, 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 fiber, graphite, magnesium hydroxide, and aluminum hydroxide. , antimony trioxide, barium sulfate, zinc borate, wollastonite, xonotrite, whiskers, and other inorganic fine particles. Examples of the organic filler include organic fine particles such as silicone, acrylic silicone, acrylic rubber, MBS (methacrylate-butadiene-styrene), polyamide, and polyimide. These fillers (fine particles) may have a uniform structure or a core-shell type structure. The filler may contain an organic filler or may contain acrylic core-shell particles, since the curing time can be more sufficiently shortened.

The filler may be contained in at least one of the base agent and the initiator. For example, the base agent may contain a filler including an organic filler, or may contain a filler including acrylic core-shell particles, since the curing time can be more sufficiently shortened.

The organic filler may contain an antioxidant. According to studies by the inventors of the present disclosure, it has been found that the smaller the amount of antioxidant in the organic filler, the more sufficiently the curing time can be shortened. The content of the antioxidant in the organic filler may be, for example, 15,000 mass ppm or less, 10,000 mass ppm or less, 5,000 mass ppm or less, or 3,000 mass ppm or less.

The filler content may be 1% by mass or more, 3% by mass or more, or 5% by mass or more, and 40% by mass or less, 30% by mass or less, or 30% by mass, based on the total amount of the base agent and initiator. % or less.

(Plasticizer)
Examples of the plasticizer include phthalic acid ester compounds, alkyl sulfonic acid ester compounds, and adipic acid ester compounds.

The content of the plasticizer may be 0.1% by mass or more, 0.2% by mass or more, or 0.3% by mass or more, and 30% by mass or less, 20% by mass or more, based on the total amount of the base agent and initiator. It may be less than 10% by mass, or less than 10% by mass.

(Crosslinking agent)
Examples of the crosslinking agent include aziridine crosslinking agents, carbodiimide crosslinking agents, and the like.

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

At least one of the main agent and the initiator includes, in addition to the above-mentioned components, an ultraviolet absorber, a dehydrating agent, a pigment, a dye, an antioxidant, an antioxidant, an antistatic agent, a flame retardant, an adhesion imparting agent, a dispersant, It may further contain a solvent or the like.

In the adhesive set of this embodiment, the adhesive composition can be prepared by mixing the base agent and the initiator. The temperature when mixing the main ingredient 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.

When mixing the main agent and the initiator, the molar ratio of the decomplexing agent in the main agent to the organoborane complex in the initiator (mole amount of decomplexing agent/mole amount of organoborane complex) is 0.3 or more, It is preferable to mix so that the ratio is 0.5 or more, 0.8 or more, or 1 or more, or 50 or less, 30 or less, 10 or less, 7 or less, 5 or less, or 3 or less.

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

The method of mixing the base agent and the initiator is not particularly limited as long as both are mixed. Examples of methods for mixing the base agent and initiator include manual mixing, hand-coating using a normal caulking gun, quantitative pumps for feeding the raw materials (e.g., gear pumps, Examples include a method of mixing using a mechanical rotary mixer, static mixer, etc., using a combination of a plunger pump (plunger pump, etc.) and a throttle valve.

The prepared adhesive composition can be applied to a predetermined location to form an adhesive layer. The formed adhesive layer acts as an adhesive layer for bonding the base materials together because the compound having a radically polymerizable group gradually increases in molecular weight and hardens. A conventionally known method such as a method using a dispenser or the like can be applied to a predetermined location.

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.

[Adhesive body and its manufacturing method]
The adhesive body of one embodiment includes 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 containing the base agent and initiator in the adhesive set described above.

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

Examples of the adhesive body include plastic laminate substrates, metal laminate substrates, electronic components, semiconductor components, display components, and the like.

A method for manufacturing an adhesive body according to one embodiment includes a step of bonding a first adherend and a second adherend together via an adhesive composition containing a base agent and an initiator. The temperature when mixing the main ingredient and the initiator in the adhesive set, the conditions for curing the adhesive composition, etc. may be the same as those described above.

Hereinafter, the present disclosure will be described in more detail with reference to Examples. However, the present disclosure is not limited to these examples.

[Preparation of adhesive set]
(Preparation of raw materials)
・Organoborane complex TEB-DAP: Triethylborane-1,3-diaminopropane complex (molecular weight: 172.1, Kishida Chemical Co., Ltd.)
・Decomplexing agent Succinic anhydride (molecular weight: 100.1, Fujifilm Wako Pure Chemical Industries, Ltd.)
・Compounds with radically polymerizable groups (polymerizable compounds)
IBXA: Isobornyl acrylate (homopolymer Tg: 97°C, molecular weight: 208.3, Kyoeisha Chemical Co., Ltd.)
FA-513AS: Dicyclopentanyl acrylate (Tg of homopolymer: 120°C, molecular weight: 206.3, Showa Denko Materials Co., Ltd.)
FA-513M: Dicyclopentanyl methacrylate (homopolymer Tg: 175°C, molecular weight: 206.3, Showa Denko Materials Co., Ltd.)
Dimethylacrylamide (homopolymer Tg: 119°C, molecular weight: 99.13, Fujifilm Wako Pure Chemical Industries, Ltd.)
FA-310AH: Phenoxyethyl acrylate (homopolymer Tg: 5°C, molecular weight: 192.2, Showa Denko Materials Co., Ltd.)
CHA: Cyclohexyl acrylate (homopolymer Tg: 15°C, molecular weight: 154.2, Osaka Organic Chemical Industry Co., Ltd.)
EBECRYL 8413: Aliphatic urethane acrylate (isobornyl acrylate content: 35%, weight average molecular weight: 37,000, Daicel Ornescu Corporation)
・Polymerization control agent Copper (II) bromide (molecular weight: 223.4, Fujifilm Wako Pure Chemical Industries, Ltd.)
・Peroxide Perloyl L (molecular weight: 398.6, 1 minute half-life temperature: 116°C, NOF Corporation)
・Inorganic filler RY200S: Surface treated silica (hydrophobic fumed silica surface treated with silicone oil, Nippon Aerosil Co., Ltd.)
・Organic filler B564: MBS-based core-shell particles (Kaneka Corporation, containing Irganox PS 800: 7800 mass ppm and Irganox 245: 6000 mass ppm as antioxidants)
M210: Acrylic core-shell particles (Kaneka Corporation, no antioxidant detected)
・Plasticizer PN-5090: Adipic acid polyester (ADEKA Co., Ltd.)
・Crosslinking agent Triaziridine: Tris[3-(1-aziridinyl)propionic acid]trimethylolpropane (Fujifilm Wako Pure Chemical Industries, Ltd.)

(Preparation of main ingredient)
Weigh out a decomplexing agent, a compound having a radically polymerizable group, a polymerization control agent, a peroxide, and a filler in a polyethylene bottle in the types and proportions (unit: parts by mass) shown in Table 1 or Table 2, Using a rotation-revolution mixer (Thinky Co., Ltd., Rentaro Awatori), the mixture was mixed for 15 minutes at 2000 rpm, and further defoamed for 5 minutes at 2000 rpm, Examples 1 to 5 and Comparative Examples. Base ingredients Nos. 1 to 7 were prepared.

(Preparation of initiator)
Weigh out the organoborane complex, plasticizer, crosslinking agent, and filler in the types and proportions (unit: parts by mass) shown in Table 1 or Table 2 in a polyethylene bottle, and then Taro), the mixture was mixed for 15 minutes at 2,000 revolutions/minute, and defoamed for 5 minutes at 2,000 revolutions/minute to prepare initiators for Examples 1 to 5 and Comparative Examples 1 to 7. Note that the initiators of Examples 1 to 5 and Comparative Examples 1 to 7 have the same components.

[Evaluation of adhesive strength]
A 0.5 mm spacer was placed between two polypropylene substrates (adherends) (size: 100 mm x 25 mm, thickness: 2 mm) so that the thickness of the adhesive layer was 0.5 mm. The base ingredients and initiators were mixed by filling each base ingredient and each initiator into a manual dispenser. It was applied between polypropylene substrates using a manual dispenser, and the polypropylene substrates were bonded together to obtain a laminate. The obtained laminate was left to stand at 23° C. and 55% RH for 72 hours to be cured to prepare an evaluation sample. A tensile test was performed on the produced evaluation sample at a distance between chucks of 100 mm and a test speed of 50 mm/min, and the shear strength (MPa) with respect to the polypropylene substrate was measured. When the shear strength is 1 MPa or more, it can be said that the adhesive has sufficient adhesive strength.

[Evaluation of flexibility]
A 2 mm spacer was placed on a release sheet (size: 150 mm x 150 mm, thickness: 0.1 mm, material: polytetrafluoroethylene) so that the thickness of the adhesive layer was 2 mm. After applying the adhesive composition in which each main ingredient and each initiator are mixed onto a release sheet, another release sheet is laminated and left at 23°C and 55% RH for 72 hours to bond with the release sheet. A laminated sheet with the cured product of the agent composition was obtained. In accordance with JIS K 6251, the laminated sheet was punched into a No. 3 dumbbell shape, and the release sheet was peeled off to prepare a test piece. Using Autograph (manufactured by Shimadzu Corporation, model number: AGS-1kNX, load cell: 50kN), the breaking strength and elongation rate of the test piece were measured at a distance between chucks of 70 mm and a tensile speed of 200 mm/min. It can be said that the larger the values of breaking strength and elongation are, the more excellent the flexibility is.

Claims (5)

A base agent containing a decomplexing agent and a compound having a radically polymerizable group, and an initiator containing an organoborane complex,
At least one of the base agent and the initiator further contains a polymerization control agent,
The compound having a radically polymerizable group is 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 weight average molecular weight of 10,000 or higher. An adhesive set containing a multifunctional polymerizable compound. The adhesive set according to claim 1, wherein the content of the polyfunctional polymerizable compound is 15% by mass or more and 60% by mass or less, based on the total amount of the compound having a radically polymerizable group. The adhesive set according to claim 1 or 2, wherein the polyfunctional polymerizable compound contains urethane acrylate. comprising 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 containing the base agent and the initiator in the adhesive set according to any one of claims 1 to 3. A method for manufacturing an adhesive body according to claim 4, comprising:
A method for producing an adhesive body, comprising a step of bonding the first adherend and the second adherend together via an adhesive composition containing the base agent and the initiator.