Adhesive set, adhesive body and manufacturing method thereof

Abstract

An adhesive kit is disclosed. The adhesive kit comprises: a main agent containing a complex breaking agent; and an initiator containing an organoborane complex. The complexing breaking agent comprises maleic anhydride. At least one of the main agent and the initiator further contains a compound having a radically polymerizable group. The main agent and / or the initiator further contains at least one compound selected from the group consisting of a metal halide salt and a compound having a thiocarbonyl sulfide structure.

Description

Technical Field

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

[0002] As an adhesive for bonding plastics such as polyethylene and polypropylene, an adhesive composition containing an organic borane complex is disclosed (for example, Patent Document 1). The organic borane complex is decomplexed by mixing with a decomplexing agent to give an organic borane. The organic borane acts as an initiator for generating free radicals by reacting with oxygen. The boric acid radicals generated here play a role in suppressing the chain transfer or stopping reaction of a compound having a free radical polymerizable group while maintaining the generation of dormant species of atom transfer radical polymerization (ATRP) including a growth reaction of surface grafting.

[0003] Previous technical literature

[0004] Patent Literature

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

[0006] Technical issues to be solved by the invention

[0007] However, in adhesive compositions, the time required to obtain sufficient adhesive strength (curing time) is required to be short from the viewpoint of process suitability (operability). However, in adhesive compositions containing conventional organoborane complexes, the curing time is extremely long, and there is still room for improvement.

[0008] Therefore, a main object of the present invention is to provide an adhesive kit capable of preparing an adhesive composition capable of substantially shortening the curing time.

[0009] Means for solving technical problems

[0010] The inventors of the present invention have studied to solve the above problems and have found that the curing time of the adhesive composition can be sufficiently shortened by using maleic anhydride which functions as a complex breaker of the organoborane complex, thereby completing the present invention.

[0011] That is, the present invention provides an adhesive kit as described below [1], an adhesive body as described below [2], and a method for manufacturing an adhesive body as described below [3].

[0012] [1] An adhesive kit comprising: a main agent containing a complex breaker; and an initiator containing an organic borane complex, wherein the complex breaker comprises maleic anhydride, and at least one of the main agent and the initiator further contains a compound having a free radical polymerizable group, and at least one of the main agent and the initiator further contains at least one selected from the group consisting of a halogenated metal salt and a compound having a thiocarbonylthio structure.

[0013] [2] An adhesive body comprising: a first adherend; a second adherend; and an adhesive layer for bonding the first adherend and the second adherend to each other, wherein the adhesive layer contains a cured product of an adhesive composition comprising the main agent and the initiator in the adhesive kit described in [1].

[0014] [3] A method for producing an adhesive body, which is the method for producing an adhesive body according to [2], comprising: a step of bonding the first adherend and the second adherend together via an adhesive composition containing the main agent and the initiator.

[0015] According to the adhesive set, an adhesive composition capable of sufficiently shortening the curing time can be prepared. Although the reason for this effect is not clear, the inventors of the present invention speculate that the reaction of, for example, decomplexing the organoborane complex to produce the organoborane is accelerated by including maleic anhydride as a complex breaker.

[0016] Furthermore, when the adhesive composition obtained from the adhesive set is used for bonding adherends, the adhesive composition tends to overflow from the specified portion, which is excellent in curing property. The reason for this effect is as follows: by including maleic anhydride as a complex breaker, for example, the product having a polymerizable group generated by the reaction of the Lewis base of the organic borane complex with maleic anhydride acts as a compound having a free radical polymerizable group. As a result, it is presumed that a three-dimensional cross-linked structure is formed to promote the curing of the overflowing portion.

[0017] Effects of the Invention

[0018] According to the present invention, an adhesive kit capable of preparing an adhesive composition capable of sufficiently shortening the curing time is provided. When an adhesive kit of a certain form is used as an adhesive composition for bonding adherends to each other, the adhesive kit has excellent curability in a portion that tends to overflow from a predetermined portion. Furthermore, according to the present invention, an adhesive body using such an adhesive kit and a method for manufacturing the same are provided. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a graph showing changes in shear strength with respect to curing time in Examples 1 and 2 and Comparative Example 1. DETAILED DESCRIPTION

[0020] Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to the following embodiments.

[0021] The same is true for the numerical value and range thereof of the present invention, and the present invention is not limited thereto. In this specification, the numerical range represented by "~" represents the range in which the numerical values ​​before and after "~" are respectively included as the minimum value and the maximum value. In the numerical range recorded in stages in this specification, the upper limit or lower limit recorded in a numerical range may also be replaced by the upper limit or lower limit of other numerical ranges recorded in stages. Moreover, in the numerical range recorded in this specification, the upper limit or lower limit of the numerical range may also be replaced by the value shown in the embodiment.

[0022] In this specification, (meth)acrylamide means acrylamide or its corresponding methacrylamide. (Meth)acrylate means acrylate or its corresponding methacrylate. Other similar expressions such as (meth)acryloyl and (meth)acrylic copolymers are also the same. In addition, the materials exemplified below may be used alone or in combination of two or more unless otherwise specified. In the case where there are multiple substances equivalent to each component in the composition, the content of each component in the composition represents the total amount of the multiple substances present in the composition unless otherwise specified.

[0023] [Adhesive Set]

[0024] The adhesive set of one embodiment includes a main agent containing a complex breaker and an initiator containing an organic borane complex. The adhesive set of this embodiment can obtain an adhesive composition containing a main agent and an initiator by mixing the main agent and the initiator.

[0025] The main agent contains a complex breaker containing maleic anhydride. The initiator contains an organic borane complex. At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group. At least one of the main agent and the initiator further contains at least one selected from the group consisting of a halogenated metal salt and a compound having a thiocarbonylsulfide structure. The initiator may contain a stabilizer. At least one of the main agent and the initiator may further contain any one of a filler, a plasticizer, etc. The following describes each component.

[0026] (Organoborane complex)

[0027] The initiator contains an organic borane complex. The organic borane complex refers to an organic borane-Lewis base complex that is complexed by coordinating a Lewis base to an organic borane. The organic borane-Lewis base complex is a compound that reacts with a complex breaker described later to give an organic borane. The organic borane undergoes free radical splitting in the presence of oxygen and generates boric acid free radicals, etc., so that it can act as an initiator for active free radical polymerization. The organic borane can be, for example, an alkyl borane (BR3, R: alkyl). The Lewis base can be, for example, an amine. The amine can be, for example, a compound having multiple amino groups, or a compound having at least an amino group constituting an amine and a group (for example, an alkoxy group, etc.) containing an atom (for example, an oxygen atom, etc.) that can coordinate with boron, in addition to the nitrogen atom of the amino group. Because these compounds play a role relative to the polydental ligand of the organic borane, they can be called polydental amines.

[0028] The organic borane complex can be an alkyl borane-amine complex or an alkyl borane-polyamine complex. As an organic borane complex, for example, triethyl borane-1,3-diaminopropane complex, triethyl borane-diethylenetriamine complex, tri-n-butyl borane-3-methoxy-1-propylamine complex, tri-n-butyl borane-1,3-diaminopropane complex, triisobutyl borane-1,3-diaminopropane complex, triethyl borane-1,6-diaminohexane complex, triisobutyl borane-1,3-diaminopropane complex, triisobutyl borane-1,6-diaminohexane complex. These can be used alone or in combination of two or more. In these, the organic borane complex can be triethyl borane-1,3-diaminopropane complex or tri-n-butyl borane-3-methoxy-1-propylamine complex. As the organoborane complex, a commercially available product may be used, or a synthetic product may be used.

[0029] From the viewpoint of developing adhesive strength, the content of the organoborane complex may be 0.1 mass % or more, 1 mass % or more, 3 mass % or more, or 5 mass % or more based on the total amount of the initiator. From the viewpoint of storage stability, the content of the organoborane complex may be 30 mass % or less, 20 mass % or less, 15 mass % or less, or 10 mass % or less based on the total amount of the initiator.

[0030] From the viewpoint of developing adhesive strength, the content of the organic borane complex may be 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, or 0.2 mass % or more, based on the total amount of the main agent and the initiator. From the viewpoint of the toughness of the adhesive layer, the content of the organic borane complex may be 10 mass % or less, 5 mass % or less, 3 mass % or less, or 1 mass % or less, based on the total amount of the main agent and the initiator.

[0031] From the viewpoint of developing adhesive strength, the content of the organic borane complex may be 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, or 0.5 mol% or more based on the total amount of the compound having a free radical polymerizable group. From the viewpoint of the toughness of the adhesive layer, the content of the organic borane complex may be 10 mol% or less, 5 mol% or less, 2 mol% or less, or 1 mol% or less based on the total amount of the compound having a free radical polymerizable group.

[0032] (Stabilizer)

[0033] The initiator may further contain a stabilizer. The stabilizer is a component that can act on the stabilization of the organic borane complex and can contribute to the stabilization of the adhesive set. As a stabilizer, for example, a tertiary amine can be cited. As a specific example of a tertiary amine, N,N-disubstituted (meth) acrylamide, a heterocyclic tertiary amine, etc. can be cited. Among them, N,N-disubstituted (meth) acrylamide represents a compound in which two hydrogen atoms on the nitrogen atom of (meth) acrylamide are replaced by groups other than hydrogen atoms. The heterocyclic tertiary amine represents a heterocyclic ring containing a nitrogen atom, and the nitrogen atom in the heterocyclic ring is a compound constituting the tertiary amine. The heterocyclic ring of the heterocyclic tertiary amine can be a three-membered ring or more, a four-membered ring or more, or a five-membered ring or more, or an eight-membered ring or less, a seven-membered ring or less, or a six-membered ring or less. Among these, the tertiary amine can be N,N-disubstituted (meth) acrylamide, or it can be N,N-disubstituted acrylamide.

[0034] The N,N-disubstituted (meth)acrylamide may be, for example, a compound represented by the following general formula (1).

[0035]

[0036] R 1 represents a hydrogen atom or a methyl group. 1 It may be a hydrogen atom.

[0037] R 2 and R 3 Each independently represents an alkyl group. The number of carbon atoms in the alkyl group may be 1 to 20, 1 to 10, 1 to 6 or 1 to 3. The alkyl group may be any of a straight-chain alkyl group, a branched-chain alkyl group or a cyclic alkyl group. The number of carbon atoms in a straight-chain alkyl group is usually 1 to 20, and may be 1 to 10, 1 to 6 or 1 to 3. The number of carbon atoms in a branched-chain alkyl group is usually 3 to 20, and may be 3 to 10 or 3 to 6. The number of carbon atoms in a cyclic alkyl group is usually 3 to 20, and may be 3 to 10 or 3 to 6.

[0038] As a straight-chain alkyl group, for example, a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-hexyl group, an n-octyl group, an n-dodecyl group, an n-hexadecyl group, etc. can be cited. As a branched alkyl group, for example, an isopropyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a 2-ethylhexyl group, a 3,7-dimethyloctyl group, a 2-hexyldecyl group, etc. can be cited. As a cyclic alkyl group, for example, a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. can be cited. Among these, the alkyl group can be a methyl group or an ethyl group, or a methyl group.

[0039] A part of the hydrogen atoms of the alkyl group may be substituted by a substituent. In this specification, a substituent refers to a group generally available in the field of organic chemistry. Specific examples of the substituent include a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), a cyano group, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an amino group, and the like.

[0040] R 2 and R 3 They may be bonded to each other or to each other through an oxygen atom to form a ring together with the nitrogen atom to which they are bonded. The formed ring (a heterocycle containing a nitrogen atom or a heterocycle containing a nitrogen atom and an oxygen atom) may be a four-membered ring or a five-membered ring or a seven-membered ring or less.

[0041] The N,N-disubstituted (meth)acrylamide may be, for example, a compound represented by the following general formula (2).

[0042]

[0043] R 4 represents a hydrogen atom or a methyl group. 4 It may be a hydrogen atom.

[0044] R 5 and R 6 Each independently represents an alkylene group. The number of carbon atoms of the alkylene group may be 1 to 20, 1 to 10, 1 to 6 or 1 to 3. The alkylene group may be any of a straight chain alkylene group and a branched chain alkylene group. The number of carbon atoms of a straight chain alkylene group is usually 1 to 20, and may be 1 to 10, 1 to 6 or 1 to 3. The number of carbon atoms of a branched chain alkylene group is usually 3 to 20, and may be 3 to 10 or 3 to 6.

[0045] As the straight chain alkylene group, for example, methylene, ethylene, propylene, butylene, pentylene, hexylene, etc. can be mentioned. As the branched chain alkylene group, isopropylene, isobutylene, dimethylpropylene, etc. can be mentioned. Among these, the alkylene group can be ethylene.

[0046] A part of the hydrogen atoms of the alkylene group may be substituted with a substituent.

[0047] The heterocyclic ring containing a nitrogen atom or a heterocyclic ring containing a nitrogen atom and an oxygen atom may be, for example, a morpholine ring.

[0048] Specific examples of N,N-disubstituted (meth)acrylamide include N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-diisopropyl (meth)acrylamide, N,N-di(n-butyl) (meth)acrylamide, N,N-di(tert-butyl) (meth)acrylamide and other N,N-dialkyl (meth)acrylamide; 4-(meth)acryloylmorpholine and the like. Among these, the N,N-disubstituted (meth)acrylamide may be 4-(meth)acryloylmorpholine or 4-acryloylmorpholine (ACMO).

[0049] In addition, since N,N-disubstituted (meth)acrylamide has a radical polymerizable group, it can also play the role of a compound having a radical polymerizable group (a (meth)acrylamide derivative) described later.

[0050] From the viewpoint that the adhesive composition exhibits adhesive strength in a short time, the content of the stabilizer can be 0.1 mass % or more, 1 mass % or more, 3 mass % or more, or 5 mass % or more based on the total amount of the initiator. The content of the stabilizer can be 30 mass % or less, 25 mass % or less, 20 mass % or less, or 15 mass % or less based on the total amount of the initiator.

[0051] From the viewpoint of the adhesive composition showing adhesive strength in a short time, the content of the stabilizer can be 0.01 mass % or more, 0.05 mass % or more, 0.1 mass % or more, or 0.5 mass % or more based on the total amount of the main agent and the initiator. From the viewpoint of the toughness of the adhesive layer, the content of the stabilizer can be 10 mass % or less, 7 mass % or less, 5 mass % or less, or 3 mass % or less based on the total amount of the main agent and the initiator.

[0052] From the viewpoint of the adhesive composition showing adhesive strength in a short time, the content of the stabilizer can be 0.01 mol% or more, 0.05 mol% or more, 0.1 mol% or more, or 0.5 mol% or more based on the total amount of the compound having a free radical polymerizable group. From the viewpoint of the toughness of the adhesive layer, the content of the stabilizer can be 10 mol% or less, 7 mol% or less, 5 mol% or less, or 3 mol% or less based on the total amount of the compound having a free radical polymerizable group.

[0053] (Network Breaker)

[0054] The main agent contains a complex breaker. The complex breaker refers to a compound that can generate an organoborane by dissociating the Lewis base in the organoborane complex (organoborane-Lewis base complex). Therefore, the organoborane complex contained in the initiator and the complex breaker contained in the main agent are mixed and reacted to generate an organoborane that can serve as an initiator for living free radical polymerization.

[0055] From the viewpoint of shortening the curing time of the adhesive composition, the complex breaker includes maleic anhydride. The complex breaker may be composed of maleic anhydride alone.

[0056] From the viewpoint of shortening the curing time of the adhesive composition, the content of maleic anhydride can be 80% by mass or more, 90% by mass or more, 95% by mass or more, 98% by mass or more, or 99% by mass or less, based on the total amount of the complex breaker.

[0057] In the range that does not hinder the effect of the present invention, the decomplexing agent may include other decomplexing agents in addition to maleic anhydride. As other decomplexing agents, for example, acids, anhydrides, aldehydes, β-keto compounds, etc. can be cited. These can be used alone or in combination of two or more. As acids, for example, Lewis acids such as SnCl4 and TiCl4, Broensted acids such as aliphatic carboxylic acids and aromatic carboxylic acids can be cited. As anhydrides, for example, acetic anhydride, propionic anhydride, succinic anhydride, phthalic anhydride, etc. can be cited. As aldehydes, for example, benzaldehyde, o-, m- and p-nitrobenzaldehyde, etc. can be cited. As β-keto compounds, for example, methyl acetoacetate, ethyl acetoacetate, tert-butyl acetoacetate, 2-methylacyloxyethyl acetoacetate, etc. can be cited.

[0058] From the viewpoint of shortening the curing time of the adhesive composition, the content of other network breakers may be 0-20 mass %, 0-10 mass %, 0-5 mass %, 0-2 mass % or 0-1 mass % based on the total amount of network breakers.

[0059] From the viewpoint of shortening the curing time of the adhesive composition, the content of the network-breaking agent can be 0.01 mass %, 0.1 mass %, 0.2 mass % or 0.3 mass % or more, based on the total amount of the main agent. From the viewpoint of ensuring the operation time from applying the adhesive composition to the adherend to laminating, the content of the network-breaking agent can be 10 mass %, 5 mass %, 3 mass %, 2 mass % or 1 mass % or less, based on the total amount of the main agent.

[0060] From the viewpoint of shortening the curing time of the adhesive composition, the content of the network-breaking agent can be 0.01% by mass, 0.1% by mass, 0.2% by mass or 0.3% by mass based on the total amount of the main agent and the initiator. From the viewpoint of ensuring the operation time from applying the adhesive composition to the adherend to laminating, the content of the network-breaking agent can be 10% by mass or less, 7% by mass or less, 5% by mass or less, 3% by mass or less or 1% by mass based on the total amount of the main agent and the initiator.

[0061] The molar ratio of the breaker to the organoborane complex (molar ratio of the breaker / molar ratio of the organoborane complex) can be, for example, more than 0.3, more than 0.5, more than 0.8 or more than 1. If the molar ratio is more than 1, it tends to obtain more sufficient bonding strength. The molar ratio of the breaker to the organoborane complex (molar ratio of the breaker / molar ratio of the organoborane complex) can be, for example, less than 50, less than 30, less than 10, less than 7, less than 5 or less than 3. The smaller the molar ratio, the more it tends to be able to more fully ensure the tendency of the operating time from applying the adhesive composition to the adherend to the bonding.

[0062] (Compound having a radical polymerizable group)

[0063] At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group. The compound having a free radical polymerizable group is a compound having a polymerizable group that reacts by free radicals. As the free radical polymerizable group, for example, (meth) acryloyl, vinyl, allyl, styryl, alkenyl, alkenylene, maleimide, etc. can be cited.

[0064] The compound having a free radical polymerizable group may contain, for example, a compound having a (meth)acryloyl group. Examples of the compound having a (meth)acryloyl group include: a monofunctional (meth)acrylate having one (meth)acryloyl group, a polyfunctional (meth)acrylate having two or more (meth)acryloyl groups, and a (meth)acrylamide derivative. Among these, the compound having a (meth)acryloyl group may be a monofunctional (meth)acrylate having one (meth)acryloyl group.

[0065] Examples of the monofunctional (meth)acrylate include (meth)acrylic acid; methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate (n-dodecyl (meth)acrylate), isobutyl (meth)acrylate, tert-butyl (meth)acrylate, n-pentyl (meth)acrylate, n-hexyl (meth)acrylate, n-octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, dodecyl (meth)acrylate (n-dodecyl (meth)acrylate), isobutyl (meth)acrylate, Alkyl (meth)acrylates having an alkyl group, such as coryl, stearyl (meth)acrylate, and isostearyl acrylate; alkenyl (meth)acrylates having an alkenyl group, such as 3-butenyl (meth)acrylate; (meth)acrylates having an aromatic group, such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; methoxytetraethylene glycol (meth)acrylate, methoxyhexaethylene glycol (meth)acrylate, methoxyoctaethylene glycol (meth)acrylate, methoxynonaethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate, methoxyheptaethylene glycol (meth)acrylate Alkoxypolyalkylene glycol (meth)acrylates such as alcohol (meth)acrylate, ethoxytetraethylene glycol (meth)acrylate, butoxyethylene glycol (meth)acrylate, butoxydiethylene glycol (meth)acrylate; (meth)acrylates having an alicyclic group such as cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and dicyclopentyl (meth)acrylate; (meth)acrylates having a hydroxyl group such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate; N,N-dimethylaminoethyl (meth)acrylate. (meth)acrylates having an amino group such as methacryloyloxyethoxy)ethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and the like; (meth)acrylates having an isocyanate group such as tetraethylene glycol mono(meth)acrylate, hexaethylene glycol mono(meth)acrylate, hexapropylene glycol mono(meth)acrylate, dipropylene glycol mono(meth)acrylate, tripropylene glycol mono(meth)acrylate, and hexapropylene glycol mono(meth)acrylate; (meth)acrylates having a siloxane skeleton. These may be used alone or in combination of two or more.

[0066] Examples of the multifunctional (meth)acrylate include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, tetrapropylene glycol di(meth)acrylate, and polypropylene glycol di(meth)acrylate. , ethoxylated polypropylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate, 1,4-butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 2-butyl-2-ethyl-1,3-propanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate aliphatic (meth)acrylates such as ethoxylated bisphenol A di(meth)acrylate, propoxylated bisphenol A di(meth)acrylate, ethoxylated propoxylated bisphenol A di(meth)acrylate, ethoxylated bisphenol F di(meth)acrylate, propoxylated bisphenol F di(meth)acrylate, Aromatic (meth)acrylates such as (meth)acrylate, ethoxylated propoxylated bisphenol F type di(meth)acrylate, ethoxylated fluorene type di(meth)acrylate, propoxylated fluorene type di(meth)acrylate, ethoxylated propoxylated fluorene type di(meth)acrylate; aromatic epoxy (meth)acrylates such as bisphenol type epoxy (meth)acrylate, phenol novolac type epoxy (meth)acrylate, cresol novolac type epoxy (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0067] 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 4-(meth)acryloylmorpholine. These may be used alone or in combination of two or more.

[0068] The compound having a radical polymerizable group may include, for example, a copolymerizable compound copolymerizable with a (meth)acryloyl group in addition to a compound having a (meth)acryloyl group. Examples of the copolymerizable compound include compounds having a radical polymerizable group other than a (meth)acryloyl group, such as styrene, 4-methylstyrene, vinylpyridine, vinylpyrrolidone, vinyl acetate, cyclohexylmaleimide, and phenylmaleimide.

[0069] The compound having a radical polymerizable group may be contained in at least one of the main agent and the initiator. For example, the main agent may contain a compound having a radical polymerizable group.

[0070] From the viewpoint of improving the toughness of the adhesive layer and improving the adhesive strength, the content of the compound having a radical polymerizable group can 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 the initiator. From the viewpoint of suppressing the sagging of the applied adhesive composition and suppressing the reduction in the toughness of the adhesive layer, the content of the compound having a radical polymerizable group can be 99% by mass or less, 98% by mass or less, 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 the initiator.

[0071] (Polymerization Control Agent)

[0072] At least one of the main agent and the initiator further contains at least one selected from the group consisting of a halogenated metal salt and a compound having a thiocarbonylthio structure as a polymerization control agent.

[0073] As the metal halide salt, for example, copper bromide (II), copper chloride (II), iron bromide (III), vanadium bromide (III), chromium bromide (III), ruthenium bromide (III), copper bromide (I), iron bromide (II), manganese bromide (II), cobalt bromide (II), nickel bromide (II), palladium bromide (II), etc. can be mentioned. These can be used alone or in combination of two or more. The metal halide salt can be, for example, copper bromide (II).

[0074] The compound having a thiocarbonylthio structure can be used without particular limitation as long as it has a thiocarbonylthio structure. For example, a chain transfer agent (RAFT agent) used in the field of RAFT polymerization (Reversible Addition / Fragmentation Chain Transfer) can be suitably used.

[0075] The polymerization control agent may be contained in at least one of the main agent and the initiator. For example, the main agent may contain the polymerization control agent.

[0076] From the viewpoint of ensuring the operation time from applying the adhesive composition to the adherend to laminating and improving the bonding strength, the content of the polymerization control agent can be 0.01 mass %, 0.02 mass %, 0.03 mass % or 0.05 mass % based on the total amount of the main agent and the initiator. From the viewpoint of the storage stability of the main agent, the content of the polymerization control agent can be 5 mass %, 3 mass %, 1 mass %, 0.5 mass % or 0.1 mass % based on the total amount of the main agent and the initiator.

[0077] From the viewpoint of ensuring the operation time from applying the adhesive composition to the adherend to laminating and improving the bonding strength, the content of the polymerization control agent can 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 the compound having a free radical polymerizable group. From the viewpoint of the storage stability of the main agent, the content of the polymerization control agent can be 5 mol% or less, 3 mol% or less, 1 mol% or less, 0.7 mol% or less, 0.5 mol% or less, or 0.2 mol% or less based on the total amount of the compound having a free radical polymerizable group.

[0078] (filler)

[0079] The filler may be, for example, an inorganic filler or an organic filler. Examples of the inorganic filler include silica, alumina, silica-alumina, titanium oxide, zirconium oxide, magnesium oxide, kaolin, talc, calcium carbonate, bentonite, mica, sericite, glass flakes, glass fibers, graphite, magnesium hydroxide, aluminum hydroxide, antimony trioxide, barium sulfate, zinc borate, wollastonite, xonotlite, crystal whiskers and other inorganic particles. When the inorganic filler is used as the filler, the inorganic filler may include a silica filler.

[0080] As organic fillers, for example, organic microparticles such as silicone, acrylic silicone, acrylic rubber, MBS (methacrylate butadiene styrene), polyamide, polyimide, etc. can be cited. These fillers (microparticles) may have a uniform structure or a core-shell structure. When an organic filler is used as a filler, the organic filler may include acrylic core-shell particles.

[0081] The organic filler may contain an antioxidant in the organic filler. The content of the antioxidant in the organic filler may be, for example, 15000 mass ppm or less, 10000 mass ppm or less, 5000 mass ppm or less, or 3000 mass ppm or less.

[0082] The filler can be contained in at least one of the main agent and the initiator. For example, the main agent can contain a filler containing an organic filler, or a filler containing acrylic core-shell particles. Furthermore, for example, the initiator can contain a filler containing an inorganic filler, or a filler containing a silica filler.

[0083] The content of the filler may be 1 mass % or more, 3 mass % or more, or 5 mass % or less, or 40 mass % or less, 35 mass % or less, or 30 mass % or less, based on the total amount of the main agent and the initiator.

[0084] (Plasticizer)

[0085] Examples of the plasticizer include phthalate-based compounds, alkylsulfonate-based compounds, and adipate-based compounds.

[0086] The plasticizer may contain at least one of a main agent and an initiator.

[0087] The content of the plasticizer may be 0.1 mass % or more, 0.3 mass % or more, or 1.0 mass % or less, or 30 mass % or less, 20 mass % or less, or 10 mass % or less, based on the total amount of the main agent and the initiator.

[0088] At least one of the main agent and the initiator may further contain, in addition to the above-mentioned components, a crosslinking agent, an ultraviolet absorber, a dehydrating agent, a pigment, a dye, an anti-aging agent, an antioxidant, an antistatic agent, a flame retardant, a tackifier, a dispersant, a solvent, and the like.

[0089] The adhesive kit of this embodiment can prepare an adhesive composition by mixing a main agent and an initiator. The temperature when the main agent and the initiator are mixed can be, for example, 10 to 35° C. The pot life of the adhesive kit can be, for example, 0.1 to 10 minutes.

[0090] When the main agent and the initiator are mixed, the molar ratio of the complex breaker in the main agent to the organic borane complex in the initiator (molar amount of the complex breaker / molar amount of the organic borane complex) is preferably greater than 0.3, greater than 0.5, greater than 0.8 or greater than 1, or less than 50, less than 30, less than 10, less than 7, less than 5 or less than 3.

[0091] When the main agent and the initiator are mixed, the main agent to the initiator is preferably mixed in a mass ratio (mass of the main agent / mass of the initiator) of, for example, 1 or more, 3 or more, or 5 or less, 200 or less, 100 or less, or 50 or less.

[0092] The method of mixing the main agent and the initiator is not particularly limited as long as the two are mixed. As a method of mixing the main agent and the initiator, for example, there can be cited: a method of mixing by hand, a method of mixing by manual coating using a common caulking gun, etc., a method of mixing using a pump (for example, a gear pump, a plunger pump, etc.) and a throttle valve that have quantitative liquid delivery for the raw material, and a method of mixing using a mechanical rotary mixer, a static mixer, etc. In addition, the mixing of the two and the coating of the adhesive composition described later can be continuously implemented by using a dispenser, a pistol, etc. that has a mechanism for separately configuring the main agent and the initiator, feeding the liquid to the nozzle, etc. from each place, mixing the two inside the nozzle, etc., and spitting out from the nozzle tip.

[0093] The prepared adhesive composition can be applied to a predetermined position to form an adhesive layer. Since the compound having a free radical polymerizable group is cured at a high molecular weight, the adhesive layer thus formed functions as an adhesive layer for bonding substrates to each other. The method of applying to a predetermined position can be applied by a previously known method such as a method using a dispenser.

[0094] The adhesive composition may be cured at a curing temperature of 10 to 35° C. and a curing time of 24 to 96 hours, for example.

[0095] [Adhesive body and method for producing the same]

[0096] An adhesive body according to one embodiment includes a first adherend, a second adherend, and an adhesive layer for bonding the first adherend and the second adherend to each other. The adhesive layer contains a cured product of the adhesive composition containing a main agent and an initiator in the adhesive set described above.

[0097] As the first adherend and the second adherend, for example, there can be mentioned plastic substrates such as polypropylene (PP), polyvinyl chloride, acrylonitrile / butadiene / styrene copolymer (ABS), polycarbonate (PC), polyamide (PA), polymethyl methacrylate (PMMA), polyester, epoxy resin, polyurethane (PUR), polyoxymethylene (POM), polyethylene (PE), ethylene / propylene copolymer (EPM), ethylene / propylene / diene polymer (EPDM), and metal substrates such as aluminum, steel, copper, and stainless steel.

[0098] Examples of the bonded body include plastic laminated substrates, metal laminated substrates, electronic components, semiconductor devices, and display components.

[0099] The manufacturing method of an adhesive body of one embodiment comprises: a step of bonding a first adherend and a second adherend via an adhesive composition containing a main agent and an initiator. The temperature when mixing the main agent and the initiator in the adhesive set, the conditions for curing the adhesive composition, etc. can be the same as above.

[0100] Example

[0101] Hereinafter, the present invention will be described in further detail with reference to Examples, but the present invention is not limited to these Examples.

[0102] <Examples 1, 2 and Comparative Example 1>

[0103] [Adhesive kit production]

[0104] (Preparation of raw materials)

[0105] Organoborane complex

[0106] TEB-DAP: Triethylborane-1,3-diaminopropane complex (molecular weight: 172.1, KISHIDA CHEMICAL Co., Ltd.)

[0107] Stabilizer

[0108] ACMO: 4-Acryloylmorpholine (N,N-disubstituted acrylamide, molecular weight: 141.2, KJ Chemicals Corporation)

[0109] Az: 2,2-Bis(hydroxymethyl)-1-butanol-tris[3-(1-aziridinyl)propionate] (molecular weight: 425.5, NIPPONSHOKUBAI CO., LTD., product name: Chemitite PZ-33)

[0110]

[0111] ·Network breaking agent

[0112] Maleic anhydride (molecular weight: 98.1, FUJIFILM Wako Pure Chemical Corporation) Succinic anhydride (molecular weight: 100.1, FUJIFILM Wako Pure Chemical Corporation)

[0113] ·Compounds having free radical polymerizable groups (polymerizable compounds)

[0114] FA-513AS: Dicyclopentyl acrylate (molecular weight: 206.3, SHOWA DENKO MATERIALSCO.,LTD.)

[0115] FA-310A: Phenoxyethyl acrylate (molecular weight: 192.2, SHOWA DENKO MATERIALSCO.,LTD.)

[0116] DMAA: N,N-dimethylacrylamide (molecular weight: 99.1, FUJIFILM Wako Pure Chemical Corporation)

[0117] Polymerization control agent

[0118] Copper(II) bromide (molecular weight: 223.4, FUJIFILM Wako Pure Chemical Corporation)

[0119] ·filler

[0120] RY200S: Fumed silica (fumed silica surface treated with silicone oil, Nippon Aerosil Co., Ltd.)

[0121] M210: acrylic core-shell particles (Kaneka Corporation, no antioxidant detected)

[0122] Plasticizer

[0123] PN-5090: Adipic acid polyester (ADEKA Corporation)

[0124] (Preparation of main agent)

[0125] The decomplexer, the compound having a free radical polymerizable group, the polymerization control agent and the filler were weighed into a plastic bottle in the types and proportions (unit: parts by mass) shown in Table 1, and mixed for 15 minutes at 2000 rpm using an autorotating stirrer (THINKY CORPORATION, Awatori Rentaro), and further defoamed for 5 minutes at 2000 rpm to prepare the main agents of Examples 1, 2 and Comparative Example 1.

[0126] (Preparation of Initiator)

[0127] The organoborane complex, stabilizer, plasticizer and filler were weighed into a plastic bottle in the types and proportions (unit: parts by mass) shown in Table 1, and mixed at 2000 rpm for 15 minutes using an orbital stirrer (THINKY CORPORATION, Awatori Rentaro), and further defoamed at 2000 rpm for 5 minutes to prepare the initiators of Examples 1 and 2 and Comparative Example 1. In addition, the initiators of Example 2 and Comparative Example 1 were the same.

[0128] [Measurement of adhesive strength]

[0129] Two polypropylene substrates (size: 100 mm × 25 mm, thickness: 2 mm) were prepared. A spacer with a thickness of 0.5 mm was arranged on one of the polypropylene substrates so that the coating area of ​​the adhesive composition had a thickness of 0.5 mm, a length direction of 12.5 mm relative to the polypropylene substrate, and a width direction of 25 mm relative to the polypropylene substrate. The main agent and the initiator were mixed by filling each main agent and each initiator into a manual dispenser. Using a manual dispenser, the adhesive coating area of ​​the polypropylene substrate equipped with the spacer was coated and bonded to another polypropylene substrate to obtain a laminate. A plurality of laminates were produced. The obtained laminate was placed at 25°C, and the shear strength was measured after each specified time to obtain the change in shear strength with respect to the curing time. The shear test was conducted at room temperature (25°C) using an automatic stereogrammer (manufactured by SHIMADZUCORPORATION, model: AGS X Plus, load cell: 50 kN) with a chuck distance of 100 mm and a pull rate of 5 mm / min. The strength at break was measured, and the shear bond strength (MPa) was calculated from the measured value and the bond area. The results are shown in Figure 1 middle.

[0130] [Curing property of overflow part]

[0131] Two polypropylene substrates (size: 100mm×25mm, thickness: 2mm) were prepared. A spacer with a thickness of 0.5mm was arranged on one of the polypropylene substrates so that the coating area of ​​the adhesive composition was 0.5mm thick, 12.5mm in the length direction relative to the polypropylene substrate, and 25mm in the width direction relative to the polypropylene substrate. The main agent and the initiator were mixed by filling each main agent and each initiator into a manual dispenser. Using a manual dispenser, the adhesive coating area of ​​the polypropylene substrate equipped with a spacer was coated and bonded to another polypropylene substrate to obtain a laminate. The laminate obtained by placing it at 25°C for 48 hours obtained an adhesive. A digital camera was used to shoot from the side of the obtained adhesive, and the state of the adhesive composition overflowing from the adherend was evaluated. The state of the adhesive composition of the overflowing portion is white as a whole and the curing is considered to be good and evaluated as "A", and the state of the adhesive composition of the overflowing portion is evaluated as "B" when it is uncured. The results are shown in Table 1.

[0132] [Table 1]

[0133]

[0134] Figure 1 Graph showing the change in shear strength with respect to curing time of Examples 1 and 2 and Comparative Example 1. Figure 1 As shown, the adhesive compositions containing maleic anhydride as the network breaker of Examples 1 and 2 have a shorter time until sufficient adhesive strength is obtained than the adhesive composition containing succinic anhydride as the network breaker of Comparative Example 1. In addition, the adhesive compositions of Examples 1 and 2 are also superior in curability of the overflow portion compared to the adhesive composition of Comparative Example 1. From these results, it can be confirmed that the adhesive set of the present invention can prepare an adhesive composition that can sufficiently shorten the curing time.

Claims

1. An adhesive kit comprising: The main agent contains a network-breaking agent; and Initiator, containing an organoborane complex, The complex breaking agent comprises maleic anhydride, At least one of the main agent and the initiator further contains a compound having a free radical polymerizable group, At least one of the main agent and the initiator further contains at least one selected from the group consisting of a halogenated metal salt and a compound having a thiocarbonylthio structure.

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

3. A method for manufacturing an adhesive body, which is the method for manufacturing an adhesive body according to claim 2, comprising: A step of bonding the first adherend and the second adherend together via an adhesive composition containing the main agent and the initiator.

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