JP2009275160A - Bonding method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a bonding method capable of omitting mixing of a base resin with a hardener before applying a two-component adhesive to adherends, provided that the bonding method is the one intended to achieve simplification and laborsaving of a bonding operation when bonding adherends by omitting a step of mixing a base resin and a hardener, which has been conventionally carried out when using two-component adhesives. <P>SOLUTION: The bonding method comprises applying a base resin to one of the adherends and applying a hardener to the other adherend without mixing a base resin and a hardener of the two-component adhesive and subsequently bonding the adhesive-applied surfaces of the adherends to each other. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for bonding a two-component adhesive comprising a main agent and a curing agent.

  Two-component adhesives have high adhesive strength, and the adhesive itself can be designed in a variety of ways from flexible to high-strength, so it can be used in various applications such as sealing materials, general-purpose adhesives, and structural adhesives. It is used.

  As two-component adhesives, polyurethane adhesives with isocyanate prepolymer as the main component and polyether polyol as the curing agent, epoxy resin adhesives with epoxy resin as the main component and polyamine compound, dicyan compound, imidazole, etc. as the curing agent Radical curable adhesives containing acrylic monomers and oligomers are known.

  A polyurethane adhesive is prepared by mixing a main agent containing an isocyanate prepolymer and a curing agent containing a polyether polyol or polyamines, and then applying the mixture to an adherend, followed by heating at room temperature or heating (see Non-Patent Document 1). .

  Epoxy resin adhesives are available in one-part types using latent curing agents such as hydrazide and dicyandiamide, but are usually used by mixing the main component epoxy resin with the curing agent polyamine, modified polyamine, polyamide, etc. (Refer nonpatent literature 2).

  The radical curable adhesive is also referred to as a second generation acrylic adhesive and is usually referred to as SGA. The SGA includes a main agent containing a curing agent, a coating type (also referred to as a primer type) composed of a primer in which a curing accelerator is dissolved or dispersed in a solvent or the like, a curing agent on one side, and a curing accelerator on the other side. It is divided into a liquid mixing type (also referred to as a two-component type) (see Non-Patent Document 3).

  The primer type is a separately coated type, but in general, the main agent is applied thickly and the primer is thinly applied in order to prevent curing failure and peeling at the adherend interface. If the primer is thicker than necessary, it will cause curing failure and adhesion failure. On the other hand, if the film thickness of the main agent becomes too thick, the curing accelerator from the primer will not sufficiently penetrate and diffuse into the main agent, resulting in poor curing and insufficient adhesion. For this reason, it is difficult to bond the adherends having complicated shapes or to adhere to the same adherend with portions having different adhesive thicknesses. In addition, the primer type has a defect that the primer tends to cause interfacial peeling on the primer application side because the primer does not contain a binder that exhibits adhesive strength.

  The radical curable adhesive is also referred to as an acrylic resin adhesive or SGA (second generation adhesive) (see Non-Patent Document 4). In Non-Patent Document 4, the radical curable adhesive is capable of rapid curing at room temperature by contact of two liquids of the main agent and the curing agent, as long as the main agent and the curing agent are in contact with each other without strict mixing. It is described to cure. However, when the mixing of the main agent and the curing agent is insufficient, the curing often remains at the contact portion, and in particular, when the adhesive film thickness is thin, the whole becomes a semi-cured state and the adhesive strength is reduced. It was a drop or interface peeling at the adherend interface. As described in Non-Patent Document 4, curing of the adhesive is started without strict mixing, but sufficient adhesive strength is not exhibited, so the main agent and the curing agent were mixed at the site where bonding is performed. It was usually applied to the adherend later.

  A technique for improving the application workability of a two-component mixed type (radical curable adhesive) is disclosed (see Patent Document 1).

  As shown in Patent Document 1, a normal radical curable adhesive is usually required to exert adhesive force up to the deep part of the adhesive, that is, the interface with the adherend, although curing is started by contacting the adhesive. Sufficient curing did not proceed, and the vicinity of the interface with the adherend was likely to cause poor curing and easily cause interface peeling. The adhesive described in Patent Document 1 cannot be carried out at the actual bonding site because of poor curing and poor bonding near the adherend interface.

Technology relating to a room temperature fast-curing two-component acrylic composition comprising a main agent to which a radical polymerization initiator is added and a specific polymerization accelerator, that is, a curing agent to which 2-mercaptobenzimidazole and a divalent copper compound are added Has been proposed (see Patent Document 2). The proposed technology is based on the premise that the main agent and the curing agent are mixed before applying the adhesive, as shown in the examples, and the proposed technology has an unusually high curing speed, so that the main agent and the curing agent are mixed. It is easily inferred that the curing to the deep part of the adhesive does not proceed sufficiently only by the contact of.
Santo Motosato, “Tocoton Easy Bonding Book”, published by Nikkan Kogyo Shimbun, 2003, p. 132-133 Santo Motosato, “Tocoton Easy Bonding Book”, published by Nikkan Kogyo Shimbun, 2003, p. 116-117 Santo Motosato, “Tocoton Easy Bonding Book”, published by Nikkan Kogyo Shimbun, 2003, p. 128-129 “15308 Chemical Products”, published by Chemical Industry Daily, 2008, p. p1462 JP 2005-179548 A JP 2003-2915 A

  The adhesion method of the present invention proposes an adhesion method in which the mixing of the main agent and the curing agent can be omitted before the two-component adhesive is applied to the adherend.

  In the bonding method of the present invention, the main component and the curing agent of the two-component adhesive are applied after the main component is applied to one of the adherends and the curing agent is applied to the other of the adherends without mixing the main agent and the curing agent. It is the adhesion | attachment method which bonds the adhesive agent coating surface of a to-be-adhered body.

  Specifically, in the bonding method of the present invention, when bonding the adherend, the mixing process of the main agent and the curing agent, which is conventionally performed with a two-component adhesive, is not performed, and the bonding operation is simplified and labor-saving is achieved. It is an adhesion method.

  In the case of a two-component adhesive, a curing reaction is started when the adhesive main agent and the curing agent are mixed, and for the pot life where the adhesive viscosity rises to a viscosity inappropriate for the application operation in a relatively short time, Although the bonding work and the bonding process were limited, in the bonding method of the present invention, it is not necessary to substantially consider the pot life in the bonding process, and therefore the bonding process, the bonding work procedure, etc. can be arbitrarily set. it can.

  Since the main component and curing agent of the two-component adhesive are not mixed before being applied to the adherend, the mixing step is omitted. In addition, since air is bubbled into the adhesive by mixing and causes a decrease in adhesive strength, a defoaming step is usually required. However, in the bonding method of the present invention, a two-component adhesive is applied to the adherend. Since the main agent and the curing agent are not mixed before, foaming does not occur and a defoaming step is unnecessary. Omitting the two steps leads to great rationalization, labor saving, and total cost reduction.

  In the case of a two-component adhesive main agent and a curing agent, particularly a radical curable two-component mixed type, the working time is limited in terms of pot life from the point of mixing. In the bonding method of the present invention, since the main agent and the curing agent are not mixed before the adhesive is applied, it is free from the troublesome problem of pot life. Furthermore, it is possible to produce the adherends to which the main agent and the curing agent are separately applied, produce them separately, store them, and bond both adherends together when necessary, There are significant advantages in planning production.

  The product to be bonded by the bonding method of the present invention is not inferior in performance as compared with the conventional bonding method in which the main agent and the curing agent are mixed in advance and then applied to the adherend. There is no variation in the bonding method of the present invention, compared to the conventional bonding method in which the adhesive force varies between the base material and the curing agent that are bonded immediately after mixing, and the one that is bonded at the very end of the pot life. , Best performance at any time.

  In the bonding method of the present invention, the main component and the curing agent of the two-component adhesive are applied after the main component is applied to one of the adherends and the curing agent is applied to the other of the adherends without mixing the main agent and the curing agent. The adhesive application surface of the adherend is bonded.

  For example, FIG. 1 shows a state in which the main agent is applied to one of the adherends and the curing agent is applied to the other of the adherends.

  In the bonding method of the present invention, the method of applying the adhesive to the adherend can also be performed by the method shown in FIGS.

  In the bonding method of the present invention, any one of the methods may be performed alone, or two or more of these methods may be combined.

  In the bonding method of the present invention, as the two-component adhesive, for example, a polyurethane-based adhesive including an isocyanate prepolymer or the like as a main component and a polyether polyol or the like as a curing agent, a bisphenol A-type epoxy resin or the like as a main component. Examples thereof include an epoxy resin adhesive that is contained in the main agent and contains dipropylene glycol diaminopropyl ether, metaxylenediamine, and the like as a curing agent, a chlorosulfonated polyethylene, a radical curable adhesive (SGA) that contains an acrylic monomer, and the like.

  In the bonding method of the present invention, the adherend is made of metals and alloys such as iron, aluminum, copper, stainless steel, nickel, titanium, ABS resin, polycarbonate resin, polyphenylene oxide resin, polypropylene resin, nylon resin, polyester resin, and the like. Thermoplastics and alloys, fiber reinforced grades, epoxy resins, unsaturated polyester resins, vinyl ester resins, thermosetting plastics such as phenolic resins, glass, cement, mortar, bricks, stones, tiles, and other inorganic materials Illustrated. In the bonding method of the present invention, these adherends can be bonded by bonding different materials such as an aluminum alloy and a carbon fiber reinforced epoxy resin, even if bonded by a single material such as an aluminum alloy and an aluminum alloy. There may be.

  In the bonding method of the present invention, the method of applying the adhesive to the adherend is, for example, applying with a brush or a spatula, applying in a stripe shape using a pump or a flow coater, or spotting using an application robot. Methods such as applying and using a tubular extruder used in sealants may also be used.

  In the bonding method of the present invention, the adherend is bonded by bonding the surfaces of the adherend to which the adhesive has been applied. In the bonding method of the present invention, the bonding may be performed only by overlapping the adhesive-coated surface of the adherend, but in consideration of the shape, material, and bonding area of the adherend, it is recommended that the bonding be performed. .

  In the bonding method of the present invention, the film thickness to which the adhesive is applied is preferably 50 μm to 10 mm, more preferably 100 μm to 8 mm, and still more preferably 100 μm to 6 mm. In the bonding method of the present invention, when the adhesive film thickness is 50 μm to 10 mm, there is a tendency that the adhesive sagging or protrusion is suppressed, the adhesive has good curability, and a strong adhesive force tends to be expressed. It can be seen.

  In the bonding method of the present invention, when the adherend to which the adhesive is applied is bonded, curing of the adhesive is started.

In the bonding method of the present invention, in order to improve the mixing and diffusion of the main component and curing agent of the two-component adhesive, to smoothly advance the curing reaction of the adhesive, and to exert a strong adhesive force, the two-component adhesive The viscosity measured at a shear rate of 5 ± 1 s ⁻¹ (25 ° C.) of the main agent and / or curing agent is preferably 500 mPa · s to 60 Pa · s, more preferably 1 Pa · s to 50 Pa · s, Preferably, it is 2 Pa · s to 30 Pa · s.

Furthermore, in the bonding method of the present invention, it is desirable that the main component and / or the curing agent of the two-component adhesive preferably exhibit thixotropic properties at a shear rate of 1 s ^{−1 to} 1000 s ⁻¹ (25 ° C.).

In the bonding method of the present invention, the viscosity of the two-component adhesive was measured at 25 ° C. using a “VAR-type Visco Analyzer” (REOLOGICA viscoelasticity measuring device). The measurement conditions were a measurement temperature of 25 ° C., a parallel plate P30ETC, a gap of 0.100 mm, and a shear rate of 0.1 s ^{−1 to} 1000 s ⁻¹ .

In the bonding method of the present invention, the viscosity measured at a shear rate of 5 ± 1 s ⁻¹ (25 ° C.) of the main component and / or the curing agent of the two-component adhesive is preferably 500 mPa · s to 60 Pa · s, shearing At a speed of 1 s ^{−1 to} 1000 s ⁻¹ (25 ° C.), preferably, when the main component of the two-component adhesive and the curing agent are bonded and brought into contact with each other by exhibiting thixotropic properties, the diffusion and mixing of the adhesive It progresses smoothly, curing proceeds to the deep part of the adhesive, and a strong adhesive force is expressed.

In the bonding method of the present invention, the viscosity A measured at a shear rate of 5 ± 1 s ⁻¹ (25 ° C.) and a shear rate of 50 ± 5 s ⁻¹ (25 ° C.) of the main component and / or the curing agent of the two-component adhesive. The ratio of the viscosity B measured in (1) is preferably 1.002 to 10, more preferably 1.005 to 8.0, and still more preferably 1.01 to 8.0. In the bonding method of the present invention, the viscosity A measured at a shear rate of 5 ± 1 s ⁻¹ (25 ° C.) and a shear rate of 50 ± 5 s ⁻¹ (25 ° C.) of the main component or curing agent of the two-component adhesive are measured. When the ratio of the viscosity B is preferably 1.002 to 10, there is a tendency for the adhesive to diffuse and mix with each other in combination with the contribution of self-structuring of the adhesive, The curing reaction of the adhesive is promoted, the curing of the adhesive at the adherend interface is promoted, and a strong adhesive force is exerted on the adherend. That is, the best performance of the adhesive used is exhibited.

  In the bonding method of the present invention, the two-component adhesive is represented by the following structural formula in the molecule.

(Here, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 8 carbon atoms.)
It is desirable to include an acrylic-acrylic graft copolymer having a branched polymer of poly (meth) acrylic acid alkyl ester.

  The branched polymer of poly (meth) acrylic acid alkyl ester can be preferably produced by using a poly (meth) acrylic acid alkyl ester macromonomer during the production of the acrylic copolymer. In the bonding method of the present invention, the poly (meth) acrylate macromonomer preferably used in the production of the acrylic copolymer is preferably a poly (n-butyl acrylate) macromonomer, a polymethyl methacrylate macromonomer, or a polymethacrylate. An acid n-butyl macromonomer etc. are illustrated. In the bonding method of the present invention, the poly (meth) acrylate macromonomer preferably used in the present invention may be used alone or in a mixture of two or more. In addition, in the bonding method of the present invention, in addition to the poly (meth) acrylate macromonomer, a polystyrene macromonomer, a polyacrylonitrile macromonomer, etc. can be used in combination for improving the physical properties and compatibilization of the adhesive. is there.

  In the bonding method of the present invention, those that are marketed as the poly (meth) acrylate macromonomer preferably used in the present invention are “Aron Macromer AA-6”, “Aron Macromer AB-6” (above, Synthetic products) and the like. Examples of polystyrene macromonomer that can be used to improve adhesive properties and compatibilization include "Aron Macromer AS-6", and polyacrylonitrile macromonomer "Aron Macromer AN-6" (from Toagosei Co., Ltd.). Is done.

  In the bonding method of the present invention, when the two-component adhesive used in the present invention includes an acrylic-acrylic graft copolymer using a poly (meth) acrylic acid alkyl ester macromonomer, the two-component adhesive The main agent and the curing agent are diffused and mixed simultaneously with the contact, and there is a tendency that the curing of the adhesive is uniform and smoothly proceeds to the deep part. As a result, the adhesive is sufficiently cured at the adherend interface, and a strong adhesive force tends to be exhibited.

  The weight average molecular weight of the poly (meth) acrylic acid alkyl ester macromonomer preferably used in the adhesion method of the present invention is preferably 2000 to 50,000, more preferably 3000 to 50,000, and still more preferably 3000 to 3 It is desirable to be 10,000. In the adhesion method of the present invention, when the weight average molecular weight is preferably 2000 to 50,000, mixing and diffusion of the main agent and the curing agent tend to be promoted at the time of bonding the adherend. At the same time, in the bonding method of the present invention, the wettability of the adhesive to various adherends is improved, and the adhesive force is improved.

  In particular, when the adherend is an organic polymer material such as polypropylene alloy, ABS resin, polycarbonate resin, polyphenylene oxide resin, and nylon resin, and these organic polymer materials and metals such as aluminum alloy, iron, and stainless steel When the dissimilar material adhesion is performed, when the weight average molecular weight of the poly (meth) acrylic acid alkyl ester macromonomer preferably used is 2000 to 50,000, there is a tendency that the performance improvement becomes remarkable. In the adhesion method of the present invention, the molecular weight was measured using gel permeation chromatography (GPC) “HLC-8220 GPC system” (Tosoh's measuring device).

  In the bonding method of the present invention, when the two-pack type adhesive contains an acrylic-acrylic graft copolymer using a poly (meth) acrylic acid alkyl ester macromonomer, an acrylic monomer used in the production of the acrylic copolymer The poly (meth) acrylic acid alkyl ester macromonomer is preferably 0.2 to 30% by weight, more preferably 0.5 to 25% by weight, further preferably 1 It is desirable to use ~ 20% by weight. In the bonding method of the present invention, when the amount of the poly (meth) acrylic acid alkyl ester macromonomer used is 0.2 to 30% by weight, the diffusion and mixing of the adhesive occurs smoothly, and the curing of the adhesive is promoted. And strong adhesive strength.

In the bonding method of the present invention, the viscosity A measured at a shear rate of 5 ± 1 s ⁻¹ (25 ° C.) and a shear rate of 50 ± 5 s ⁻¹ (25 ° C.) of the main component and / or the curing agent of the two-component adhesive. In order to make the ratio (A / B) of the viscosity B measured in 1.00 to 10.0, it is preferable that the two-part adhesive preferably contains an acrylic-acrylic graft copolymer. In the adhesion method of the present invention, which is recommended to be, the two-part adhesive preferably contains an acrylic-acrylic graft copolymer, whereby the self-structuring behavior of the acrylic-acrylic graft copolymer, Thixotropic properties are naturally expressed by the formation of the microphase separation structure. In the bonding method of the present invention, at this time, when the main agent and the curing agent of the two-component adhesive come into contact with each other, the diffusion and mixing action of the main agent and the curing agent is promoted, and the adhesive is uniformly and smoothly cured. In the bonding method of the present invention, the two-pack type adhesive has a chemical structure represented by the following structural formula in the molecule.

(Where R3 is a hydrogen atom or a methyl group, R4 is an alkyl group having 2 to 4 carbon atoms, R5 is a hydrogen atom or an alkyl group having 1 to 8 carbon atoms, and n is 0 or 1) Represents 10 to 10 integers.)
It is recommended to include an acrylic resin having

  In the adhesion method of the present invention, the chemical structure represented by the following structural formula in the molecule

(Here, R3 is a hydrogen atom or a methyl group, R4 is an alkyl group having 2 to 4 carbon atoms, R5 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 1 to 10) Represents an integer.)
In the acrylic resin production, the acrylic resin having, preferably 2-methoxyethyl acrylate, 2-ethoxyethyl acrylate, 2-ethoxyethoxyethyl acrylate, 3-methoxypropyl acrylate, 4-methoxybutyl acrylate, Methoxypolyethylene glycol monoacrylate, methoxypolypropylene glycol monoacrylate, methoxypolybutylene glycol monoacrylate, 2-methoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-ethoxyethoxyethyl methacrylate, 3-methoxypropyl methacrylate, methacrylic acid 4-methoxybutyl, methoxypolyethylene glycol monomethacrylate, methoxypolypropylene glycol monomethacrylate, methoxypolybutylene glycol Alkoxy group-containing acrylic monomers such as methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, 4-hydroxybutyl acrylate, polyethylene glycol monoacrylate, polypropylene glycol monoacrylate, polytetramethylene glycol monoacrylate, By using hydroxyl-containing acrylic monomers such as 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate, polyethylene glycol monomethacrylate, polypropylene glycol monomethacrylate, polytetramethylene glycol monomethacrylate, etc. Can be manufactured. In the bonding method of the present invention, these acrylic monomers may be used alone or in a mixture of two or more.

  In the adhesion method of the present invention, an alkoxy group-containing acrylic monomer or a hydroxyl group-containing acrylic monomer is preferable as the acrylic monomer used in the production of the acrylic resin. The alkoxy group-containing acrylic monomer or hydroxyl group-containing acrylic monomer that is preferably used, with the total amount of acrylic monomers being 100% by weight, is preferably 0.5-30% by weight, more preferably 3%. It is desirable to use -30% by weight, more preferably 5-25% by weight. In the bonding method of the present invention, when the two-pack adhesive contains the acrylic resin, the amount of the alkoxy group-containing acrylic monomer or hydroxyl group-containing acrylic monomer that is preferably used is 0.5 to 30% by weight. %, The cohesive force of the adhesive is improved and a strong adhesive force is expressed.

  In the bonding method of the present invention, the two-part adhesive is preferably a chemical structure represented by the following structural formula in the molecule.

(Where R6 is a hydrogen atom or a methyl group, R7 is an alkyl group having 1 to 6 carbon atoms, R8 is an alkyl group having 2 to 4 carbon atoms, and R9 is a hydrogen atom or a methyl group. To express.)
It is recommended to include an acrylic resin having

  In the bonding method of the present invention, the chemical structure represented by the following structural formula that is preferably contained in the molecule of the acrylic resin that is preferably used in the two-pack adhesive is:

(Where R6 is a hydrogen atom or a methyl group, R7 is an alkyl group having 1 to 6 carbon atoms, R8 is an alkyl group having 2 to 4 carbon atoms, and R9 is a hydrogen atom or a methyl group. To express.)
Preferably an acrylic resin having a hydroxyl group in the molecular side chain, and preferably an isocyanate group-containing acrylic monomer represented by the following structural formula

(Here, R12 represents a hydrogen atom or a methyl group, and R13 represents an alkyl group having 2 to 4 carbon atoms.)
It is desirable to produce by addition reaction with.

  In the bonding method of the present invention, the isocyanate group-containing acrylic monomer preferably used for the production of the two-component adhesive is 2-isocyanate ethyl acrylate, 2-isocyanate ethyl methacrylate, 3-isocyanate propyl acrylate, 3- Illustrative examples include isocyanate propyl methacrylate, 4-isocyanate butyl acrylate and 4-isocyanate butyl methacrylate. In the bonding method of the present invention, these isocyanate group-containing acrylic monomers preferably used may be used alone or in a mixture of two or more.

  In the bonding method of the present invention, in the bonding method of the present invention, the two-component adhesive is preferably a chemical structure represented by the following structural formula in the molecule.

(Where R6 is a hydrogen atom or a methyl group, R7 is an alkyl group having 1 to 6 carbon atoms, R8 is an alkyl group having 2 to 4 carbon atoms, and R9 is a hydrogen atom or a methyl group. To express.)
Including an isocyanate group-containing acrylic resin having a two-component adhesive exhibits radical curability, forms a tough network structure after curing, and has strong adhesive force, chemical resistance, heat resistance, etc. There is a tendency to demonstrate.

  In the bonding method of the present invention, the isocyanate group-containing acrylic monomer preferably used for the production of the two-component adhesive is preferably 5 to 100 mol%, more preferably, based on the hydroxyl group of the acrylic resin molecule side chain. It is desirable to use 8 to 90 mol%, more preferably 10 to 85 mol%. At this time, the acrylic resin preferably used has a hydroxyl value of preferably 5 to 80 mgKOH, more preferably 8 to 60 mgKOH, and further preferably 10 to 45 mgKOH. In the bonding method of the present invention, the hydroxyl value of the acrylic resin is such that the total amount of acrylic monomers used in the acrylic resin is 100% by weight, and the amount of the hydroxyl-containing acrylic monomer used is (OH)% by weight. In this case, the hydroxyl value of the acrylic resin (mgKOH) = (OH) ÷ (molecular weight of the hydroxyl group-containing acrylic monomer) × 561.

  In the bonding method of the present invention, when the hydroxyl value of the acrylic resin is 5 to 80 mg KOH and the amount of the isocyanate group-containing acrylic monomer is 5 to 100 mol%, the two-component adhesive has the best curability and adhesion. Demonstrate power.

  In the bonding method of the present invention, the two-part adhesive is preferably a chemical structure represented by the following structural formula in the molecule.

(Here, R10 represents a hydrogen atom or a methyl group, an R11 hydrogen atom or a methyl group.)
It is recommended to include an acrylic resin having

  In the bonding method of the present invention, the chemical structure represented by the following structural formula that is preferably contained in the molecule of the acrylic resin that is preferably used in the two-component adhesive is:

(Here, R10 represents a hydrogen atom or a methyl group, and R11 represents a hydrogen atom or a methyl group.)
Preferably, an acrylic resin having a carboxyl group in the molecular side chain, and preferably an epoxy group-containing acrylic monomer represented by the following structural formula

(Here, R14 represents a hydrogen atom or a methyl group.)
It is desirable to produce by addition reaction with.

  In the bonding method of the present invention, examples of the epoxy group-containing acrylic monomer include glycidyl acrylate and glycidyl methacrylate. In the bonding method of the present invention, these epoxy group-containing acrylic monomers may be used alone or in combination of two kinds.

  In the bonding method of the present invention, the two-component adhesive preferably has a chemical structure represented by the following structural formula in the molecule.

(Here, R10 represents a hydrogen atom or a methyl group, and R11 represents a hydrogen atom or a methyl group.)
By containing, the two-component adhesive comes to exhibit radical curability and forms a tough network structure after curing, and exhibits strong adhesive force, chemical resistance, heat resistance, and the like.

  In the bonding method of the present invention, the acrylic resin having a carboxyl group in the molecular side chain preferably contained in the two-pack adhesive has an acid value of preferably 3 to 80 mgKOH, more preferably 5 to 65 mgKOH, Preferably, it is 5 to 50 mgKOH.

  In the bonding method of the present invention, the acid value of the acrylic resin was measured according to JIS K 6407: 1997.

  In the bonding method of the present invention, the epoxy group-containing acrylic monomer preferably used for the production of the two-pack type adhesive is preferably 5 to 100 mol%, more preferably of the carboxyl group of the acrylic resin side chain. 8 to 85 mol%, more preferably 10 to 80 mol%. In the bonding method of the present invention, when the acid value of the acrylic resin is 3 to 80 mg KOH and the usage amount of the epoxy group-containing acrylic monomer is 5 to 100 mol%, the curability of the two-component adhesive is improved and strong. Adhesive strength is demonstrated.

  In the bonding method of the present invention, the acrylic resin preferably used for the two-component adhesive in the present invention has a weight average molecular weight of preferably 20,000 to 200,000, more preferably 30,000 to 160,000, and even more preferably. Is recommended to be 35,000 to 120,000. More desirably, the ratio of the weight average molecular weight to the number average molecular weight (hereinafter also referred to as molecular weight distribution) is preferably 1.2 to 4.5, more preferably 1.5 to 4.0, and still more preferably. 2.5 to 3.5 is recommended. In the bonding method of the present invention, when the weight average molecular weight of the acrylic resin preferably used for the two-component adhesive used in the present invention is 20,000 to 200,000 and the molecular weight distribution is 1.2 to 4.5 Diffusion and mixing properties are improved when the main component and the curing agent of the two-component adhesive are bonded, and the curability of the adhesive is improved and the adhesive strength is improved.

  In the bonding method of the present invention, the acrylic-acrylic graft copolymer and acrylic resin preferably used for the two-component adhesive used in the present invention are preferably α-methylstyrene dimers having the following structural formula, that is, 2 , 4-Diphenyl-4-methyl-1-pentene

It is desirable to be produced by bulk radical copolymerization in the presence of. Here, in the bonding method of the present invention, bulk radical polymerization is performed, for example, in a book (eg, “Radical Polymerization Handbook” (issued by NTS), 1999, p. 6,491, 499, 505, 566). It is the method described. That is, in the bonding method of the present invention, bulk radical copolymerization is one of the methods used for radical copolymerization of monomers having vinyl groups such as acrylic monomers and styrene monomers. Without using a solvent, polymerization is carried out by heating only a monomer having a vinyl group such as an acrylic monomer or a styrene monomer or by adding a polymerization initiator such as azobisisobutyronitrile or benzoyl peroxide. Is the method.

  In the bonding method of the present invention, α-methylstyrene dimer, that is, 2,4-diphenyl-4-methyl-1-pentene, is, for example, Goi Kasei Co., Ltd., Honshu Chemical Industry Co., Ltd., Asahi Kasei Finechem Co., Ltd. ) And the like, and those that are commercially available can be arbitrarily selected and used.

  In the adhesion method of the present invention, in the production of the acrylic-acrylic graft copolymer and acrylic resin preferably used in the present invention, the polymerization initiator is preferably 0.02 to 1.0 mol of α-methylstyrene dimer. It is desirable to use 1.0 mole.

  In the adhesion method of the present invention, in the production of the acrylic-acrylic graft copolymer and acrylic resin preferably used in the present invention, as a polymerization initiator, for example, benzoyl peroxide, t-butylperoxy-2-ethylhexano , Organic peroxides such as t-butylperoxybenzoate, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) And organic azo polymerization initiators such as 2,2′-azobisisobutyronitrile and 2,2-azobis [2- (2-imidazolin-2-yl) propane]. In the bonding method of the present invention, these polymerization initiators may be used alone or in a mixture of two or more.

  In the adhesion method of the present invention, among these polymerization initiators, 2,2′-azobis (4-methoxy-2,4-dimethylvaleronitrile), 2,2′-azobis (2,4- Organic azo polymerization initiators such as dimethylvaleronitrile), 2,2′-azobisisobutyronitrile, 2,2-azobis [2- (2-imidazolin-2-yl) propane] are preferably recommended.

  In the adhesion method of the present invention, in the production of the acrylic-acrylic graft copolymer and acrylic resin preferably used in the present invention, the polymerization initiator is preferably 0.02 per 1 mol of α-methylstyrene dimer. It is desirable to use -1.0 mol, more preferably 0.1-1.0 mol, and still more preferably 0.2-0.95 mol. In the production method of the acrylic resin preferably used in the present invention, in the adhesion method of the present invention, when the amount of the polymerization initiator used is less than 0.02 mol, it is difficult to increase the polymerization rate, and it is a reality from an industrial viewpoint. It is not a typical technique. When the amount of the polymerization initiator used exceeds 1.0 mol, the heat generated during the production of the acrylic-acrylic graft copolymer and acrylic resin is large, and a runaway reaction is likely to occur, which may cause a safety problem.

  Next, specific embodiments of the present invention will be illustrated.

1. Acrylic resin production example A flask equipped with a reflux condenser, thermometer, nitrogen gas inlet tube, and stirrer was mixed with nitrogen gas / air mixture gas (oxygen concentration 3 vol%) (oxygen concentration was digital oximeter XO-326ALB (new Was measured using a measuring device of Cosmos Electric Co., Ltd.), and the oxygen concentration in the flask was adjusted to 3 vol%.

  N-butyl acrylate / 2-methoxyethyl acrylate / 2-hydroxyethyl methacrylate / methacrylic acid / “Aron Macromer AA-6” (polymethyl methacrylate macromonomer manufactured by Toagosei Co., Ltd., weight average molecular weight 6000) (= 80. 5/10/5 / 1.5 / 3 wt.%) Of an acrylic monomer mixed solution (1000 g) was prepared, and 300 g of the mixture was charged into the flask. The flask was further charged with 70 g of α-methylstyrene dimer (7% of the total amount of acrylic monomers) and heated to 92 ° C. over 30 minutes.

  24.3 g of α, α-azobisisobutyronitrile (1/2 mol of α-methylstyrene dimer) was dissolved in 700 g of the remaining acrylic monomer mixed solution and added dropwise to the flask over 3 hours. After completion of the dropwise addition, the polymerization was carried out at 92 ° C. for 2 hours, and then the temperature was raised to 105 ° C. and the mixture was further aged for 2 hours. A branched polymer of hydroxyl group, carboxyl group, methoxy group and polymethyl methacrylate was added to the acrylic resin side chain. An acrylic-acrylic graft copolymer having the following structure was prepared.

  The temperature of the polymerization system was lowered to 80 ° C., a nitrogen gas / air mixture (oxygen concentration: 8 vol%) was blown in, and the oxygen concentration in the flask was adjusted to 8 vol%.

Into the flask, 1.03 g of p-methoxyphenol (polymerization inhibitor) and 2.06 g of dibutyltin dilaurate (addition reaction catalyst) were charged and dissolved. 20.9 g of 2-isocyanatoethyl methacrylate (35 mol% of 2-hydroxyethyl methacrylate) was added dropwise over 30 minutes, and thereafter an NCO group was measured with a Fourier transform infrared spectrophotometer (FT-IR) while sampling at any time. Based on the above, an addition reaction was performed until absorption in the vicinity of 2300 cm ⁻¹ disappeared to produce an acrylic resin having an acrylic unsaturated bond in the molecular side chain. The weight average molecular weight of the acrylic resin was 58,000, the molecular weight distribution was 3.2, and the acid value was 9.5.

2. Production Example of Radical Curing Adhesive 25 g of acrylic resin, 46.2 g of dicyclopentenyloxyethyl methacrylate, 20 g of “NK ester BPE-200” (EO modified bisphenol A diacrylate manufactured by Shin-Nakamura Chemical Co., Ltd.), 0.8 g of methacrylic acid, 8.0 g of 2-hydroxyethyl methacrylate, 0.02 g of p-methoxyphenol (polymerization inhibitor), 0.5 g of “DISPARON 308” (thixotropic agent made by Enomoto Kasei), “LUVAX-1266” (manufactured by Nippon Seiwa) Wax) was further mixed, and further stirred and mixed with “Mazerustar KK-100” (Kurabo stirring, mixing and defoaming apparatus).

  The prepared mixture was divided into two parts, and 2.5 g of “Parkmill H-80” (Nippon Yushi Co., Ltd., cumene hydroperoxide) was added to produce the main component of the two-part adhesive. 1 g of ethylenethiourea was added to produce a curing agent for a two-component adhesive.

3. Adhesion method using radical curing type adhesion As an adherend, a test piece of an aluminum alloy (JIS A-2017P: 1999) whose adhesion surface was polished with sandpaper was prepared, and the main agent was used as the adherent film thickness. Was applied to a thickness of 200 to 300 μm, and the other was coated with a curing agent so that the adhesive film thickness was 200 to 300 μm. The adherend-coated surfaces of the adherends were bonded together and left at 30 ° C. for 1 hour to complete the adhesion.

4). Production Example of Epoxy Resin Adhesive 70 g of “jER828” (Bisphenol A type epoxy resin manufactured by Japan Epoxy Resin), 20 g of “jER152” (Novolak type epoxy resin manufactured by Japan Epoxy Resin), and 10 g of acrylic resin are uniformly mixed. The main component of the liquid adhesive was produced.

  16 g of 2-ethyl-4-methylimidazole, 4 g of tri (2,4,6-dimethylaminomethyl) phenol, and 5 g of an acrylic resin were uniformly mixed to produce a curing agent for a two-component adhesive.

5. Adhesion method using an epoxy resin adhesive As an adherend, a test piece of an aluminum alloy (JIS A-2017P: 1999) whose adhesion surface is polished with sandpaper is prepared. Was applied to a thickness of 200 to 300 μm, and a curing agent was applied to the other so that the adhesive film thickness was 50 to 100 μm. The adherend-coated surfaces of the adherends were bonded together, precured at 80 ° C. for 30 minutes, and further cured at 100 ° C. for 1 hour to complete the adhesion.

  Examples of the present invention will be described below with reference to examples. In the examples, the composition ratio was weight ratio unless otherwise specified.

  In the examples, tests, evaluation methods, etc. were carried out according to the following.

1) Oxygen concentration (vol%)
The measurement was performed using a digital oximeter XO-326ALB (a measuring device manufactured by Shin Cosmos Electric Co., Ltd.).

2) Weight average molecular weight (also called Mw)
It measured using the gel permeation chromatography (GPC) HLC-8220GPC (the test device of Tosoh Corporation).

3) Heating residue (%)
Measured according to JIS K 5407: 1997. However, the measurement temperature was 140 ° C. and the measurement time was 30 minutes.

4) Acid value (mgKOH)
Measured according to JIS K 5407: 1997.

5) Viscosity measurement of adhesive The viscosity of the adhesive was measured at 25 ° C. using a “VAR-type Visco Analyzer” (measuring device manufactured by Jusco International).

6) Tensile shear strength (MPa)
It measured at 23 degreeC according to JISK6850: 1999.

    An aluminum alloy (JIS A-2017P: 1999) was used as the adherend.

1. Production Example of Acrylic-Acrylic Graft Copolymer (1) A 2 L four-necked flask having a nitrogen gas inlet tube, a reflux condenser, a stirrer, and an acrylic monomer charging port was charged with nitrogen gas and the oxygen concentration in the flask was 5 vol. The nitrogen gas / oxygen gas mixture was continuously blown to adjust the oxygen concentration to 3 to 5 vol% during the polymerization.

  775 g of n-butyl acrylate, 100 g of 2-methoxyethyl acrylate, 80 g of 2-hydroxyethyl methacrylate, 15 g of methacrylic acid, 30 g of “Aron Macromer AA-6” (polymethyl methacrylate macromer made by Toagosei) (= 77. 5/10/8 / 1.5 / 3) of 1000 g of acrylic monomer mixture solution and 300 g of α-methylstyrene dimer (7 parts by weight when the total amount of acrylic monomer is 100 parts by weight) in the flask The temperature was raised to 92 ° C.

  In the remaining 700 g of the acrylic monomer mixed solution, 24.4 g of 2,2′-azobisisobutyronitrile (polymerization initiator) (0.50 mol when α-methylstyrene dimer was 1 mol) was dissolved. The monomer solution was dropped into the flask in 3 hours. Thereafter, polymerization was carried out at 92 ° C. for 3 hours, and the temperature was raised to 105 ° C., followed by further polymerization for 2 hours. An acrylic having a hydroxyl group, a methoxyethyl group, a carboxyl group and a polymethyl methacrylate branch polymer in the molecular side chain. -An acrylic graft copolymer (1) was produced.

  The acrylic-acrylic graft copolymer (1) had a weight average molecular weight of 56,000, a molecular weight distribution of 3.2, a hydroxyl value of 34.5 mgKOH, and an acid value of 9.8 mgKOH.

2. Production example of acrylic resin (1) In the same manner, an acrylic-acrylic graft copolymer (1) was produced.

  The temperature inside the flask was set to 80 ° C., and an oxygen / air mixed gas (oxygen concentration: 8 vol%) was blown in until the oxygen concentration in the flask became 12 vol% or less, and the oxygen / air mixed gas continued during the subsequent addition reaction. (Oxygen concentration 8 vol%) was blown.

The flask was charged with 1.03 g of p-methoxyphenol and 2.07 g of dibutyltin dilaurate. 33 g of 2-isocyanatoethyl methacrylate (35 mol% of 2-hydroxyethyl methacrylate) was added dropwise over 30 minutes, and then 2300 cm ⁻ while tracing the reaction with a Fourier transform infrared spectrophotometer (FT-IR). ^The addition reaction was carried out until there was no absorption near ¹ . After cooling to room temperature, an acrylic resin (1) having a methacryloyl group derived from an isocyanate group-containing acrylic monomer in the molecular side chain was produced. The acrylic resin (1) had a weight average molecular weight of 62,000, a hydroxyl value of 22.4 mgKOH, an acid value of 9.8 mgKOH, and a heating residue of 99.8%.

3. Production Example of Acrylic Resin (2) Nitrogen gas is introduced into a 2 L four-necked flask having a nitrogen gas inlet tube, a reflux condenser, a stirring device, and an acrylic monomer charging port until the oxygen concentration in the flask becomes 5 vol% or less. During blowing and polymerization, blowing of a nitrogen gas / oxygen gas mixture adjusted to an oxygen concentration of 3 to 5 vol% was continued.

  820 g of n-butyl acrylate, 2-methoxyethyl acrylate 100 g, 2-hydroxyethyl methacrylate 50 g, methacrylic acid 30 g, “Aron Macromer AA-6” (polymethyl methacrylate macromer made by Toagosei) 30 g (= 82 / 10/8/3/3) of an acrylic monomer mixed solution of 10/8/3/3) and 300 g of α-methylstyrene dimer (70 parts by weight when the total amount of acrylic monomers is 100 parts by weight) were charged into the flask, and 92 The temperature was raised to ° C.

  In the remaining 700 g of the acrylic monomer mixed solution, 24.4 g of 2,2′-azobisisobutyronitrile (polymerization initiator) (0.50 mol when α-methylstyrene dimer was 1 mol) was dissolved. The monomer solution was dropped into the flask in 3 hours. Thereafter, polymerization was carried out at 92 ° C. for 3 hours, and the temperature was raised to 105 ° C., followed by further polymerization for 2 hours. An acrylic having a hydroxyl group, a methoxyethyl group, a carboxyl group and a polymethyl methacrylate branch polymer in the molecular side chain. -An acrylic graft copolymer (2) was produced.

  The acrylic-acrylic graft copolymer (2) had a weight average molecular weight of 56,000, a molecular weight distribution of 3.1, a hydroxyl value of 21.5 mgKOH, and an acid value of 19.6 mgKOH.

  The temperature inside the flask was set to 95 ° C., and a mixed gas of oxygen / air (oxygen concentration 8 vol%) was blown in until the oxygen concentration in the flask was 12 vol% or less, and the oxygen / air mixed gas continued during the subsequent addition reaction. (Oxygen concentration 8 vol%) was blown.

  The flask was charged with 1.03 g of p-methoxyphenol and 2.05 g of N, N-dimethylbenzylamine. 25 g of glycidyl methacrylate (50 mol% of methacrylic acid) was added dropwise over 30 minutes, and then an addition reaction was performed until the acid value became 10 mgKOH or less. After cooling to room temperature, an acrylic resin (2) having a methacryloyl group derived from glycidyl methacrylate in the molecular side chain was produced. The acrylic resin (2) had a weight average molecular weight of 65,000, a hydroxyl value of 20.5 mgKOH, an acid value of 9.8 mgKOH, and a heating residue of 99.8%.

1. Production Example of Epoxy Resin Adhesive (1) (1) jER828 (Bisphenol A type epoxy resin from Japan Epoxy Resin) / jER157 (Novolac type epoxy resin from Japan Epoxy Resin) / Acrylic-acrylic graft copolymer (1) (= 70/20/10) 100 g of the mixed solution is stirred, mixed, and defoamed using “Mazerustar KK-100” (Kurabo's stirring, mixing, and defoaming device), and the epoxy resin adhesive The main agent was manufactured. (Epoxy main agent-1) The viscosity A of the epoxy main agent-1 at a shear rate of 4.7 s ^-1 was 23 Pa · s, and the viscosity B at a shear rate of 54 s ^-1 was 22.5 Pa · s. Viscosity A / Viscosity B = 1.02.

(2) Metaxylenediamine / 2-ethyl-4-methyl-imidazole / tri (2,4,6-dimethylaminomethyl) phenol / acryl-acrylic graft copolymer (1) (= 60/27/3/10 ) Was stirred, mixed, and defoamed using “Mazerustar KK-100” (Kurabo stirring, mixing and defoaming device) to produce a curing agent for an epoxy resin adhesive. (Epoxy curing agent-1)
As described above, an epoxy resin adhesive (1) that has been imparted with thixotropy by an acrylic graft copolymer (1) composed of epoxy main agent-1 and epoxy curing agent-1 (mixing ratio is main agent / curing agent = 70/30). ) Was manufactured.

2. Production Example of Epoxy Resin Adhesive (2) (1) jER828 (Bisphenol A type epoxy resin from Japan Epoxy Resin) / jER157 (Novolac type epoxy resin from Japan Epoxy Resin) / Acrylic resin (1) / Dicyclopentenyloxy To 100 g of a mixed solution of ethyl methacrylate (= 70/20/8/2), 0.4 g (acrylic resin (1) and dicyclopentenyl) Parkmill H-80 (Nippon Yushi Co., Ltd. organic peroxide, cumene hydroperoxide) Add 4% to the total amount of oxyethyl methacrylate) and use “Mazerustar KK-100” (Kurabo's stirring, mixing and defoaming device) to stir, mix and defoam, and bond with epoxy resin The main agent of the preparation was produced. Viscosity A at (epoxy main agent -2) shear rate 4.7S ^-1 epoxy main agent -2 25 Pa · s, the viscosity B at a shear rate of ^{54s -1} was 21.3Pa · s. Viscosity A / Viscosity B = 1.17.

(2) Metaxylenediamine / 2-ethyl-4-methyl-imidazole / tri (2,4,6-dimethylaminomethyl) phenol / acrylic resin (1) / dicyclopentenyloxyethyl methacrylate (= 60/27/3) / 8/2), 0.2 g of ethylenethiourea (2% with respect to the total amount of acrylic resin (1) and dicyclopentenyloxyethyl methacrylate) is added to “Mazerustar KK-100” (manufactured by Kurabo Industries). The agitation, mixing, and defoaming apparatus were used to produce a curing agent for the epoxy resin adhesive. (Epoxy curing agent-2)
As described above, an epoxy resin adhesive (2) to which thixotropy is imparted is manufactured with an acrylic resin (1) composed of epoxy main agent-2 and epoxy curing agent-2 (mixing ratio is main agent / curing agent = 70/30). did.

Examples 1 and 2 and Comparative Examples 1 and 2
Epoxy resin adhesives 1 and 2 were used to test adhesion. The test results are shown in Table 1.

  In Table 1, Example 1 and Comparative Example 1, Example 2 and Comparative Example 2 are cases where the main agent and the curing agent are separately applied (Examples 1 and 2), and when the main agent and the curing agent are mixed in advance (Comparison) A comparison of Examples 1 and 2) is shown.

  In Table 1, the usage method, main agent / curing agent coating means that the epoxy main agent is applied to one of the aluminum test pieces so that the adhesive film thickness is about 380 μm, and the curing agent is applied to the other of the aluminum test pieces. This refers to a method in which the adhesive application surface is bonded to each other after the application so that the film thickness is about 120 μm (main agent / curing agent ratio = 69/31). The main agent / curing agent mixture is a mixture of an epoxy main agent and an epoxy curing agent at a blending ratio of 69/31, and then stirred using "Mazerustar KK-100" (Kurabo's stirring, mixing, defoaming device) It refers to a method in which mixing and defoaming are performed, and the adhesive coating surface is bonded to the both sides of the aluminum test piece so as to have an adhesive film thickness of about 250 μm. The pot life indicates the time when the adhesive viscosity is more than doubled and the adhesive application work is judged to be difficult. The tensile shear strength was obtained by pasting the adhesive-coated surface of the adherend every predetermined time shown in Table 1, precuring at a curing temperature of 80 ° C. for 30 minutes, and further post-curing at 100 ° C. for 30 minutes. The test results after curing for 12 hours are shown.

  As can be seen in Example 1 and Example 2, in the method of separately applying the main agent and the curing agent proposed by the present invention, no pot life is seen in the adhesive, and the bonding operation is free in time. On the other hand, as seen in Comparative Examples 1 and 2, when the main agent and the curing agent are mixed in advance, the pot life appears in a short time, and the bonding operation becomes substantially impossible. Further, since the curing of the adhesive has been started, even if the bonding is attempted after a certain time (120 minutes in Table 1) has passed, it can no longer be bonded.

  Although it is clear by comparing the data immediately after application of the adhesive, the main agent and the curing agent can be applied separately (Examples 1 and 2), but the main agent and the curing agent are mixed and then bonded (Comparative Examples 1 and 2). However, there is no significant difference in tensile shear strength (adhesive strength), and it can be seen that the adhesion method in which the adhesive is applied is excellent in adhesion workability and adhesive handling.

1. Production Example of Acrylic Adhesive (1) 20 g of acrylic-acrylic graft copolymer (1), 51 g of “Fancryl FA-512M” (dicyclopentenyloxyethyl methacrylate manufactured by Hitachi Chemical Co., Ltd.), “NK Ester BPE-200” After mixing 20 g of ethylene oxide-modified bisphenol A diacrylate (manufactured by Shin-Nakamura Chemical Co., Ltd.), 1 g of methacrylic acid, 8 g of 2-hydroxyethyl methacrylate “LUVAX-1266” (wax made by Nippon Seiwa), “Mazerustar Using KK-100 "(Kurabo's stirring, mixing and defoaming apparatus), stirring, mixing and defoaming were performed to produce an acrylic adhesive.

The acrylic adhesive was divided into two parts, and 2.5 g of “Park Mill H-80” (a polymerization initiator, cumene hydroperoxide manufactured by NOF Corporation) was added to make an acrylic main agent-1. The viscosity A of the acrylic main agent-1 at a shear rate of 4.7 s ⁻¹ was 3.2 Pa · s, and the viscosity B at a shear rate of 54 s ⁻¹ was 2.8 Pa · s. Viscosity A / Viscosity B = 1.14. On the other side, 1 g of ethylenethiourea was added to produce acrylic curing agent-1.

2. Production Example of Acrylic Adhesive (2) 40 g of acrylic resin (1), “Fancryl FA-512M” (dicyclopentenyloxyethyl methacrylate) manufactured by Hitachi Chemical Co., Ltd., “NK Ester BPE-200” (Shin Nakamura Chemical Co., Ltd.) 20 g of ethylene oxide-modified bisphenol A diacrylate), 1 g of methacrylic acid, 8 g of 2-hydroxyethyl methacrylate and 0.1 g of “LUVAX-1266” (wax made by Nippon Seiwa) were mixed, and then “Mazerustar KK-100” Using (Kurabo's stirring, mixing and defoaming apparatus), stirring, mixing and defoaming were performed to produce an acrylic adhesive.

The acrylic adhesive was divided into two parts, and 2.5 g of “Park Mill H-80” (a polymerization initiator made by Nippon Oil & Fats, cumene hydroperoxide) was added to make an acrylic main agent-2. The viscosity A of the acrylic main agent-2 at a shear rate of 4.7 s ⁻¹ was 12.3 Pa · s, and the viscosity B at a shear rate of 54 s ⁻¹ was 11.7 Pa · s. Viscosity A / Viscosity B = 1.05. On the other side, 1 g of ethylenethiourea was added to produce acrylic curing agent-2.

3. Production Example of Acrylic Adhesive (3) 40 g of acrylic resin (2), 31 g of “Fancryl FA-511A” (dicyclopentenyl acrylate manufactured by Hitachi Chemical Co., Ltd.), “NK Ester BPE-200” (manufactured by Shin-Nakamura Chemical Co., Ltd.) After mixing 20 g of ethylene oxide-modified bisphenol A diacrylate), 1 g of methacrylic acid, 8 g of 2-hydroxyethyl methacrylate, and 0.1 g of “LUVAX-1266” (wax made by Nippon Seiwa), “Mazerustar KK-100” (Kurabo) Stirring, mixing, and defoaming were performed using an agitating, mixing, and defoaming device manufactured to produce an acrylic adhesive.

The acrylic adhesive was divided into two, and 2.5 g of “Park Mill H-80” (a polymerization initiator, cumene hydroperoxide manufactured by NOF Corporation) was added to make an acrylic main agent-3. The viscosity A of the acrylic main agent-3 at a shear rate of 4.7 s ⁻¹ was 10.5 Pa · s, and the viscosity B at a shear rate of 54 s ⁻¹ was 9.9 Pa · s. Viscosity A / Viscosity B = 1.06. On the other side, 1 g of ethylenethiourea was added to produce an acrylic curing agent-3.

Examples 3, 4, 5 and Comparative Examples 3, 4, 5
Adhesion tests were performed using acrylic adhesives 1-3. The test results are shown in Table 2. In Table 2, the main agent / curing agent coating method is the application of the acrylic main agent to one aluminum test piece with an adhesive film thickness of 250 μm and the acrylic hardener to the other aluminum test piece with an adhesive film thickness of 250 μm ( Main agent / curing agent ratio = 50/50) This refers to a method in which the adhesive application surface is bonded to each other after application. The main agent / curing agent mixture is a mixture of acrylic main agent and acrylic curing agent at a blending ratio of 50/50, followed by stirring using “Mazerustar KK-100” (Kurabo stirring, mixing, defoaming device) It refers to a method in which mixing and defoaming are carried out, and after an adhesive film thickness of 250 μm is applied to both of the aluminum test pieces, the adhesive application surface is pasted during bonding. The pot life indicates the time when the adhesive viscosity is more than doubled and the adhesive application work is judged to be difficult.

  The tensile shear strength shows the result after bonding the adhesive-coated surface of the adherend every predetermined time shown in Table 1, curing for 30 hours at a curing temperature of 30 ° C., and curing for 12 hours. The tensile shear strength shows the test results after bonding the adhesive-coated surface of the adherend every predetermined time shown in Table 2, curing at a curing temperature of 30 minutes, and curing for 12 hours.

  As seen in Example 3, Example 4, and Example 5, in the method of separately applying the main agent and the curing agent proposed by the present invention, the pot life is not seen in the adhesive, and the bonding work is free in time. . On the other hand, as seen in Comparative Examples 3, 4, and 5, since the acrylic adhesive has a short pot life, it no longer shows adhesiveness 30 minutes after mixing the main agent and the curing agent.

  As is apparent from comparison of the data immediately after application of the adhesive, the main agent and the curing agent can be applied separately (Examples 3, 4 and 5), but the main agent and the curing agent are mixed and then bonded (Comparative Examples 3, 4 and Even if 5), there is no significant difference in the tensile shear strength (adhesive force), and it can be seen that the adhesion method in which the adhesive is applied is excellent in adhesion workability and adhesive handling.

The schematic diagram of the state which applied the main ingredient to one side of the to-be-adhered body, and applied the hardening | curing agent to the other to-be-adhered body. The schematic diagram which shows another form of the state which apply | coated the main ingredient to the to-be-adhered body. The schematic diagram which shows another form of the state which apply | coated the hardening | curing agent to the to-be-adhered body.

Claims (7)

After the main agent and the curing agent of the two-component adhesive are mixed with the main agent and the curing agent in a state where the main agent and the curing agent are not mixed, the adhesive is applied to one of the adherends and the curing agent is applied to the other of the adherends. Adhesion method to paste the coated surface. The viscosity of the two-component adhesive and / or the curing agent measured at a shear rate of 5 ± 1 s ⁻¹ (25 ° C.) is 500 mPa · s to 60 Pa · s. The bonding method according to claim 1, wherein the curing agent exhibits thixotropic properties at a shear rate of 1 s ^{−1 to} 1000 s ⁻¹ (25 ° C.). A viscosity A measured at 2-part adhesive of the main agent and / or curing agent a shear rate 5 ± ^1s -1 of (25 ° C.), a viscosity B which is measured at a shear rate 50 ± ^5s -1 (25 ℃) The bonding method according to claim 1 or 2, wherein the ratio (A / B) is 1.002 to 10.0. A two-component adhesive is represented by the following structural formula in the molecule

(Here, R1 represents a hydrogen atom or a methyl group, and R2 represents an alkyl group having 1 to 8 carbon atoms.)
The adhesion method according to any one of claims 1 to 3, comprising an acrylic-acrylic graft copolymer having a branched polymer of poly (meth) acrylic acid alkyl ester. The two-pack adhesive has a chemical structure represented by the following structural formula in the molecule

(Here, R3 is a hydrogen atom or a methyl group, R4 is an alkyl group having 2 to 4 carbon atoms, R5 is a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n is 1 to 10) Represents an integer.)
The adhesion | attachment method in any one of Claims 1-4 containing the acrylic resin which has this. The two-pack adhesive has a chemical structure represented by the following structural formula in the molecule

(Where R6 is a hydrogen atom or a methyl group, R7 is an alkyl group having 1 to 6 carbon atoms, R8 is an alkyl group having 2 to 4 carbon atoms, and R9 is a hydrogen atom or a methyl group. To express.)
The adhesion | attachment method in any one of Claims 1-5 containing the acrylic resin which has. The chemical structure in which the two-component adhesive is represented by the following structural formula in the molecule

(Here, R10 represents a hydrogen atom or a methyl group, and R11 represents a hydrogen atom or a methyl group.)
The adhesion | attachment method in any one of Claims 1-5 containing the acrylic resin which has.

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