JP2009197160A - Adhesive composition, bonding method, bonded form, and method for producing bonded form - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an adhesive composition capable of quickly hardening a joint part in high adhesivity and accomplishing high durability of the joint part, to provide a bonding method using the same, and to provide a method for producing the same. <P>SOLUTION: The two-part adhesive composition is characterized by comprising a first liquid containing (A) a nitrile-butadiene rubber containing 5-30 mass% of acrylonitrile units, (B) a polymerizable (meth)acrylic composition and (C) an organic peroxide and a second liquid containing (E) a reaction condensate of an amine and an aldehyde and (F) a copper-containing reducing agent. The bonding method using the above adhesive composition and the method for producing the same are also provided, respectively. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to an adhesive composition, a joining method, a joined body obtained by using them, and a method for producing the joined body.

  The demand for an adhesive that cures at room temperature in a short time tends to increase from the viewpoint of improving production line efficiency and reducing costs. Well-known normal temperature fast curing adhesives include two-component fast curing epoxy adhesives, instant adhesives, anaerobic adhesives, non-anaerobic acrylic adhesives, and the like.

  The two-component rapid curing type epoxy adhesive is used by metering and mixing the main agent and the curing agent. If the metering and mixing are not sufficiently performed, there is a possibility that a significant decrease in strength may occur. In addition, there is a problem that the peel strength and impact strength are low even if the weighing and mixing are sufficiently performed.

  On the other hand, instant adhesives have excellent workability, but generally have low peel strength and impact strength, and are inferior in heat resistance and moisture resistance, so that the range of use is remarkably limited.

  On the other hand, the anaerobic adhesive is an adhesive that is cured by pressure-bonding between the materials to which the adhesive is to be bonded and shuts off the air, and naturally, a portion that comes into contact with air, such as a protruding portion, is not cured. Therefore, when the porous adherend and the balance between the adherends are poor, there is a problem that the adhesive is not sufficiently cured and adhesion failure occurs.

  On the other hand, in general, non-anaerobic acrylic adhesives called second generation acrylic adhesives (SGA) are two-component, but do not require accurate metering of two-components. It has been used widely because it has excellent workability of curing at room temperature for several minutes to several tens of minutes, has high peel strength and impact strength, and has excellent curing at the protruding portion.

  However, from the viewpoint of improving production line efficiency and reducing costs, there is an increasing demand for further shortening of the curing time for acrylic adhesives having a curing time of several minutes to several tens of minutes at room temperature.

  For example, it is described that the adhesive of Patent Document 1 is composed of urethane acrylate, an acrylate monomer, an aromatic perester, an organic acid, and a transition metal, and is cured with a set time of 45 seconds.

  Further, the adhesive of Patent Document 2 is composed of an accelerator composed of a specific urethane acrylate, an acrylate monomer, a peroxyester and a compound forming a redox system, and is described to be cured with a fast set time of less than 1 minute. ing.

  The adhesive composition of Patent Document 3 is composed of a composition in which chlorosulfonated polyethylene and a specific acrylic monomer are mixed at a specific ratio, cumene hydroperoxide, aldehyde-amine condensate, transition metal oxidizing organic compound, It is described that it is cured in a curing time of several seconds.

  Patent Documents 4 and 5 indicate that a fast-curing acrylic adhesive can be obtained by using a reaction condensate of peroxyester and amine-aldehyde, a copper salt, and an aromatic hydroxyl group-containing compound as an acrylic monomer. Are listed.

U.S. Pat. No. 4,348,503 JP 60-199085 A Japanese Patent Laid-Open No. 55-065277 Japanese Patent Laid-Open No. 03-134080 Japanese Patent Laid-Open No. 03-134081

  However, each of the adhesive compositions disclosed in Patent Documents 1 to 5 has improvements such as strength reduction under high temperature and high humidity conditions. Further, in the adhesive compositions of Patent Document 4 and Patent Document 5, the initial adhesiveness is good, but the strength is lowered under high temperature and high humidity conditions, and therefore further improvement has been desired.

  Further, the adhesive compositions disclosed in Patent Documents 1 to 5 are expected to be further improved in that interfacial fracture occurs on the metal steel sheet and strong adhesion to the adherend cannot be obtained. It was rare.

  The present invention has been made in view of the above circumstances, and aims to provide an adhesive composition having high adhesiveness and high-speed curability, and excellent durability under high temperature and high humidity conditions. To do.

  As a result of intensive studies to solve the above problems, the present inventor has found that an adhesive composition having a specific composition has high adhesiveness and high-speed curability and durability under high temperature and high humidity conditions. As a result, the present invention has been found.

  That is, according to the present invention, (A) a nitrile butadiene rubber containing 5 to 30% by mass of an acrylonitrile unit, (B) a polymerizable (meth) acrylic composition, and (C) an organic peroxide are contained. And a second liquid containing (E) a reaction condensate of amine and aldehyde and (F) a reducing agent containing copper. The

  By combining specific components, this adhesive composition can quickly cure the joint with high adhesiveness, and can realize excellent durability of the joint.

  In addition, according to the present invention, there is provided a joined body in which a plurality of adherend surfaces or adherends are joined by the above adhesive composition. The joined body is joined with an adhesive composition having a specific composition, thereby having a joint portion having excellent adhesiveness and durability.

  Moreover, according to this invention, it is the joining method of two to-be-adhered surfaces or to-be-adhered bodies, Comprising: (A) Nitrile butadiene rubber containing 5-30 mass% acrylonitrile unit, (B) Polymerizable ( A step of applying a first liquid containing a (meth) acrylic composition and (C) an organic peroxide to one of the adherend surface or the adherend, (E) a reaction condensate of an amine and an aldehyde, and (F) The process of apply | coating the 2nd liquid containing the reducing agent containing copper to the other of said adherend surface or an adherend, and the process of joining together said two adherend surfaces or an adherend Is provided.

  According to this bonding method, by using an adhesive composition in which specific components are combined, the bonded portion can be quickly cured with high adhesiveness, and excellent durability of the bonded portion can be realized. .

  Further, according to the present invention, there is provided a method for producing a joined body obtained by joining two adherend surfaces or adherends, (A) a nitrile butadiene rubber containing 5-30% by mass of an acrylonitrile unit, (B) a step of applying a polymerizable (meth) acrylic composition and a first liquid containing (C) an organic peroxide to one of the adherend surface or the adherend, and (E) an amine And (F) a step of applying a second liquid containing a reducing agent containing copper to the other of the adherend surface or the adherend, and the two adherend surfaces or the adherends described above. And joining the bodies together to obtain the above-described joined body.

  According to this manufacturing method, by using an adhesive composition in which specific components are combined, the bonded portion can be quickly cured with high adhesiveness, and a bonded body with excellent bonded portion durability can be manufactured. It becomes possible.

  According to the present invention, by using an adhesive composition in which specific components are combined, the joint can be quickly cured with high adhesiveness, and excellent durability of the joint can be realized.

[Explanation of terms]
“Adhesion” or “joining” in this specification means fixing a structure and another structure in a combined state. As a matter of course, the case where different parts in the same structure are bonded to each other is also included in “adhesion” or “joining” in this specification. At this time, the structure to be bonded is referred to as an “adhered body”, and the surface to be bonded in the adherend is referred to as an “adhered surface”. Called.

  In addition, the “adhesive composition” in the present specification refers to an application for fixing a structure and another structure in a combined state via the composition, that is, the above-described “adhesion” or “joining” application. It means the composition used.

  The “two-component adhesive composition” in the present specification means an adhesive composition having the two-component adhesive composition described above as a substantial adhesive component. For example, the purpose of the present invention In the application surface, the adhesive composition further containing another third liquid as long as it is not damaged, or each component of the first liquid or the second liquid is continuously applied to the adherend surface. An embodiment that substantially constitutes the first liquid or the second liquid is also included in the “two-component adhesive composition” in the present specification.

  In addition, the “joined body” in this specification means a structure that is fixed in a state where a certain adherend and a certain adherend are combined. As a matter of course, a structure in which different adherend surfaces in the same structure are combined is also included in the “bonded body” in this specification.

  Each numerical range in this specification includes an upper limit value and a lower limit value indicated by “to”.

  Embodiments of the present invention will be described below.

[Adhesive composition]
An embodiment of the present invention contains (A) a nitrile butadiene rubber containing 5-30 wt% acrylonitrile units, (B) a polymerizable (meth) acrylic composition, and (C) an organic peroxide. And a second liquid containing (E) a reaction condensate of amine and aldehyde and (F) a reducing agent containing copper.

  By properly combining the following components, this adhesive composition has high adhesion, high-speed curability (preferably high-speed curability in seconds), excellent storage stability, and excellent durability of the joint. Made possible.

  Below, each component which comprises the composition which concerns on this embodiment is demonstrated.

[(A) component: nitrile butadiene rubber]
(A) Nitrile butadiene rubber (or NBR, nitrile butadiene rubber or nitrile rubber) component is a polymer (polymer) having acrylonitrile and 1,3-butadiene as structural units and having rubber-like elasticity at room temperature. Yes, it can be obtained by copolymerizing butadiene and acrylonitrile. By containing this component in combination with other components, it is possible to achieve high durability and excellent durability of the joint, particularly durability under high temperature and high humidity conditions.

  (A) Content of the acrylonitrile (AN) unit in a nitrile butadiene rubber component is 5-30 mass% of a nitrile butadiene rubber. By using a nitrile butadiene rubber having an acrylonitrile unit content of 5% by mass or more, a sufficient improvement in durability is observed, and by using a nitrile butadiene rubber having a content of 30% by mass or less, a metal such as copper is coated. Corrosion reactions such as oxidation of the adherend when it is set as the deposition target can be prevented, and higher adhesion can be achieved. The lower limit of the content of the acrylonitrile unit is preferably 10% by mass or more, and when a nitrile butadiene rubber having an acrylonitrile unit content of 10% by mass or more is used, the durability is further improved in terms of moisture resistance and heat resistance. Sex can be achieved. The upper limit of the content of acrylonitrile units is preferably 25% or less, and the use of a nitrile butadiene rubber having a content of acrylonitrile units of 25% or less by mass further reduces the adverse effects on the object to be adhered and provides high adhesion. Can be realized. More preferably, the upper limit of the content of acrylonitrile units is 20% or less.

  (A) The addition amount of the nitrile butadiene rubber component is not particularly limited, and can be freely set by those skilled in the art within a range not impairing the object of the present invention. Preferably, (B) polymerizable (meth) acrylic is used. It is 1-25 mass parts with respect to 100 mass parts of system composition components, More preferably, it is 5 mass parts or more, or is 15 mass parts or less further. When 1 part by mass or more is added, the durability is greatly improved, and when 5 parts by mass or more is added, further improvement in durability is observed, and it is advantageous in terms of work at the time of use such as adhesion at room temperature. When the addition amount is suppressed to 25 parts by mass or less, adverse effects such as corrosion on the object to be deposited such as metal can be greatly suppressed, and when the addition amount is limited to 15 parts by mass or less, higher adhesiveness can be realized, By realizing an appropriate viscosity, it is advantageous in terms of work at the time of use.

  (A) Although a nitrile butadiene rubber component is not limited to this, What can melt | dissolve or disperse | distribute to the polymerizable (meth) acrylic-type composition of (B) is preferable. Moreover, it is also possible to use 1 type, or 2 or more types of nitrile butadiene rubber if it is acceptable compatibility.

  (A) The nitrile butadiene rubber component may be introduced with a third monomer other than butadiene and acrylonitrile (for example, isoprene, styrene, methacrylic acid, etc.) as long as the object of the present invention is not impaired. Preferably, the content of the other structural unit is 10% by mass or less, preferably 5% by mass or less, more preferably 1% by mass or less of the butadiene rubber.

  Further, the (A) nitrile butadiene rubber component may be partially subjected to modification such as hydrogenation or vulcanization within a range not impairing the object of the present invention.

[(B) component: polymerizable (meth) acrylic composition]
(B) As a polymerizable (meth) acrylic composition component, any (meth) acrylic composition capable of polymerization, particularly radical polymerization can be used without any particular limitation. Here, the (meth) acrylic composition is one or two of methacrylic acid, methacrylic acid ester or acrylic acid ester (hereinafter referred to as ~ (meth) acrylate). The composition which consists of the above is described. By containing this component, the function as an adhesive is given to the composition, and by combining it with other components, high durability and excellent durability and holding power of the joint are realized. can do.

  Such polymerizable (meth) acrylic compositions include, but are not limited to, for example, methacrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, Dicyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclotriene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, -Hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, alkyloxypolypropylene glycol (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrafurfuryl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified acrylate , Paracumylphenol ethyleneoxy modified acrylate, nonylphenol ethylene oxide modified acrylate, nonyl Enol polypropylene oxide modified acrylate, 2-ethylhexyl carbitol acrylate, polyglycerol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,4 butanediol (meth) acrylate, 1,6 hexanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, epoxy (meth) acrylate (manufactured by Osaka Organic Chemical Co., “Biscoat # 540”), polyester (meth) acrylate (manufactured by Toa Gosei Co., Ltd., “ Aronix M-6100 ", manufactured by Kyoei Chemical Co., Ltd.," epoxy ester 3000M "), urethane acrylate (manufactured by Toagosei Co., Ltd.," Aronix M-1100 "), polyethylene glycol urethane modified di ( (Meth) acrylate, polypropylene glycol urethane modified di (meth) acrylate, epoxy acrylate (manufactured by Toagosei Co., Ltd., “Aronix M-5710”), polybutadiene dimethacrylate (manufactured by Nippon Soda Co., Ltd., “TE-2000”), acrylonitrile butadiene Methacrylate (manufactured by Ube Industries, “HyCAr VTBNX”), benzyl (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2,2-bis (4-methacryloxyphenyl) ) Propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxypropo) Cyphenyl) propane, 2,2-bis (4-methacryloxytetraethoxyphenyl) propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, pentaerythritol tetra (meth) acrylate, dipentaeri Stall hexa (meth) acrylate, toluene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like are included.

  (B) The polymerizable (meth) acrylic composition component is preferably isobornyl (meth) acrylate, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, 2,2-bis (4 -Methacryloxyethoxyphenyl) propane and trimethylolpropane tri (meth) acrylate. By using these, high durability and high retention rate under high temperature and high humidity conditions of the joint can be exhibited.

[(C) component: organic peroxide]
(C) As an organic peroxide component, arbitrary organic peroxides can be used as long as the object of the present invention is not impaired. The organic peroxide functions as a polymerization initiator and cures the resin composition. Such organic peroxides include, but are not limited to, for example, t-butyl peroxybenzoate, t-butyloxyacetate, t-butyl peroxyisobutyrate, t-butyl peroxyphthalate. , Cumene hydroperoxide and the like. From the viewpoint of exhibiting rapid curing, t-butyl peroxybenzoate is preferable, and from the viewpoint of rapid curing and storage stability, cumene hydroperoxide is preferable.

  (C) The addition amount of the organic peroxide component is not particularly limited, and can be set by those skilled in the art within the range not impairing the object of the present invention. (B) Polymerizable (meth) acrylic composition component 0.1 to 10 parts by mass is preferable with respect to 100 parts by mass, more preferably 0.5 parts by mass or more, or even more preferably 8 parts by mass or less, still more preferably 1 part by mass or more, or even more preferably 7 parts by mass or less. . (C) When 0.1-10 mass parts of organic peroxide components are added, sufficient curability is obtained and a stable adhesive composition is obtained. When (C) 0.5 parts by mass or more of the organic peroxide component is added, faster curing is achieved, and when 1 part by mass or more is added, sufficient rapid curing is achieved. Further, when the addition amount is suppressed to 8 parts by mass or less, high storage stability is achieved, and when the addition amount is suppressed to 7 parts by mass or less, sufficient storage stability is achieved.

[(D) component: basic compound having an amine structure]
The adhesive composition in this embodiment can further contain (D) a basic compound component having an amine structure as an additional component. As an example of a preferable adhesive composition, the above-mentioned adhesive composition is characterized in that the first liquid further contains (D) a basic compound having an amine structure. When the product is used, further rapid curing is realized. (D) As a basic compound component which has an amine structure, the basic compound which comprises arbitrary amine structures can be used in the range which does not impair the objective of this invention. Examples of the basic compound having an amine structure capable of assisting high-speed curing include a basic compound comprising a primary amine structure or a secondary amine structure.

  Examples of basic compounds having an amine structure include, but are not limited to, benzotriazole, phenothiazine, saccharin, 1-acetyl-2-phenylhydrazine, polyethyleneimine, modified polyethyleneimine (Nippon Shokubai Co., Ltd.). N, N, -dimethylaniline, modified dihydropyridine, 2-methylimidazole, 2-hydroxyethyl paratoluidine, ethanolamine, diethanolamine, diethylethanolamine, methyldiethanolamine, butyldiethanolamine, diethylamine, triethylamine, n-butylamine, 2 , 2-bipyridine, 1,10-phenanthroline, ammonia, alkylidenemalonic acid ester, δ-iminomalonic acid ester, ethylazane, phenylamine, benzylamine 1-benzofuran-2-amine, 4-quinolylamine, pentane-1,2,5-triamine, benzene-1,2,4,5-tetraamine, bis (2-chloroethyl) amine, butyl (ethyl) methylamine, ( 2-chloroethyl) (propyl) amine, hexane-1-imine, isopropylideneamine, ethane-1,2-diimine, carbodiimide, o-acetylhydroxylamine, o-carboxyhydroxylamine, hydroxylamine-o-sulfonic acid, o -Hydroxyaniline, phenylpropanolamine hydrochloride, catecholamine, indoleamine, polyacrylamine, dicyclohexylcarbodiimide, acetylthiourea, benzoylthiourea, 2-phenylhydrazine-1-carbaldehyde, 2,2,2-trifluoro Rho-N′-phenylacetohydrazide, 1-crotonoyl-2-phenylhydrazine, 1- (2-carboxyacryloyl) -2-phenylhydrazine, 1-carbamoyl-2-phenylhydrazine, 1,4-diphenylthiosemicarbazide, 2 , 4-diphenylthiosemicarbazide, N, N′-diacetylthiourea, 2-thioxoimidazolidin-4-one, 1-acetyl-2-thiohydantoin and the like. Among the basic compounds having the above amine structure, saccharin and phenothiazine are particularly preferable. These are because (B) the solubility to the polymerizable (meth) acrylic composition component is high, and by using these, curing is accelerated at a very high speed. Moreover, said basic compound can be used in combination of 2 types or more.

  (D) The addition amount of the basic compound component having an amine structure is not particularly limited, and can be set by those skilled in the art within a range not impairing the object of the present invention. (B) Polymerizable (meth) acrylic 0.01-30 mass parts is preferable with respect to 100 mass parts of composition components, Furthermore, 0.1 mass part or more, or 20 mass parts or less is more preferable, Furthermore, 1 mass part or more, Furthermore, 10 mass parts or less are more. Even more preferred. By adding within these numerical ranges, further rapid curing can be achieved while maintaining high adhesiveness and durability of the present adhesive composition.

[(E) component: reaction condensate of amine and aldehyde]
(E) A reaction condensate component of an amine and an aldehyde is a condensate obtained by condensing an arbitrary amine (alkylamine and arylamine) and an arbitrary aldehyde, not only having a single structure, Also included are mixtures or composites resulting from the condensation reaction. As the reaction condensate of amine and aldehyde, for example, at least 1 mol, preferably 1.5 to 3 mol of aldehyde is reacted at 40 to 70 ° C. with respect to 1 mol of amine in the presence of carboxylic acid or inorganic acid. The amine complex mixture obtained in (1) is mentioned. As an example of the carboxylic acid or inorganic acid, propionic acid, phosphoric acid or acetic acid is used. As an example of the amine and aldehyde, for example, butylamine or aniline and butyraldehyde are used.

  (E) The reaction condensate component of amine and aldehyde is desirably in a liquid state, and exhibits a better effect as a curing accelerator when dissolved or dispersed in a solvent, particularly a volatile solvent, to form a second liquid. To do. Suitable solvents include, but are not limited to, acetone, methanol, ethanol, butanol, isopropyl alcohol, ethyl acetate, toluene, methylene chloride, trichloroethane, tetrahydrofuran, hexane, N, N-dimethylformamide, N , N-dimethyl sulfoxide, benzene, chloroform and the like.

  Moreover, (meth) acrylic composition and a plasticizer are mentioned as a component (solvent) which melt | dissolves or disperse | distributes the reaction condensate component of (E) amine and an aldehyde similarly to the above. Here, the (meth) acrylic composition is a composition composed of one or more of methacrylic acid ester or acrylic acid ester (hereinafter referred to as ~ (meth) acrylate). It is a general record of things. These components have further effects such as not using an organic solvent in the system of the adhesive composition, or imparting flexibility and heat resistance to the cured adhesive.

  The above components for dissolving or dispersing the reaction condensate of amine and aldehyde are not limited thereto, but include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (Meth) acrylate, 2-ethylhexyl (meth) acrylate, isooctyl (meth) acrylate, isodecyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, di Cyclopentanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, isobornyl (meth) acrylate, methoxylated cyclotriene (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, polyethylene glycol (meth) acrylate, alkyloxypolypropylene glycol (meth) Acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, glycidyl (meth) acrylate, caprolactone modified tetrafurfuryl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, phenol ethylene oxide modified Acrylate, paracumylphenol ethyleneoxy modified acrylate, nonylphenol ethylene oxide modified acrylate, noni Phenol polypropylene oxide modified acrylate, 2-ethylhexyl carbitol acrylate, polyglycerol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,4 butanediol (meth) acrylate, 1,6 hexanediol di (meth) acrylate , Neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, epoxy (meth) acrylate (manufactured by Osaka Organic Chemical Co., “Biscoat # 540”), polyester (meth) acrylate (manufactured by Toa Gosei Co., Ltd., “ Aronix M-6100 ", manufactured by Kyoei Chemical Co., Ltd.," epoxy ester 3000M "), urethane acrylate (manufactured by Toagosei Co., Ltd.," Aronix M-1100 "), polyethylene glycol urethane modified di (Meth) acrylate, polypropylene glycol urethane modified di (meth) acrylate, epoxy acrylate (manufactured by Toagosei Co., Ltd., “Aronix M-5710”), polybutadiene dimethacrylate (manufactured by Nippon Soda Co., Ltd., “TE-2000”), acrylonitrile pig Gen methacrylate (manufactured by Ube Industries, “HyCAr VTBNX”), benzyl (meth) acrylate, glycerol (meth) acrylate, glycerol di (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, 2,2-bis (4-methacryloxy) Phenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxyethoxyphenyl) propane, 2,2-bis (4-methacryloxypro) Xylphenyl) propane, 2,2-bis (4-methacryloxytetraethoxyphenyl) propane, 2,2-bis [4- (methacryloxypolyethoxy) phenyl] propane, pentaerythritol tetra (meth) acrylate, dipentaeri Stall hexa (meth) acrylate, toluene diisocyanate, 4,4-diphenylmethane diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate and the like. Further, as a plasticizer, phthalic acid such as dimethyl phthalate, diethyl phthalate, dibutyl phthalate, bis (2-ethylhexyl) phthalate, di-n-octyl phthalate, diisodecyl phthalate, butyl benzyl phthalate, diisononyl phthalate, ethyl phthalyl ethyl glycolate Esters, tris (2-ethylhexyl) trimellitate, dimethyl adipate, dibutyl adipate, diisobutyl adipate, bis (2-ethylhexyl) adipate, diisononyl adipate, diisodecyl adipate, bis (butyldiglycol) adipate, bis (2-ethylhexyl) azelate, dimethyl Fatty acid dibasic acid ester such as sebacate, dibutyl sebacate, bis (2-ethylhexyl) sebacate, diethyl succinate Tetra, trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (butyl ethyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, cresyl diphenyl phosphate, 2-ethylhexyl diphenyl phosphate, etc. Examples include esters such as ricinoleate such as ricinoleate, acetates such as glyceryl triacetate and 2-ethylhexyl acetate, and sulfonamides such as N-butylbenzenesulfonamide.

  From the viewpoint of flexibility and heat resistance of the curable composition, it is particularly preferable to use 2-hydroxyethyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and (2-ethylhexyl) adipate. preferable.

  Moreover, said component can be used 1 type or in combination of 2 or more types.

  (E) The compounding amount of the reaction condensate component of amine and aldehyde is not particularly limited and can be freely set by those skilled in the art within a range not impairing the object of the present invention. 0.05% by mass or more is preferable, and more preferably 0.5% by mass or more, or further 40% by mass or less. The solvent is also preferably used so that the amount of the (E) amine and aldehyde reaction condensate component is in the above ratio. (E) Curing is accelerated by adding 0.05% by mass or more of the reaction condensate component of amine and aldehyde, and by blending 0.5% by mass or more, faster curing and flexibility of the adhesive composition Property and adhesive strength. Moreover, it becomes advantageous in terms of durability of the adhesive composition by suppressing the blending amount to 40% by mass or less.

[(F) component: reducing agent containing copper]
(F) The reducing agent component containing copper can use the reducing agent containing arbitrary copper in the range which does not impair the objective of this invention. Such a reducing agent is important in the initiation of the polymerization reaction because it reacts with the (C) organic peroxide to generate radicals. Examples of the reducing agent containing copper include, but are not limited to, copper acetate, copper naphthenate, copper octylate, acetylacetone copper complex, copper sulfate, and copper oxide. (E) From the viewpoint of forming a stable copper catalyst by coexistence with the reaction condensate component of an amine and an aldehyde, copper naphthenate and copper octylate are particularly preferable.

  (F) The addition amount of the reducing agent component containing copper is not particularly limited and can be set by those skilled in the art within a range not impairing the object of the present invention. (B) Polymerizable (meth) acrylic composition 0.05 to 10 parts by mass or less is preferable with respect to 100 parts by mass of the component, more preferably 0.1 parts by mass or more, or even more preferably 8 parts by mass or less, further 0.5 parts by mass or more, or even 5 parts by mass or less. Is most preferred. A reliable curing effect can be achieved with an addition amount of 0.05 parts by mass or more. With an addition amount of 0.1 parts by mass or more, a higher curing rate, and with an addition amount of 1 part by mass or more, a higher curing rate is obtained. Achieved. When the addition amount is suppressed to 10 parts by mass or less, the possibility that an unreacted reducing agent remains is reduced, and when the addition amount is suppressed to 8 parts by mass or less, higher adhesion is provided, and the addition amount is 5 parts by mass or less. If this is suppressed, high adhesive strength can be achieved.

  The liquid containing the (A) component, the (B) component and the (C) component, and optionally the (D) component as the first liquid, and the (E) component and the (F) component as the second liquid. In doing so, the adhesive composition containing these two liquids can be cured quickly and in a short time by bringing the first liquid and the second liquid into contact with each other.

  When two adherends are bonded using the adhesive composition in the present embodiment, since the curing rate of the adhesive composition is extremely fast, the first liquid is applied to one adherend, and the second liquid Is preferably applied to the other adherend, and the application surfaces of the adherends are joined together. Furthermore, when a 2nd liquid contains a volatile solvent, after apply | coating a 2nd liquid to a to-be-adhered body and volatilizing this, you may join.

[(G) component: photopolymerization initiator]
Moreover, the further embodiment of this invention is said adhesive composition, wherein said 1st liquid further contains (G) photoinitiator.

  For example, in the case where the first liquid is applied to one adherend, the second liquid is applied to the other adherend, and the application surfaces of the adherends are joined together, the first liquid and the second liquid are bonded. In the case where a protruding part or the like that is not properly contacted with the liquid occurs, by adding a photopolymerization initiator to the first liquid, it can be reliably cured by irradiating the protruding part with ultraviolet light after joining. It becomes.

  The said (G) photoinitiator can use the arbitrary chemical | medical agents which can photopolymerize the (B) polymerizable (meth) acrylic-type composition in the range which does not impair the objective of this invention. Such photopolymerization initiators include, but are not limited to, for example, benzophenone, 4-phenylbenzophenone, benzyl, benzoin, benzoylisopropyl ether, benzoylbenzoic acid, 2,2-diethoxyacetophenone, bis Diethylaminobenzophenone, benzyldimethyl ketal, 1-hydroxycyclohexyl phenyl ketone, thioxanthone, 1- (4-isopropylphenyl) 2-hydroxy-2-methylpropan-1-one, 1- (4- (2-hydroxyethoxy) -phenyl -2-methyl-1-propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, camphorquinone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4 , 6-tri Tylbenzoyl) -phenylphosphine oxide, 2-methyl-1- (4- (methylthio) phenyl) -2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) ) -1-butanone-1-one, bis (2,6-dimethoxybenzoyl) -2,4,4-trimethyl-pentylphosphine oxide and the like.

  (G) The addition amount of the photopolymerization initiator component is not particularly limited, and can be set by those skilled in the art within a range not impairing the object of the present invention, but (B) a polymerizable (meth) acrylic composition component. 0.01 to 10 parts by mass or less is preferable with respect to 100 parts by mass, more preferably 0.1 parts by mass or more, or even more preferably 5 parts by mass or less, and further preferably 0.5 parts by mass or more, or even 3 parts by mass or less. Most preferred. By adding a photopolymerization initiator in these ranges, curing by ultraviolet irradiation can be performed more reliably.

  Moreover, in the range which does not impair the objective of this invention, said adhesive composition may further contain the following additional components.

[Adhesion imparting agent]
For example, a further embodiment of the present invention is the above adhesive composition, wherein the first liquid further contains an adhesion imparting agent. In the case where the first liquid is applied to one adherend, the second liquid is applied to the other adherend, and the application surfaces of the adherends are joined together and joined, the adhesion imparting agent to the first liquid is applied. By adding, the contact between the first liquid and the second liquid is improved more appropriately by improving the adhesion to the adherend, and it is possible to prevent the protruding portion from being generated.

  Any adhesive agent can be used as long as the adhesiveness-imparting agent is an adhesive agent, particularly an adhesiveness-imparting agent that is used in a two-component adhesive, as long as the object of the present invention is not impaired. Examples of such adhesion imparting agents include, but are not limited to, γ-chloropropyltrimethoxysilane, vinyltrimethoxysilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyl-tris (β- Methoxyethoxy) silane, γ-methacryloxypropyltrimethoxysilane, γ-acryloxypropyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ- Mercaptopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldimethoxysilane, γ- Ureidopropyltriethoxysila , Hydroxyethyl methacrylate phosphate ester, methacrylonitrile Roxio carboxyethyl acid phosphate include methacrylonitrile Roxio carboxyethyl acid phosphate Tomono ethylamine half salt and the like. From the viewpoint of adhesion to a metal deposition target, methacryloxyoxyethyl acid phosphate and methacryloxyoxyethyl acid phosphate monoethylamine half salt are particularly preferable.

[Inorganic filler]
For example, a further embodiment of the present invention is the above adhesive composition, wherein the first liquid further contains an inorganic filler. By containing the inorganic filler, it is possible to impart further rigidity and low curing shrinkage.

  As the inorganic filler, any inorganic filler that is usually used can be used as long as the object of the present invention is not impaired. Examples of such inorganic fillers include, but are not limited to, silica powder such as quartz, quartz glass, fused silica, and spherical silica, spherical alumina, crushed alumina, magnesium oxide, beryllium oxide, and oxidation. Oxides such as titanium, nitrides such as boron nitride, silicon nitride and aluminum nitride, carbides such as silicon carbide, hydroxides such as aluminum hydroxide and magnesium hydroxide, copper, silver, iron, aluminum, Examples include metals and alloys such as nickel and titanium, and carbon-based fillers such as diamond and carbon.

[Other ingredients]
Further, the adhesive composition in the present embodiment includes various elastomers such as acrylic rubber and urethane rubber, methyl methacrylate-butadiene-styrene graft copolymer, and acrylonitrile-butadiene as long as the object of the present invention is not impaired. -Use additives such as graft copolymers such as styrene-based graft copolymers, solvents, extenders, reinforcing materials, plasticizers, thickeners, colorants, flame retardants, rust inhibitors and surfactants. Can do. Moreover, the said additive can also use various polymerization inhibitors, antioxidant, etc. for the improvement of storage stability.

(Joining method)
Another embodiment of the present invention is a method for joining two adherend surfaces or adherends, wherein (A) a nitrile butadiene rubber containing 5-30% by mass of acrylonitrile units, (B) polymerization A step of applying a first liquid containing a possible (meth) acrylic composition and (C) an organic peroxide to one of the adherend surface or the adherend, and (E) a reaction between an amine and an aldehyde. The step of applying the second liquid containing the condensate and the reducing agent containing (F) copper to the other of the adherend surface or the adherend and the two adherend surfaces or the adherend are combined. A bonding method including a bonding step.

  The above bonding method reflects the characteristics of the above adhesive composition, and it is possible to bond adherends to each other in a very short time, and the adhesive strength is high. It is excellent in durability such as in wet conditions and has a high retention rate.

〔Production method〕
Moreover, other embodiment of this invention is a manufacturing method of the joined body formed by joining two adherend surfaces or a to-be-adhered body, Comprising: (A) Nitrile containing 5-30 mass% acrylonitrile unit A step of applying a first liquid containing butadiene rubber, (B) a polymerizable (meth) acrylic composition and (C) an organic peroxide to one of the adherend surface and the adherend; E) applying a second liquid containing a reaction condensate of amine and aldehyde and (F) a reducing agent containing copper to the other of the adherend surface or the adherend, and the two adherend surfaces described above Alternatively, the adherends are joined together and joined to obtain the joined body.

  Said manufacturing method can improve productivity in various production lines by the joining of the adherends by said adhesive composition in an extremely short time, and can contribute to rationalization. Further, it is possible to produce a bonded body having high adhesiveness, excellent durability such as high temperature and high humidity conditions, and having a high retention rate.

  Another embodiment of the present invention is a joined body in which a plurality of adherend surfaces or adherends are joined by the above-described adhesive composition.

  Another embodiment of the present invention is a joined body in which a plurality of adherend surfaces or adherends are joined by the joining method described above.

  Moreover, other embodiment of this invention is a conjugate | zygote manufactured by said manufacturing method.

  When the above bonded body is bonded with the above-described adhesive composition, the bonded portion has high adhesiveness, is excellent in durability such as high temperature and high humidity conditions, and has a high retention rate.

  The material of the adherend in the above embodiment is not limited to this, and examples thereof include metal, ceramic, paper, wood, glass, rubber, plastic, mortar, concrete, and the like. Since the adhesive composition exhibits excellent adhesive properties particularly to metals and ceramics, it can be suitably used for metal parts, ceramic parts and the like.

  Note that the compositions, methods, and the like described by the above-described embodiments are not intended to limit the present invention, but are disclosed with the intention of illustrating them. The technical scope of the present invention is defined by the description of the claims, and those skilled in the art can make various design changes within the technical scope of the invention described in the claims.

  For example, the respective operations on the two adherend surfaces or adherends in the above embodiment are performed continuously or simultaneously on three or more adherend surfaces or adherends, and the above method is substantially performed continuously or simultaneously several times. Such a mode may be repeated, and such a mode is substantially included in the method for two adherend surfaces or adherends, and, of course, is also included in the technical scope of the present invention.

  In addition, for example, when the second liquid further contains a volatile solvent, the above-described method further including a step of volatilizing the solvent after applying the second liquid is also a further embodiment of the present invention.

  In addition, for example, in the case where the first liquid further contains (G) a photopolymerization initiator component, after the step of joining the two adherend surfaces or adherends together, the adherend surface or The above-described method further comprising the step of irradiating the joint part of the body with ultraviolet rays is a further embodiment of the present invention. By irradiating with ultraviolet light after joining, it is possible to eliminate the tack of the protruding portion and to cure it reliably.

  EXAMPLES Hereinafter, although an Example demonstrates this invention concretely, these are examples and this invention is not limited to these.

[Examples 1-8 and Comparative Examples 1-4]
As shown in Table 1, the components (A) to (D) and (G) and additives were mixed in the proportions shown in Table 1, and an elastomer (butadiene / methyl (meth) acrylate / styrene copolymer) was added to adjust the viscosity. (Hereinafter referred to as “butadiene / MMA / ST copolymer”) was added to form a first liquid. N-Butyraldehyde aniline as component (E), copper naphthenate (copper concentration 5%) as component (F), and acetone as the other diluent were mixed in the ratio shown in Table 1 to obtain a second solution.

  The fixing time of the adhesive composition composed of the first liquid and the second liquid and the tensile shear bond strength of the cured body were measured by the following methods.

(Measurement of fixing time)
Apply the first liquid to one of the test pieces for tensile shear strength measurement, apply the second liquid to the other test piece, and volatilize the volatile solvent of the second liquid, and then apply the coated surface of each adherend. Adhering together, the time until it could not be removed even when a load of 4 kg was applied was defined as the fixing time.

(Tensile shear bond strength)
A 1.6 mm-thick iron test piece (sandblasted) as an adherend was bonded by the above coating method and measured with a tensile tester (tensile speed of 10 mm / min).

(Moisture resistance evaluation)
A test piece similar to the above-described tensile shear bond strength evaluation was prepared using the test piece for tensile shear bond strength measurement, left in an atmosphere at a temperature of 60 ° C. and a humidity of 90% for 500 hours, and taken out. After leaving for 30 minutes or more in a room at 50 ° C. × RH, the tensile shear bond strength was measured.

The above results are shown in Table 1.

  When bonded using the adhesive compositions of Examples 1 to 8, it can be fixed in a short fixing time of 30 seconds or less, and the bonded portion has a tensile shear adhesive strength at room temperature of around 20 MPa. Furthermore, the tensile shear bond strength was higher than 10 MPa even after being left under high temperature and high humidity, and sufficient durability could be achieved. In particular, in the adhesive compositions of Examples 1 to 5 and 8 containing a basic compound having an amine structure (D), a further shortening of the fixing time was observed as 10 seconds or less or 15 seconds.

  On the other hand, in Comparative Example 1, the content of the acrylonitrile unit in the nitrile butadiene rubber component was too much, so that the tensile shear adhesive strength under high temperature and high humidity was inferior to 10 MPa or less. Since Comparative Example 2 does not contain a reaction condensate component of an amine and an aldehyde, it takes a very long time to bond, and the tensile shear bond strength at room temperature is not sufficient. Since the comparative example 3 did not contain the reducing agent component containing copper, it did not harden. Since Comparative Example 4 did not contain a nitrile butadiene rubber component, the tensile shear bond strength under high temperature and high humidity was inferior to 10 MPa or less.

(Example 9 and Comparative Example 5)
About the joined body obtained by adhere | attaching a copper plate using the adhesive composition of Example 1 and Comparative Example 1, the copper plate corrosion test was implemented in the airtight glass container. The copper plate (Example 5) adhered using the adhesive composition of Example 1 is not changed, whereas the copper plate (Comparative Example 8) adhered using the adhesive composition of Comparative Example 1 is a copper plate. Surface oxidation was observed.

(Example 10)
One part of benzyl dimethyl ketal as a photopolymerization initiator was added to the first liquid of the adhesive composition of Example 1 and dissolved to prepare the composition. Apply the second liquid of Example 1 so that it does not protrude onto the adhesive surface of the iron test piece for tensile shear bond strength measurement, and apply the above composition to the other test piece so that the composition protrudes. Glued. When this protruding portion was irradiated with ultraviolet rays, the tack was completely eliminated even when the surface of the cured product was touched with a finger.

  From the above results, it was confirmed that the adhesive composition of the present invention can quickly bond and cure the bonded portion with high adhesiveness and can realize excellent durability of the bonded portion.

  The adhesive composition of the present invention has an extremely fast curing reaction at room temperature and is excellent in adhesiveness and durability (moisture resistance). Therefore, when applied to various production lines, production time can be shortened or rationalized. It is very useful in industry.

Claims (11)

  (A) a nitrile butadiene rubber containing 5 to 30% by mass of an acrylonitrile unit, (B) a polymerizable (meth) acrylic composition and (C) a first liquid containing an organic peroxide; A two-component adhesive composition comprising: a reaction condensate of an amine and an aldehyde; and (F) a second liquid containing a reducing agent containing copper.   The adhesive composition according to claim 1, wherein the first liquid further contains (D) a basic compound having an amine structure.   3. The adhesive composition according to claim 2, wherein the basic compound (D) having an amine structure is a basic compound comprising a primary amine structure or a secondary amine structure.   The adhesive composition according to any one of claims 1 to 3, wherein the first liquid further contains (G) a photopolymerization initiator.   The adhesive composition according to any one of Claims 1 to 4, wherein the (B) polymerizable (meth) acrylic composition further contains isobornyl (meth) acrylate.   The adhesive composition according to any one of claims 1 to 5, wherein the organic peroxide (C) is cumene hydroperoxide or t-butyl peroxybenzoate.   The adhesive composition according to any one of claims 1 to 6, wherein the reaction condensate of (E) amine and aldehyde is aldehyde aniline.   A joined body formed by joining a plurality of adherend surfaces or adherends with the adhesive composition according to claim 1.   A method for joining two adherends or adherends, wherein (A) a nitrile butadiene rubber containing 5 to 30% by mass of an acrylonitrile unit, (B) a polymerizable (meth) acrylic composition and ( C) a step of applying a first liquid containing an organic peroxide to one of the adherend surface and the adherend, (E) a reaction condensate of amine and aldehyde, and (F) a reducing agent containing copper A joining method comprising: applying a second liquid to be applied to the other of the adherend surface or the adherend, and joining the two adherend surfaces or the adherend together.   The bonding method according to claim 9, further comprising a step of irradiating the bonding surface or the bonding portion of the body with ultraviolet rays after the step of bonding the two bonding surfaces or the bonding objects together.   A method for producing a joined body obtained by joining two adherend surfaces or adherends, wherein (A) a nitrile butadiene rubber containing 5 to 30% by mass of an acrylonitrile unit, (B) a polymerizable (meta ) A step of applying a first liquid containing an acrylic composition and (C) an organic peroxide to one of the adherend surface or the adherend, (E) a reaction condensate of amine and aldehyde, and (F) A step of applying a second liquid containing a reducing agent containing copper to the other of the adherend surface or the adherend, and a step of joining the two adherend surfaces or the adherend together to obtain the joined body A manufacturing method comprising: