JP2002105109A - Curable resin composition, cured body, adhesive composition, and joined body - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curing resin composition excellent in heat resistance, having a high curing speed, having good adhesiveness, and especially exhibiting excellent heat resistance when used for producing motors. SOLUTION: This curing composition contains (1) polymerizable vinyl monomers, (2) zeolite, and (3) a naphthenic acid metal salt. Further, the composition preferably contains (4) a thiourea derivative, (5) a curing agent, (6) elastomer components, and (7) an acidic phosphate compound. The composition may be used as the adhesive composition. The polymerizable vinyl monomers preferably comprise (a) an epoxy (meth)acrylate and (b) polymerizable vinyl monomers other than the epoxy (meth)acrylate.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curable resin composition having excellent moisture resistance, a high curing speed, and good adhesion. In particular, the present invention relates to an acrylic adhesive composition which has a remarkably improved rust preventive effect when exposed to a high-temperature and high-humidity atmosphere in a motor using a galvanized steel sheet whose surface is subjected to chromate treatment, and is suitable for fixing a ferrite to a yoke.

[0002]

2. Description of the Related Art An ordinary-temperature fast-curing adhesive that cures in a short time at ordinary temperature is increasingly used year by year for pollution-free, labor-saving, resource-saving and energy-saving purposes.

In particular, a one-component heat-curable epoxy adhesive is generally used for assembling a motor. However, since a huge amount of electric power is required for heating, there is a disadvantage that it is not economically preferable. . Therefore, a room-temperature quick-setting adhesive has come to be used.

FIGS. 1 and 2 show the structure of a rotary motor. The rotary motor has a configuration in which a rotor (rotor) including a winding 4 and a rotating shaft 5 is inserted into a stator (stator) formed by joining a yoke 1 and a magnet 2 with an adhesive composition 3. I have.

[0005] Known cold-setting adhesives include two-pack type fast-curing epoxy adhesives, anaerobic adhesives, instantaneous adhesives, and second-generation acrylic adhesives (SGA).

[0006] The two-pack type fast-curing epoxy adhesive is one in which a main agent and a curing agent are measured and mixed, applied to an adherend, and cured by a reaction between the main agent and the curing agent. However, the two-part cold curing epoxy adhesive may cause a remarkable decrease in the adhesive strength if the main agent and the curing agent are insufficiently measured and mixed, and even when the measurement and mixing are sufficiently performed. There was a drawback that peel adhesion strength and impact adhesion strength were low.

[0007] The anaerobic adhesive is cured by pressing the adhesive composition between adherends and blocking air.
However, when a part of the adhesive composition comes out of the adherend at the time of pressure bonding, there is a disadvantage that the part that comes out comes into contact with air and does not cure. Further, there is a disadvantage that the composition does not cure even when the clearance between the adherends is large.

The instant adhesive usually contains cyanoacrylate as a main component and has excellent workability. However, there was a drawback that peel adhesion strength and impact adhesion strength were low. or,
Because of poor moisture resistance and water resistance, there was a drawback that the range of use was significantly limited.

Although SGA is a two-pack type, it does not require accurate and lightweight two-packs, and can be cured in a few minutes to tens of minutes at room temperature by imperfect weighing and mixing, and sometimes even by only two-pack contact. Excellent workability, high peel adhesion strength and high impact adhesion strength,
It is widely used because of good curing of the exposed portion (Japanese Patent Publication No. 58-34513, Japanese Patent Publication No. 58-5).
954 and JP-A-54-141826).
Specifically, it has come to be used for motor adhesives as an alternative to epoxy adhesives.

[0010]

In recent years, among motors, the demand for on-vehicle motors used in automobiles has been increasing. Automotive motors are required to have high characteristics due to the location of use, the climate in the area of use, and the heat generated during operation of the engine and the self-heating of the motor. Therefore, it is required to exhibit high adhesiveness for a long time.

As a result of intensive studies, the present invention has shown that a curable resin composition comprising (2) a zeolite and, further, (3) a metal salt of naphthenic acid and (4) a thiourea derivative, if necessary, as a reducing agent. Have the following effects and have been found to be very useful as adhesives for use in motors, leading to the solution of the present invention.

(A) It exhibits high adhesiveness over a long period of time in a high-temperature and high-humidity exposure test of 1000 hours or more in a 160 ° C atmosphere and 500 hours or more in a 180 ° C atmosphere, and has good adhesiveness and heat resistance. As described above, since the effect of improving the adhesive strength when heated is excellent, it is suitable for assembling motors that are constantly exposed to high-temperature atmosphere due to the use environment and self-heating during motor rotation, etc., as in Japan. Can be used.

(B) When the motor is manufactured by automation, the fixing time is short due to the effect of accelerating hardening, and the use of the jig can be greatly reduced, and mass production is possible.

[0014]

That is, the present invention provides:
A curable resin composition containing (1) a polymerizable vinyl monomer, (2) zeolite, and (3) a metal salt of naphthenic acid, and further (4) the curable resin containing a thiourea derivative. A curable resin composition comprising (1) a polymerizable vinyl monomer containing (a) an epoxy (meth) acrylate, and (1) a polymerizable vinyl monomer comprising (a) an epoxy (meth) Acrylate and (A)
The curable resin composition containing a polymerizable vinyl monomer other than the epoxy (meth) acrylate, (1)
(A) The curable resin composition wherein the epoxy (meth) acrylate is an epoxy (meth) acrylate represented by the following general formula (A),

Embedded image Furthermore, (5) the curable resin composition containing a curing agent, (6) the curable resin composition containing an elastomer component, and (7) the following general formula: The curable resin composition containing an acidic phosphoric acid compound represented by (B),

Embedded image The two-part curable resin composition comprising at least (5) a curing agent in the first part and at least (3) a metal salt of naphthenic acid and (4) a thiourea derivative in the second part. is there. And it is a cured body of the curable resin composition. Further, it is an adhesive composition comprising the curable resin composition.
Further, the present invention provides a bonded body obtained by bonding an adherend using the adhesive composition, wherein the adherend is a galvanized steel sheet whose surface is subjected to chromate treatment.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail.

The (1) polymerizable vinyl monomer used in the present invention may be any as long as it is capable of radical polymerization, and a vinyl monomer having a carbon-carbon unsaturated double bond is preferred. Among the polymerizable vinyl monomers, it is preferable that the polymerizable vinyl monomer is a polymerizable (meth) acrylic acid derivative in terms of curing speed, adhesiveness, and the like. Further, the polymerizable (meth) acrylic acid derivative is more preferably 70 parts by mass or more in 100 parts by mass of the polymerizable vinyl monomer, and most preferably, all the polymerizable vinyl monomers are the polymerizable (meth) acrylic acid derivative. preferable.

Here, the polymerizable (meth) acrylic acid derivative means a polymerizable acrylic acid derivative and / or a polymerizable methacrylic acid derivative. These are usually used in liquid or solid form.

Among the polymerizable (meth) acrylic acid derivatives, it is preferable to contain (a) an epoxy (meth) acrylate.

(A) Since the use of epoxy (meth) acrylate has an excellent effect of improving the adhesive strength under heat, the curable resin composition used in the present invention is always used due to the use environment and self-heating during motor rotation. Very useful for motors exposed to high temperature atmospheres. In particular, since epoxy (meth) acrylate has a curing acceleration effect, it is useful for manufacturing a motor in the following points.

In the manufacture of the motor, in order for the motor to exhibit a sufficient performance, it is necessary to precisely assemble the yoke 1 and the magnet 2 so as not to be displaced, and to keep the assembly constant. Therefore, it was necessary to fix the magnet using a large amount of jigs until the adhesive composition 3 was cured. When the motor is manufactured by automation, if the fixing time is short, the use of the jig can be greatly reduced, and the industrial use is extremely high because the jig can be mass-produced.

The epoxy (meth) acrylate used in the present invention is obtained by adding (meth) acrylic acid to an epoxy compound. Further, (meth) acrylic anhydride may be used instead of (meth) acrylic acid.

(A) Among the epoxy (meth) acrylates, the effect of improving the adhesive strength is remarkable, and
The epoxy (meth) acrylate represented by is preferable.

[0023]

Embedded image

Epoxy (meth) represented by formula (A)
As acrylates, epoxy acrylate “Epoxyester 3000M” (manufactured by Kyoeisha Kogyo), epoxy acrylate “Epoxyester 3000A” (manufactured by Kyoeisha Kogyo) and epoxy acrylate “Biscoat V #”
540 "(manufactured by Osaka Organic Chemical Industry Co., Ltd.). One or more of these may be used.

Epoxy (meth) represented by formula (A)
Among acrylates, epoxy methacrylate represented by the following general formula (A ') is preferable because the effect of improving the adhesive strength is remarkable.

[0026]

Embedded image

The epoxy methacrylate represented by the general formula (A ') includes "Epoxyester 3000M"
(Manufactured by Kyoeisha Chemical Co., Ltd.).

Component (A) is used in an amount of 1 part by mass in a total of 100 parts by mass of component (1) and component (6) used as required.
It is preferably from 30 to 30 parts by mass, more preferably from 5 to 15 parts by mass. If the amount is less than 1 part by mass, the adhesive strength under heat may be low, and if it exceeds 30 parts by mass, the adhesiveness and adhesion may be deteriorated due to carbonization of the adhesive layer under high-temperature exposure conditions.

Further, the polymerizable (meth) acrylic acid derivative may be used in combination with (a) an epoxy (meth) acrylate and (a) a polymerizable vinyl monomer other than the epoxy (meth) acrylate from the viewpoint of improving adhesiveness. preferable.

(A) Among the polymerizable vinyl monomers other than the epoxy (meth) acrylate, a polymerizable (meth) acrylic acid derivative other than the epoxy (meth) acrylate may be used in terms of curing speed and adhesiveness. Preferably, (meth) acrylates other than epoxy (meth) acrylate are more preferable.

Examples of the (meth) acrylate other than the epoxy (meth) acrylate include methyl acrylate,
Methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, cyclohexyl methacrylate, 2-hydroxyethyl acrylate, 2 methacrylate -Hydroxyethyl, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, glycidyl acrylate, glycidyl methacrylate, diethylene glycol diacrylate, diethylene glycol dimethacrylate, dipropylene glycol acrylate, dipropylene glycol methacrylate, trimethylolpropane triacrylate, Trimethylolpropane trimethacrylate, pentaerythritol tetraacrylate, Taerythritol tetramethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, trisacryloyloxyethyl isocyanurate, trismethacryloyloxyethyl isocyanurate, 2,2-bis (4-acryloxyphenyl) propane, 2,2-bis (4-methacryloxyphenyl) propane, 2,2-
Bis (4-acryloxyethoxyphenyl) propane,
2,2-bis (4-methacryloxyethoxyphenyl)
Propane, 2,2-bis (4-acryloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-
Acryloxypropoxyphenyl) propane, 2,2-
Bis (4-methacryloxypropoxyphenyl) propane, 2,2-bis (4-acryloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloxytetraethoxyphenyl) propane, dicyclopentenyloxyethyl acrylate, Examples include dicyclopentenyloxyethyl methacrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, and tricyclo [5,2,1,0] decanyl (meth) acrylate. One or more of these may be used.

Of these, mono (meth) acrylates are preferred from the viewpoints of adhesiveness, heat resistance and shortening of fixing time, and 2-hydroxyethyl (meth) acrylate,
One or more of the group consisting of methyl (meth) acrylate and isobornyl (meth) acrylate is preferable, and methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and isobornyl (meth) acrylate are preferred. Most preferably, they are used in combination. When methyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and isobornyl (meth) acrylate are used in combination, the amount of each component used is determined by the amount of (meta) in terms of adhesiveness, heat resistance and shortening of fixing time. ) Methyl acrylate, 2-hydroxyethyl (meth) acrylate and isobornyl (meth) acrylate
35 to 55 parts by mass of methyl (meth) acrylate: 10 to 30 parts by mass of methyl 2-hydroxyethyl (meth) acrylate: 25 to 35 parts by mass of isobornyl (meth) acrylate in 100 parts by weight of acrylate in total.

The amount of component (a) used is 5 parts per 100 parts by weight of the total of component (1) and component (6) used as required.
It is preferably from 5 to 90 parts by mass, more preferably from 65 to 85 parts by mass. If the amount is less than 60 parts by mass, the viscosity may be too high to produce the adhesive composition. If the amount is more than 95 parts by mass, the viscosity and the impact adhesive strength may be significantly reduced.

In the present invention, (2) zeolite is used.
The use of zeolites significantly improves the bond strength after exposure to high temperatures.

The zeolite used in the present invention is preferably a dehydrated zeolite from the viewpoint of heat resistance and adhesiveness, and more preferably a zeolite having a water content of 3% by mass or less. Water content 3
The zeolite of less than mass% can be easily obtained by heating a commercially available ordinary synthetic zeolite to 300 ° C. or more.
The zeolite has the general formula M _{2 / K} · Al ₂ O ₃ · xSiO ₂ · yH
₂ O (M is the metal cation, k is the valence of the metal cation,
x and y are arbitrary numbers) Group 1A or 2A of the periodic table represented by
Natural and synthetic products can be used as long as they are crystalline aluminosilicates of the group III elements. As a commercially available product, “Synthetic zeolite 3
A powder (manufactured by Union Showa), "synthetic zeolite 4A powder" (manufactured by Union Showa), "synthetic zeolite 5A powder" (manufactured by Union Showa), "synthetic zeolite 13X powder" (manufactured by Union Showa), " Zeolam (A-3 powder) "(manufactured by Tosoh Corporation),
4 powder) "(manufactured by Tosoh Corporation)," Zeolam (A-5 powder) "(manufactured by Tosoh Corporation) and" Zeolam (F-9 powder) "
(Manufactured by Tosoh Corporation). One or more of these may be used.

Of these, the 3A type is preferable because the effect of improving heat resistance is remarkable.

The amount of component (2) used is preferably 1 to 15 parts by mass, more preferably 2.5 to 10 parts by mass, based on 100 parts by mass of component (1) and component (6) used as required. Is more preferred. If the amount is less than 1 part by mass, adhesion and adhesion may be deteriorated due to carbonization of the adhesive layer under high-temperature exposure conditions, and heat resistance may not be improved. If it exceeds 15 parts by mass, the adhesion may be deteriorated.

In the present invention, (3) a metal salt of naphthenic acid is used. By using the metal naphthenate, particularly when used in combination with (4) thiourea described later, the effect of accelerating the curing is excellent, and the effect of improving the adhesive strength under heat becomes remarkable.

Among the metal naphthenates, cobalt naphthenate and copper naphthenate are preferred, and copper naphthenate is more preferred, from the viewpoint of having an excellent curing promoting effect and improving the adhesive strength when heated.

The amount of the component (3) used is preferably 0.05 to 1.6 parts by mass, more preferably 0.08 to 100 parts by mass of the total of the component (1) and the component (6) used as required. ~ 0.
8 parts by mass is more preferred. If the amount is less than 0.05 parts by mass, the shear strength at the time of heating may not be improved. If the amount exceeds 1.6 parts by mass, the curability may be deteriorated, and the shear strength at the time of heating may not be improved.

In the present invention, it is preferable to use a thiourea derivative (4) because when used in combination with a metal salt of naphthenic acid, it has an excellent effect of accelerating hardening and has a remarkable effect of improving the adhesive strength when heated.

Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, cybutylthiourea, tetramethylthiourea, and ethylenethiourea. One or more of these may be used. Among these, ethylenethiourea is preferred because it has an excellent curing promoting effect and improves the adhesive strength when heated.

The amount of component (4) used is preferably from 0.1 to 10 parts by mass, more preferably from 0.5 to 5 parts by mass, based on 100 parts by mass of component (1) and component (6) used as required. Parts by mass are more preferred. If the amount is less than 0.1 part by mass, there is a possibility that the effect of promoting the curing may not be obtained. If the amount exceeds 10 parts by mass, an unreacted reducing agent remains, and the adhesion may be reduced.

According to the present invention, (5)
It is preferred to use a curing agent.

As the curing agent (5) used in the present invention,
A so-called polymerization initiator can be used. Among the curing agents, organic peroxides are preferred in terms of reactivity.

As organic peroxides, cumene hydroperoxide, paramenthane hydroperoxide,
Examples include tert-butyl hydroperoxide, diisopropylbenzene dihydroperoxide, methyl ethyl ketone peroxide, benzoyl peroxide, tert-butyl peroxybenzoate, and the like, and one or more of these may be used. Among them, cumene hydroperoxide is preferable in terms of reactivity.

The amount of component (5) to be used is preferably 0.5 to 10 parts by mass, more preferably 1 to 8 parts by mass, based on 100 parts by mass of component (1) and component (6) used as required. Parts are more preferred. If the amount is less than 0.5 part by mass, there is a possibility that there is no curing acceleration effect, and if it is less than 10 parts by mass, the storage stability may be deteriorated.

In the present invention, from the viewpoint of improving the adhesive strength,
(6) It is preferable to use an elastomer component.

The (6) elastomer component used in the present invention refers to a polymer material having rubber-like elasticity at room temperature, and those which can be dissolved or dispersed in a vinyl monomer are preferable from the viewpoint of adhesiveness.

As such an elastomer component, acrylonitrile-butadiene-methacrylic acid copolymer,
Acrylonitrile-butadiene-methyl methacrylate copolymer, butadiene-styrene-methyl methacrylate copolymer (MBS), acrylonitrile-styrene-
Butadiene copolymer, and acrylonitrile-butadiene rubber, linear polyurethane, styrene-butadiene rubber, various synthetic rubbers such as chloroprene rubber and butadiene rubber, natural rubber, styrene-based thermoplastic elastomers such as styrene-polybutadiene-styrene-based synthetic rubber, Polyolefin-based thermoplastic elastomers such as polyethylene-EPDM synthetic rubber, urethane-based thermoplastic elastomers such as caprolactone type, adipate type and PTMG type, polyester-based thermoplastic elastomers such as polybutylene terephthalate-polytetramethylene glycol multi-block polymer, and nylon-polyol Polyamide-based thermoplastic elastomers such as block copolymers and nylon-polyester block copolymers; Butadiene thermoplastic elastomer, and include vinyl chloride based thermoplastic elastomer. If these elastomer components have good compatibility,
One or more kinds may be used.

Among these, acrylonitrile-butadiene-methacrylic acid copolymer, acrylonitrile-butadiene-methyl methacrylate copolymer, butadiene-styrene-methyl are preferred because of their good solubility in polymerizable vinyl monomers and good adhesive strength. One or more members selected from the group consisting of a methacrylate copolymer and acrylonitrile-butadiene rubber are preferred, and a combined use of an acrylonitrile-butadiene copolymer and a butadiene-styrene-methyl methacrylate copolymer is more preferred.

Component (6) is used in an amount of 5 parts by weight based on a total of 100 parts by mass of component (1) and optional component (6).
It is preferably from 40 to 40 parts by mass, more preferably from 10 to 25 parts by mass. If the amount is less than 5 parts by mass, the viscosity is too low, so that the adhesive composition is sagged, the workability is reduced, and the adhesive strength may not be improved. If the amount exceeds 40 parts by mass, the viscosity is too high, and It is difficult to prepare, and the adhesive strength may not be improved.

In the present invention, in order to improve the adhesion,
(7) It is preferable to use an acidic phosphoric acid compound represented by the following general formula (B).

[0054]

Embedded image

The acidic phosphoric acid compound represented by the general formula (B) (7) used in the present invention includes acid phosphooxyethyl acrylate, acid phosphooxyethyl methacrylate, acid phosphooxypropyl acrylate, and acid phosphooxypropyl methacrylate. ,
Bis (2-acryloyloxyethyl) acid phosphate and bis (methacryloyloxyethyl) acid phosphate are exemplified. One or more of these may be used.

Of these, bis (methacryloyloxyethyl) acid phosphate is preferred because of its good adhesion.

The amount of component (7) used is preferably 0.05 to 20 parts by mass, preferably 0.5 to 20 parts by mass, based on 100 parts by mass of component (1) and component (6) used as required. 10 parts by mass is more preferred. If the amount is less than 0.05 part by mass, the adhesion may be small, and if it exceeds 20 parts by mass, the adhesion may be deteriorated.

The curable resin composition used in the present invention contains paraffins in order to accelerate curing of a portion in contact with air, and various oxidizing agents containing a polymerization inhibitor in order to improve storage stability. Inhibitors and the like can be used respectively.

In addition, for the purpose of adjusting viscosity and fluidity,
Polymers such as chlorosulfonated polyethylene, polyurethane, styrene-acrylonitrile copolymer and polymethyl methacrylate, and finely divided silica may also be used.

In addition, other known substances such as a filler and a colorant can be used if desired.

As an embodiment used in the present invention, an adhesive composition is preferable, and it is more preferable to use it as a two-part adhesive composition. For the two-part type, all the essential components of the adhesive composition of the present invention are not mixed during storage, the adhesive composition is divided into a first part and a second part, and at least a curing agent is added to the first part, It is preferable to store at least the metal salt of naphthenic acid and the thiourea derivative separately in the two agents. The two-pack type is preferred in that it has excellent storage stability. In this case, the two components can be used as a two-part adhesive composition by simultaneously or separately applying and contacting and curing. In the case of the two-pack type, the amount of each component used is represented by an amount based on the total of the first and second packs.

The adherend is joined with the adhesive composition used in the present invention to produce a joined body. There are no restrictions on the materials of the adherend, such as paper, wood, ceramics, glass, ceramics, rubber, plastics, mortar, concrete, and metals, but when the adherend is metal, it exhibits excellent adhesiveness, When at least one of the adherends is a galvanized steel sheet subjected to a chromate treatment, more excellent adhesion is exhibited.

In the case where at least one of the adherends is a galvanized steel sheet subjected to chromate treatment, the use of the present invention is as follows.
It is preferably used for motors because of its excellent heat resistance when exposed to high temperatures, and more preferably used as a material for the yoke 1 of the motor is a galvanized steel sheet that has been subjected to chromate treatment and used for bonding the yoke 1 and the magnet 2. .

Conventionally, the yoke 1 is made of iron and retains the anticorrosion property by post-coating. However, since the post-coating can be saved in labor, a plated steel sheet having excellent corrosion resistance is being used as the yoke 1. . When a chromate-treated galvanized steel sheet is used for an in-vehicle motor as an adherend, the adhesive layer does not carbonize under high-temperature exposure conditions,
Shows good adhesion. As a plated steel sheet having excellent corrosion resistance, a chromate-treated galvanized steel sheet is preferable because it is easily available.

[0065]

The present invention will be described in more detail with reference to the following examples. Hereinafter, the unit of the amount of each substance used is shown in parts by mass.
Commercial products were used as each substance. However, epoxy (meth) acrylate is "epoxy ester 3000M"
(Manufactured by Kyoeisha Chemical Co., Ltd.), using "synthetic zeolite 3A powder" (manufactured by Union Showa, dehydrated zeolite, water content of 3% by mass or less) as the zeolite, and bis (methacryloyloxyethyl) acid as the acidic phosphoric acid compound. Phosphate was used. In addition, various physical properties were measured as follows.

(Fixing time) In a 23 ° C. and 50% humidity environment, one test piece (1) was used in accordance with JIS K 6850.
First and second agents of the adhesive composition were mixed and applied in equal amounts to one side of a 00 mm × 25 mm × 1.6 mm, sand-blasted iron plate) with a static mixer, and immediately thereafter, another test piece (100 mm × 25mm x 1.6m
m, an iron plate subjected to sand blasting) was laminated and bonded to obtain a sample for measuring a fixing time. The fixation time (unit: minute) of the sample was measured immediately after the application under an environment of a temperature of 23 ° C. and a humidity of 50%, and immediately after the push-pull gauge (Model S, Komu).
(manufactured by Ra Co., Ltd.) until the adhesive strength of 0.39 [MPa / 3.125] or more was developed.

(Tensile shear bond strength at 120 ° C. hot) Temperature 2
One test piece (100 mm × 25 mm × 1.6 m) in an environment of 3 ° C. and 50% humidity in accordance with JIS K 6850.
m, an equal amount of the first agent and the second agent of the adhesive composition were mixed and applied to one side of a sandblasted iron plate with a static mixer, and immediately thereafter, another test piece (100 m
(M × 25 mm × 1.6 mm, sandblasted iron plate) were laminated and bonded, and cured under the same environment for 24 hours was used as a measurement sample. The test piece was heated to 120 ° C
Under an environment of a temperature of 120 ° C. and a tensile speed of 10 mm / min. Under the conditions described above, the tensile shear adhesive strength at 120 ° C. when heated was measured.

(Tensile shear bond strength at 120 ° C. when heated by plated steel sheet) JIS in an environment of a temperature of 23 ° C. and a humidity of 50%.
According to K 6850, one test piece (100 mm × 2
One side of a 5 mm × 1.4 mm, chromate-treated galvanized steel sheet) was mixed and applied with an equivalent amount of the first agent and the second agent of the adhesive composition by a static mixer, and immediately thereafter, another test piece (100 mm) × 25mm × 1.4mm,
Chromate-treated galvanized steel sheets) were laminated and bonded, and cured for 24 hours in the same atmosphere to obtain a measurement sample. The test piece was left for 30 minutes in an environment at a temperature of 120 ° C., and then subjected to a tensile speed of 10 mm / min.
Under the conditions described above, the tensile shear adhesive strength at 120 ° C. when heated was measured.

(160 ° C. heat resistance) Temperature 23 ° C., Humidity 50
% Environment, the first agent and the second agent of the adhesive composition are applied to one surface of one test piece (100 mm x 25 mm x 1.4 mm, chromate-treated galvanized steel sheet) in accordance with JIS K-6850. Equivalent amounts were mixed and applied using a static mixer, and immediately thereafter, another test piece (100 mm × 2
A 5 mm x 1.4 mm, chromate-treated galvanized steel sheet) was laminated and bonded, cured for 24 hours in the same atmosphere, and then exposed to an environment at a temperature of 160 ° C for 1000 hours to obtain a measurement sample. After curing for several hours in an environment of a temperature of 23 ° C. and a humidity of 50%, a tensile speed of 10 mm / min. The tensile shear adhesive strength (unit: MPa) was measured under the following conditions.

(180 ° C. heat resistance) Temperature 23 ° C., humidity 50
% Environment, the first agent and the second agent of the adhesive composition are applied to one surface of one test piece (100 mm x 25 mm x 1.4 mm, chromate-treated galvanized steel sheet) in accordance with JIS K-6850. Equivalent amounts were mixed and applied using a static mixer, and immediately thereafter, another test piece (100 mm × 2
5 mm x 1.4 mm, chromate-treated galvanized steel sheet) were laminated and bonded together, cured for 24 hours in the same atmosphere, and then exposed to an environment at a temperature of 180 ° C for 500 hours to obtain a measurement sample. After curing for several hours in an environment of a temperature of 23 ° C. and a humidity of 50%, a tensile speed of 10 mm / min. The tensile shear adhesive strength (unit: MPa) was measured under the following conditions.

(Initial Adhesion by Real Motor) At room temperature, using an adhesive composition 3, as shown in FIG. 3, a stator in which a yoke 1 made of a chromate-treated galvanized steel sheet and a magnet 2 made of ferrite were bonded. A sample for measurement was used. In an environment of a temperature of 23 ° C. and a humidity of 50%, a metal ball 6 was dropped on the side surface of the yoke 1 to perform a falling ball impact test to confirm the adhesion. ◎: when the magnet 2 was broken by material or the adhesive composition 3 was cohesively broken, を: when cohesive failure of the adhesive composition 3 and interfacial peeling between the magnet 2 and the adhesive composition 3 were mixed, O: adhesion The case where the interface of the agent composition 3 peeled off was designated as x.

Experimental Example 1 An adhesive composition having the composition shown in Table 1 and comprising a first agent and a second agent was prepared, and various physical properties were evaluated. Table 2 shows the results.

[0073]

[Table 1]

[0074]

[Table 2]

Experimental Example 2 An adhesive composition having the composition shown in Table 3 and comprising a first agent and a second agent was prepared, and various physical properties were evaluated. Table 3 shows the results.

[0076]

[Table 3]

EXPERIMENTAL EXAMPLE 3 At the manufacturing site of an automated stator, an experiment No. The yoke 1 and the magnet 2 were bonded using the two-part adhesive composition 3 of 1-4 to manufacture a stator. In the manufacture of the stator, the use of jigs could be greatly reduced and mass production was possible.

[0078]

According to the present invention, excellent moisture resistance, high curing speed, good adhesion, and high adhesion even when exposed to a high temperature atmosphere such as 1000 hours or more in a 160 ° C atmosphere and 500 hours or more in a 180 ° C atmosphere. An extremely large curable resin composition is obtained. The motor can be used under high-temperature exposure conditions, particularly when used in the manufacture of a motor using a galvanized steel sheet whose surface is chromated.

[Brief description of the drawings]

FIG. 1 is a sectional view of a rotary motor.

FIG. 2 is a front view directly above a rotary motor.

FIG. 3 is a measurement diagram of initial adhesion by a real motor.

[Explanation of symbols]

 DESCRIPTION OF SYMBOLS 1 Yoke 2 Magnet 3 Adhesive composition 4 Winding 5 Rotation axis 6 Metal ball

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 4J011 PA13 4J040 CA002 FA011 FA262 HA296 HB27 HD08 HD24 JB07 MA03 4J100 AJ03Q AL03Q AL04Q AL08Q AL59Q AL62Q AL66P BA02P BA03Q BA42Q BC04Q BC08Q BC28Q BC43P BC43Q BC54P JA03

Claims (13)

[Claims] A curable resin composition comprising (1) a polymerizable vinyl monomer, (2) zeolite, and (3) a metal salt of naphthenic acid. 2. The curable resin composition according to claim 1, further comprising (4) a thiourea derivative. 3. The curable resin composition according to claim 1, wherein (1) the polymerizable vinyl monomer contains (A) an epoxy (meth) acrylate. 4. The method of claim 1, wherein (1) the polymerizable vinyl monomer comprises (a) an epoxy (meth) acrylate and (a) an epoxy (meth)
The curable resin composition according to claim 1, further comprising a polymerizable vinyl monomer other than acrylate. 5. The curable resin composition according to claim 3, wherein (1) the epoxy (meth) acrylate (a) is an epoxy (meth) acrylate represented by the following general formula (A). Embedded image 6. The curable resin composition according to claim 1, further comprising (5) a curing agent. 7. The curable resin composition according to claim 1, further comprising (6) an elastomer component. 8. The curable resin composition according to claim 1, further comprising (7) an acidic phosphoric acid compound represented by the following general formula (B). Embedded image 9. The first agent comprises at least (5) a curing agent, and the second agent comprises at least (3) a metal salt of naphthenic acid and (4) a thiourea derivative. 2. The two-part curable resin composition according to claim 1. 10. A cured product of the curable resin composition according to claim 1. An adhesive composition comprising the curable resin composition according to any one of claims 1 to 9. 12. A bonded body obtained by bonding an adherend using the adhesive composition according to claim 11. 13. The joined body according to claim 12, wherein the adherend is a galvanized steel sheet whose surface is subjected to chromate treatment.