JP2002088107A - Curable resin composition, cured material, adhesive composition and adhered product - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a curable resin composition excellent in moisture resistance, having high curing speed and good adhesion, especially for production of a motor. SOLUTION: This curable resin composition comprises (1) a polymerizable vinyl monomer, (2) a polymer initiator, (3) triazoles and (4) one or more kinds of compounds from a group consisting of tertiary amine, thiourea derivatives and transition metal salts and optionally (5) an elastomer component and (6) an acidic phosphoric acid compound. The resin composition may be used as an adhesive composition.

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. The on-vehicle motor is required to have high characteristics due to the location of use, the climate of the use area, heat generation during engine operation, and self-heating of the motor. For example, high temperature and high humidity of 250 hours or more in an atmosphere of 80 ° C x 95% humidity. It has become required to exhibit high adhesiveness for an exposure test for a long period of time.

As a result of intensive studies on the present invention, it has been found that (2) thiazoles are used as rust inhibitors and (3) one or more of the group consisting of tertiary amines, thiourea derivatives and transition metal salts are used as reducing agents. Since the curable resin composition using a compound composed of two or more compounds has the following effects, it has been found that the curable resin composition is very useful as an adhesive used for a motor, and the present invention has been solved.

(A) 250 ° C. at 80 ° C. × 95% humidity
Long-term high temperature and high humidity exposure test for 500 hours or more, shows high adhesiveness for a long time, rust prevention effect is significantly improved,
Good adhesiveness and adhesion. As described above, the effect of improving the adhesive strength under high-temperature and high-humidity conditions is excellent, so that it is constantly exposed to a high-temperature atmosphere in a high-humidity climate, such as Japan, due to the use environment and self-heating during motor rotation. Can be used to assemble a motor.

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

[0014]

That is, the present invention provides (1)
A curable resin containing a polymerizable vinyl monomer, (2) a triazole, and (3) a reducing agent comprising one or more members selected from the group consisting of tertiary amines, thiourea derivatives, and transition metal salts. A composition, further comprising (4) a curable resin composition containing a polymerization initiator, and (5) a curable resin composition containing an elastomer component. (6) The curable resin composition containing an acidic phosphoric acid compound represented by the general formula (A),

Embedded image (1) The curable resin composition wherein the polymerizable vinyl monomer is (a) a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, wherein the curable resin composition is a first agent and a second agent. Divided into two parts, the first part comprises at least (4) a polymerization initiator, and the second part comprises at least (2) a triazole and (3) a tertiary amine, a thiourea derivative and a transition metal salt. A two-part curable resin composition containing one or more compounds of the group. 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.

The polymerizable (meth) acrylic acid derivative preferably contains (a) a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups in the following points.

(A) By using a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups, the effect of improving the adhesive strength under high-temperature and high-humidity conditions is excellent. This is very useful for a motor that is always exposed to a high-temperature atmosphere under the use environment and self-heating during rotation of the motor. In particular, epoxy (meth)
Since 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.

(A) Polyfunctional (meth) acrylates having two or more (meth) acryloyl groups include epoxy (meth) acrylate "Biscoat # 540" (manufactured by Osaka Organic Chemical Industry Co., Ltd.) and epoxy (meth) acrylate. Epoxy (meth) acrylates such as acrylate "Epoxyester 3000M" (manufactured by Kyoeisha Chemical Co., Ltd.), polyethylene glycol di (meth) acrylate, polyglycerol di (meth)
Acrylate, polypropylene glycol di (meth) acrylate, polybutylene glycol di (meth) acrylate, 1,4-butanediol di (meth) acrylate
G, 1,6-hexanediol- (meth) acryle
G, neopentyl glycol di (meth) acrylate,
Trimethylolpropane tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tris (meth) acryloyloxyethyl isocyanurate
2,2-bis (4- (meth) acryloxyphenyl) propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4-
(Meth) acryloxydiethoxyphenyl) propane,
2,2-bis (4- (meth) acryloxypropoxyphenyl) propane, 2,2-bis (4- (meth) acryloxytetraethoxyphenyl) propane, polyester acrylate "Aronix M-6100" (manufactured by Toagosei Co., Ltd.) ), Urethane acrylate "Aronix M-1
100 "(manufactured by Toa Gosei Co., Ltd.), polybutadiene methacrylate" TE-2000 "(manufactured by Nippon Soda Co., Ltd.) and acrylonitrile butadiene acrylate" Hycar VTB "
NX "(manufactured by Ube Industries, Ltd.). One or more of these can be used.

Of these, epoxy (meth) acrylate is preferable because the effect of improving the adhesive strength is remarkable.

The epoxy (meth) acrylate is a polyfunctional (meth) acrylate obtained by reacting one molecule of an epoxy compound having two or more epoxy groups with two or more (meth) acrylic acids. Say. Further, when producing the epoxy (meth) acrylate, (meth) acrylic anhydride may be used instead of (meth) acrylic acid.

Among the epoxy (meth) acrylates,
The point that the effect of improving the adhesive strength is remarkable, the following general formula (A)
Is preferred.

[0025]

Embedded image

As the epoxy methacrylate represented by the general formula (A), “Epoxy ester 3000M” (manufactured by Kyoeisha Chemical Co., Ltd.) can be mentioned.

Further, as polymerizable (meth) acrylic acid derivatives, (a) polyfunctional (meth) acrylates having two or more (meth) acryloyl groups and (b) (meth) acryloyl It is preferable to use a monofunctional (meth) acrylate having one group in combination.

(B) Monofunctional (meth) acrylates include 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
(Meth) acrylates such as methyl and stearyl (meth) acrylate, 2-hydroxyethyl (meth)
Hydroxyalkyl (meth) acrylates such as acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate; polyethylene glycol Mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, alkyloxypolyethylene glycol mono (meth) acrylate, alkyloxypolypropylene glycol mono (meth) acrylate, phenoxypolyethylene glycol mono (Meth) acrylate, phenoxypolypropylene glycol mono (meth) acrylate, phenyl (meth) acrylate, cyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentenyl ( Meta) ac Les - DOO, isobornyl (meth) acrylate - DOO, methoxylated tricyclodecanyloxy triene (meth) acrylate - DOO, dicyclopentenyloxyethyl (meth)
Acrylate, tetrahydrofurfuryl (meth) acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, glycidyl (meth) acrylate
, Caprolactone-modified tetrahydrofurfuryl (meth) acrylate, 3-chloro-2-hydroxypropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl ( (Meth) acrylate, t-butylaminoethyl (meth) acrylate, morpholine (meth) acrylate,
Ethoxycarbonylmethyl (meth) acrylate, ethylene oxide-modified phthalic acid (meth) acrylate, ethylene oxide-modified succinic acid (meth) acrylate, trifluoroethyl (meth) acrylate, tetrafluoropropyl (meth) acrylate And 2-hydroxy-3-
(Meth) acryloyloxypropyltrimethylammonium chloride and the like. One or more of these can be used. Also, (meth) acrylic acid can be used.

Of these, alkyl (meth) acrylates and / or hydroxyalkyl (meth) acrylates are preferred, and alkyl (meth) acrylates are preferred from the viewpoints of adhesiveness, heat and moisture resistance and shortening of fixing time. And hydroxyalkyl (meth) acrylate in combination.

When the alkyl (meth) acrylate and the hydroxyalkyl (meth) acrylate are used in combination, the amounts of the alkyl (meth) acrylate and the hydroxyalkyl (meth) acrylate used are as follows: adhesiveness, heat resistance and humidity resistance. In terms of properties and shortening of the fixing time, the total of alkyl (meth) acrylate and hydroxyalkyl (meth) acrylate is 100
In the parts by mass, alkyl (meth) acrylate: hydroxyalkyl (meth) acrylate = 50 to 65 parts by mass: 3
5 to 50 parts by mass are preferred.

When the component (a) and the component (b) are used in combination, the amount of the component (a) and the component (b) used is different from that of the component (a) in terms of adhesiveness, heat and moisture resistance and shortening of fixing time. In a total of 100 parts by mass of the component (b), the component (a): the component (b) = 10
50 parts by mass: preferably 50 to 90 parts by mass, 20 to 40 parts by mass
Parts by mass: 60 to 80 parts by mass is more preferable.

The (2) triazoles used in the present invention have a short fixing time and can greatly reduce the use of jigs, so that a large number of motors can be manufactured in a short time.
The rust prevention effect when exposed to a high-temperature and high-humidity atmosphere such as exposure for 250 hours or 500 hours at a humidity of 95% is remarkably improved, adhesion and adhesion are improved, and initial adhesion of the motor is improved.

(2) Triazoles include benzotriazole, tolyltriazole, carboxybenzotriazole, 4,5,6,7-tetrahydrobenzotriazole, 4,5,6,7-tetrahydrotriazole, 2- (2 '-Hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-
5′-tert-butylphenyl) benzotriazole, 2- (2′-hydroxy-3′5′-di-tert)
-Butylphenyl) benzotriazole and 2- (2 ′
-Hydroxy-4-octoxyphenyl) benzotriazoles such as benzotriazole. One or more of these can be used.

Among these, since the fixing time is short, a large number of motors can be manufactured, for example, in a short time, the rust prevention effect when exposed to a high-temperature and high-humidity atmosphere is remarkably improved, and the adhesiveness and adhesion are improved. In that the initial adhesion becomes good,
Benzotriazoles are preferred, and benzotriazole is more preferred.

(2) The amount of the triazole used is (1)
0.1 to 100 parts by mass of the total of the polymerizable vinyl monomer and the elastomer component (5) used as required.
5 parts by mass is preferable, and 0.2 to 3 parts by mass is more preferable. If the amount is less than 0.1 part by mass, the fixing time is prolonged, and the rust-preventive effect, adhesiveness and adhesion may be reduced when exposed to a high-temperature and high-humidity atmosphere. There is a possibility that.

The reducing agent used in the present invention is a compound consisting of at least one of the group consisting of (3) a tertiary amine, a thiourea derivative and a transition metal salt.

The tertiary amines include triethylamine, tripropylamine, tributylamine and N, N
-Dimethyl-para-toluidine and the like.

Examples of the thiourea derivative include 2-mercaptobenzimidazole, methylthiourea, dibutylthiourea, tetramethylthiourea and ethylenethiourea. Among them, in terms of high curing acceleration effect,
Ethylenethiourea is preferred.

Examples of the transition metal salt include cobalt naphthenate, copper naphthenate and vanadyl acetylacetonate. Of these, vanadyl acetylacetonate is preferred because of its high curing promoting effect.

One or more of these can be used.
Of these, transition metal salts are preferred because of their high curing promoting effect.

(3) The amount of the reducing agent comprising at least one member selected from the group consisting of a tertiary amine, a thiourea derivative and a transition metal salt is as follows: (1) a polymerizable vinyl monomer and, if necessary, a reducing agent. (5) 0.05 to 3 parts by mass, preferably 0.1 to 3 parts by mass, based on 100 parts by mass of the elastomer component in total.
1.5 parts by mass is more preferred. When the amount is less than 0.05 part by mass, there is no curing promoting effect, the fixing time is long, and the adhesion may be reduced. When the amount exceeds 3 parts by mass, an unreacted reducing agent remains and the adhesion may be reduced. .

According to the present invention, (4)
It is preferable to use a polymerization initiator.

Among the (4) polymerization initiators used in the present invention, organic peroxides are preferred from the viewpoint of reactivity.

As the organic peroxide, cumene hydroperoxide, paramenthan 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 (4) 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 (5) 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.

The (5) elastomer component used in the present invention refers to a polymer substance having rubber-like elasticity at room temperature, and those which can be dissolved or dispersed in a polymerizable vinyl monomer are preferable from the viewpoint of adhesiveness.

The elastomer component (5) used in the present invention refers to a high molecular substance having rubber-like elasticity at room temperature, and is preferably one which can be dissolved or dispersed in a polymerizable vinyl monomer.

As such an elastomer component, an 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 and adhesive strength to polymerizable vinyl monomers. 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 (5) 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 (5).
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 curing acceleration effect, the adhesive strength under heat and humidity resistance and the adhesion at room temperature,
(6) It is preferable to use an acidic phosphoric acid compound represented by the following general formula (A).

[0052]

Embedded image

(6) The acidic phosphoric acid compound represented by the general formula (A) used in the present invention includes (2-hydroxyethyl) methacrylic acid phosphate, acid phosphooxyethyl acrylate, acid phosphooxyethyl methacrylate, acid Phosphooxypropyl acrylate, acid phosphooxypropyl methacrylate, bis (2-acryloyloxyethyl) acid phosphate and bis (methacryloyloxyethyl)
Acid phosphate and the like. One or more of these may be used.

Among these, from the viewpoints of good curing acceleration effect, good adhesive strength under heat and humidity resistance and good adhesion at room temperature,
Bis (methacryloyloxyethyl) acid phosphate is preferred.

The amount of the component (6) is preferably 0.05 to 20 parts by mass, more preferably 0.5 to 20 parts by mass, based on 100 parts by mass of the component (1) and the component (5) 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.

In the curable resin composition used in the present invention, various kinds of paraffins can be used in order to quickly cure the portion in contact with air and to make it non-anaerobic. Examples of paraffins include paraffin, microcrystalline wax, carnauba wax, beeswax, lanolin, whale wax, ceresin, candelilla wax and the like. One or more of these can be used. Of these, paraffin is preferred.

The amount of the paraffin used is preferably 0.1 to 5 parts by mass with respect to 100 parts by mass of the total of (1) the polymerizable vinyl monomer and (5) the elastomer component used as required. If the amount is less than 0.1 part by mass, curing of the portion in contact with the air may be deteriorated. If the amount exceeds 5 parts by mass, the adhesive strength may be reduced.

An embodiment of the curable resin composition used in the present invention is preferably an adhesive composition, particularly preferably a two-part adhesive composition.
For the two-pack type, all the essential components of the adhesive composition of the present invention are not mixed during storage, and the adhesive composition is divided into a first part and a second part. The agent is separately stored in the second agent at least a reducing agent comprising at least one of the group consisting of (2) a triazole and (3) a tertiary amine, a thiourea derivative and a transition metal salt. The two-pack type is preferred in that it has excellent storage stability. In this case, the two agents 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.

An 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.

When at least one of the adherends is a galvanized steel sheet subjected to a chromate treatment, the use of the present invention is as follows.
As described below, it is preferable to use it for motors because of its excellent heat resistance during exposure to high temperature and high humidity. A galvanized steel sheet which has been subjected to chromate treatment is used as a material for the yoke 1 of the motor. It is more preferable to use for adhesion.

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 plating layer does not corrode under high-temperature and high-humidity exposure conditions and exhibits good adhesion. As a plated steel sheet having excellent corrosion resistance, a chromate-treated galvanized steel sheet is preferable because it is easily available.

[0062]

The present invention will be described in more detail with reference to the following experimental 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.), and bis (methacryloyloxyethyl) acid phosphate was used as the acidic phosphoric acid compound. Various physical properties were measured as follows.

(Fixing time) In an environment of a temperature of 23 ° C. and a humidity of 50%, according to JIS K 6850, one side of a test piece (100 mm × 25 mm × 1.6 mm, sand-blasted iron plate) is coated with an adhesive composition. The first and second agents were mixed and applied in equal amounts by a static mixer, and immediately thereafter, another test piece (100 mm × 25 mm × 1.
6 mm, a sandblasted iron plate) were stacked and bonded to obtain a sample for measuring the 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.

(23 ° C. Tensile shear bond strength) Temperature: 23 ° C.
According to JIS K 6850 in an environment of 50% humidity,
One side of a test piece (100 mm × 25 mm × 1.4 mm, chromate-treated galvanized steel sheet) was mixed and applied with an equal 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 x 25 mm x 1.4 mm, chromate-treated galvanized steel sheet) were laminated and bonded, and cured for 24 hours in the same atmosphere to obtain a measurement sample. 23
C., an environment of 50% humidity and a tensile speed of 10 mm / min.
The tensile shear strength at 23 ° C. was measured under the conditions described above.

(80 ° C. × 95% RH × 250 hours tensile shear bond strength) Under an environment of a temperature of 23 ° C. and a humidity of 50%, JI
According to SK 6850, one test piece (100 mm ×
One side of a 25 mm × 1.4 mm, chromate-treated galvanized steel sheet) was mixed and applied with an equivalent amount of a first agent and a second agent of an adhesive composition by a static mixer, and immediately thereafter, another test piece (100 mm) × 25mm × 1.4m
m, a chromate-treated galvanized steel sheet) were laminated and bonded together, cured for 24 hours in the same atmosphere, and exposed for 250 hours in an environment of a temperature of 80 ° C. and a humidity of 95% to obtain a measurement sample. After curing for several hours in an environment of a temperature of 23 ° C. and a humidity of 50%, the tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min. In addition, the presence or absence of corrosion was checked for the measurement sample.

(Adhesion of tensile shear strength at 80 ° C. × 95% RH × 250 hours) Adhesion was 80 ° C. × 95% RH × 2
The following evaluation criteria were used to evaluate the state of fracture in the 50-hour tensile shear adhesion strength measurement test. Generally, strong adhesive strength is obtained when cohesive failure occurs. Therefore, cohesive failure is preferable in a broken state. ：: Cohesive failure and interfacial delamination are mixed. △: Cohesive destruction and interfacial destruction are mixed and partially corroded. X: No cohesive destruction, interfacial delamination or corrosion delamination is present.

(80 ° C. × 95% RH × 500 hours tensile shear bond strength) In an environment of a temperature of 23 ° C. and a humidity of 50%, JI was used.
According to SK 6850, one test piece (100 mm ×
One side of a 25 mm × 1.4 mm, chromate-treated galvanized steel sheet) was mixed and applied with an equivalent amount of a first agent and a second agent of an adhesive composition by a static mixer, and immediately thereafter, another test piece (100 mm) × 25mm × 1.4m
m, a chromate-treated galvanized steel sheet) were laminated and bonded together, cured for 24 hours in the same atmosphere, and then exposed for 500 hours in an environment of a temperature of 80 ° C. and a humidity of 95% to obtain a measurement sample. After curing for several hours in an environment of a temperature of 23 ° C. and a humidity of 50%, the tensile shear bond strength (unit: MPa) was measured at a tensile speed of 10 mm / min. In addition, the presence or absence of corrosion was checked for the measurement sample.

(Adhesion of tensile shear strength at 80 ° C. × 95% RH × 500 hours) Adhesion was 80 ° C. 95% RH × 50.
From the fracture state in the 0 hour tensile shear bond strength measurement test,
The evaluation was made according to the following evaluation criteria. ：: Cohesive failure and interfacial delamination are mixed. △: Cohesive destruction and interfacial destruction are mixed and partially corroded. X: No cohesive destruction, interfacial delamination or corrosion delamination is present.

(Initial Adhesion by Real Motor) Using an adhesive composition 3 at room temperature, 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.場合 indicates that the magnet 2 was destroyed by material or the adhesive composition 3 was cohesively fractured, and △ indicates that cohesive failure of the adhesive composition 3 and interfacial peeling between the magnet 2 and the interface of the adhesive composition 3 were mixed. The case where the interface of the agent composition 3 peeled off was designated as x.

(Experimental Example 1) A two-part adhesive composition having the composition shown in Table 1 was prepared and its physical properties were measured. Table 2 shows the results.

[0071]

[Table 1]

[0072]

[Table 2]

Experimental Example 2 A two-part adhesive composition having the composition shown in Table 3 was prepared, and the physical properties were measured. Table 4 shows the results.

[0074]

[Table 3]

[0075]

[Table 4]

(Experimental Example 3) The physical properties of the two-part adhesive composition of 1-3 were measured. Table 5 shows the results.

[0077]

[Table 5]

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

[0079]

According to the present invention, excellent moisture resistance, high curing speed, good adhesion, and prevention even when exposed to a high-temperature and high-humidity atmosphere such as 250 hours or more or 500 hours or more in an 80 ° C. × 95% humidity atmosphere. A curable resin composition having an extremely large rust effect is obtained. In particular, when used in the manufacture of a motor using a galvanized steel sheet whose surface is chromate-treated, the motor can be used under conditions of high temperature and high humidity exposure.

[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 (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08F 20/34 C08F 20/34 4J040 290/02 290/02 4J100 291/02 291/02 4K044 299/00 299 / 00 C08K 5/3472 C08K 5/3472 5/521 5/521 C08L 101/00 C08L 101/00 C09J 4/00 C09J 4/00 4/02 4/02 4/06 4/06 C23C 28/00 C23C 28 / 00 CF term (reference) 4J002 AC012 AC032 AC072 AC082 AC092 AC111 BB152 BG041 BG051 BN142 BN152 BN162 BP012 CD201 CF172 CF271 CH051 CK021 CK022 CL082 EU166 EU176 EW047 GJ01 4J011 PA43 PA46 PA02 PA78 PA78 PA78 PA07 CA08 CA10 EA04 EA05 4J026 AA06 AA12 AA13 AA17 AA45 AA49 AA67 AA68 AA69 AA71 AA72 AB02 AB08 AB28 AC02 AC15 AC16 AC18 BA27 BA28 BA29 BA30 BA50 BB03 DB05 DB09 DB16 4J027 AA04 AB01 AB03 AB10 AC04 AE01 AE02 AG01 BA07 BA08 BA13 BA19 BA23 BA26 BA28 CA08 CA25 CA27 CB07 CC02 CD09 4J040 CA011 CA012 CA051 CA052 CA061 CA062 CA071 CA072 CA081 CA082 CA151 CA152 DC021 DC022 DM011 FA032 EF031 012 003 FA232 AA02 AB03 BA10 BA15 BA21 BB04 BC02 BC04 CA16 CA18 CA53

Claims (10)

[Claims] 1. A reducing agent comprising one or more members of the group consisting of (1) a polymerizable vinyl monomer, (2) a triazole, and (3) a tertiary amine, a thiourea derivative and a transition metal salt. A curable resin composition comprising: 2. The curable resin composition according to claim 1, further comprising (4) a polymerization initiator. 3. The curable resin composition according to claim 1, further comprising (5) an elastomer component. 4. The curable resin composition according to claim 1, further comprising (6) an acidic phosphoric acid compound represented by the general formula (A). Embedded image (1) The polymerizable vinyl monomer is (a)
The curable resin composition according to claim 1, which is a polyfunctional (meth) acrylate having two or more (meth) acryloyl groups. 6. The curable resin composition according to claim 2, wherein the curable resin composition is divided into a first agent and a second agent, wherein the first agent contains at least (4) a polymerization initiator, Two-part curing wherein the second agent contains at least one compound selected from the group consisting of (2) a triazole and (3) a tertiary amine, a thiourea derivative and a transition metal salt. Resin composition. 7. A cured product of the curable resin composition according to claim 1. 8. An adhesive composition comprising the curable resin composition according to claim 1. 9. A bonded body obtained by bonding an adherend using the adhesive composition according to claim 8. 10. The joined body according to claim 9, wherein the adherend is a galvanized steel sheet whose surface is subjected to a chromate treatment.