JPH0676578B2 - Anaerobic curable adhesive composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial field of application] The present invention relates to anaerobic curability used for bonding metal parts, sealing seals, preventing loosening of fastening materials such as bolts, fixing parts of fitting parts, etc. Of the adhesive composition.

[Background of the Invention]

An anaerobic curable adhesive composition does not cure while in contact with air or oxygen and is stable for a long period of time, but is easily polymerized by, for example, sandwiching it between two adjacent member surfaces to block air. A curable adhesive composition having the property of curing.

It goes without saying that this kind of adhesive composition is required to be rapidly cured under anaerobic conditions and to have high impact strength and peel adhesion strength.

[Conventional technology]

Conventionally known as this kind of adhesive composition is a composition containing a radically polymerizable (meth) acrylic acid ester monomer as a main component and an organic peroxide blended as a polymerization initiator. is there.

Such an adhesive composition is prohibited from polymerizing under aerobic conditions in which it is in contact with oxygen, but when used, it is coated on two member surfaces, which are the materials to be adhered, so as to block air. When placed under anaerobic conditions, it initiates polymerization and hardens.

[Problems to be solved by the invention]

However, since the above-mentioned conventional anaerobic curable adhesive composition has hard and brittle physical properties after curing, there is a problem that it is impossible to obtain sufficient impact strength and peel adhesion strength.

Although an adhesive composition which provides a cured product having some flexibility in order to improve the hard and brittle physical properties of the cured product of the above anaerobic curable adhesive composition, the curing rate under anaerobic conditions is also provided. However, as a means for solving the above-mentioned problems, the present invention has a hydroxyl group-containing (meth) acrylate (A) and an organic polyisocyanate (B). ) And a polycarbonate diol (C), which is a reaction product of (meth) acryloyloxy group-containing polycarbonate diol-modified urethane prepolymer [I], and / or two or more thereof, and / or a hydroxyl group-containing (meth) acrylate (A). ), An organic polyisocyanate (B), and a polycarbonate diol (C)
And one or more of polycarbonate diol-modified urethane prepolymers [II] having a (meth) acryloyloxy group, which is a reaction product of a polyol (D), and the above-mentioned polymer Bonate diol having a (meth) acryloyloxy group. One or more kinds of (meth) acrylic acid ester compounds [III] other than the modified urethane prepolymers [I] and [II], and an organic peroxide [IV]
And an anaerobic curable adhesive composition comprising a polymerization accelerator [V].

The (meth) acrylate (A) is a generic term for acrylates and methacrylates, and the polycarbonate diol-modified urethane prepolymer [I] is a generic term for polycarbonate diol-modified urethane prepolymers having a (meth) acryloyloxy group. The (meth) acrylic acid ester-based compound [III] will be described later (meth) acrylic acid ester-based compounds (1) to (1
It is one or more kinds of (meth) acrylic acid ester compounds selected from the group consisting of 1).

The details of each component constituting the anaerobic curable adhesive composition of the present invention will be described below.

<Polycarbonate diol-modified urethane prepolymer [I]> The urethane prepolymer [I] is a reaction product of a (meth) acrylate (A) having a hydroxyl group, an organic polyisocyanate (B), and a polycarbonate diol (C).

Specific examples of the synthetic raw materials (A), (B), and (C) are as follows.

[(Meth) Acrylate (A) Having Hydroxyl Group]

Specific examples of the (meth) acrylate (A) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) arylate, hydroxybutyl (meth) acrylate, hydroxyhexyl (meth) acrylate and hydroxyoctyl (meth). ) Acrylate, 2-hydroxy-3-phenoxypropyl (meth) acrylate, and 2-hydroxy-3-chloropropyl (meth) acrylate.

[Organic polyisocyanate (B)]

Specific examples of the organic polyisocyanate (B) include toluene diisocyanate, 4,4'-diphenyl diisocyanate,
4,4'-diphenylmethane diisocyanate, dianthine diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diphenyl ether diisocyanate, p-phenylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, ethylene diisocyanate, cyclohexylene diisocyanate , Nonamethylene diisocyanate, octadecamethylene diisocyanate, 2-chloropropane diisocyanate, 2,2'-diethyl ether diisocyanate, tetrachlorophenylene diisocyanate, xylene diisocyanate, and 1,4,3-
Low molecular weight organic polyisocyanates, such as heptene diisocyanate, and excess amounts of these low molecular weight organic polyisocyanates, as already known, can be combined with primary amines, secondary amines, or polyhydric alcohols such as glycerol, polyoxy Add ethylene oxide and / or propylene oxide to ethylene triol, polyoxypropylene triol, polyoxyethylene tetraol, polyoxyprolene tetraol, polypropylene glycol, polyethylene glycol, polycaprolactone polyol, polytetramethylene ether glycol, bisphenol A There is a high molecular weight organic polyisocyanate obtained by reacting with a polyhydric alcohol such as an ether type glycol obtained by the above.

Particularly preferred organic polyisocyanates in the present invention are toluene diisocyanate, 4,4'-diphenylmethane diisocyanate and hexamethylene diisocyanate.

[Polycarbonate diol (C)]

The polycarbonate diol is a C _{2 to} C ₁₂ alkylene group, and / or a C _{1 to} C ₂₂ alkyl group, and / or a C _{6 to} C ₂₂ aromatic hydrocarbon group, and / or a C ₆
To C ₂₂ carbonic acid ester having a cycloparaffinic hydrocarbon group and a C _{2 to} C ₂₂ alkylene group, and / or C _{6 to} C ₂₂
And / or a C _{6 to} C ₂₂ aromatic hydrocarbon group, and / or a C _{1 to} C ₂₂ cycloparaffinic hydrocarbon group-containing diol.

Specific examples of the carbonic acid ester include ethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and dicyclohexyl carbonate.

Further, specific examples of the diol include 1,6-hexanediol,
1,4-cyclohexanedimethanol, 3-methyl 1,5-pentanediol, 1,5-pentanediol, polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, polycaprolactone diol,
Examples include trimethylhexanediol and 1,4-butadiol.

A particularly suitable production method of the polycarbonate diol-modified urethane prepolymer [I] of the present invention is a predetermined amount of organic polyisocyanate (B) and polycarbonate diol (C).
Are first reacted with each other to produce a polycarbonate diol-modified urethane prepolymer (E) having an unreacted isocyanate group, and then the urethane prepolymer (E)
And (meth) acrylate (A) having a predetermined amount of hydroxyl groups
Is a method of reacting with.

(A) + (B) = (E) → (E) + (A) = (I) The reaction temperature during the production of the polycarbonate diol-modified urethane prepolymer [I] is preferably 120 ° C. or lower. If the temperature is too high, it may cause thickening of the reaction product or gelation during the reaction. If the reaction temperature is too low, the viscosity of the reaction product will be high, and the unreacted raw materials will be insufficiently dispersed / mixed to make smooth reaction difficult. Therefore, it is preferably carried out at 50 ° C to 120 ° C, more preferably 55 ° C to 100 ° C. It is preferable. The synthesis of the polycarbonate diol-modified urethane prepolymer [I] is carried out at each stage with the group -NCO.
When the infrared absorption spectrum analysis is performed on the group -NCO, the group -NCO exhibits strong absorption at around 2250 cm ^-1 , and therefore the progress of the reaction depends on the group -NCO in the reaction product. It can be easily confirmed by performing an external absorption spectrum analysis and tracing the consumption amount from the intensity change of the absorption characteristic, and the end point of each reaction stage may be determined when the consumption of the group -NCO is stopped. Examples of catalysts for smoothly proceeding the reaction include metal compounds such as tertiary amines such as triethylenediamine and tin such as dibutyltin dilaurate. In order to adjust the reaction rate, the latter dibutyltin dilaurate is preferable, and the addition amount thereof is 50 to 2000 p based on 100 parts by weight of the reaction product.
pm is preferable, and more preferably 100 to 1500 ppm with respect to 100 parts by weight of the reactant. Further, as the radical polymerization inhibitor, hydroquinone monomethyl ether, phenothiazine and the like may be added in appropriate amounts according to the reaction conditions. Further, when the viscosity of the reaction product becomes too high, an organic solvent having no active hydrogen group such as toluene or acetone, or a (meth) acrylate having no active hydrogen group may be used as a reaction diluent.

<Polycarbonate diol-modified urethane prepolymer [II]> The urethane polymer [II] has a hydroxyl group (meth).
Acrylate (A) and organic polyisocyanate (B)
And a polycarbonate diol (C) and a polyol (D).

The synthetic raw materials (A), (B), and (C) are the same as those of the urethane prepolymer [I], and specific examples of the polyol (D) are as follows.

[Polyol (D)]

Specific examples of the polyol (D) include 1,6-
Hexanediol, 1,4-cyclohexanedimethanol, 3-methyl-1,5-pentanediol, 1,5-pentanediol, polyoxyethylene diol, polyoxypropylene diol, polyoxybutylene diol, polycaplacton diol, trimethyl There are hexanediol, 1,4-butanediol, etc., and as the trihydric or higher polyol, trimethylolethane, pentaerythritol, trimethylolpropane, polyoxyethylenetriol, polyoxybropyrenetriol, trishydroxyethylylisocyanate, etc. Examples include nurate, polyoxyethylene tetraol, polyoxypropylene tetraol, glycerin, and polyphosphoric acid.

A particularly suitable production method for the polycarbonate diol-modified urethane prepolymer [II] of the present invention is a predetermined amount of organic polyisocyanate (B) and polycarbonate diol (C).
Are first reacted with each other to produce a polycarbonate diol-modified urethane prepolymer (E) having an unreacted isocyanate group, and then the urethane prepolymer (E)
And (meth) acrylate (A) having a predetermined amount of hydroxyl groups
Is a method of producing an unreacted isocyanate group-containing (meth) acryloyloxy compound (F), and further reacting the (meth) acryloyloxy compound with a predetermined amount of the polyol (D).

(A) + (B) = (E) → (E) + (A) = (F) → (F) + (D) = [II] The reaction conditions in the above production method are the same as those for the urethane prepolymer [I]. It is the same.

<(Meth) acrylic ester compound [III]> The (meth) acrylic ester compound [III] means a (meth) acrylic ester compound other than the urethane prepolymers [I] and [II]. The present invention improves the cohesive force and interfacial adhesive force of the adhesive of the present invention, and is, for example, one or two selected from the group consisting of the following (meth) acrylic acid ester compounds (1) to (11). The above-mentioned (meth) acrylic acid ester compounds can be mentioned.

[(Meth) acrylic ester compound (1)] The (meth) acrylic ester compound (1) has the following general formula.

In the formula, R ₁ is hydrogen or —CH ₃ , and R ₂ is a straight or branched alkyl group having 2 to 4 carbon atoms in which one or more hydrogen atoms are replaced with —OH and / or halogen. Indicates an alkyl group.

Specific examples of the (meth) acrylate (1) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 1,2-dihydroxyethyl (meth) acrylate, and 3-chloro-2-. Examples include hydroxypropyl (meth) acrylate.

[(Meth) acrylic ester compound (2)] The (meth) acrylic ester compound (2) has the following general formula.

In the formula, R ₃ is hydrogen or —CH ₃ , R ₄ is hydrogen, —CH ₃ , —C ₂ H ₅ , —
CH ₂ OH, or R ₅ is hydrogen, chlorine, -CH ₃ or -C ₂ H _5, R ₆ is hydrogen, -OH,
Or , M is an integer of 1 to 8, n is an integer of 1 to 20, and p is 0.
Or 1 is shown.

The (meth) acrylate (2) is specifically diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, tetraethylene glycol (meth) acrylate, 1,2-propylene glycol di (meth) acrylate, Dipropylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, diglycerol di (meth) acrylate, glycerin tri (meth) acrylate, trimethylolpropane tri (meth) acrylate, di-glycerol tetra (meth) acrylate, etc. Can be given.

[(Meth) acrylic ester compound (3)] The (meth) acrylic ester compound (3) has the following general formula.

In the formula, R ₇ is hydrogen or —CH ₃ , and R ₈ is hydrogen or a carbon number of 1 to
4 is a linear or branched alkyl group, R ₉ is a linear or branched alkylene group having a carbon number of C _{2 to} C ₄ , and m is an integer of 1 to 10.

The (meth) acrylate (3) is specifically 2,2-
Bis (4-methacryloxydiethoxyphenyl) propane, 2,2-bis (4-allyloxydiethoxyphenyl)
Propane, 2,2-bis (4-methacryloxytriethoxyphenyl) propane, 2,2-bis (4-acryloxypentaethoxyphenyl) propane, 2-2bis (4-
Methacryloxyhexaethoxyphenyl) propane, 2,
2-bis (4-acryloxyheptaethoxyphenyl)
Propane, 2,2-bis (4-methacryloxyoctaethoxyphenyl) propane, 2,2-bis (4-acryloxydipropoxyphenyl) propane, 2,2-bis (4-
Methacryloxytripropoxyphenyl) propane, 2,
2-bis (4-acryloxydiptoxyphenyl) propane, 2,2-bis (4-methacryloxyoctabutoxyphenyl) propane, 2- (4-methacryloxydiethoxyphenyl) -2- (4-methacryl Roxytriethoxyphenyl) propane, 2- (4-acryloxydipropoxyphenyl) -2- (4-acryloxytriethoxyphenyl) propane and the like.

[(Meth) acrylic ester compound (4)] The (meth) acrylic ester compound (4) has the following general formula.

In the formula, R ₁₀ is hydrogen or —CH ₃ , and R ₁₁ is hydrogen or carbon number 1.
~ 4 straight-chain or branched alkyl group, and n represents 0 or an integer of 1-10.

The (meth) acrylate (4) is specifically dicyclopentenyl (meth) acrylate, dicyclopentenyloxymethyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyloxypropyl (meth). Acrylate and the like.

[(Meth) acrylic ester compound (5)] The (meth) acrylic ester compound (5) has the following general formula.

In the formula, R ₁₂ is hydrogen or —CH ₃ , and R ₁₃ is hydrogen or 1 carbon atom.
~ 18 straight or branched alkyl group, or 5 to 5 carbon atoms
A cyclic alkyl group having 20 carbon atoms, a phenyl group, a tetrahydrofurfuryl group, or a linear or branched alkyl group having 5 to 20 carbon atoms having these groups is shown.

The (meth) acrylate (5) is specifically methacrylic acid, acrylic acid, methyl (meth) acrylate, cyclohexyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, phenyl ( Examples thereof include meth) acrylate and benzyl (meth) acrylate.

[(Meth) acrylic ester compound (6)] The (meth) acrylic ester compound (6) has the following general formula.

In the formula, R ₁₄ is hydrogen or —CH ₃ , R ₁₅ is a substituted alkylene group in which 3 or 4 carbon atoms are replaced with —OH at any position of a linear or branched alkyl group, and R ₁₆ is 1 to 3 carbon atoms. 18 straight or branched alkyl groups are shown.

Specific examples of the (meth) acrylate (6) include 2-hydroxy-3-phenoxypropyl (meth) acrylate, cyclohexynoxy-β-hydroxypropyl (meth) acrylate, tetrahydrofurfuroxy-β-hydroxypropyl ( Examples thereof include (meth) acrylate and nonyloxy-β-hydroxypropyl (meth) acrylate.

[(Meth) acrylic ester compound (7)] The (meth) acrylic ester compound (7) has the following general formula.

In the formula, R ₁₇ is hydrogen or —CH ₃ , and R ₁₈ is a linear or branched alkyl group having 1 to 20 carbon atoms, an alkenyl group, an aryl group, an aralkyl group, or a linear or branched alkoxyalkyl group.

Specific examples of the (meth) acrylate (7) include methoxycarbonylmethyl (meth) acrylate, ethoxycarbonylmethyl (meth) acrylate, heptoxycarbonylmethyl (meth) acrylate, and isopropoxycarbonylmethyl (meth) acrylate. Can be mentioned.

[(Meth) acrylic acid ester compound (8)] In the formula, R ₁₉ is hydrogen or —CH ₃ , and R ₂₀ is a linear or branched alkyl group having 2 to 4 carbon atoms, m is an integer of 1 to 10, and n is 1 or 2.

[(Meth) acrylic ester compound (9)] The (meth) acrylic ester compound (9) has the following general formula.

In the formula, R ₂₁ is hydrogen or -CH ₃ , m is an integer of 1 to 10, and n is 1.
Or 2.

Specific examples of the (meth) acrylates (8) and (9) include acidtophosphoxyethyl (meth) acrylate, 3-chloro-2-acitophosphooxypropyl (meth) acrylate, and acitophosphooxypropyl (meth) acrylate. Examples thereof include (meth) acrylate.

[(Meth) acrylic ester compound (10)] A reaction product of (meth) acrylate (A) having a hydroxyl group and organic polyisocyanate (B).

[(Meth) acrylic acid ester compound (11)] Reaction of (meth) acrylate (A) having a hydroxyl group, organic polyisocyanate (B), and trivalent or higher valent polyol and / or diol (D) It is a product.

The (meth) acrylate (A) having a hydroxyl group and the organic polyisocyanate (B) polyol (D) in the (meth) acrylic acid ester compounds (10) and (11) are the same as those of the urethane prepolymers [I] and [II]. It is the same as the raw material.

The (meth) acrylic acid ester compounds (1) to (1
Among 1), the most preferable compounds as the adhesive of the present invention are as follows.

(1): 2-hydroxyethyl (meth) acrylate (2): trimethylolpropane tri (meth) acrylate (3): 2,2-bis (4- (meth) acryloxydiethoxyphenyl) propane (4): Dicyclopentenyl (meth) acrylate (5): Methyl (meth) acrylate (6): 2-Hydroxy-3-phenoxypropyl (meth) acrylate (7): Ethoxycarbonylmethyl (meth) acrylate (8): Acid Dephosphooxypropyl (meth) acrylate (9): 3-chloro-2 acid phosphooxypropyl (meth) acrylate (10): 2-hydroxyethyl (meth) acrylate and bisphenol A ethylene oxide tolylene diisocyanate modified Reaction products with substances (11): Two components of (10) and Reaction product with methylolpropane <Organic peroxide [IV]> Specific examples of the organic peroxide [IV] to be blended in the composition in the present invention include benzoyl peroxide, methyl ethyl ketone peroxide, cumene hydro. Examples thereof include peroxide, cyclohexanone peroxide, ditertiarybutyl peroxide, tert-butylperoxybenzoate, diisopropylbenzene hydroperoxide, lauroyl peroxide, and dicumyl peroxide. The kind and the addition amount thereof function as a polymerization initiator as is well known, and may be a catalytic stoichiometric amount sufficient to impart anaerobic curing property to the composition, and it may be a commonly used amount. It's enough.

<Polymerization accelerator [V]> Examples of the polymerization accelerator to be added to the composition of the present invention include:
1,2,3,4-Tetrahydroquinoline, saccharin, triethylamine, N, N-dimethylaniline and the like are used, and the addition amount varies depending on the type of the polymerization accelerator, which cannot be generally stated, but an example is shown. [(Meth) acrylate compound [III]] 100 parts by weight of 1,2,3,4-
Tetrahydroquinoline 0.1-5 parts by weight, saccharin 0.1
˜3 parts by weight and triethylamine 0.1 to 1 part by weight are preferred.

The mixing ratio of each component described above is as follows.

The polycarbonate diol-modified urethane prepolymer [I] and / or [II] is the adhesive composition 100 of the present invention.
It is preferably 10 to 80 parts by weight, more preferably 20 to 10 parts by weight.
It is 65 parts by weight.

The (meth) acrylic acid ester compound [III] is preferably 20 to 90 parts by weight, more preferably 35 to 80 parts by weight, based on 100 parts by weight of the anaerobic curable adhesive composition of the present invention.

<Desired additive component> In addition to the components described above, various substances may be added to the composition of the present invention for various purposes.

For example, oxalic acid, dinitrosolesorcinol, and quinones for the purpose of improving stability, occupation and pigments for the purpose of coloring, thixotropic agents such as silica for the purpose of imparting thixotropic properties, and the purpose of thickening and increasing the amount. It is possible to add acrylic resin, urethane resin, epoxy resin, silica, etc., respectively.

The anaerobic curable adhesive composition according to the present invention can be easily prepared by mixing and dissolving the components described above at room temperature or under heating.

[Curing means]

The anaerobic curable adhesive composition according to the present invention can be used in the same manner as the conventional anaerobic curable adhesive composition.

(One-Liquid Anaerobic Curing) When the adherend is a metal, polymerization curing can be easily achieved by sandwiching the anaerobic curable adhesive composition of the present invention between two adjacent adherends and blocking air. .

(Anaerobic curing with curing acceleration primer) If you want to increase the adhesion speed from a few seconds to a few minutes, or if you want to adhere plastic or ceramic, apply the curing acceleration primer to one adherend and then the other adherend. Polymerization and curing can be easily achieved by applying the anaerobic curable adhesive composition of the present invention to the above, adhering the both, and blocking the air. The curing-accelerating primer used in this case, cobalt naphthenate, copper naphthenate, and metal organic acid salts described in JP-B-53-24231.
Dimethylparatoluidine, dimethylaniline, 1,2,3,4
And tertiary amines such as tetrahydroquinoline, thioamide compounds such as ethylene thiourea and tetramethyl thiourea.

Production Example 1 Approximately 12.7 parts by weight of toluene diisocyanate as an organic polyisocyanate (B) and about 200 ppm of dibutyltin dilaurylate were placed in a reactor, and a molecular weight of about 2000 was obtained as a polycarbonate diol (C) while maintaining a reaction temperature of about 70 ° C. About 77.8 parts by weight of polycarbonate diol (manufactured by Toagosei Kagaku Kogyo Co., Ltd .: a reaction product of ethylene carbonate and 1,6-hexanediol) is gradually added with stirring and stirred for about 1 hour to react, and then dilauryl. Approximately 200 ppm of dibutyltin acid salt was added, and further, about 9.5 parts by weight of 2-hydroxyethyl methacrylate as a (meth) acrylate (A) having a hydroxyl group was gradually added to the mixture while stirring and maintaining the reaction temperature at 70 ° C. to react, Analyzing the reaction solution by external absorption spectrum, characteristic absorption of group-NCO (around 2250 cm ^-1 )
The reaction was continued until disappearance was confirmed.

As a result, 100 parts by weight of a rubber-like solid polycarbonate diol-modified urethane prepolymer [I] was obtained at room temperature. Further, as a result of analyzing the polycarbonate diol-modified urethane prepolymer [I] by infrared absorption spectrum, the following main peaks were confirmed.

-NHCOO- absorption; 1520 ~ 1550cm ^-1 , 1720 ~ 1740cm ^-1 Production Example 2 About 13.1 parts by weight of toluene diisocyanate as an organic polyisocyanate (B) and about 200 ppm of dibutyltin dilaurate were placed in a reactor, and a molecular weight of about 2000 was obtained as a polycarbonate diol (C) while maintaining a reaction temperature at about 70 ° C. About 80.3 parts by weight of polycarbonate diol (manufactured by Toagosei Kagaku Kogyo Co., Ltd .: reaction product of ethylene carbonate and 1,6-hexanediol) is gradually added under stirring to about 1
After stirring and reacting for about an hour, about 200 ppm of dibutyltin dilaurate was added, and about 4.9 parts by weight of 2-hydroxyethyl methacrylate as a (meth) acrylate (A) having a hydroxyl group was kept under stirring and the reaction temperature was maintained at 70 ° C. While gradually adding and reacting for about 2 hours, about 1.7 parts by weight of trimethylolpropane as the polyol (D) is gradually added with stirring and maintaining the reaction temperature at 70 ° C. to react with infrared light. Analyze the reaction solution by absorption spectrum,
The reaction was continued until it was confirmed that the characteristic absorption of the group -NCO (around 2250 cm ^-1 ) disappeared.

As a result, 100 parts by weight of a polycarbonate diol-modified urethane prepolymer [II], which was a rubber-like solid at room temperature, was obtained. In addition, as a result of analyzing the polycarbonate diol-modified urethane prepolymer [II] by infrared absorption spectrum, the following main peaks were confirmed.

-NHCOO- absorption; 1520 ~ 1550cm ^-1 , 1720 ~ 1740cm ^-1 Example Using the polycarbonate diol-modified urethane prepolymers [I] and [II] obtained in Production Examples 1 and 2, anaerobic curable adhesive compositions No. 1 to No. 6 having the compositions shown in Table 1 were prepared. did.

Anaerobic curing adhesive performance is the first using carbon steel adherend
Apply the anaerobic curable adhesive composition to one of the adherends on the table,
Curing acceleration primer (Toagosei Chemical Industry Co., Ltd .: AT.Qu
icka V3) is applied to the other adherend and allowed to air dry, then the adherends are overlaid, and the tensile shear adhesion strength according to JIS K-6850 and impact adhesion according to JIS K-6855 The T-type peeling adhesive strength was measured according to JIS K-6854. The adhesion curing time was 3 days at room temperature.

The results are shown in Table 2.

[Effects of the Invention] The anaerobic curable adhesive composition according to the present invention has high impact bond strength and peeling when used for adhesion of metal parts, sealing seals, loosening prevention, fixing of fitting parts, etc. It is excellent in that it exhibits adhesive strength, and has significantly improved impact adhesive strength and peel adhesive strength as compared with the conventional ones.

Claims (1)

[Claims] 1. A polycarbonate diol-modified urethane prepolymer having a (meth) acryloyloxy group, which is a reaction product of a (meth) acrylate (A) having a hydroxyl group, an organic polyisocyanate (B), and a polycarbonate diol (C). A reaction product of one or more of [I] and / or a hydroxyl group-containing (meth) acrylate (A), an organic polyisocyanate (B), a polycarbonate diol (C), and a polyol (D). Polycarbonate diol-modified urethane prepolymer having a (meth) acryloyloxy group [I
One or two or more of [I] and one or two of (meth) acrylic acid ester-based compounds [III] other than the polycarbonate diol-modified urethane prepolymers [I] and [II] having the (meth) acryloyloxy group. Anaerobic curable adhesive composition comprising the above and organic peroxide [IV] and polymerization accelerator [V]