JP2646107B2 - Anaerobic and moisture-curable resin composition - Google Patents

Description

The present invention relates to a resin composition used for bonding, fixing, or sealing screws, bolts, fitting portions, flange surfaces, etc., and particularly to air contact. The adhesive is hardened by anaerobic hardening inside the bonding surface that does not, and is moisture-hardened by the moisture in the air at the protruding parts that come into contact with air, that is, the above-mentioned adhesion is maintained by maintaining both the properties of anaerobic hardening and moisture hardening together The present invention relates to an anaerobic and moisture-curable resin composition capable of completely and quickly fixing or sealing.

[Conventional technology]

Conventionally, an anaerobic-curable resin composition or a reactive liquid sealant such as a solvent-type or moisture-curable resin composition is used as a resin composition for bonding, fixing, or sealing screws, bolts, fitting portions, flange surfaces, and the like. Sealants such as molds and drying oils are known.

[Problems to be solved by the invention]

However, in the former anaerobic-curable resin composition, since the inside of the bonding surface is shut off from the air, it is anaerobically cured, but the protruding portion of the resin and a large portion of the clearance are not cured because they come into contact with oxygen in the air. Therefore, there is a disadvantage that a secondary process such as heat curing of this portion or blending of a photopolymerization initiator and curing by ultraviolet irradiation is required.

In addition, the latter liquid sealant has a drawback that it takes a considerable time to cure to the inside of the joint surface, which is cut off from the air, since all of the liquid sealants cure only from the surface in contact with the air.

Therefore, the object of the present invention is to maintain both characteristics of anaerobic curing and moisture curing together, to be cured by anaerobic curing inside the joint surface that does not come into contact with air, An object of the present invention is to provide an anaerobic and moisture-curable resin composition in which the above-mentioned bonding, fixing or sealing is completely and promptly achieved by moisture-curing with water and the disadvantages of the above-mentioned known technique are improved.

[Means for solving the problem]

According to the present invention, there is provided an anaerobic-curable resin having one or more ethylenic double bonds in a molecule, and a moisture-curable resin having one or more hydrolyzable reactive groups in a molecule. And a anaerobic curing initiator and a moisture-curing catalyst.

The above-described anaerobic curable resin is a compound having one or more ethylenic double bonds in the molecule, and may be a monomer, oligomer, or polymer as long as it is compatible with other components.

Ethylenic double bonds are acrylic acid, methacrylic acid,
It refers to unsaturated carboxylic acids such as maleic acid, fumaric acid, crotonic acid, itaconic acid and derivatives thereof.

Specific examples of the anaerobic curable resin described above include methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, and 2- (meth) acrylate.
Monoesters such as ethylhexyl (meth) acrylate, phenyl (meth) acrylate, and benzyl (meth) acrylate; hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; Polyesters such as acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylpropane tri (meth) acrylate, and pentaerythritol tetraacrylate; (meth) acrylonitrile, (meth) acrylamide, N- Substituted (meth) acrylamide, etc .; vinyl esters such as vinyl acrylate, vinyl acetate, vinyl propionate, vinyl succinate; vinyl ethers, styrene , Halogenated styrene, divinylbenzene, vinylnaphthalene, N-vinylpyrrolidone, diallyl phthalate, diallyl maleate, triallyl isocyanate, vinyl compounds such as triallyl phosphate, etc., and these monomers are used alone or in combination of two or more. It can be used as a mixture.

Examples of the oligomer include a curable resin having a malate group, a fumarate group, an allyl group, and a (meth) acrylate group, an isocyanate-modified acrylic oligomer, an epoxy-modified oligomer, a polyether acrylic oligomer, and a polyester acrylic oligomer. These oligomers can be used alone or as a mixture of two or more kinds, or as a mixture with a polymerizable monomer.

Further, as the polymer, unsaturated polyester resin,
Polymerizable unsaturated polymers such as unsaturated acrylic resins, unsaturated polyether resins, unsaturated acrylic urethane resins, unsaturated silicone resins, etc., and these polymers may be used alone or in combination of two or more types including monomers and oligomers. It can be used as a mixture.

The above-mentioned moisture-curable resin is a compound having one or more hydrolyzable reactive groups in the molecule and is compatible with other components. The hydrolyzable reactive group refers to a reactive group capable of undergoing a hydrolysis reaction with moisture in the air and cross-linking with another compound, and includes, for example, an isocyanate group, an alkoxy group, an enamine group, and a ketimine group. These compounds may be monomers or polymers, and compounds having a reactive group capable of reacting with these reactive groups may be used as a mixture. Examples of the isocyanate group include a hydroxyl group, a mercapto group, an amino group, and a carboxyl group. If it is an alkoxy group, a silanol group and the like can be mentioned. In the case of an enamine group or a ketimine group, an epoxy group, an isocyanate group, a carboxyl group and the like can be mentioned.

As the isocyanate group-containing compound, aromatic compounds such as tolylene diisocyanate, diphenyl methane diisocyanate, polymethylene polyphenyl polyisocyanate, tolidine diisocyanate, naphthalene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, xylylene diisocyanate, hydrogenated xylylene diisocyanate Isocyanates, aliphatic compounds such as dicyclohexyl methediisocyanate and the like,
Further, a polymer having a main chain of polyether, polyester, polybutadiene, polyacrylonitrile, polysiloxane, or the like, and having an isocyanate group added to the molecular chain or at the terminal thereof can also be used. The isocyanate group-containing compound can be cured alone or may be mixed with a compound having a reactive group that reacts with an isocyanate group in order to further modify the substance. Specific examples thereof include polypropylene glycol, polymer polyol, Polyethers such as polytetramethylene glycol; polyesters such as adipate polyols, polycaprolactone polyols, and polycarbonate polyols; and other polybutadiene polyols and acrylic polyols. As the alkoxysilyl group-containing compound, a compound obtained by reacting an organic reactive group of various silane coupling agents with an organic compound capable of reacting with the organic silyl group can be used. As long as it contains at least three, preferably three or more improve the curability. General formula for silane coupling agent Wherein X represents an organic reactive group, a chloro group,
Examples include an amino group, a mercapto group, an epoxy group, a vinyl group, a (meth) acryloyl group, and an isocyanate group.
R ¹ represents an alkylene group, and R ² represents hydrogen or C 1
Represents an alkyl group having up to 5 hydrocarbons. R ³ represents an alkyl group or an allyl group. n is a positive number of 1 to 3. The organic compound capable of reacting with X (organic reactive group) may be any compound having one or more organic reactive groups capable of reacting with X in one molecule, and is a flexible and tough cured product. And the like, in which the main chain is composed of polyether, polyester, polybutadiene, polyacrylotrile, polyacrylurethane, or polysiloxane, and has an organic reactive group capable of reacting with X in the molecular chain or at the molecular terminal. Is mentioned. For example, a compound obtained by reacting hydroxyldimethyldimethoxysilane with polypropylene glycol having an allyl group at both ends and specifically having two functional methoxysilanes added to both ends is commercially available. "Kaneka MS Polymer 20A" manufactured by Kaneka Chemical Co., Ltd.
And "Kaneka Cyril".

Further, as the anaerobic curing initiator used in the present invention,
Generally used in anaerobic compositions, for example, cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, methyl ethyl ketone peroxide, cyclohexane peroxide, dicumyl peroxide, diisopropylbenzene hydroperoxide And organic peroxides such as ketone peroxides, diallyl peroxides, and peroxyesters. These polymerization initiators can be used alone or as a mixture of two or more.

The amount of the anaerobic curing initiator is 0.0 based on the total weight of both components of the anaerobic curable resin and the moisture curable resin.
01 to 10 parts by weight. In this case, if it is less than 0.01 part by weight, it is insufficient to cause a polymerization reaction, and if it is more than 10 parts by weight, the stability of the anaerobic curable resin composition is reduced. Further, as the above-mentioned moisture-curable catalyst, a reaction catalyst generally used for isocyanate group, alkoxysilyl group and the like may be used, for example, stannas octoate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin phthalate , Tetraisopropyl, organometallic compounds such as orthotitanate, triethylamine, triethylenediamine, N,
N, N ', N'-tetramethylpropylenediamine, N
Amines such as -methyl morpholine.

The compounding amount of the moisture-curable catalyst is also 0.1% based on the total weight of both components of the anaerobic-curable resin and the moisture-curable resin.
01 to 20 parts by weight. In this case, if the amount is less than 0.01 part by weight, a sufficient reaction rate cannot be obtained, and if the amount is more than 10 parts by weight, physical properties of a cured product may be deteriorated.

Furthermore, the mixing ratio of the anaerobic curable resin and the moisture curable resin described above is a molar ratio of 90:10 to 10:90, preferably 70:30 to 3
If the mixing ratio is in the range of 0:70 and one of them has a mixing ratio of 10 or less, the physical properties of the cured product by anaerobic curing or moisture curing become extremely weak.

In addition, the above-described composition of the present invention can optionally use an accelerator to increase the reaction rate of anaerobic curing,
Examples of the accelerator include organic sulfimides, primary amines such as tertiary amines and primary alkylamines, and secondary amines such as heterocyclic secondary amines. Further, the composition of the present invention is a benzoquinone, hydroquinone, a radical absorber such as hydroquinone monomethyl ether, ethylenediaminetetraacetic acid or its 2-sodium salt, oxalic acid, acetylacetone, o-aminophenol and the like to improve storage stability. A metal chelate compound or the like may be added, and as a dehydrating agent, methyltrimethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, tetraethoxysilane It is also possible to add a silane compound having a hydrolyzable silyl group such as an alkoxy compound such as orthoformic acid methyl ester and orthoformic acid ethyl ester, and it is also possible to cure by ultraviolet light if a photopolymerization initiator is blended. And in this case The photopolymerization initiator for example,
Benzophenone, benzoin alkyl ether, 2, 2
-Dimethoxy-2-phenylacetophenone, 2,2-
Diethoxy acetophenone, 1-hydroxycyclohexyl phenyl ketone, etc., and also, various diluents for lowering the viscosity and various plasticizers for lowering the hardness of the cured product and increasing the elongation. Or a dye, a filler, a thixotropic agent, an ion trapping agent, a flame retardant, and the like.

The above-mentioned composition of the present invention is preferably prepared by mixing each component under a stream of dry nitrogen gas or oxygen gas.For storage, avoid contact with metals as much as possible and place in a plastic container such as polyethylene or polypropylene or a glass container. It is desirable to keep. Further, when storage stability is further required, the storage life can be greatly extended by adjusting the polymerization initiator and the polymerization accelerator to be two-part separated from each other.

[Action]

Since the above-described composition of the present invention contains both a combination of an anaerobic curable resin and an anaerobic curing initiator, and a combination of a moisture curable resin and a moisture-curable catalyst, both of the properties of anaerobic curing and moisture curing are retained. Therefore, the inside of the joint surface that does not come into contact with air undergoes anaerobic curing by a combination of anaerobic curing, and in the protruding portion that comes into contact with air, receives moisture in the air by a combination of moisture curing and cures as a result. Adhesion, fixation, or sealing of screws, flange surfaces, etc. is completed completely and quickly.

〔Example〕

Each formulation shown in Table 1 was prepared. In Table 1, P-1
Is a moisture-curable resin, which is prepared by mixing 33.6 g of hexamethylene diisocyanate (HDI) and 0.04 g of dibutyltin dilaurate in 300 g of polypropylene glycol diol having an average molecular weight of 3000 in a reaction vessel, and heating at 80 ° C. for 2 hours under a stream of N ² gas. Stir and react. Thereafter, 44.2 g of γ-aminopropyltrimethoxysilane was added dropwise with stirring to react, and G
A polyether prepolymer having a trimethoxysilyl group at both ends with an average molecular weight of about 3,800 by PC.

MS-20 is a modified silicone base polymer manufactured by Kanegafuchi Chemical Co., Ltd., which is a moisture-curable resin having the following structural formula.

Bisphenol A-based dimethacrylate is an anaerobic curable resin having the following structural formula.

Spirane dimethacrylate is an anaerobic curable resin having the following structural formula.

Phthalic acid-based dimethacrylate is an anaerobic curable resin having the following structural formula.

2HEMA is 2-hydroxyethyl methacrylate, an anaerobic curable resin.

Orthobenzoixulfimide is an accelerator for anaerobic curable resins.

 EDTA sodium salt is a stabilizer.

BHT is a stabilizer, butoxyhydroxytoluene or 2.6-di-tert-butylparacresol.

 THQ is an accelerator.

CHP is cumene hydroperoxide, an anaerobic curing initiator.

# 918 is an organic tin compound manufactured by Sankyo Organic Synthesis Co., Ltd., which is a moisture-curable catalyst.

 Methylmethoxysilane is a stabilizer.

 Fumed silica is a reinforcing agent.

The following various evaluation tests were performed on each of the compounds in Table 1, and the results are shown in Table 2.

<Evaluation test> * Tack-free time: The time required for a sample to be exposed to air at a temperature of 25 ° C and a humidity of 50% RH until it touches with your fingertips and no longer adheres.

* Tensile shear adhesive strength: Apply a sample to an iron plate of 1 x 25 x 100 mm and bond it with an overlap of 25 x 25 mm, 10 kgf /
With a cm ² force. After leaving it at a temperature of 25 ° C. and a humidity of 50% RH for 2 hours, the adhesive strength is measured with a tensile tester at a tensile speed of 10 mm / min.

* Curing ratio: Measure the resin ratio of the part cured by the above-mentioned shear adhesion test piece.

* Withstand pressure test: Apply a sample with a clearance of 0.02 mm and 0.2 mm using an iron flange with an inner diameter of 100Φ and a surface width of 8 mm. This is left at room temperature, and the leak pressure is measured after 30 minutes, 1 hour, 2 hours, and 24 hours. Pressing speed, 5kgf / cm ² · min, pressurizing medium: turbine oil.

As is evident from Table 2, the resin composition according to the present invention has good tack-free time, tensile shear adhesive strength, curing ratio, and leak pressure, and the adhesion is completely improved by anaerobic curing and moisture curing. It means that it has been achieved.

〔The invention's effect〕

As described above, the composition according to the present invention is cured by anaerobic curing inside the bonding surface not in contact with air by maintaining both properties of anaerobic curing and moisture curing.
In addition, at the protruding part that comes into contact with the air or at the joint part with a large clearance, the moisture in the air cures moisture and achieves adhesion and fixing or sealing completely and quickly,
This is a practically useful invention.

Claims (2)

(57) [Claims] An anaerobic curable resin having at least one ethylenic double bond in a molecule, a moisture curable resin having at least one hydrolyzable reactive group in a molecule, and an anaerobic curing initiator. Anaerobic and moisture-curable resin composition comprising a water-curable catalyst. 2. The composition according to claim 1, wherein the molar ratio of the anaerobic curable resin to the moisture curable resin is in the range of 90:10 to 10:90. Curable resin composition.