JPH01287115A - Anaerobic and moisture-curable type resin composition - Google Patents

Abstract

PURPOSE:To obtain the title composition comprising interior part of bonding face not to be brought into contact with air, curable by anaerobic curing and protruded part to be brought into contact with air, curable with water in air by moisture curing, containing a specific compound, anaerobic curing initiator and a moisture curing catalyst. CONSTITUTION:The aimed composition comprising (A) a compound [preferably compound shown by the formula (n is 1-2,000)] containing one or more (meth) acryloyl groups and one or more hydrolyzable reactive groups in one molecule, (B) an anaerobic curing initiator (e.g. cumene hydroperoxide) and (C) a moisture curing catalyst (e.g. stannous octoate or triethylamine). The blending ratio is preferably 0.01-10pts.wt. component B and 0.01-20pts.wt. component C base don 100pts.wt. component A.

Description

Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a resin composition used for adhering, fixing, or sealing screws, bolts, fitting parts, flange surfaces, etc. The interior of the bonded surfaces that are not exposed to heat is cured by anaerobic hardening, and the protruding parts that come into contact with air are cured by moisture in the air.In other words, by maintaining both anaerobic and moisture hardening characteristics, The present invention relates to an anaerobic and moisture-curable resin composition that can completely and quickly achieve adhesion, fixation, or sealing.

[Conventional technology]

Conventional resin compositions used to bond, fix, or seal screws, bolts, fitting parts, flange surfaces, etc. to each other include anaerobic curing resin compositions, reactive liquid sealants, For example, solvent type sealants, moisture curing type sealants, drying oil sealants, and the like are known.

Furthermore, a technique is also known that uses a combination of ultraviolet curing and moisture curing, which consists of a compound having both a (meth)acroyl group and a hydrolyzable group in one molecule and a photocuring initiator. (Refer to Japanese Unexamined Patent Publication No. 127718/1983).

[Problem that the invention seeks to solve]

However, in the former anaerobic curable resin composition, the inside of the joint surface is isolated from the air, so it is cured anaerobically, but the protruding parts of the resin and parts with large clearances are not cured because they come into contact with oxygen in the air. This inconvenience arises,
For this reason, it has had the disadvantage of requiring secondary steps such as heating and curing this portion or adding a photopolymerization initiator and curing it by irradiating ultraviolet rays.

In addition, all of the following liquid sealants have the disadvantage that since they only harden from the surface that is in contact with air, it takes a considerable amount of time for the sealants to harden to the inside of the bonded surface that is cut off from the air.

Furthermore, the latter type of ultraviolet curable composition is not cured by anaerobic curing but by ultraviolet irradiation, which adds the step of ultraviolet irradiation, thereby complicating the process.

Therefore, the purpose of the present invention is to maintain both anaerobic curing and moisture curing characteristics, so that the inside of the joint surface that does not come into contact with air is cured by anaerobic hardening, and the protruding parts that come into contact with air are cured in the air. The object of the present invention is to provide an anaerobic and moisture-curable resin composition which can be cured by moisture to completely and quickly achieve the above-mentioned adhesion, fixation or sealing, and which has improved the drawbacks of the above-mentioned known techniques.

[Means for solving problems]

In order to achieve the above-mentioned object, according to the present invention, a compound each having one or more (meth)acroyl groups and one or more hydrolyzable reactive groups in one molecule, an anaerobic curing initiator, It is characterized by comprising a moisture curing catalyst.

The aforementioned compounds each having one or more (meth)acroyl groups and one or more hydrolyzable reactive groups in one molecule are specifically as shown in (1) to (5) below.

(1) A diisocyanate compound is reacted with a compound having hydroxyl groups at both terminals, and the reaction product contains a compound having an active hydrogen group and a (meth)acroyl group in one molecule, and an active hydrogen group and an alkyl group in one molecule. Compounds having a koxysilyl group are mixed at a desired mixing ratio, for example 90:
A compound obtained by reacting at a ratio of 10 to 10:90 (mole ratio).

Specifically, a molecular weight of 30 having both terminal hydroxyl groups
00 polypropylene glycol is reacted with tolylene diisocyanate (TD+) in the presence of diptyltin dilaurate to produce a compound with isocyanate at both ends.

A compound having the following structural formula obtained by reacting this reaction product with 2HEMA and γ-aminopropyltrimethoxysilane at a mixing ratio of 1:1 (molar ratio).

(However, n = integer from l to 2000) ...(
1) (2) In a compound having silanol groups at both ends, 1
A compound obtained by reacting a silane compound with a (meth)acroyl group and a hydrolyzable reactive group in the molecule.

Specifically, it has the following structural formula obtained by reacting dimethylpolysiloxane (n = 250, viscosity 5000C3) having hydroxyl groups at both ends with methacrylfurohyltrimethoxysilane in the presence of dibutyltin diacetate. Compound.

(However, n = 250) (3) - Shown by the formula (where R4 represents a hydroxyl group or an alkyl group having 1 to 5 carbon atoms, R5 represents an alkylene group, and R6 represents an aliphatic or aromatic difunctional hydrocarbon) Compound.

The compound of formula (5) has the general formula...(6) (R' is a hydroxyl group or an alkyl group having 1 to 5 carbon atoms, R%
represents an alkylene group. ) per mole of epoxy acrylate monomer (specifically, manufactured by Kyoeisha Yushi Kagaku Kogyo Co., Ltd. [epoxy ester 40EMJ etc.)]
It is produced by dropping 2 moles of a bifunctional isocyanate compound in the presence of a tin catalyst, replacing the hydroxyl groups of the epoxy acrylate monomer with isocyanate groups, and then dropping 2 moles of, for example, aminopropylmethyldimethoxysilane.

The compound of formula (5) is schematically shown as follows, and is a compound having one unsaturated double bond and two methoxysilyl groups at both ends.

(4) - A compound represented by the formula % (8) (wherein R6 is an aliphatic or aromatic bifunctional hydrocarbon, and R7 or -CthCHzCH2CHz-1m is a positive number of 1 or more).

The compound of formula (8) is a polyether polymer having a methyl methacrylic group and an isocyanate group at both ends, and the main chain of the polymer is lengthened to increase the elongation of the cured product. is generated. First, 1 mole of a polyether polyol having an average molecular weight of 3,000 or more is reacted with 2 moles of a bifunctional isocyanate compound to substitute both ends with isocyanate groups. For example, 2 mol of glycerol monomethacrylate per 1 mol of polyether polyol is reacted with this, and the following formula (
The compound shown in 9) is produced.

CH3C, Ha ・ ・ ・ (9) Here, R6 is an aliphatic or aromatic difunctional hydrocarbon,
R7 is -C)1. CH, CHI CH, -1m represents a positive number of 1 or more.

Next, this compound of formula (9) is further reacted with a bifunctional isocyanate compound to produce a compound of formula (8).

(5) - Formula (where R6 is an aliphatic or aromatic bifunctional hydrocarbon, R7 is CH3CH2CH3 CH2CH2-1-C1l CL-1-6ucHz
-1 or -Cth C1h C)12 CH2-1m
is a positive number greater than or equal to 1. ).

This compound 200 is produced by further reacting the compound of formula (8) with aminopropylmethyldimethoxysilane and replacing the terminal isocyanate with a difunctional alkoxysilyl group.

Further, the anaerobic curing initiator used in the present invention is one that is generally used in anaerobic compositions, such as cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, methyl ethyl ketone peroxide, Examples include hydroperoxides such as cyclohexane peroxide, dicumyl peroxide, and diisopropylbenzene hydroperoxide, and organic peroxides such as ketone peroxides, diallyl peroxides, and peroxy esters. These polymerization initiators can be used alone or as a mixture of two or more.

The amount of the above-mentioned anaerobic curing initiator is 0.0 parts by weight per 100 parts by weight of the compound having one or more (meth)acroyl groups and one or more hydrolyzable reactive groups in each molecule.
It is 1 to 10 parts by weight. In this case, if it is less than 0.01 part by weight, sufficient curability cannot be obtained, and if it is more than 10 parts by weight, stability will be reduced.

The moisture-curing catalyst mentioned above may be a reaction catalyst used for boat fishing, such as an isocyanate group or an alkoxysilyl group, such as stannous octoate, dibutyltin dilaurate, dibutyltin oxide, dibutyltin diacetate, dibutyltin Organometallic compounds such as phthalate, tetraisopropyl, orthotitanate, triethylamine, triethylenediamine, N, N, N
', N'-tetramethylpropylene diamine, N-methyl morpholine, and other amines.

The amount of the moisture curing catalyst is 0.0 parts by weight per 100 parts by weight of the compound having one or more (meth)acryloyl groups and one or more hydrolyzable reactive groups in each molecule.
It is 1 to 20 parts by weight. In this case, if it is less than 0.01 part by weight, sufficient curing may not be obtained, and if it is more than 20 parts by weight, there is a risk that the physical properties of the cured product may deteriorate.

In addition, the above-mentioned composition of the present invention can use an accelerator to accelerate the reaction rate of anaerobic curing, if necessary. Examples of the accelerator include organic sulfimides, tertiary amines, primary alkyl Examples include primary amines such as amines, and secondary amines such as heterocyclic secondary amines.

Furthermore, in order to improve the storage stability of the composition of the present invention,
Radical absorbers such as henzoquinone, hydroquinone, hydroquinone monomethyl ether, ethylenediamine 4
Acetic acid or its 2-sodium salt, oxalic acid, acetylacetone, metal chelate compounds such as 0-aminophenol, etc. may be added, and methyltrimethoxy as a dehydrating agent may be added to improve storage stability due to moisture curing. Silane compounds having a hydrolyzable silyl group such as silane, tetramethoxysilane, vinyltrimethoxysilane, methyltriethoxysilane, and tetraethoxysilane, and alkoxy compounds such as orthoformic acid methyl ester and orthoformic acid ethyl ester can also be added. In addition, if a photopolymerization initiator is added, curing by ultraviolet rays becomes possible. Examples of the photopolymerization initiator in this case include benzophenone, hendiyne alkyl ether, 2,2-dimethoxy-2-phenylacetophenone, 2.2-Jethoxyacetophenone, ■-Hydroxycyclohexylphenylketone, etc., and various diluents to lower the viscosity and various plasticizers to lower the hardness of the cured product and increase its elongation. Alternatively, other dyes, fillers, thixotropic agents, ion trapping agents, flame retardants, etc. can also be added.

The composition of the present invention described above is preferably blended with each component under a stream of dry nitrogen gas or oxygen gas, and is stored in a plastic container such as polyethylene or polypropylene, a glass container, etc., avoiding contact with metals as much as possible. It is desirable to keep it. Furthermore, when further storage stability is required, the storage life can be greatly extended by adjusting the polymerization initiator and polymerization accelerator to be two-component, separated from each other.

[Effect]

The composition of the present invention described above has one or more (
A compound containing a meta)acroyl group and one or more hydrolyzable reactive groups possesses both anaerobic and moisture curing properties, and the combination of this compound with an anaerobic curing initiator and a moisture curing catalyst results in anaerobic curing. It also maintains both the properties of moisture curing, and therefore anaerobic hardening occurs inside the bonded surfaces that do not come into contact with air, and moisture hardening occurs at protruding areas that come into contact with air due to the moisture in the air. , to completely and quickly achieve adhesion, fixation, or sealing of screws, flange surfaces, etc.

〔Example〕

Each formulation shown in Table 1 was prepared. In Table 1, P-1 is a moisture-curable resin, in which 300 g of polypropylene glycol diol with an average molecular weight of 3000, 33.6 g of hexamethylene diisocyanate (CHDI), and 0.04 g of dibutyltin dilaure) are mixed in a reaction vessel, and N2
Stir and react at 80° C. for 2 hours under a gas stream. Then, γ-aminopropyltrimethoxysilane 44.2
A polyether prepolymer having trimethoxysilyl groups at both ends with an average molecular weight of 3800 was determined by GPC.

M-1 is a compound represented by the above-mentioned formula (5), each having one or more (meth)acroyl groups and one or more hydrolyzable reactive groups in one molecule, and is produced as follows. be done.

First, as an epoxy acrylate monomer represented by the above-mentioned formula (6), (11) is prepared. 33.6 g of HDI and 0.01 g of dibutyltin silaureide were added to 346 g of epoxy acrylate monomer of this formula, and the mixture was heated at 80°C under a stream of N2 gas.
, stir for 2 hours and react. Next, 44.2 g of γ-aminopropyltrimethoxysilane was added dropwise to this while stirring to react, thereby forming a compound (M-1) having two methacrylic groups and two trimethoxysilyl groups in one molecule. > obtained.

P-2 is a compound shown in the above formula fil, each having one or more (meth)acroyl groups and one or more hydrolyzable groups in one molecule, and is produced as follows. .

First, 33.6 g of HD+ and 0.04 g of dibutyltin dilaurate were added to 300 g of polypropylene glycol diol with an average molecular weight of 3000, and the
Stir and react at 0°C for 12 hours. Next, 32.0 g of glycerol monomethacrylate was added, and the mixture was stirred and reacted at 80° C. for 2 hours under a N2 gas stream.

Further, 33.6 g of HDI was added thereto, and the mixture was stirred and reacted at 80° C. for 2 hours, and then 44.2 g of γ-aminopropyltrimethoxysilane was added dropwise with stirring. The thus produced prepolymer was measured by GPC and was found to be a polyether (P-2) having a methacrylic group and a trimethoxysilyl group at both ends of the molecular positioning piece 4200.

Bisphenol A-based dimethacrylate is an anaerobic curable resin L having the following structural formula. 2HEMA is 2-hydroxyethyl methacrylate and is an anaerobic curable resin.

Orthobenzoic sulfimide is an accelerator for anaerobic curing resins.

EDTA sodium salt is a stabilizer.

THQ is an accelerator.

CHP is cumene hydroperoxide and is an anaerobic curing initiator.

#918 is an organotin compound manufactured by Sankyo Organic Synthesis Co., Ltd., and is a moisture curing catalyst.

Methylmethoxysilane is a stabilizer.

Fuyumudoshiri force is a reinforcing agent.

Table-1 ■ "-N- "tt ■ ]- "-1me・1fu- The following various evaluation tests were conducted on each of the formulations in Table-1.
The results are shown in Table-2.

*Tack-free time: Sample at 25℃ and humidity 50%
How long does it take to be exposed to RH air and rubbed with your fingertips until it no longer sticks?

*Tensile shear adhesive crab 1 x 25 x loo, apply the sample to the iron plate and overlamp 25 x 25 m1
and then sandwiched with a force of 10 kgf/cn. After leaving this at a temperature of 25° C. and a humidity of 50% RH for 24 hours, its adhesive strength was measured using a tensile tester at a tensile rate of Lofi/min.

*Curing rate: Measure the resin pre-metal of the cured part using the above shear adhesive strength test piece.

*Pressure test: Apply the sample using an iron flange with an inner diameter of 100Φ and a surface width of 8fi with a clearance of 0.02m and 0.2N. Leave this at room temperature and after 30 minutes, 1 hour, 2
After 24 hours, the leakage pressure is measured. Pressure speed, 5
kg f /cl-min, pressurizing medium: turbine oil.

Table 2 As is clear from Table 2, the resin composition of the present invention has excellent tank free time, tensile shear adhesive strength, curing ratio, and leakage pressure, and this is due to anaerobic curing and moisture curing. This means that it has been completely achieved.

〔Effect of the invention〕

As described above, the composition according to the present invention has both anaerobic curing and moisture curing characteristics, so that it cures by anaerobic curing inside the joint surface that does not come into contact with air, and also cures by anaerobic curing inside the joint surface that does not come into contact with air. This is a practically useful invention because large joints are cured by moisture in the air to completely and quickly achieve adhesion, fixation, or sealing.

Patent Applicant: Three Bond Co., Ltd. Procedural Amendment December 7, 1988 Director General of the Patent Office Yoshi 1) Takeshi Moon 1, Indication of the Case Patent Application No. 114843 of 1988 2, Title of Invention Anaerobic and Moisture Curing Type Resin composition 3, relationship with the case of the person making the amendment Patent applicant address: 1456 Hazama-cho, Hachioji-shi, Tokyo Name: Three Pond Co., Ltd. 4, Agent 5, Date of amendment order Voluntary 6, Invention increased by the amendment No. 7, subject of amendment: "Detailed Description of the Invention" column of the description.

8. Contents of the amendment as shown in the attached sheet.

Replace Table 2 on page 22-1 of the present specification with the attached sheet. (Table-2 middle, lower row [leakage pressure J term added) Spring Table-2

Claims (8)

[Claims] (1) a compound each having one or more (meth)acroyl groups and one or more hydrolyzable reactive groups in one molecule;
An anaerobic and moisture curing resin composition comprising an anaerobic curing initiator and a moisture curing catalyst. (2) In the composition according to claim 1, the compound having both terminal hydroxyl groups is reacted with a diisocyanate compound, and the reaction product has an active hydrogen group and a (meth)acroyl group in one molecule. a compound having
A composition that is a compound obtained by reacting a compound having an active hydrogen group and an alkoxysilyl group in one molecule at a desired mixing ratio. (3) The composition according to claim 2, wherein the compound is a compound having the formula ▲ A mathematical formula, a chemical formula, a table, etc. ▼ (where n = an integer from 1 to 2000). (4) In the composition according to claim 1, the compound having silanol groups at both ends is reacted with a silane compound having a (meth)acroyl group and a hydrolyzable reactive group in one molecule. A composition that is a compound obtained by (5) The composition according to claim 4, wherein the compound is a compound having the formula ▲ A mathematical formula, a chemical formula, a table, etc. ▼ (where n = an integer from 1 to 25,000). (6) In the composition according to claim 1, the compound has a general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (However, R^4 is a hydroxyl group or an alkyl group having 1 to 5 carbon atoms, R^ 5 represents an alkylene group, and R^6 represents an aliphatic or aromatic bifunctional hydrocarbon. (7) In the composition according to claim 1, the compound has a general formula ▲a mathematical formula, a chemical formula, a table, etc.▼ (where R^6 is an aliphatic or aromatic difunctional hydrocarbon, R^7 is -CH_2CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or -CH_2CH_2CH_2CH_2-, m is 1
is a positive number greater than or equal to ) A composition that is a compound represented by (8) In the composition according to claim 1, the compound has a general formula ▲A mathematical formula, a chemical formula, a table, etc.▼ (However, R^6 is an aliphatic or aromatic difunctional hydrocarbon, R^7 is -CH_2CH_2-, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, ▲There are mathematical formulas, chemical formulas, tables, etc.▼, or -CH_2CH_2CH_2CH_2-, m is 1
is a positive number greater than or equal to ) A composition that is a compound represented by