JPS61291667A - Anaerobic adhesive composition - Google Patents

Abstract

PURPOSE:To titled composition for fixing screw parts of bolts and nuts, having improved rapidly curing properties and heat resistance, comprising a (meth) acryloyl group-containing (meth) acryloyl oligomer, a nucleus-substituted N- phenylmaleimide and a free group polymerization initiator. CONSTITUTION:(A) A (meth) acryl oligomer [e.g., ethylene glycol di(meth) acrylate, etc.] containing one or more (meth) acryloyl groups is blended with (B) a nucleus-substituted N-phenylmaleimide [e.g., N-(o-chlorophenyl) maleimide, etc.] and (C) a free group polymerization initiator (preferably t-butyl hydroperoxide, etc.) preferably in ratio of the component A/B=70-95/30-5 (weight ratio) and in a ratio of 0.1-3 pts.wt. component C to 100 pts. wt. components A+B, to give the aimed composition.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an anaerobic adhesive composition that has excellent fast curing properties and heat resistance.

(Prior Art) Anaerobic adhesive compositions normally remain liquid and do not harden when in contact with air or oxygen, but they have the property of rapidly polymerizing and hardening when cut off from air or oxygen. Therefore, various sealants have been widely put into practical use, for example, for fixing threaded parts of bolts and nuts, and for fixing bearing shafts.

However, with the development of the electronics industry in recent years,
Applicability to more types of materials, improvement to faster curing,
There are many issues that need to be resolved, such as improving heat resistance.

Many attempts have been made to address these issues. For example, a method of achieving rapid curing by combining a hydrophilic anaerobically polymerizable monomer that can contain water from the raw material, a limited catalyst system, and water (Japanese Patent Application Laid-open No. 59-207977), Method for increasing heat resistance using di(meth)acrylate (JP-A-54-150491)
No.), a method for improving thermal properties using di(meth)acrylate oligomers and phenylmaleimide or bismaleimide, which are solid at room temperature (Japanese Patent Publication No. 59-13555)
Although these products are fast-curing, they still have problems such as insufficient water resistance and heat resistance, and although they improve heat resistance, they do not have sufficient fast-curing properties. At present, there is a strong demand for an anaerobic adhesive composition that is fast-curing and has excellent heat resistance.

(Problems to be Solved by the Invention) In order to solve the above-mentioned problems, the present inventors have conducted extensive research and found that anaerobic bonding is possible by combining (meth)acrylic oligomers, specific monomaleimide compounds, and free radical polymerization initiators. The present invention was completed based on the discovery that it exhibits fast curing properties and excellent heat resistance when used as an agent.

(Means and effects for solving the problems) That is, the present invention provides a (meth)acrylic oligomer (A) having one or more (meth)acryloyl groups in one molecule, a nuclear-substituted N-phenylmaleimide ( 8) and a free radical polymerization initiator (
The present invention relates to a fast-curing anaerobic adhesive composition containing C) and having excellent adhesive properties and heat resistance.

acrylic oligomer (A) used in the present invention
includes all those containing one or more (meth)acryloyl groups in one molecule, but mainly di(meth)acrylate oligomers containing two or more (meth)acryloyl groups in one molecule. Generally, they are used in various combinations. The optimal combination of these (meth)acrylic oligomers (A) may be selected depending on the purpose of use.

Examples of (meth)acrylic oligomers <A) include ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, and tetraethylene glycol Di(meth)acrylate, dibrobylene glycol di(meth)acrylate, dipentamethylene glycol di(meth)acrylate, tetraethylene diglycerol tetra(meth)acrylate, tetramethylene di(meth)acrylate, neobentyl glycol di( meth)acrylate, 1,3-butanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate,
dipentaerythritol hexa(meth)acrylate,
Di(meth)acrylate of bisphenol A alkylene oxide adduct, di(meth)acrylate of halogenated bisphenol A alkylene oxide adduct, di(meth)acrylate of bisphenol S alkylene oxide adduct
Acrylate, poly(meth)acrylates of polyhydric alcohols such as glycerin di(meth)acrylate, polyester poly(meth)acrylates, urethane poly(meth)acrylates, epoxy poly(meth)acrylates, methyl(meth)acrylates Acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, cyclohexyl (meth)acrylate, phenoxyethyl (meth)acrylate, lauryl (meth)acrylate, diphenyl (meth)acryloyloxyethyl phosphate , dibutyl (meth)acryloyloxyethyl phosphate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, tris(
Examples include meth)acryloyloxyethyl phosphate, tris(meth)acryloyloxyethyl isocyanurate, tri(meth)acryloylhexahydro-8-triazine, and the like.

The nuclear-substituted N-phenylmaleimide (B) used in the present invention is a monomer that characterizes the fast curing properties and excellent heat resistance of the adhesive composition of the present invention. These nuclear-substituted N-phenylmaleimides (B) include, for example, N-phenylmaleimide (B).
-(o-chlorophenyl)maleimide, N-(3-chlorophenyl)maleimide, N-(4-chlorophenyl)
maleimide, N-(4-bromophenyl)maleimide,
N-(2,4,6-dolychlorphenyl)maleimide,
N-(2,4,6-dribromophenyl)maleimide,
N-(2-methylphenyl)maleimide, N-(3-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2-tert-butylphenyl)
Maleimide, N-(3-tert-butylphenyl)maleimide, N-(4-tert-butylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2-nitrophenyl)maleimide, N- (3-
nitrophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-(2,4-dinitrophenyl)maleimide, N-(2-hydroxyphenyl)maleimide, N-(3-hydroxyphenyl)maleimide, N-(
4-hydroxyphenyl)maleimide, N-(2-methoxyphenyl)maleimide, N-(3-methoxyphenyl)maleimide, N-(4-methoxyphenyl)maleimide, N-(4-ethoxyphenyl)maleimide, N-
(2-methoxy-4-chlorophenyl)maleimide, N
-(4-phenylphenyl)maleimide, N-(4-phenyloxyphenyl)maleimide, N-(4-benzylphenyl)maleimide, N-(4-benzyloxyphenyl)maleimide, N-(4-phenoxymethylphenyl) ) maleimide, N-(2-chloro-4-phenoxyphenyl)maleimide, N-naphthylmaleimide, N-(2
-carboxyphenyl)maleimide, N-(4-carboxyphenyl)maleimide, etc., and one or more of these can be used.

As the free radical polymerization initiator (C), known free radical polymerization initiators such as hydroperoxides, ketone peroxides, dialkyl peroxides, peroxy esters, etc. can be used. ! Although a polymerization initiator can be used, hydroperoxides such as t-butyl hydroperoxide, cumene hydroperoxide, diisopropylbenzene hydroperoxide, and p-menthane hydroperoxide are preferred.

It is the main component of the anaerobic adhesive composition of the present invention (
meth)acrylic oligomer (A), maleimide compound (
The blending ratio of B) and free radical polymerization initiator (C) is not specified, but usually (meth)acrylic oligomer (A)/nucleically substituted N-phenylmaleimide (B) = 50 to 99.
The ratio is in the range of 150 to 1 (weight ratio), preferably (meth)acrylic oligomer (A)/nucleically substituted N-7 enylmaleimide (B) = 70 to 95/30 to 5 (weight ratio), In addition, the free radical polymerization initiator (C) is used in an amount of 0°05 to 100 parts by weight of the (meth)acrylic oligomer (A) and the nuclear-substituted N-phenylmaleimide (B).
It is used in proportions ranging from 5 parts by weight, preferably from 0.1 to 3 parts by weight. If blended in a ratio outside this range, an anaerobic adhesive composition that is fast-curing and has excellent adhesiveness and heat resistance after curing may not be obtained.

Known accelerators used for the purpose of accelerating anaerobic polymerization, such as benzosulfimide and secondary or tertiary organic amines, may be appropriately used in the composition of the present invention. In addition, phenol-based and quinone-based polymerization inhibitors, known stabilizers such as oxalic acid and ethylenediamine/tetraacetate,
Silane coupling agent, Titanium Coupling IIJ.

It is also possible to add colorants, thickeners, thixotropic agents, plasticizers, etc. as appropriate.

Furthermore, when the composition of the present invention is used as an ultraviolet curable anaerobic adhesive by using a known photopolymerization initiator such as benzoin, benzyl, benzoin alkyl ether, benzophenone, or acetophenone, nuclear-substituted N-phenyl Since maleimide (B) exhibits the effect of increasing the curing speed, curing bonding can be achieved in a shorter time, which is very advantageous.

(Effects of the Invention) The anaerobic adhesive composition of the present invention is fast-curing and has excellent heat resistance and adhesive properties after anaerobic curing, so it can be used for fixing threaded parts of bolts and nuts, and for fixing electrical and electronic parts. It is applied in a wide range of fields such as adhesion and adhesion of automobile parts.

Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by the Examples. In addition,
In the examples, parts are parts by weight, and % is weight %. In addition, the performance test of each adhesive was conducted by the following method.

(1) Adhesion start time After applying the adhesive composition onto the thread of the MIO bolt, screwing in the nut and fixing it without applying any tightening torque, leave it at 23°C. The time until it stopped moving was measured.

(2) Breaking torque strength Adhesive start time measurement The bolts and nuts fixed by applying an adhesive composition in the same manner as in the test were left at 23°C for 24 hours, then returned using a torque wrench and started to move for the first time. The torque strength at that time was measured and defined as the breaking torque strength.

(3) Escape Torque Strength After measuring the breaking torque strength, the torque strengths of 1/4, 1/2, 3/4 and 4/4 rotations were similarly measured, and the average value thereof was determined to be the escape torque strength.

(4) Heat Resistance Strength Bolts and nuts fixed and cured in the same manner as the escape torque strength test were heated at 180° C. for 6 hours, and then the escape torque strength was determined in the same manner in the heated state to determine the heat resistance strength.

Example 1 An anaerobic adhesive composition of the present invention was prepared according to the following formulation and a performance test was conducted.

Bisphenol A ethylene oxide 3 mole adduct 75 parts dimethacrylate N-(0-chlorphenylene 25 parts)maleimidocumene hydroperoxide 1 part O-benzsulfimide 0.5 part N,N-dimethylaniline 0.5 part The test results are shown in Table 1.

Comparative Example 1 A comparative anaerobic adhesive composition was prepared in the same manner as in Example 1, except that N-phenylmaleimide was used instead of N-(o-chlorophenyl)maleimide in Example 1, and the performance was evaluated. We conducted a test. The test results are shown in Table 1. The curing speed was considerably slower than that of the adhesive composition obtained in Example 1.

Comparative Example 2 In d5 of Example 1, 100 parts of dimethacrylate, a 3 mole adduct of bisphenol A ethylene oxide, and N
A comparative anaerobic adhesive composition was prepared in the same manner as in Example 1, except that -(o-chlorophenyl)maleimide was not used, and a performance test was conducted. The test results are shown in Table 1.

Both the curing speed and heat resistance were inferior to the adhesive composition obtained in Example 1.

Example 2 An anaerobic adhesive composition of the present invention was prepared according to the following formulation and a performance test was conducted.

Bisphenol A ethylene oxide 3 mole adduct 60 parts dimethacrylate cumene hydroperoxide 1.5 parts 0-benzsulfimide 0.5 parts 6-methylquinoline 0.5 parts oxalic acid
The results of the 0.005 part test are shown in Table 1.

Example 3 An anaerobic adhesive composition of the present invention was prepared according to the following formulation and a performance test was conducted.

Tetraethylene glycol 8o parts Dimethacrylate N-(0-chlorphenylene 20 parts) Maleimidocumene hydroperoxide 1.0 parts 1.1-
Dimethylhydrazine 0.5 part Hydroquinone mono 0.05 part Methyl ether oxalic acid 0.005 part The test results are shown in Table 1.

Chapter 1 Table

Claims (1)

[Scope of Claims] 1. A (meth)acrylic oligomer (A) having one or more (meth)acryloyl groups in one molecule, a nuclear-substituted N-phenylmaleimide (B), and a free radical polymerization initiator ( C) An anaerobic adhesive composition comprising: