JPS5883075A - Anaerobically curable composition - Google Patents

Abstract

PURPOSE:To provide an anaerobically polymerizable compsn. which has a high breaking torque and is useful for bonding of metal parts, etc. and fixation of fitted parts, prepared by adding a specified phosphorus and chlorine-contg. cpd. to a mixt. of (meth)acrylic ester monomer and organic peroxide. CONSTITUTION:The compsn. is prepared by adding a phosphorus and chloride- contg. compd. of formulaI, formula II (where R<1> is H, CH3 or C2H5; R<2> is -CH2-, -C2H4, -C3H6-), formula III or formula IV (where n is 1-10)[e.g. bis(3- chloro-2- (acid phosphoxy)propylmethacrylate), 3-chloro-2-(acid phosphoxy)propyl methacrylate]to a mixt. of (meth)acrylic ester monomer[e.g. methoxyethyl (meth) acrylate]and organic peroxide as polymerization initiator (e.g. methyl ethyl ketone peroxide). The compd. is added in >=0.05% based on the weight of (meth) acrylic ester monomer.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anaerobic curable composition with excellent breaking torque. An anaerobic curable composition is a curable composition that is stable for a long period of time while in contact with air or oxygen, but easily polymerizes and cures by blocking air or oxygen between two adjacent surfaces. This composition is used for adhesion, sealing, and loosening of metal parts, and for fixing fitting parts.

This type of anaerobic curable composition conventionally contains acrylic ester monomers and/or methacrylic ester monomers [herein referred to as "-(meth)acrylic ester monomers"]. collectively. ] was known as a compound containing monomer K as a main component and an organic peroxide as a polymerization initiator, but for example, when an iron bolt or nut is fixed anaerobically, its breaking torque is only a very small value. Didn't show it. Ninth, unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and itafonic acid, and λ-hydroxyethyl (
meth)acrylate, co-hydroxypropyl(meth)
It is known that fCC air-curable compositions are made by adding monomers similar to hydroxyl group-containing (meth)acrylates such as acrylate and ethylene glycol monomethacrylate, but they are either effective or not effective in increasing fracture torque. 4) It had the disadvantage of being highly toxic to the skin, which caused problems in use.

In short, conventional anaerobic curable compositions used for applications such as Fi adhesion, sealing, and fixing have the following various drawbacks.

(1) Since the breaking torque is low, the effect of preventing loosening of the bolt donut is poor.

(λ) Compositions containing unsaturated carbonic acids such as methacrylic acid or hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl methacrylate improve the breaking torque somewhat, but are highly toxic to the skin and may cause rashes. Become.

With the aim of improving the disadvantages of conventional anaerobic curable compositions, the present inventors have developed a composition whose main component is a (meth)acrylic acid ester monomer blended with an organic peroxide polymerization initiator. As a result of searching for compounds that can improve the breaking torque of anaerobic curable compositions, we have discovered a series of compounds that exhibit significantly superior breaking torque even with the addition of only a small amount of violet, and have arrived at the present invention.

In other words, the anaerobic composition of the present invention with excellent fracturing torque is
In a composition comprising an anaerobically polymerizable (meth)acrylic acid ester monomer and an organic peroxide, the composition has a general formula (in each formula, R is H, CH, or C, H, selected from the group of compounds containing chlorine and phosphorous represented by At least one monomer is added to the (MeI) acrylic acid ester monomer to give at least 0. It is made by adding 1 amount of Oj9.

The composition of the present invention is an anaerobic curable composition with high breaking torque. That is, when this composition is used for fitting bolt donuts and shafts, it produces a high breaking torque and is therefore extremely effective in preventing loosening.

The main monomer used in the composition of the present invention is an acrylic ester and/or a methacrylic ester.

Examples of the acrylic ester and/or methacrylic ester, that is, the (meth)acrylic ester monomer, include ethers such as methoxyethyl (meth)acrylate, methoxydiethylene glycol (meth)acrylate, and methoxypolyethylene glycol (meth)acrylate. Type-functional (meth)acrylate; ethylene glycol di(meth)acrylate), /, j-butylene glycol di(methacrylate, neopentyl glycol di(meth)acrylate) alkylene functional (
meth/)acrylate; diethylene glycol di(meth)
Acrylate, polyethylene glycol di(meth)acrylate, polypropylene/glyfur di(meth)acrylate, triethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, ether type bifunctional (meth)acrylate; trimethylol Trifunctional (meth)acrylates such as propane tri(meth)acrylate, trimethylolethane tri(meth)acrylate; pentaerythritol tetra(meth)acrylate
acrylate, dipentaerythritol poly(meth)acrylate, polyfunctional (meth)acrylate of the tetramethylolmethanetetra(meth)aryl group; tetramethylolmethanetri(meth)acrylate, pentaerythritol tri(meth)acrylate, 2.3 - Containing polar groups or substituent atoms (meth) such as dibromopropyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, λ-chloroethyl (meth) acrylate, etc.
Acrylate; J, 2'-bis(4L-acryloxy-jethoxyphenyl)propane di(meth)acrylate, bisoxypolyethylated bisphenol A
- Epoxy (meth)acrylates such as di(meth)acrylate, bisoxypropylenated bisphenol A-di(meth)acrylate, bisoxy-hydroxyethylated bisphenol A-di(meth)acrylate: adipic acid-/, B- Polyester-type di(meth)acrylates such as Φsandiorouzi(meth)acrylate and the like are used. These (meth)acrylic esters may be used alone or in combination.

Further, in some cases, a small amount of other monomers other than the (meth)acrylic ester can be used in combination with these (meth)acrylic esters. Examples of other monomers that can be used in combination with item 7 include styrene and tetraethylene glycol dicrotonate.

The composition of the present invention comprises at least /S of the monomers selected from the group of compounds represented by the general formulas (A) and CB) as adhesion-imparting monomers. This is the most significant feature of the present invention.

As the adhesion-imparting polymer containing chlorine and phosphorus represented by the general formula (A), Hikiebabis (3-chlorocoacide phosphooxypropyl methacrylate) is used.
, bis(3-chloro-λ-acid phosphooxypropyl acrylate), and bis(na-chloro-3-acid phosphooxybutyl methacrylate), and chlorine and Examples of monomers containing / include 3-chlorocoacidphosphoxyprobyl metatarylate, 3-chlorocoacidphosphoxyprobyl acrylate, and ≠-chloro3-acidphosphocyptylmethacrylate. Acrylate etc. can be opened.

The amount of the monomer containing chlorine and phosphorus added is at least 1 t51 b of O,OS, preferably 0.7 to 70 t51 b, of the above-mentioned (meth)acrylic acid ester monomer.

Organic peroxide polymerization initiators in the compositions of the invention include, for example, keto/peroxides such as methyl ethyl ketone peroxide, cyclohecamperoxide, methylcyclohexane peroxide; benzoyl peroxide, lauroyl peroxide; , diacyl peroxides such as acetyl peroxide; peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxy acetate, electro-butyl peroxy maleate; diquil peroxide, di-t- Butyl peroxide, t-butyl cumyl peroxide, dialkyl peroxide groups; cumenohydrobar oxide, t-butyl hydroperoxide, p
-menthane hydroperoxide, methyl ethyl ketone hydroperoxide, diisopropylbenzene hydroperoxide, 2,j-dimethylhexane,
Examples include hydroperoxides such as 2,j-dihydroperoxide. Particularly preferred polymerization initiators are hydroperoxides. It is also possible to use two or more of these polymerization initiators in combination.The blending ratio of 1 polymerization initiator is 0 to the total amount of radically polymerizable monomers.
．． 0/~10.0 weight 9, preferably 0. /~70 weight 9.

In addition to the above-mentioned components, various substances can be added to the composition of the present invention for various purposes.

For example, polymerization accelerators such as O-benzoic sulfide, N,N-dimethyl-para-toluidine, or lauryl mercaptan are used to improve curing speed, and polymerization inhibitors such as quinones are used to improve stability. Filling with dyes or pigments for the purpose of thickening, filling with a ticlitropic agent for the purpose of imparting ticlitropy, and filling with a curable polymer for the purpose of thickening. I can do it.

The anaerobic curable composition of the present invention can be easily prepared by mixing and dissolving the above-mentioned components at room temperature or under heating.

Next, Examples and Comparative Examples of the present invention will be described in detail. In these examples, the portion indicates a heavy background portion.

In addition, the performance tests for each of the compositions obtained in these examples were conducted in accordance with the Japan Adhesive Industry Association standard ``Anaerobic Adhesive Test Method JJ''.
The following simple method was used in accordance with AIA-/RI7 (hereinafter referred to as "JAI standard").

(1) Measurement of adhesion strength The test specimen is a, based on the JAI standard, pitch fj (coarse) - 1 screw thread, joint length, nut thickness) mm.
Use a Bolt Fist Nut (MIO) and wash it with trichlorethylene.

The measurement method is to apply the composition to be tested to the thread between the bolt and nut mentioned above, tighten the nut with zero tightening torque (state 111 that can be moved with fingers without resistance), and then tighten the nut to 1. .In a constant temperature room at 2OC! Leave it for 44 hours and measure the breaking torque and escape torque based on JAI standards.

Examples/~-Reference Comparative Examples 7~/2 Anaerobically polymerizable methacrylic acid ester monomer, chlorine- and phosphorus-containing monomer of the present invention as an adhesion-imparting monomer, or a known adhesion-imparting monomer Monomers, organic peroxides, and accelerators were blended in the proportions shown in Table 1 and uniformly mixed and dissolved to prepare the compositions of Examples 214 and 214 and Comparative Examples 2 to 2.

Each of the obtained compositions was tested for breaking torque and escape torque according to the above test method. The result is
It was as shown in Table-7.

The compositions of each example have superior fracture torque compared to the compositions of comparative examples in which known adhesion-imparting monomers are blended or the comparative examples in which monomers containing chlorine and phosphorus are not blended.

Examples 3 to ≠ 9 Comparative Examples 13 to 1 10.7 parts of 4A-benzoquino and 3 parts of cumene hydroperoxide were added to 100 parts of Hirotriethylene glycol dimethacrylate, and further chlorine and phosphorus were added. Bis(3-chloro-2-acid phosphoxypropyl methacrylate) and/or 3 as a monomer containing
Anaerobic curable compositions were prepared by adding chloro-1-acid phosphoxypropyl methacrylate in various proportions shown in Table No. The breaking torque and escape torque of each of the six ml products obtained were measured, and the results were as shown in Table λ.

As is clear from the results in Table C, the addition i of monomers containing chlorine and phosphorus is at least O, OS, &
t96, preferably 0. / - / This is Toshiku 0ju.

If the amount is less than this violet, the effect of improving the breaking torque will be extremely small, and even if it is added more than this amount, no significant improvement in the effect will be observed.

In addition, when considering the results in Tables 1 and 2, compared to conventionally known adhesion-imparting monomers such as methacrylic acid and 2-hydroxyethyl methacrylate,
The monomer containing chlorine and phosphorus used in the present invention exhibits high breaking torque even when added in a very small amount. Therefore, it is very advantageous in terms of toxicity.

Patent applicant: Cemedine Co., Ltd. i　　　　　-、ノ

Claims (1)

[Scope of Claims] f A composition comprising an anaerobically polymerizable (meth)acrylic acid ester monomer and an organic peroxide, wherein the composition has a general formula (in each formula, R1 is H, CH , or C, H, and l is -CH, -1-C, H, -1-C, H, -1CH. Excellent breaking torque is achieved by adding at least seven types of monomers selected from the group of compounds containing O,OS to the (meth)acrylic acid ester monomer. Anaerobic curable composition. U. Claims in which the amount of the monomer selected from the group of compounds containing chlorine and phosphorus is 0.7 to 9 IO by weight based on the anaerobically polymerizable (meth)acrylate monomer. The composition according to item 7.