JPS58113276A - Anaerobically curable composition - Google Patents

Abstract

PURPOSE:The titled composition that is composed of radically polymerizable monomers such as an acrylate, contg. an organic peroxide polymerization initiator, a pyrazole compound and a pyrazolone compound as curing accelerators, thus showing high storage stability. CONSTITUTION:The objective composition is prepared by combining (A) radically polymerizable monomers mainly consisting of acrylates or methacrylate with (B) an organic peroxide polymerization initiator, preferably a hydroperoxide, (C) (i) a pyrazole, preferably pyrazole or 3,5-dimethylpyrazole, and (ii) a pyrazolone, preferably 3-methyl-5-pyrazolone, 1-phenyl-3-methyl-5-pyrazolone as curing accelerators where the amount of component B is, based on component A, 0.01- 10.0wt%, component C, 0.01-10.0wt%, and the weight ratio of (i) to (ii) is 2.95/ 0.05-0.05/2.95 in component C.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to acrylate and/or metal. The present invention relates to an anaerobic curable composition that contains acrylate as a main monomer component and can be instantly anaerobically cured. An anaerobic curable composition is a curable composition that easily polymerizes and cures by blocking air or oxygen in a space that is stable for a long period of time in contact with air or oxygen, such as between two surfaces. This composition is used for adhesion, sealing, locking, and fixing of fitting parts.

As this type of anaerobic curable composition, conventionally, arylate and/or methacrylate [hereinafter, these may be collectively referred to as "(meth)acrylate"] are used. ] was known as a monomer with organic peroxide as a polymerization initiator as the main component, but for example, iron bolts,
It took an extremely long time at room temperature to fix the nuts anaerobically. Furthermore, even if a polymerization accelerator such as tertiary azate, orthobenznulfimide, and dracin compounds are added to this type of composition, the anaerobic fixation may take several tens of minutes to several hours, and instantaneous However, anaerobic curing compositions for the purpose of instant curing are also known, which use a combination of mercaptan carbon esters and organic amines as curing accelerators. 2-≠6-73), this anaerobic curing composition has a short storage stability of only a few months.

To sum up, conventional anaerobic curable compositions have the following various drawbacks when used for adhesive, sealing, and fixing purposes.

(1) Due to the slow polymerization rate, the fixation time (set time) requires several tens of minutes to several hours, and the time required to reach the maximum strength is long. The storage stability of round, instant-curing products is extremely poor.

(...) Furthermore, even if the adhesive is instantly curable at the time of preparation, the ability of the accelerator decreases during long-term storage and the instant adhesive performance is lost.

(1v) In the end, in the past, some kind of additional means was required, such as making the composition instantly curable, or making it a two-component type, and the use of such a composition itself was problematic.

The present inventors improve the above-mentioned drawbacks in conventional anaerobic curable compositions. For this purpose, we searched for a compound containing an organic peroxide polymerization initiator to promote the polymerization (curing) of a radically polymerizable monomer whose main component is FC (meth)acrylate. It has been discovered that the combination of a pyrazole compound and a virazone compound exhibits an extremely excellent nonapolymerization (hardening) promoting effect, and the present invention has been achieved.

Pyrazole compounds and virazone compounds are excellent even when used alone, and have a curing accelerating effect (1?1
Please forgive me! j-/ reference λri No. 3, and j! -/41-7! (No. 7), when both compounds are used together, an even higher curing accelerating effect is exhibited.

That is, an organic peroxide polymerization initiator, at least seven types of pyrazole-based compounds, and at least seven types of pyrazolone-based compounds are added to the 1j11Fi of the present invention, a radically polymerizable monomer containing acrylate and/or methacrylate as a main component. This is an anaerobic curable composition.

The composition of the present invention cures instantly anaerobically and has a long-term O
It is an excellent anaerobic curable composition that does not gel or deteriorate its anaerobic curing ability even when stored with iEK. That is, if air is blocked between the composition line, for example, between two adjacent surfaces, polymerization will start in just a few seconds at room temperature, and the purpose of adhesion, sealing and fixing can be achieved in a few minutes. Moreover, despite its medium curing speed, it has excellent storage stability, being stable for 7 years at room temperature and 30 days under jOc heating conditions. or the strength of adhesion or adhesion will not decrease. Therefore, this composition does not require the use of a primer or the heating 4! required to achieve instant adhesion in conventional anaerobic curable compositions. is not required at all.

The monomer in the present invention is a radically polymerizable monomer containing acrylate and/or methacrylate as a main component,
Those consisting only of acrylate and/or methacrylate are preferred.

Atarylates and/or dimethylacrylates, i.e., (meth)acrylates include nine alkyl groups such as methyl (meth)acrylate, ethyl (meth)acrylate, stearyl (meth)acrylate, and benzyl (meth)acrylate. or substituted alkyl type acrylates, alkyl type double-blind (meth)acrylates such as neobentyl glycol di(meth)acrylate; diethylene glycol di(meth)arylate, polyethylene di9
Ether-type difunctional (meth)acrylate 5#I such as ful di(meth)acrylate, polypropylene dalycol di(meth)acrylate, triethylene dalycol di(meth)acrylate, and tetraethylene glyfur di(meth)acrylate; Methylolpropane tri(meth)
Trifunctional (meth)acrylates such as acrylate and trimethylolethane tri(meth)acrylate; multifunctional poly(meth)acrylates such as pentaerythritol tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, and tetramethylolmethanetetra(meth)acrylate (
meth)acrylate; λ-hydroxyethyl (meth)acrylate, tetramethylolmethane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, co,3-dibutetramuprovir (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, λ−
Chloroethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate Cicada's polar group is substituted atom-containing (meth)acrylate);, 2,2'-bis(≠-acryloxyjetoxyphenyl)propane di(meth)acrylate , bisoxypolyethylated bisphenol A
-di(meth)acrylate, bisoxypropylenated bisphenol A--, >(meth)acrylate, bisoxy-1-hydroxyethylated bisphenol A-di(
Epoxy (meth)acrylates such as metacoacrylate; adipic acid-/, 4-hemanadioluge (meth)
Polyester type di(meth)acrylates such as acrylates; and urethane(meth)acrylates. These (meth)acrylates may be used alone or in combination of two or more, and in some cases, other monomers other than (meth)acrylates may be added to these (meth)acrylates. can be used together in small amounts. Examples of other monomers that can be used in combination include styrene, tetraethylene glycol ditarotonate, and the like.

Examples of the organic peroxide polymerization initiator in the present invention include methyl ethyl ketone peroxide, cyclohexane peroxide, methylcyclohexane peroxide-based ketone/(-oquinides; benzoyl peroxide, lauroyl peroxide, acetyl peroxide, etc. Diasilver oxides; Peroxy esters such as t-phthyl peroxybenzoate, t-butyl peroxy acetate, and t-butyl peroxy maleate; dicumyl peroxide, di-1-butyl peroxide, Dialkyl peroxides such as t-butylcumyl peroxide; cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, methyl ethyl ketone hydroperoxide, diisopropylbenzene hydroperoxide, λ,!-dimethylhexane Examples include hydroperoxides such as 21!-cybide rubber oxide.Particularly preferred polymerization initiators are hydroperoxides.Two or more of these polymerization initiators can be used in combination.Polymerization initiation The blending ratio of the agent is o, o7 to io with respect to the total amount of radically polymerizable monomers.
, o weight 9, preferably 0.7 to 7.0 weight 9.

The most distinctive feature of the present invention is the combined use of a pyrazole compound, which is a specific curing accelerator, and a pyrazolone metal compound.KT
oru.

The pyrazole compound refers to a pyrazole represented by the tautomeric formula of Shimani, and a compound in which each hydrogen atom is substituted with a substituent or a substituent atom.

HC-CHHC=CH 1111□ 11 Specific examples of the pyrazole compound include pyrazole; 3-methylpyrazole,! -Methylpyrazole, /, 3-dimethylpyrazole, /, ≠-dimethylpyrazole, /,! -dimethylpyrazole, j, +-dimethylpyrazole, 4<, j-dimethylpyrazole, 3
．． 3-dimethylpyrazole, /, 3, trimethylpyrazole, /, 3.3-trimethylpyrazole, /1 shot, t-)dimethylpyrazole, /-phenylpyrazole, 3-phenylpyrazole, t-phenylpyrazole,
Na-phenylpyrazole, 3-methyl-/-phenylpyrazole,! -Methyl-/-phenylhyrasole, +-
M+L/-phenylpyrazole, /-methyl-3-phenylpyrazole, /-methyl-yo-phenylpyrazole, 3-methyl-! -phenylpyrazole, j, 41-
Dimethyl-/-phenylvirazole, ≠, j-dimethyl-/-phenylpyrazole, 3. j-dimethyl-/-phenylpyrazole, /, 3-diphenylpyrazole, /
,j-diphenylpyrazole,/,3,tIL-)diphenylpyrazole,/,3. ! -Tripheelpyrazole, /, II,! -Triphenylpyrazole, /-benzylpyrazole, /-benzoylpyrazole type alkyl and/or -arylpyrazole 04 bodies; -Chlorvirazole, ≠-brompyrazole, q-dopyrazole, ≠-chloro-3-methylpyrazole , ≠-chloro-7-phenylpyrazole, ≠-prom-7-phenylhyrasole, ! - halogenated pyrazole I conductor in the group of chloro-3-methylpyrazole;
-Ethoxy-/-phenylpyrazole, β-me), β-fif-phenylpyrazole,! -ethoxy 3-methyl-7-phenylvirazole, j-me) now! -Methyl-/-phenylpyrazole, /-oxymethylpyrazole, /-oxymethyl-3 (Fig.
)-Methylpyrazole, /-oxymethyl-3,3-dimethylpyrazole, l-oxymethyl-3,≠(or≠,j]-dimethylpyrazole, 3-oxymethylpyrazole, 3-odP'/)fruvirazole , t-oxymethyl-i,J,β-)dimethylpyrazole, dar(
Sibylazole derivatives in alcohols such as I-oxyethyl)pizole; ≠-nitropyrazole, Hiro-J=nidro-
Phenylhyrasole, 3(or j)-methyl-≠-
Nitropyrazole, /, J-dimethyl-≠-nitropyrazole, /, J-dimethyl-nitrovirazole, nonitropyrazole derivative; Hiro-nitrosohirazole, ≠
-nitroso/-7 ale pyrazole, 3 (or 1t
j) Nitrosopyrazole derivatives such as -methyl-≠-nitrosopyrazole, l,3-dimethyl-≠-nitronepyrazole; 3 (FjL< is j)-aminopyrazole,
≠-aminopyrazole, j(i-flj)-amino-
3 (or Hari-7 Alevirazole,!-Amino 3
-Methyl-/-phenylpyrazole, 3-7217/
-j-phenylpyrazole, ≠-74/-, 3. jt-
dimethyl-/-phenylpyrazole, ≠-amino/,
3.3-) dimethylpyrazole, 3. ! -diaminopyrazole, /-dimethylamitsumethylpyrazole, 3-(
β-Acinoethyl)pyrazole, San-(β-Aminoethyl)L? /-ru, cubenzeneazo/-phenylpyrazole, ≠-(β-adenoethyl)-/-benzylpyrazole, ≠-benzeney7zoj-methyl-7-phenylpyrazole% seabenzeneazo-3-methyl-7 -1111 avirazoles such as pyrazole, hiro-(p-aminophenyla ζ)) pyrazole; j-pyrazole aldehyde,! -Methyl-7-pheervirazole-3-aldehyde, /-phenylpyrazole-!
-aldehyde, j(li or 3)-ethoxycarbonylpyrazole-3 (or polyaldehyde, 3,3-
dimethyl-/-phenylpyrazole-hiro-aldehyde,
j-methyl-/, 3-1>phenylpyrazole-≠-aldehyde, +, t-pyrazole dialdehyde, 3-ethoxycarbonyl-t,! - Aldehyde pyrazole derivatives of the virazole-dicarboxaldehyde group; 3 (or Hir-acetyl-Hiro-methylpyrazole, Hiroshi-acetyl-/-phenylpyrazole, 3-Aryuthyl-!-methyl-/-phenylpyrazole, J, 3- Diacetyl Tei
Methyl pyrazole, 3. j-Diacederu≠-phenylpyrazole, /-benzoylpyrazole, combined-penzoyl-/-phenylpyrazole, ≠-benzoyl-7°!
- pyrazole ketone derivatives based on diphenylpyrazole;
/-pyrazolecarboxylic acid, 3 (or j) pyrazolecarboxylic acid, +-pyrazolecarboxylic acid, ≠-methyl-3-pyrazolecarboxylic acid, /, Hiro-dimethyl-3-
Pyrazole carboxylic acid, /, 4'-dimethyl-3-pyrazole carboxylic acid,! -Methyl-3-pyrazolecarbo/acid, 3. j-pyrazoledicarboxylic acid, j-phenyl-3-pyrazolecarboxylic acid, 3. Hiroshi (or Fi, +
, t)-Hirasolsica, rubonic acid, /-phenyl-3
, goovirazole dicarboxylic acid, j-methyl-3, derpyrazole dicarboxylic acid, 3゜j-virazole dicarboxylic acid, /-phenyl-3,! -Pyrazoledicarboxylic acid, 3-ether-/-phenyl-3-pyrazolecarboxylic acid,! -ethyl-7-phenyl-J-'razolecarbonyl-544-ethol-J, -L'razoledicarboxylic acid, phenyl-3゜j-pyrazoledicarboxylic acid, j,4',j-pyrazole tricarboxylic acid, oxy-3(or j)-pyrazolecarboxylic acid, t-
# * '/ -/-Phenyl-3-pyrazolecarboxylic acid derivative of pyrazolecarboxylic acid; oxypyrazole-3,J-ethyl dicarboxylate %≠-methyl-2
- pyrazole carboxylic acid ester crocodile conductor such as pyrazole-3, methyl j-dicarboxylate, ethyl t-pyrazolecarboxylate, methyl 3 (or more specifically 3)-pyrazolecarboxylate; and! -Mercapto λ, 3-dimethyl-/-
Phenylpyrazole (thiopyrine), 3-methyl-j-
Methyl mercaf) -/- phenylpyrazole,! Examples include mercaptopyrazole derivatives such as -mercapto-3-methyl-7-phenylpyrazole and j-methylmercapto-3-methyl-/-phenylpyrazole.

Pyrazole compounds used in combination with pyrazole compounds include 3-pyrazolone, Hiro-pyrazolone,! - pyrazolones and compounds in which the hydrogen atoms of each of these pyrazolones are replaced by other atoms and/or Fi atomic groups.

3-pyrazolone is a compound represented by the structural formula, and goupyrazolone is a compound represented by the structural formula 1)1. ! t-pyrazolone is a compound with a structural formula of In addition to the hydrogen atom, halogen atom, and oxygen atom (also referred to as the oxy-iso group) in each pyrazolone compound,
[Child s alkyl group, phenyl group, nitrophenyl group, nitro group, nitroso group, isonitroso group, acylamido group, acylide group, carboxyl group, carboxylated alkyl group, carboalkoxyl group, sulfonic acid group, *
F axyl groups, halogen-substituted alkyl groups, pentyloxy groups, and other atomic groups such as 7 or 7 or more types of atomic groups substituted with pyrazolone-conductor molecules in these pyrazolone compounds. Pyrazolone derivatives in which two or three of these are dehydrogenated to each other or bonded to each other with an al)dF rene group such as a methylene group interposed therein are also used as the curing accelerator of the present invention. When used in combination with a pyrazole compound, 7 can be obtained.

Specific examples of these pyrazolones and their derivatives include:
For example, 3-pyrazolone, ≠-pyrazolone, 3-pyrazolone; J-)thiru-j-pyrazolone, ≠-methyl-7-
Pyrazolone, 3(or j)-phenyl-! (or 3)-pyrazolone, /-phenyl-3-methyl-! −
Pyrazolone, /-phenyl-3-ethyl-3-pyrazolone, 3-n-/'ropyruj-pyrazolone, 3-n-
Butyl-3-pyrazolone, l-phenyl-≠-methyl! -pyrazolone, /-phenyl-j, hiro-silchiru 3
-pyrazolone, /-phenyl-! -Methyl-3-pyrazolone, /, 3-dimethyl-! -pyrazolone, /, j-dimethyl-3-pyrazone, /-phenyl≠-methyl-
3-Alkyl and/or monomonolylated pyrazolone derivatives such as pyrazolone; ≠-etro! -pizzolone, 3-methyl-hiro-edro-3-pyrazone, /-CP-nitrophenyl) -J-ifru≠-etro-j-pyrazolone (also known as pitaloronic acid a), / (p-nitrophenyl)-3- Methyl +, +'-dinitro! -pyrazolone, ≠, μ'-bis(/-(p-nitrophenyl)-
j-pyrazolone] pyrazocyst derivative containing a group of the genus fathom;
/-Phenyl-tris-nitroso-omethyl-3-pyrazolone, j-)? Lou≠-nido shisoj-! 5 Zolone-based nitroso group-containing pyrazolone derivatives -isoetroso-3-pyrazolone, 3-methyl-guinnitroso-j
- isonitroso group-containing pyrazolone derivatives such as pyrazolone;
3-phenyl-≠, 44-dibu pmu j-pyrazolone%
'/-Methyl-2-phenyl-sulfur-bromo-j-boommethyl-3-pyrazolone and other halogen-containing birazo pn #S conductors: 3-benzamide-! -pyrazolone, 3-acedoζdoj-pyrazolone, /-methyl-3-benzamide-! - Amidated hilazolone derivative of pyrazolone group; /-A7? Lou 3 - Acetoxy! -pyrazolone acetylimide, /-methyl-3-oxy-j-pyrazoloneimide, 3 (or ij j )-pyrazoloneimide, /-7er-3-methyl-! -Hirazolone (#)'
,/CP-nitrophenyl)-3-methyl-! -Pyrazoloneimide, 3-pentyloxy-/-methylpyrazolone-! -benzoylimide, 3-oxy-/-methylpyrazolone-j-benzoylimide, 3-oxene-phenyl-! - Imidized pyrazolone enzyme conductors such as pyrazolone imide: j-pyrazolone-3-carboxylic acid, s-
Pyrazolone-≠-carboxylic acid, no-methyl-j-pyrazolone-j-1-carboxylic acid, /-phenyl-j-pyrazolone-carboxylic acid, /-phenyl-3-pyrazolone-carboxylic acid, j(, fL<aj )-pyrazolone-≠-
Ylacetic acid, /-phenyl-! - a carboxyl group-containing pyrazolone derivative based on hyrazolone-3-ylpropion;
l-methyl-! -ethyl pyrazolone-3-carboxylate,
Ethyl 3-pyrazolone-3-yl acetate,! - Methyl pyrazolone-3-ylpropionate, carboalfxyl group-containing pyrazoquaternine derivative based on methyl phenyl-yy-virazon-3-ylpropionate; 3-methyl-j-pyrazolone-sulfonic acid, j- Pyrazolone-≠-sulfonic acid group-containing pyrazolone derivative; /-phenyl-3-oxy-3-pyrazolone, Hiroshi, 1I-1)
Engineering f roux 3-o middle sea/-phenyl-! - Hydroxyl group-containing pyrazolone trout conductor of Pyrazolone Gin: 3-methyl-oxo-7-pheeru! -Hirazolone, /
, oxopyrazolone derivatives such as 3-simefl-l-osho-j-pyrazolone and the like.

The curing accelerator in the present invention is a combination of seven or two or more of the above-mentioned nine pyrazole compounds and one or two or more of the pyrazolone compounds. Furthermore, if necessary, other curing accelerators such as organic acids, inorganic acids, amides, imides, etc. (
This is sometimes referred to as a "co-promoter" and can be used in combination with ). By using such a co-promoter in combination, the effect of accelerating curing can be further enhanced, and at the same time, storage stability may be improved.

Such promoters include L%9, for example monoethylamine,
Aliphatic amines such as diethylamine, triethylamine, cyclohexylamine, benzyl 7-in, N,N-dimethylandylene;
-toluidine, N,N-dimethyl-p-)luidine,
N,N-dimethyl-o-)luidine, N-dimethyl-m-)luidine, N-dimethylaniline, N,
Aromatic amines such as N-diethylaniline; /, λ, J
, Reference? (k) Complex amines such as quinoline, piperidine, pyridine, N-methylpyrrolidone, piperazine, pyridine, viroline, pyrrole, pyridine;
Acetic acid, monochloroacetic acid, dichloroacetic acid, tritaloacetic acid, benzoic acid, narachilic acid, orthonitrobenzoic acid, phenol, p-nitrophenol, hyfuric acid,
ll, p-) Organic acids such as luenesulfonic acid, methacrylic acid, sieic acid, sulfosalicylic acid, λ-mercaptopropionic acid, thioglycolic acid, ascorbic acid, sulfinic acid, phenoic acid, gallic acid, actaric acid, methacrylic acid, etc. II
! ! Inorganic acids such as phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid; compounds such as benzide and formamide; and imides such as fumerimide, succinimide, and O-benzoic sulfide.

The blending ratio of the curing accelerator in Kj+P of the present invention is the total amount of the pyrazole compound and the pyrazolone compound, and the radically polymerizable monocap K? j, usually 0.01 to 10.0
The weight is 96, and the weight is 9.

Various substances can further be added to the composition of the present invention for various purposes. For example, dyes and I
I4 material, a quinone-based polymerization inhibitor for the purpose of improving stability, a thixotropic agent for the purpose of imparting thixotropy, a soluble polymer for the purpose of thickening, and a plasticizer for the purpose of adjusting the adhesion strength. A filler can be added to each for the purpose of thickening or increasing the volume.

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

Next, an example of the present invention and a comparative example will be described in detail. The parts/1i rich parts in these examples are shown.

In addition, the performance tests for each composition obtained in these examples were conducted in accordance with the Japan Adhesive Industry Standards "Anaerobic Adhesive Side Test Method JA
IIs-/Re7 (hereinafter abbreviated as "rJAI standard") K compliance, and the following simple method was used.

(/) Bolts and nuts (M 10) with a pitch tj (coarse), thread grade λ class, joint length and nut thickness) j mm were prepared based on the FiJAI standard on a hardening speed ilj constant test specimen. This was used after washing with trichlorethylene.

The preparation method is to mix the composition to be tested with the bolts and
Apply it to the threads between the nuts, tighten the nuts with zero tightening torque (1li that you can move them with your fingers without resistance), leave them in a constant temperature room at -120'C, and let them harden for 9 hours (bolts).・The time until you feel resistance when turning it with your fingers), the fixation time (the time until you can no longer move it with your fingers), and the tube side.

(-) Measurement of adhesive strength The same bolts and nuts as above were coated with the composition and left in a constant temperature room at 20C for 2≠ hours, and the failure torque and escape torque tIIIJ were determined based on the JAI standard. good.

(3) Measurement of storage stability Gelation time on IOC was measured.

To measure the gelation time of lOC, place the composition to be tested in a glass test tube and place it in a glass tube.

The time required for the sample to gel was measured while keeping the sample at a temperature of 100 mL/C. It is said that if the gelation time of IOC is 60 minutes or more, it can be stored at room temperature for 7 years or more.

Example/~2g Comparative example/~λ7 100 parts of triethylene glycol dimethacrylate,
/, tII--benzoquinone o, og parts and 1 part of cumene hydroveroxide are added, and each compound listed in Table 7 is added as a curing accelerator in the number of parts listed in 1+:n-7. The compositions of Examples and Comparative Examples were
#L.

Each of these compositions was tested for cure speed, storage stability, and adhesive strength according to the test methods described above.

The results are shown in Tables 1 and 2. The compositions of each example were compared with comparative examples containing known curing accelerators.
Compositions of Comparative Example/-1 in which a pyrazole compound and a pyrazone compound were used alone, Compositions of Comparative Examples λ7 to -7 in which a known promoter was added to a pyrazole compound or a pyrazolone compound. It has a medium curing speed, excellent storage stability, and high adhesive strength compared to other materials.

Example 29 To 100 parts of triethylene glycol dimethacrylate, ≠-benzoquinone o, og part and cumene hydroperoxide part were added, and further 3. ! -Dimethylpyrazole and 7-phenyl-3-methyl-3-pyrazolone were blended in various ratios shown in Table 2 to prepare anaerobic curable compositions. For each composition obtained, the curing speed, storage stability, and adhesive strength were added by 111, and the results are shown in Table C. If the total amount of curing accelerator added is too small, the curing speed will be 3.j-dimethylvirashield 7-
The blending ratio of phenyl-3-methyl-3-pyrazolone,
The effect of combined use is remarkable over a wide range of 0.0! to 0, OJ:13.

Example 30 l, ≠-benzoquinone o, o, r parts based on 100 parts by weight of triethyleneglyfur dimethacrylate, 3.
45 parts of j-dimethylpyrazole and 63 parts of /-phenyl-3-methyl-j-pyrazolone were added, and cumene hydroperoxide was further added as a polymerization initiator at various ratios shown in Table 3 to obtain anaerobic curability. Composition Tk was prepared. The curing speed, storage stability, and adhesive strength of each of the resulting compositions were measured.

The results are shown in Table 3. If the amount of polymerization initiator is too small, the curing speed will be slow, and if it is too large, the storage stability will be poor.

Examples 37-3 For 100 m of the radically polymerizable (meth)acrylate shown in Table ≠, respectively /1 tlt-benzoquinone o, o r part, cumene hydroperoquinide part, 3,3-dimethyl An anaerobic curable composition was prepared by adding 1.3 parts of pyrazole and 70,743 parts of /-phenyl-3-methyl-j-pyra.

The results of measuring the curing rate, storage stability, and adhesive strength of each of the compositions of T. and T. et al. are shown in Table q.

From these results, it was found that the combination of 3゜j-dimethylpyrazole and 7-phenyl-3-methyl-j-pyrazolone as a curing accelerator is extremely effective against various radically polymerizable (meth)acrylates; In this case, an excellent anaerobically curable composition was also obtained.

Example DA-≠7 Comparative Example 2g Triethyleneglyfur dimethacrylate 100mK was treated with 7.0% as a polymerization inhibitor. ≠-0.01 part of benzoquinone and 3,j-dimethylpyrazole 43 as a curing accelerator
part and/-phenyl-3-methyl-j-pyrazone A!
% and further as a polymerization initiator. An anaerobic curable composition was prepared by adding a portion of each of the various organic peroxides described in .

For comparison, a composition was prepared in the same manner except that no polymerization initiator was added (Comparative Example 1).

Each of these compositions was tested for curing speed, weighing stability, and adhesive strength. The results are shown in Table J. Although each organic peroxide is effective as a polymerization initiator, hydroperoxides are preferred because they have a fast curing speed and high adhesive strength.

Example 1, r-A, 27,000 g parts of triethylene glycol dimethacrylate, 27,000 g parts of benzene, v parts of cumene hydroperoxide, 3,3-dimethylpyrazole as a curing accelerator, j parts and/ -phenyl-3-methyl-j
- anaerobic curable composition ty4 was prepared by adding 70,743 parts of Pyra 70,743 parts and further adding 7 parts each of various known promoters shown in Table 6.◎Cure of each of these compositions The results of measuring speed, storage stability, and adhesive strength are shown in Table-
As shown in 6.

The results of the examples shown in Table 1 and the ratio examples 7q to 7 of combinations of known curing accelerators and co-accelerators shown in Table 1
As is clear from the comparison of curing properties, the curing speed and storage stability can be further improved by combining the curing accelerators used in the present invention and adding a known co-accelerator. To improve the sex #1 of the young fruit, known hardening accelerators and accelerators are added together.

Claims (1)

[Scope of Claims] t A radically polymerizable monomer containing acrylate and/or memethacrylate as a main component, an organic peroxide polymerization initiator, at least seven pyrazole compounds as a curing accelerator, and a bitzone-based An anaerobic curable composition comprising at least seven types of compounds. Upyrazole-based compounds are pyrazole, FiJ, J-
The composition according to claim 7, which is dimethyl pyrazole. 1 Pyrazolone compound is 3-methyl-! -Pyrazolone or/-phenyl-3-methyl-j-pizzolone in Claim Ii! ! The composition according to item 7 or item 2. B. The composition according to claim 1, 2 or 3, wherein the total amount of the curing accelerator is 0.0/~io, o9 by weight based on the radically polymerizable monomer. . The blending ratio of the pyrazole compound and the pyrazolone compound is j: 0.0j to 0.0j in terms of weight ratio. t: up to Utah. Direct organic peroxide polymerization initiator is radically polymerizable JlIL
Iw1. The composition according to claim 1, 2, 3, 1 or 3, wherein αQ/~Iα0 Oho-maru is