JPS6410534B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to an anaerobically curable composition that contains acrylate and/or methacrylate as a main monomer and can be instantly anaerobically cured. 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, loosening prevention, fixing of fitting parts, etc. of metal parts, etc. Conventionally, this type of anaerobic curable composition has a monomer mainly composed of acrylate and/or methacrylate (hereinafter, these may be collectively referred to as "(meth)acrylate") and a polymerization initiator. However, it took an extremely long time at room temperature to anaerobically fix iron bolts and nuts, for example.
Furthermore, even if a tertiary amine, orthobenzsulfimide, hydrazone compound, etc. are added as a polymerization accelerator to this type of composition, it takes tens of minutes to several hours for the anaerobic fixation, and instant curing is slow. It was far away. In addition, anaerobic curable compositions for instant curing that use a combination of mercaptan carboxylic acid or its ester and organic amines as a curing accelerator are also known (see Japanese Patent Publication No. 46273/1983). Anaerobic curable compositions have a short storage stability of several months. In short, conventional anaerobic curable compositions
When used for purposes such as sealing and fixing, there were various drawbacks as described below. (i) Due to the slow polymerization rate, several tens of minutes to several hours are required for fixing time (set time), and it takes an extremely long time to obtain the maximum strength. (ii) Those made instant-curable using a polymerization accelerator have extremely poor storage stability. (iii) 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. (iv) In the end, conventionally, in order to achieve instant curing and improve storage stability, some additional means such as using a surface activator such as a primer, curing by heating, or making it a two-component type were required. However, the use of such a composition itself was inconvenient. In order to improve the above-mentioned drawbacks of conventional anaerobic curable compositions, the present inventors developed a radically polymerizable monomer containing (meth)acrylate as a main component blended with an organic peroxide polymerization initiator. As a result of searching for compounds that promote the polymerization (curing) of , they discovered a series of compounds that have an extremely excellent effect of promoting polymerization (curing), and arrived at the present invention. That is, the present invention provides 3-pyrazolone, 4-pyrazolone, and 5-pyrazolone to a radically polymerizable monomer mainly composed of acrylate and/or methacrylate.
At least one curing accelerator selected from the group consisting of pyrazolones and pyrazolone derivatives corresponding to compounds in which the hydrogen atom of each of these pyrazolones is replaced with another atom and/or an atomic group, and an organic peroxide. This is an anaerobic curable composition containing a polymerization initiator. The composition of the present invention is an excellent anaerobic curable composition that instantly cures anaerobically and does not gel or lose its anaerobic curing ability even after long-term storage. That is, if this composition blocks air between two adjacent surfaces, for example,
Polymerization starts 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 fast curing speed, it has extremely good storage stability, being stable for one year at room temperature and 40 days under heating conditions of 50℃, during which time it will not gel or deteriorate its instant curing performance. or the strength of fixation or adhesion will not decrease.
Therefore, this composition does not require the use of a primer or heating at all, which are necessary to achieve instant adhesion with conventional anaerobic curable compositions. The monomer in the present invention is a radically polymerizable monomer containing acrylate and/or methacrylate as a main component, and preferably consists only of acrylate and/or methacrylate. the acrylate and/or methacrylate,
In other words, examples of (meth)acrylate include methyl (meth)acrylate and ethyl (meth)acrylate.
Alkyl or substituted alkyl type monofunctional (meth)acrylates such as acrylate, stearyl (meth)acrylate, benzyl (meth)acrylate; methoxyethyl (meth)acrylate;
Methoxydiethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)
Ether type monofunctional (meth)acrylate such as acrylate; ethylene glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate
Alkylene type bifunctional (meth)acrylates such as acrylate, neopentyl glycol di(meth)acrylate; diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate; ) acrylate, ether-type bifunctional (meth)acrylates such as tetraethylene glycol di(meth)acrylate; trifunctional (meth)acrylates such as trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate; pentaerythritol Polyfunctional (meth)acrylates such as tetra(meth)acrylate, dipentaerythritol poly(meth)acrylate, tetramethylolmethanetetra(meth)acrylate; 2-hydroxyethyl(meth)acrylate, tetramethylolmethanetri(meth)acrylate, Polar groups or substituted atoms such as pentaerythritol tri(meth)acrylate, 2,3-dibromopropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, 2-chloroethyl(meth)acrylate, dimethylaminoethyl(meth)acrylate, etc. Containing (meth)acrylate; 2,2'-bis(4-acryloxy-diethoxyphenyl)propane di(meth)acrylate, bisoxypolyethylated bisphenol A-di(meth)acrylate,
Epoxy (meth)acrylates such as bisoxypropylenated bisphenol A-di(meth)acrylate, bisoxy-2-hydroxyethylated bisphenol A-di(meth)acrylate; adipic acid-1,6-hexanediol-di( Polyester type di(meth)acrylate etc.
Acrylate; and urethane (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more. Furthermore, in some cases, a small amount of other monomers other than (meth)acrylates may be used in combination with these (meth)acrylates. Examples of other monomers that can be used in combination include styrene, tetraethylene glycol dicrotonate, and the like. Examples of the organic peroxide polymerization initiator in the present invention include ketone peroxides such as methyl ethyl ketone peroxide, cyclohexane peroxide, and methyl cyclohexane peroxide; diacyl peroxides such as benzoyl peroxide, lauroyl peroxide, and acetyl peroxide. ; Peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxy acetate, t-butyl peroxy maleate; dicumyl peroxide, di-
Dialkyl peroxides such as t-butyl peroxide and t-butylcumyl peroxide;
Cumene hydroperoxide, t-butyl hydroperoxide, p-menthane hydroperoxide, methyl ethyl ketone hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5
- Hydroperoxides such as dihydroperoxide and the like can be mentioned. Particularly preferred polymerization initiators are hydroperoxides. Two or more of these polymerization initiators may be used in combination depending on the case. The blending ratio of the polymerization initiator is 0.01 to 10.0% by weight, preferably 0.1 to 7.0% by weight, based on the total amount of radically polymerizable monomers. In the present invention, 3-
The present invention uses pyrazolone, 4-pyrazolone, 5-pyrazolone, and pyrazolone derivatives corresponding to compounds in which the hydrogen atom of each of these pyrazolones is replaced with another atom and/or an atomic group. This is the biggest feature of . What is 3-pyrazolone? Structural formula 4-pyrazolone is a compound represented by the structural formula 5-pyrazolone is a compound represented by the structural formula Each of these pyrazolone compounds can be effectively used as a curing accelerator in the present invention, and the hydrogen atom in each of these pyrazolone compounds is a halogen atom, an oxygen atom (also known as an oxo group). Other atoms such as alkyl groups, phenyl groups, nitrophenyl groups, nitro groups, nitroso groups, isonitroso groups, acylamido groups, acylimide groups, carboxyl groups, carboxylated alkyl groups, carboalkoxyl groups, sulfonic acid groups, hydroxyl groups , pyrazolone derivatives corresponding to compounds substituted with one or more atomic groups such as halogen-substituted alkyl groups and benzoyloxy groups, and furthermore, two of these pyrazolone compounds or pyrazolone derivative molecules mutually dehydrate. Pyrazolone derivatives corresponding to elementary bonds can also be effectively used as the curing accelerator of the present invention. Specific examples of these pyrazolones and their derivatives used as curing accelerators include 3-pyrazolone, 4-pyrazolone, 5-pyrazolone; 3-methyl-5-pyrazolone, 4-methyl-5-pyrazolone, 3-methyl-5-pyrazolone, (or 5)-phenyl-
5 (or 3)-pyrazolone, 3-methyl-1-
Phenyl-5-pyrazolone, 3-ethyl-1-phenyl-5-pyrazolone, 3-n-propyl-5
-Pyrazolone, 3-n-butyl-5-pyrazolone, 4-methyl-1-phenyl-5-pyrazolone, 3,4-dimethyl-1-phenyl-5-pyrazolone, 5-methyl-1-phenyl-3-pyrazolone , 1,3-dimethyl-5-pyrazolone, 1,
5-dimethyl-3-pyrazolone, 4-methyl-1
-alkyl such as phenyl-3-pyrazolone and/or
or arylated pyrazolone derivative; 4-nitro-
5-pyrazolone, 4-nitro-3-methyl-5-
Pyrazolone, 3-methyl-4-nitro-1-(p
-nitrophenyl)-5-pyrazolone (also called picloronic acid), 3-methyl 4,4'-dinitro-1-(p-nitrophenyl)-5-pyrazolone,
4,4'-bis[1-(p-nitrophenyl)-5-
Nitro group-containing pyrazolone derivatives such as pyrazolone; 5-methyl-1-phenyl-4-nitroso-
3-pyrazolone, 3-methyl-4-nitroso-5
- Nitroso group-containing pyrazolone derivatives such as pyrazolone; isonitroso group-containing pyrazolone derivatives such as 4-isonitroso-5-pyrazolone and 4-isonitroso-3-methyl-5-pyrazolone; 3,4-dibrom-3-phenyl-5-pyrazolone , 3, 4
-dibromo-3-phenyl-5-pyrazolone,
Halogen-containing pyrazolone derivatives such as 4,4-dibromo-3-phenyl-5-pyrazolone, 4-bromo-5-bromomethyl-1-methyl-2-phenyl-3-pyrazolone; 3-benzamide-5-pyrazolone, 3- acetamido-5-pyrazolone,
Amidated pyrazolone derivatives such as 3-benzamido-1-methyl-5-pyrazolone; 3-acetoxy-1-acetyl-5-pyrazolone acetylimide, 3-oxy-1-methyl-5-pyrazolone imide, 3 (or 5) -pyrazolone imide, 3-
Methyl-1-phenyl-5-pyrazoloneimide,
3-Methyl-1-(p-nitrophenyl)-5-pyrazoloneimide, 3-benzoyloxy-1-methylpyrazolone-5-benzoylimide, 3-oxy-1-methylpyrazolone-5-benzoylimide, 3-oxy- Imidized pyrazolone derivatives such as 1-phenyl-5-pyrazolone imide; 5-pyrazolone-3-carboxylic acid, 5-pyrazolone-4
-carboxylic acid, 1-methyl-5-pyrazolone-3
-Carboxylic acid, 1-phenyl-5-pyrazolone-
Carboxyl group-containing pyrazolones such as 4-carboxylic acid, 1-phenyl-3-pyrazolone-4-carboxylic acid, 3 (or 5)-pyrazolone-4-yl acetic acid, 1-phenyl-5-pyrazolone-3-ylpropionic acid Derivative; ethyl 1-methyl-5-pyrazolone-3-carboxylate, 5-pyrazolone-3-
Carboalkoxyl group-containing pyrazolone derivatives such as ethyl yl acetate, methyl 5-pyrazolon-3-ylpropionate, and methyl 1-phenyl-5-pyrazolon-3-ylpropionate; 3-methyl-5
- Sulfonic acid group-containing pyrazolone derivatives such as pyrazolone-4-sulfonic acid and 5-pyrazolone-4-sulfonic acid; 3-oxy-1-phenyl-5-pyrazolone, 4,4-diethyl-3-oxy-1-phenyl Hydroxyl group-containing pyrazolone derivatives such as -5-pyrazolone; 3-methyl-4-oxo-1
-Phenyl-5-pyrazolone, oxopyrazolone derivatives such as 1,3-dimethyl-4-oxo-5-pyrazolone, and the like. As the curing accelerator in the present invention, one type selected from the above-mentioned pyrazolones and derivatives thereof may be used, or two or more types thereof may be used in combination. Furthermore, other curing accelerators (sometimes referred to as "co-accelerators") such as organic amines, organic acids, inorganic acids, amides, imides, etc. are used in combination with this curing accelerator, if necessary. be able to. and,
The combined use of such a co-promoter may further enhance the curing accelerating effect and at the same time may improve storage stability. Such promoters include, for example, monoethylamine, diethylamine, triethylamine, cyclohexylamine, benzylamine, N,N-
Aliphatic amines such as dimethylbenzylamine; aniline, N-ethyl-p-toluidine, N,N-
Dimethyl-p-toluidine, N,N-dimethyl-
Aromatic amines such as o-toluidine, N,N-dimethyl-m-toluidine, N,N-dimethylaniline, N,N-diethylaniline; 1,2,3,
Heterocyclic amines such as 4-tetrahydroquinoline, piperidine, pyridine, N-methylpyrrolidone, piperazine, pyrimidine, pyrroline, pyrrole, pyrrolidine; acetic acid, monochloroacetic acid, dichloroacetic acid, trichloroacetic acid, benzoic acid, salicylic acid,
Orthonitrobenzoic acid, phenol, p-nitrophenol, picric acid, malonic acid, p-toluenesulfonic acid, tartaric acid, oxalic acid, sulfosalicylic acid, 2-mercaptopropionic acid, thioglycolic acid, ascorbic acid, sulfamic acid, citric acid, Organic acids such as gallic acid, acrylic acid, and methacrylic acid; Inorganic acids such as phosphoric acid, hydrochloric acid, nitric acid, and sulfuric acid; Amides such as benzamide and formamide;
and imides such as phthalimide, succinimide, and o-benzoic sulfimide. The blending ratio of the curing accelerator in the present invention is usually determined based on the total amount of the accelerator relative to the radically polymerizable monomer.
0.01-10.0% by weight, preferably 0.1-5.0% by weight. Various substances can be further added to the composition of the present invention for various purposes. For example, dyes and pigments are used for coloring purposes, polymerization inhibitors such as quinones are used to improve stability, thixotropic agents are used to impart thixotropic properties, soluble polymers are used to increase viscosity, and soluble polymers are used to improve fixing strength. A plasticizer can be added for the purpose of adjustment, and a filler can be added for the purpose of thickening or increasing the volume. 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. Parts in these examples indicate parts by weight. In addition, the performance tests of each composition obtained in these examples were conducted in accordance with the Japan Adhesive Industry Association standard "Anaerobic adhesive test method JAI 6-1979 (hereinafter referred to as "JAI standard"). This was done using the following simple method. (1) Measurement of curing speed Based on the JAI standard, the test specimen had a pitch of 1.5.
Bolts and nuts (M10) with thread grade 2 (coarse thread) and a joint length (nut thickness) of 8 mm were used after being cleaned 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 (a state in which it can be moved with fingers without resistance), and then tighten the nut at 20℃. The hardening start time (time until you feel resistance when turning the bolt/nut with your fingers) and fixation time (time until you can no longer move it with your fingers) were measured. (2) Measurement of adhesive strength The same bolts and nuts as above were coated with the composition and left in a constant temperature room at 20℃ for 24 hours.
Breaking torque and escape torque were measured based on JAI standards. (3) Measurement of storage stability A 10-day storage test at 50°C and gelation time at 80°C were measured. The 10-day storage test at 50°C is based on the JAI standard, in which half of the composition to be tested is placed in a 50 c.c. polyethylene container, and this is stored at 50°C
After being stored for 10 days in a hot air circulation constant temperature bath at 2°C, the appearance, curing speed, and adhesive strength of the composition were measured. Note that if there is no significant change in the above measured values before and after storage under these conditions, the shelf life is said to be one year or more at room temperature. To measure gelation time at 80℃, put the composition to be tested in a glass test tube and
The time required for the sample to gel was measured. It is said that if the gelation time at 80°C is 60 minutes or more, it can be stored at room temperature for more than a year. Examples 1-15 Comparative Examples 1-11 Triethylene glycol dimethacrylate 100
1,4-benzoquinone as a polymerization inhibitor
Each composition of Examples and Comparative Examples was prepared by adding 0.08 parts and 4 parts of cumene hydroperoxide as a polymerization initiator, and further adding 3 parts each of various compounds listed in Table 1 as curing accelerators. . Each of the resulting compositions was tested for curing speed, storage stability, and adhesive strength according to the test methods described above. The results were as shown in Table-1. The composition of each example has a faster curing speed than the composition of a comparative example containing a known curing accelerator,
It has excellent storage stability and high adhesive strength.

【table】

[Table] Example 16 Triethylene glycol dimethacrylate 100
0.08 part of 1,4-benzoquinone and 4 parts of cumene hydroperoxide, and further added 1,3-dimethyl-5-pyrazolone in various proportions shown in Table 2 to prepare an anaerobic curable composition. was prepared. The results of measuring the curing speed, storage stability, and adhesive strength of each of the obtained compositions are shown in Table 2. , storage stability and adhesive strength are particularly excellent (Experiment No.
5 and No. 6). However, if the amount of 1,3-dimethyl-pyrazolone added is too small, the curing speed will be slow, and if it is too large, the storage stability will be poor. In addition, in the above composition, the amount of 1,3-dimethyl-5-pyrazolone added was 3 parts, and the amount of cumene hydroperoxide added was varied as shown in Table 2'. The results of a similar test were shown in Table 2'. If the amount of cumene hydroperoxide added is too small, the curing speed will be slow, and if it is too large, the storage stability will be poor. Furthermore, for the composition of Experiment No. 5 in Table 2 (i.e., Experiment No. 13 in Table 2'),
The results of measuring the curing speed and adhesive strength of the samples stored at 50°C for 10 days and those stored at 50°C for 40 days are as shown in Table 2''. Even after storage under these conditions, Almost no change in performance was observed.

【table】

【table】

[Table] Examples 17-24 Triethylene glycol dimethacrylate 100
1,4-benzoquinone as a polymerization inhibitor
0.08 part and curing accelerator 1,3-dimethyl-5-
Various anaerobic curable compositions were prepared by adding 3 parts of pyrazolone and further adding 4 parts each of various organic peroxides listed in Table 3 as polymerization initiators. The results of testing the curing speed, storage stability and adhesive strength of each of the obtained compositions are shown in Table 3. All organic peroxides are effective as polymerization initiators, and hydroperoxides in particular have a fast curing speed and strong adhesive strength.
preferable.

[Table] Examples 25 to 32 1,4-benzoquinone 0.08 part, cumene hydroperoxide 4
and 3 parts of 1,3-dimethyl-5-pyrazolone to prepare an anaerobic curable composition. The results of measuring the curing rate, storage stability and adhesive strength of each of the obtained compositions are shown in Table 4. 1,3-dimethyl-5-pyrazolone is extremely effective as a curing accelerator for various radically polymerizable (meth)acrylates, and anaerobic curable compositions with excellent performance were obtained in all cases.

【table】

[Table] Examples 33 to 56 Comparative Examples 12 to 15 In each example, for each 100 parts of triethylene glycol dimethacrylate, 0.08 part of 1,4-benzoquinone, 4 parts of cumene hydroperoxide, and 1,3- Dimethyl-5-pyrazolone 3
% of each, and further added as a co-promoter.
Various anaerobic curable compositions were prepared by adding one part of each of the various known curing accelerators shown in No. 5. In addition, in each comparative example, 3 parts of various known curing accelerators shown in Table 5 were used instead of the 1,3-dimethyl-5-pyrazolone curing accelerator used in the examples, and Anaerobic curable compositions were prepared in the same manner as in the examples except that one part of the various known curing accelerators shown in Table 1 were used as co-accelerators. Each of the obtained compositions was tested for curing speed, storage stability, and adhesive strength, and the results are shown in Table 5.

【table】

[Table] As is clear from the results shown in Table 5, by using the curing accelerator used in the present invention together with a known curing accelerator as a co-accelerator, the curing speed and storage stability can be further improved. I was able to do that.
Furthermore, the performance improvement effect is far superior to that of the composition of the comparative example in which a known curing accelerator was used in combination with a known curing accelerator as a co-accelerator.

Claims (1)

[Scope of Claims] 1 A radically polymerizable monomer containing acrylate and/or methacrylate as a main component, including 3-pyrazolone, 4-pyrazolone, 5-pyrazolone, and the hydrogen atoms of each of these pyrazolones combined with other atoms and/or
or an anaerobic curable composition comprising at least one curing accelerator selected from the group consisting of pyrazolone derivatives corresponding to compounds substituted by atomic groups and an organic peroxide polymerization initiator. . 2. The composition according to claim 1, wherein the organic peroxide polymerization initiator is blended in an amount of 0.01 to 10.0% by weight based on the radically polymerizable monomer. 3 The curing accelerator acts against the radically polymerizable monomer.
The composition according to claim 1 or 2, wherein the composition is blended in an amount of 0.01 to 10.0% by weight.