JPS58138765A - Anaerobic curable composition having improved stability - Google Patents

Abstract

PURPOSE:The titled composition having high curing rate, improved shelf stability and bond strength, obtained by blending monomers comprising acrylate and/or methacrylate as main components with a polymerization initiator, a polymerization inhibitor and a compound having a specific constitutional unit. CONSTITUTION:(A) Radically polymerizable monomers comprising acrylate and/ or methacylate (e.g., alkylene type bifunctional methacrylate and/or acrylate such as neopentyl glycol dimethacrylate/acrylate, etc.) as main components are blended with (B) 0.1-7.0wt% polymerization initiator of an organic peroxide (e.g., cumene hydroperoxide, etc.) based on the component A, (C) 0.01-0.1wt% quinone-based polymerization inhibitor (e.g., hydroquinone, etc.) based on the component A and (D) 0,0005-0.05wt% compound (e.g., pyridine-2-carboxylic acid, etc.) containing a constitutional unit shown by the formula based on the component A.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an anaerobically curable composition having improved storage stability and having acrylate and/or L-methacrylate as the main monomer component. *Air-curable compositions are stable for long periods of time while in contact with air or oxygen, but are easily polymerized and cured by, for example, blocking air or oxygen between two adjacent surfaces. It is a curable composition, and this composition can be used to seal metal parts.
It is used to prevent loosening, and to fix the fitting part.

This type of anaerobic curable composition is usually packaged in a polyethylene container. It is sold commercially filled with a valley shape that is about half the size of the F container. This anaerobic curable composition is prevented from polymerizing and curing by the space OaX inside the container and the #@ which permeates through the container, and is stored in a hostile state.

However, anaerobic curable compositions generally contain an organic peroxide polymerization initiator and further contain a curing accelerator. The curing accelerator acts with the metal on the surface of the object to be bonded or bonded to accelerate curing when the composition is applied to those surfaces. Accordingly, in the anaerobic curable composition,
If trace amounts of metals are mixed into the raw materials used or during the manufacturing process, the stability of the 411 product will be affected, causing the product to melt or harden in the storage container, and there is a risk that it will become unusable.

In the past, several methods have been proposed to solve the problems that adversely affect storage stability.

For example, there is a method of adding phenols to quinone, and a method of adding a rater to metals to inactivate metal impurities that adversely affect stability! ik (Tokukai Akira!/-ko033
(Refer to Bulletin No. 1) A method using a combination of Hyde Wenon and a metal chelating agent (Refer to the Reference Publication of Special Publication Sho! Reference No. 36) has been proposed; It has been difficult to obtain an anaerobic curable composition that satisfies long-term storage stability and curing properties at the same time, as those with a slow curing speed and poor storage stability.

The inventors of the present invention have conducted various studies to overcome the above-mentioned drawbacks of conventional anaerobic curable compositions, and as a result, have developed a radically polymerizable monomer containing acrylate and/or methacrylate as a main component. The purpose is achieved by adding a composition -K containing an organic peroxide polymerization initiator and a bionic polymerization inhibitor to the body, and a compound containing a constituent unit represented by the formula -N-C-COOH in its molecule. This led to the discovery of the present invention.

That is, the present invention provides a radically polymerizable monomer containing acrylate and/or methacrylate as a main component, an organic peroxide polymerization initiator, a quinone polymerization inhibitor and the formula -N=C.
The anaerobic curable composition according to the present invention, which is an anaerobic curable composition prepared by adding a compound containing a structural unit represented by -COO)i in its molecule, has the following characteristics and effects.

(1) The storage stability is improved by adding a compound containing a composition ratio of -N, C-C0OH in the molecule.It does not polymerize and harden during storage. The addition of the compound has no adverse effect on the curing properties; in other words, although the storage stability is improved by the addition of the same compound, the curing properties are not impaired.

(-) As a result of improved storage stability, a highly active curing accelerator that could not be used in the past can be used, and the curing rate can be improved.

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

The acrylate and/or methacrylate [hereinafter may be collectively referred to as (meth)acrylate. ], for example, alkylene-type difunctional (meth)acrylates such as neopentyl glycol di(meth)acrylate; diethylene glycol di(meth)acrylate, polyethylene glycol di(meth)arylate, polypropylene glycol di(meth)acrylate; ) acrylate, ether-type bifunctional (meth)acrylates such as triethylene glycol di(meth)acrylate, and tetraethylene glycol di(meth)acrylate;
Trifunctional (meth)acrylate of Cape Meta)acrylate;
Polyfunctional (meth)acrylates such as pentaerythritol tetra(meth)acrylate, diben I erythritol poly(meth)acrylate, and tetramethylolmethanetetra(meth)acrylate; Droxyethyl(meth)acrylate, tetramethylolmethane tri(meth)acrylate , pentaerythritol tri(meth)acrylate, λ, 3-dibromopropyl(meth)acrylate, tetrahydrofurfuryl(meth)acrylate, cochloroethyl(meth)acrylate, dimethyla with a polar group such as noethyl(meth)acrylate, or Substituted atom-containing (meth)acrylate;
) acrylate, bisoxypolyethylated bisphenol A-di(meth)acrylate, dipropylenated bisphenol moo-di(meth)acrylate in bis-oxyhydro, diethyl bisphenol-di(meth)acrylate-based epoxy(meth)acrylate in bisoxy-cohydro. acrylate; adipic acid-7,6-hexanethioluge (meth)
Examples include acrylate-based polyester lid di(meth)acrylate; and urethane (meth)acrylate. These (meth)acrylates may be used alone or in combination of two or more. In some cases, these (meth)acrylates may be used in combination with other monomers other than (meth)acrylates. Other monomers that can be used in combination include styrene, tetraethyleneglyfur dicrotonate, diallyl phthalate, alkyl, vinyl ether, butadiene with vinyl groups at both ends (W: 1 = -) ru rubber (VTBN rubber) , triallyl isocyanurate, triallyl trimellitate, N,N'-methylene/-bis-acrylamide,
N-methysylacrylic acid and N-n-butoxymethylacrylic oxide can be used, and when the cured product is required to have flexibility, VTHN rubber can be used. Examples of oxide polymerization initiators include ketone peroxides, diasilyl oxides, peroxy esters, silyl rubber oxides, hydride peroxides, peroxy esters, etc. is described in Japanese Unexamined Patent Publication No. 18jo-Taro No. 16. Particularly preferred polymerization initiators are hydroperoids such as cumene hydroperoxide and t-butyl hydroperoxide. It is also possible to use two or more types of these polymerization initiators in combination.
The blending ratio of the polymerization initiator is o, oi to 10. O weight 9, preferably modified/
-7,0 weight round.

Examples of the quinone polymerization inhibitor in the present invention include hydroquinone, benzoone, naphthoquinone, and hydroquinone monomethyl ether. When added to an anaerobic curable composition, these have the effect of improving storage stability, but at the same time they also have the effect of slowing down the curing rate. Therefore, it is difficult to obtain an anaerobic curable composition that has storage stability and curing properties at the same time using just a quinone polymerization inhibitor, and it is difficult to obtain an anaerobic curable composition that has storage stability and curing properties at the same time. The preferable addition amount of the quinone polymerization inhibitor is o, ooi to O1! based on the total amount of radically polymerizable monomers. Weight j6, preferably o, oi to 0.7 weight 9.

? - The amount of the quinone polymerization inhibitor O is much lower than the curing speed of the anaerobic curable composition.

The most distinctive feature of the present invention is the use of a specific storage stabilizer.
By using a compound containing a structural unit represented by N-C-COOH in the molecule9, by adding these compounds,
The anaerobic curable composition K, in which the amount of quinone polymerization inhibitor added is kept low with emphasis on rapid curing properties, can be given good storage stability. These compounds include pyridinecarboxylic acids represented by the following formula (1), coquinocarboxylic acids represented by the following formula (2), and pyrazinecarboxylic acids represented by the following formula (3). It will be done. These are used in their acid form, in the form of alkali metal salts such as sodium, potassium, and lithium salts, or in the form of hydrates.

(1) (ko) (3) (In the formula, Xt, X@, Xa high f tL 4
h CHa, -COOHl-OH%-〇OH, -C)
i, 0H1-represents) these formulas -N-rich C-C0OH
Specific examples of compounds containing structural acid units shown in the molecule include α-pifric acid (i.e., pyridine-cocarboxylic acid), quinolinic acid (i.e., pyridine-cocarboxylic acid), dibituric acid ( Copyridinecarboxylic acids and their alkali metal salts; 2-carboxylic acid), nurenic acid (i.e. nardicic acid), acridic acid (
That is, examples thereof include quinoline-carboxylic acids and zeta-carboxylic acids such as quinoline-2,1-dicarzenic acid, quinoline-2,1-dicarzenic acid, and alkali metal ring moieties thereof. You can use 70 types of these compounds, or you can use several types in combination.

The amount of these compounds to be used is preferably o, oooi to 0.744 parts by weight based on the total amount of radically polymerizable monomers.
, o o o z~0. Oj parts by weight.

In addition, known stabilizing agents such as polymerization inhibitors such as phenothiazine, phenolic anti-aging agents such as butylhuman citoluene, nitroso compounds such as O-nitronephenol, cuperone, and tomethyl-N-nitrosoaniline, and picric acid. , Co, Zinide■ Aromatic nitro compound of phenol group, galpinoxyl, /, /-diphenylene--picrylhydrazyl, co-diphenylated 7-
Several types of radical scavengers such as picrylhydrazyl-based radical scavengers are used as stabilizers of the present invention, formula -N-C-00.
By using the structural unit represented by 08 in combination with a compound contained in the molecule, stability can be further improved. 1? The amount of these additives added to the pigeonhole must be such that they do not harm the curing speed of the anaerobic curable composition.

Various substances can further be added to the composition of the present invention for various purposes. For example, for the purpose of coloring, the pigment in the dye is thixotropic for the purpose of imparting thixotropic properties, and for the purpose of thickening and improving strength, urethane rubber and phenoxy resin are used as soluble polyesters. 9 non-reactive acrylic oligomers (9, for example, trade name Nikalide /
Eve Resin 2 (manufactured by Nippon Carbide Kogyo Co., Ltd. Jyoyo Co., Ltd.) il is mixed with dibutyl phthalate and butylpenzyl phthalate for the purpose of adjusting the adhesion strength! Plasticizers such as silane coupling agents such as vinyl silane, azunosilane, and epoxy silane to improve adhesion, acid phosphaoxyethyl methacrylate, 3-chlorocoacid phosphor, dipropyl methacrylate, etc. phosphorus-containing (meth)acrylate t,
A filler may be added for the purpose of increasing the viscosity during thickening, and a known curing accelerator may be added for the purpose of increasing the curing speed.

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, an example of the present invention and a comparative example will be given and explained in detail. The parts subtracted from Example K in these examples indicate parts by weight.

The performance tests for each composition obtained in these examples were conducted in accordance with the Japan Adhesive Industry Association standard "Anaerobic Adhesive Test Method JA
This is carried out using the following simple method in accordance with IA-/R7 (hereinafter referred to as the "JAI standard") K.

(1) Measurement of curing speed The test specimens were prepared with pitch /, j′(
Coarse thread), thread grade λ class, joint length and nut thickness) l
Use commercially available bolts and nuts (Mlo) and clean them with trichlorethylene.

The measurement method is to apply the composition #IIj 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), I left it in a constant temperature room at JOC and measured the fixation time (the time it took until I could no longer move it with my fingers).

(-) III Determination of Adhesive Strength The same bolts and nuts as in 11e were coated with the composition and left in a constant temperature room at JOC for a period of time, and the breaking torque and escape torque were measured based on the JAI standard.

(3) Measurement of storage stability JOC was subjected to a 10-day storage test and gelation time in IOC was measured.

ZOC's 10-day storage test has a JAIIIil rating of 4t
Toduki/Pour the composition to be tested into a 00 ee polyethylene container by the container capacity, and add 30±, 2
It was stored for 10 days in a hot air circulation constant temperature bath (C), and the appearance of the composite was then measured. If there is no slight change before and after storage under these conditions, shelf life is said to be 7 years or more at room temperature.

In addition, to measure the gelation time of IOC, put a portion of the test specimen composition into a J cc polyethylene container, place it in a hot air circulation thermostat at 10±-〇, and wait until the sample gels. The time it took to do so was measured. It is said that if the gelation time of IOc is 60 minutes or more, it can be stored at room temperature for one year or more.

Example/~7g Comparative example/~IO Triethylene glycol dimethacrylate OsK, 2
-Hydroxyethyl methacrylate 10 phenoxy resin (Shell Chemical Co., Ltd.) lj part, vinyl-terminated butadiene acrylonitrile rubber (BF Gutdrich product name [
High it -VT dl 'J Mar VTBN /3
00XJ2J) 3 parts, 3-chlorocoacid phosphoxypropyl methacrylate (Oil Products Co., Ltd.
1 company's product name "Hosmer CIJ" o, 3 parts, and cumene hydropero medium yaid (NOF Co., Ltd. product name [Percmil H-10J parts were added, and further table -/
Each of the compositions of Examples and Comparative Examples was prepared by adding the various compounds described in Table 1 in the numbers shown in Table 1.

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

The results are as shown in Table 1, and the comparative examples λ, ≠, Otsu, 7, and ri without the addition of a stabilizer and the compositions with the addition of tetrasodium ethylenediaminetetraacetate, a known stabilizer, were used. Compared to the compositions of Comparative Example 3, j%t, and io, the compositions of Examples 7 to 1, in which the stabilizer compound of the present invention was added, had excellent storage stability and other performances. are equivalent. This tendency is noticeable when a highly active curing accelerator is used, and until now this type of anaerobic curing composition
It becomes possible to use a highly active curing accelerator that is rarely available in the conventional method, and it becomes possible to supply an anaerobically curable composition with poor storage stability despite the extremely fast curing rate of K.

-5 (Example/R~, 2j Triethylene glycol dimethacrylate 0 Iku ni λ-
7. Hydroxyethyl methacrylate IO part; Hiro-penzoquinone O, OS part, phenoxy resin (manufactured by Shell Chemical Co., Ltd.) 73 parts, terminal vinylated butadiene acrylonitrile rubber (BP Gutdrich Co., Ltd. trade name [Hiker VT Bo U w
-VTBN/300X22J) 7 parts, 0.7 parts of 3-chlorocoacid phosphoramide methyl methacrylate (product name: "Hosmer CIJ" from Yushi Products Co., Ltd.), 1.7 parts of pyrazole, and 0.3 parts of lauryl mercaptan. and further added 0.03 parts of various compounds each containing a structural unit represented by the formula -N-C-COOH shown in Table 2 in the molecule as a stabilizer to prepare various anaerobic curable compositions. (II Examples 79 to -j) were prepared.The results of measuring the curing rate, storage stability, and adhesive strength of each of these compositions are as shown in Table-λ. Although the curing speed is fast, the storage stability is poor, w! The adhesion strength is high.

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Claims (1)

[Scope of Claims] A. Acrylate and/or methacrylate [the radically polymerizable monomer as the main component, an organic peroxide polymerization initiator,
An anaerobic curable composition comprising a quinone polymerization inhibitor and a compound containing a structural unit represented by the formula -N=C-COOH in its molecule.