KR950012773B1 - Anaerobic curable composition - Google Patents

Abstract

The anaerobic curable adhesive and filler compsn. is composed of a polymerizable acrylate or methacrylate monomer having at least vinyl functional gp., 0.1-10 wt.% of an organic peroxide i. e. cumene hydroperoxide, tertiary butyl hydroperoxide, cumene peroxide, tertiary butyl peroxide or benzoly peroxide as a polymerization initiator, 0.1-10 wt.% of an auxiliary promotor i. e. formamide, phthalimide, succineamide and/or benzoic sulfoimide, and 1-10 wt.% of an organic phosphorus deriv. i. e. triphenyl phosphine, triphenyl phosphate, hexamethyl phosphoamide and/or hexaethyl phosphorus triamide. The curable compsn. has a good adhesiveness among the metal surfaces, and storage stability.

Description

Anaerobic Curable Composition

FIELD OF THE INVENTION The present invention relates to polymerizable compositions, and in particular, to anaerobic curable compositions comprising organophosphorus derivatives in polymerizable monomers used for adhesion and filling between two adjacent surfaces.

The anaerobic curable composition comprises a polymerizable monomer and is cured by a polymerization reaction inhibited by oxygen. These anaerobic compositions remain in an unpolymerized liquid state as long as contact with air or oxygen is maintained, and when the air or oxygen is removed, polymerization proceeds spontaneously and quickly hardens to a solid state.

These anaerobic curable adhesive and filler compositions are used for fastening screw assemblies, filling porous parts, reinforcing and structural fitting of cylindrical parts, giving good adhesion to adjacent metal surfaces, in particular bolts and nuts.

It is well known that the polymerization of acrylic and methacrylic esters can be initiated by addition of small amounts of conventional peroxide catalysts such as benzoyl peroxide. However, these catalysts do not impart anaerobic curing properties to the acrylic ester monomers, and thus the polymerization does not depend on the existence of known materials.

It is also known that certain types of polymerizable acrylate monomers can be stabilized against polymerization even if they are passed through air or oxygen, even at high temperatures or at elevated temperatures. US Pat. No. 2,628,178 discloses an oxygenated polyacrylate monomer that exhibits anaerobic curing properties, but air must be continuously blown to prevent automatic polymerization during storage of the composition containing the same.

US Pat. No. 2,895,950 then discloses an anaerobic curable composition using an unoxygenated polyacrylate monomer which solidifies rapidly and spontaneously by removal of air or oxygen in the presence of an organic peroxide catalyst. These polyacrylate systems ensure adequate storage stability without the need for blowing air as long as external contact with air is provided, where the organic peroxides are potential polymerization initiators of these monomers and the mixture with the monomer This is because the polymer is very sensitive to contact, and remains in an inactive state in the presence of oxygen, and polymerization of the monomer is initiated when oxygen is removed. Tertiary amines, ascrobic acid, organic phosphites, and quaternary ammonium salts for reducing the amount of organic peroxide catalyst used also disclose conventional accelerators.

U. S. Patent No. 3,046, 262 promotes cure rate by adding imide and / or formamides accelerator as an accelerator to an anaerobic curable composition, but may cause problems with storage stability.

In US Pat. No. 3,218,305, curing accelerators and storage stability have been sought by adding stabilizers such as quinones and organic amines to a composition comprising a monomer, a peroxide catalyst and a sulfimide.

Later, U.S. Patent No. 4,044,044 adds a kind of organic phosphorus ester to the anaerobic adhesive and filler composition, which greatly improves the adhesive strength of these compositions, but not only increases the time required for curing but also requires a curing temperature of more than 100 ° C. Therefore, there was a problem in practical use.

Recently, it has been found that anaerobic curable adhesive and filler compositions containing such organophosphorus esters can lower the curing time curing temperature by the introduction of tertiary dimethylarylamine. There was a problem of phosphate engagement and insoluble gels. U.S. Patent No. 4,322,509 discloses an effective amount of carboxylated nitrile elastomer in an anaerobic curable adhesive and filler composition comprising an anaerobic polymerizable material having a terminal ethylene unsaturated group, a polymerization initiator, an organic phosphorus ester and a tertiary dimethylarylamine. It is disclosed that the gel formation can be prevented.

The present inventors have conducted various studies on organophosphorus derivative compounds as components of the anaerobic curable adhesive and filler composition, and have shown that trialkyl or triarylphosphine, trialkyl or triaryl phosphate and hexaalkylphosphoramide, hexaalkylphosphorastamide compound It has been found that it can act as this adhesion promoter to improve the adhesion of the adhesion and filler composition and to improve the storage stability, leading to the completion of the invention.

That is, an object of the present invention is to provide an anaerobic curable adhesive and filler composition that can be stored in a liquid state for a long time and can be cured quickly, and can achieve strong adhesion between adjacent surfaces even at room temperature.

The anaerobic curable composition of the present invention for achieving the above object is a polymerizable monomer having at least one vinyl functional group, and at least one monofunctional acrylate or methacrylate monomer, in which organic peroxide is 0.1 to 10% by weight of the monomer, amide And at least one organophosphorus derivative selected from the group consisting of 0.1-10% by weight of the monomer weight and a compound of the following general formulas (1) to (4): 1-10% by weight of the monomer. It is characterized by including in%.

R ₃ P (RO) ₃ P (R'N) ₃ P = O (R ' ₂ N) ₃ P

(1) (2) (3) (4)

R represents lower alkyl or lower aryl group, and R 'represents lower alkyl. Lower alkyl includes, for example, methyl, ethyl, propyl, isopropyl and butyl, and lower aryl includes, for example, benzyl, phenyl and the like.

The organophosphorus derivative is used in an amount of 1 to 10% by weight of the monomer, because when the amount used is less than 1% by weight of the monomer, it is difficult to give an initial curing rate, and when it is more than 10% by weight, the storage stability is greatly reduced. . As the organophosphorus derivative, compound (1) is preferably trialkyl phosphine as trialkyL phosphine or triaryl phosphine, and compound (2) is trialkyl phosphate or tree Triaryl phosphate is preferred as aryl phosphate. In addition, the organophosphorus derivative compound (3) is preferably hexaalkyl phosphoramide as hexaalkyl phosphoramide, and hexamethyl phosphoamide and hexaethyl phosphoamide, and compound (4) is hexaalkyl phosphorous triamide. triamide) is preferably hexamethyl phosphorus triamide and hexaethyl phosphorus toriamide.

As the polymerizable acrylate or methacrylate monomer of the present invention, a monofunctional or polyfunctional monomer may be used, and may be used alone or in combination. Monofunctional monomers include, for example, 2-hydroxy aryl acrylate, 2-hydroxy propyl acrylate, 3-hydroxy propyl acrylate, 3-chloro-2-hydroxy acrylate, 2-hydroxy ethyl methacrylate. , 2-hydroxy propyl methacrylate, 3-hydroxy propyl methacrylate, 3-chloro-2-hydroxy methacrylate, glycidyl methacrylate, tetrahydrofurfuryl methacrylate, cyclohexyl methacrylate Rate and the like. Examples of the polyfunctional monomers include ethylene glycol diacrylate, diethylene glycol diacrylate, triethylene glycol diacrylate, tetraethylene glycol diacrylate, ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, Triethylene Glycol Dimethacrylate, Tetraethylene Glycol Dimethacrylate, Tripropylene Glycol Dimethacrylate, Tetrapropylene Glycol Dimethacrylate, Bisphenol A Dioxy Diethylene Glycol Dimethacrylate, Bisphenol A Dioxy Diff Lopoxy di (2-hydroxy) propyl dimethacrylate, trimethylol propane trimethacrylate, pentaerythritol trimethacrylate, diglycerol tetramethacrylate and the like.

Among the monomers, the adhesive composition using the monomer having a strong polarity in the molecular structure is particularly excellent in adhesion. These monomers are generally graded reagents containing stabilizers or inhibitors such as hydroquinone and the like without further purification.

Organic peroxides used as polymerization initiators in the anaerobic curable compositions of the present invention include tertiary butyl hydroperoxide, cumene hydroperoxide, tertiary butyl peroxide, cumin peroxide, benzoyl peroxide and the like. Tertiary butyl hydroperoxide and cumin hydroperoxide are particularly preferred.

In the present invention, the polymerization initiator and the organophosphorus derivative compound are preferably used in equimolar numbers.

Amides and imides used as co-promoters in the anaerobic curable composition of the present invention include, for example, formamide, phthalimide, succinimide and benzoic sulfimide, with benzoic sulfimide being particularly preferred.

The organic peroxide polymerization initiator, the amide, and the imide co-promoter are each used at 0.1 to 10% by weight of the monomer weight. When the amount used is less than 0.1% by weight of the monomer weight is difficult to give the initial curing rate, when more than 10% by weight because the storage stability is greatly reduced should be used in 0.1 to 10% by weight.

In addition to the above components, the anaerobic curable composition of the present invention may include other thickeners, polymerization inhibitors, stabilizers and the like.

The present invention will be described in more detail with reference to the following examples. However, the following examples are only examples of the present invention, and the present invention is not limited thereto.

The properties of the compositions prepared in Examples of the present invention were evaluated according to the following measuring methods.

How to measure

(1) adhesion test

A few drops of the prepared anaerobic curable composition were dropped on bolts and nuts, and cured at room temperature. Breakaway torque is the torque at which the nut begins to turn, and prevailing torque is the work it takes to rotate a certain angle, for example 90 °, 180 °, 270 °, 360 ° rotational torque is measured. In general, about 13.84 kg · f · cm is sufficient for 3 / 8-inch bolts and nuts.

(2) storage stability

The prepared anaerobic curable composition was subjected to an accelerated test in a thermostat controlled at 82 ° C. to measure the instant of gelation.

Example 1

600 mg of cumin hydroperoxide (3.94) in the monomer components of 15 g of general grade hydroxyethyl methacrylate, 15 g of tetrahydrofurfuryl methacrylate, 15 g of triethylene glycol dimethacrylate, and 15 g of detra ethylene glycol dimethacrylate. mmole) and 150 mg of sulfimide of benzo are added, mixed until a homogeneous solution, and divided into three equal fractions.

The first fraction was sample 1, the second fraction was sample 2, and 178 mg (1.31 mmol) of N, N-dimethyl-4-toluidine was added. The third fraction was sample 235 mg (1.31 mmol) of hexamethylphosphoamide. Added.

Adhesion test results for Shiro L 2,3 are shown in the following [Table 1].

TABLE 1

Example 2

To 45g of hydroxy propyl methacrylate of general grade, 450mg of cumin hydroperoxide (2.96mnK) le) was added 150mg of benzoic silphimide, mixed until a uniform solution, and then mixed into equal volume fractions. Divide.

The first fraction was added to sample 1 with 133 mg (0.98 mmole) of N, N-dimethyl-4-toluidine, the second fraction was added with sample 257 mg (0.98 mmole) of triphenyl phosphine, and the third fraction was sampled. 176 mg (0.98 mmol) of hexamethylphosphoramide was added.

Adhesion test and storage stability results for Samples 1,2,3 are shown in the following [Table 2].

TABLE 2

Example 3

To 60 g of general grade 3-chloro-2-hydroxypropyl methacrylate, add 600 mg (3.94 mmol) of cumin hydroperoxide and 200 mg of benzoic sulfimide, mix until a uniform solution, and then mix Divide into fractions.

The first fraction was added to sample 1 with 133 mg (0.98 mmole) of N, N-dimethyl-4-toluidine, the second fraction was added with 257 mg (0.98 mmole) of triphenylphosphine as sample 2, and the third fraction was added to sample 3 Then, 321 mg (0.98 mm) of triphenyl phosphate were added, and the fourth fraction was added to Shiloh, and 176 mg (0.98 mmole) of hexamethylphosphoramide was added.

The adhesion test results for the samples 1,2,3,4 are shown in the following [Table 3].

TABLE 3

Example 4

In a monomer component of 30 g of general grade bisphenol A dioxy dipropoxy di (2-hydroxy) propyl dimethacrylate and 15 g of 2-hydroxyethyl methacrylate, 450 mg (2.96 mmol) of cumin hydroperoxide and benzoic sulfide 150 mg of pimide is added and mixed until a uniform solution is divided into three equal parts.

The first fraction was sample 1, 133 mg (0.98 mmole) of N, N-dimethyl-4-toluidine was added, the second fraction was added 2 hours, and 321 mg (0.98 mmole) of triphenylphosphate was added, and the third fraction was sample 3 176 mg (0.98 mmol) of hexamethylphosphoramide was added thereto.

The adhesion test results for the samples 1,2,3 are shown in the following [Table 4].

TABLE 4

Example 5

To 60 g of general grade tetrahydrofurfuryl methacrylate, 600 mg (3.94 mmol) of cumin hydroperoxide and 200 mg of benzoic sulfimide are added and mixed until a uniform solution is divided into four equal fractions.

The first fraction is sample 1, 133 mg (0.98 mmol) of N, .N-dimethyl-4-toluidine is added, the second fraction is sample 2, 257 mg (0.98 mmol) of triphenylphosphine is added, and the third fraction is sample 161 mg (0.98 mmol) of hexamethyl phosphorustriamide was added as 3, and 176 mg (0.98 mmol) of hexamethyl phosphoroamide was added as Sample 4 as the fourth fraction.

The adhesion test results for the samples 1,2,3,4 are shown in the following [Table 5].

TABLE 5

As shown in the above examples and test results, an anaerobic curable composition comprising a polymerizable monomer, an organic peroxide polymerization initiator, and an imide accelerator is used in a trialkyl or triaryl phosphine, trialkyl or trialkyl phosphate, hexa alkyl phosphamide, and The addition of organophosphorus derivative compounds, such as hexaalkyl phosphorustriamide, shows that adhesiveness and especially storage stability are superior to the addition of the conventional organic amine derivative.

Therefore, the anaerobic curable adhesive and filler composition of the present invention can be stored in a liquid state for a long time, and can be cured quickly under anaerobic conditions to give a strong adhesive force between two adjacent surfaces, and thus can be particularly useful for adhesion and filling between metal surfaces. .

Claims (5)

As a polymerizable monomer having at least one vinyl functional group, to a monofunctional or higher acrylate or methacrylate monomer, an organic peroxide is 0.1 to 10% by weight of the monomer weight, and at least one of amide and imide is 0.1 to 10% by weight of the monomer. %, At least one organophosphorus derivative selected from the group consisting of compounds of the following general formulas (1) to (4) comprises 1 to 10% by weight of the monomer weight, anaerobic-curable composition. R ₃ P (RO) ₃ P (R ' ₂ N) ₃ P = O (R' ₂ N) ₃ P (1) (2) (3) (4) R represents lower alkyl or lower aryl group, and R 'represents lower alkyl. The anaerobic curable composition according to claim 1, wherein the organic peroxide and the organophosphorus derivative are included in an equimolar number. The compound of claim 1, wherein the organophosphorus derivative is triphenylphosphine as a compound of formula (1), triphenyl phosphate as a compound of formula (2), hexamethylphosphoamide as a compound of formula (2), and An anaerobic curable composition, characterized in that hexaethylphosphoramide, hexamethylphosphorustriamide and nucleus ethyl phosphorusamide, as compounds of the general formula (4). The anaerobic curable composition according to claim 1, wherein the organic peroxide is at least one of cumin hydroperoxide, tertiary butyl hydroperoxide, cumin peroxide, tertiary butyl peroxide and benzoyl peroxide. The anaerobic curable composition according to claim 1, wherein the amide and the imide are formamide, phthalimide, succinimide and benzoic sulfimide.