JPH05105847A - Anaerobic adhesive composition quickly curable with ultraviolet ray - Google Patents

Abstract

PURPOSE:To prepare the title compsn. which cures in a short time and is excellent in adhesion and sealing effect. CONSTITUTION:The title compsn. is prepd. by incorporating 1-(2- carboxyacryloyl)-2-phenylhydrazine into a mixture contg. a polymerizable acrylic ester, an org. peroxide, a photoinitiator, and, pref., o-benzoic sulfimide.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-curing type anaerobic adhesive composition, and in particular, a portion which can be irradiated with ultraviolet rays is cured by ultraviolet rays in a short time and at the room temperature between two adjacent surfaces such as fine gaps of metal or the like. The present invention relates to an ultraviolet-curable anaerobic adhesive composition that cures in an extremely short time and exhibits excellent adhesion and sealing effects.

[0002]

2. Description of the Related Art Various anaerobic adhesive (filler) compositions have been conventionally known, and typical examples thereof include a polymerizable acrylate ester such as polyethylene glycol dimethacrylate or urethane acrylate and a stable peroxy initiator. This is combined with a polymerization inhibitor for enhancing the properties, and further, a polymerization accelerator such as amines, amides, imides and the like is added thereto as desired. These polymerization accelerators have the functions of accelerating the curing rate of the composition and enabling long-term storage stability. Further, by combining a photoinitiator with these anaerobic adhesive compositions to impart ultraviolet curability,
There has also been proposed a type in which an ultraviolet ray-irradiating portion such as an adhesive end portion, which is easily exposed to air during use, is irradiated with ultraviolet rays to surely cure the entire rest in a shorter time. However, many of these adhesive compositions using conventionally known polymerization accelerators still have to be improved. For example, the stability as an adhesive is low, the curing speed is slow, or the surface tack does not occur even when ultraviolet curing. It has drawbacks such as remaining.

US Pat. No. 4,321,3 as a polymerization accelerator for a polymerizable acrylate ester type anaerobic adhesive composition.
No. 49 discloses a hydrazine derivative having a specific structure. Although the polymerization accelerators disclosed therein exhibit certain effects, they are not entirely satisfactory in some respects.
For example, there are drawbacks that the curing speed is slow, the final strength is low, and the polymerization accelerator is not incorporated into the adhesive composition.

Further, in such a multi-component type anaerobic adhesive composition, there are many cases in which the effect is largely different depending on the partner to be combined, and the development of a combination sufficiently satisfying the curing rate and the storability is strong. Is desired.

An object of the present invention is to provide a UV-curable anaerobic adhesive composition which is improved from the drawbacks of the prior art.

[0006]

The present invention provides a polymerizable acrylate ester containing 1- (2-carboxyacryloyl).
-2-Phenylhydrazine, an organic peroxide, and a photoinitiator are contained in a UV-curable anaerobic adhesive composition having a fast curing property, which is particularly preferably 0-benzo. It also contains Ixlufimide.

As the polymerizable acrylate ester which is the basic component of the present invention, any known one can be used as appropriate. Typical ones are classified into polyacrylate esters and polyurethane acrylates. Specific examples of the polyacrylate esters include di, tree or tetraethylene glycol dimethacrylate, di (pentamethyl glycol) dimethacrylate, tetraethylene glycol diacrylate, diglycerol acrylate, diglycerol tetramethacrylate, petylene glycol dimethacrylate, neo. Examples include benzyl glycol diacrylate and trimethylolpropane triacrylate. Monofunctional acrylate esters (esters containing one acrylate group) can likewise be used. Typical examples of monofunctional acrylate esters include cyclohexyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl acrylate, hydroxypropyl methacrylate, t-putylaminoethyl methacrylate, cyanoethyl acrylate and the like. Polyurethane acrylates are obtained by reacting a monomer having an acrylic group and active hydrogen with a polyisocyanate and a compound having active hydrogen. For example, hydroxyethyl acrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, 3-
Hydroxy- and amino-group-containing monomers such as hydroxypropyl methacrylate, aminopropyl methacrylate and hydroxyhexyl acrylate, polyisocyanates such as hexamethylene diisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, and polyether diols (Polypropylene glycol, polytetramethylene glycol, polyethylene glycol, etc.), polyolefin diols, polybutadiene diols, polybutadiene-acrylonitrile copolymer terminal diols,
There are reaction products with polyacrylic acid ester-terminated diols and the like. These reactants may be at room temperature or about 40 ° C to 15 ° C.
Bonding can be done while heating to a temperature of 0 ° C.

The essence of the present invention is to use 1- (2-carboxyacryloyl) -2-phenylhydrazine as a polymerization accelerator. This compound

[Chemical 1] It is shown by the chemical formula.

1- (2-carboxyacryloyl) -2
The amount of phenylhydrazine used is preferably 0.001 to 5 parts by weight, more preferably 0.005 to 3 parts by weight, based on 100 parts by weight of the polymerizable acrylate ester. If the amount is too small, the curing will be delayed, and if the amount is too large, improvement of the effect cannot be expected.

1- (2-carboxyacryloyl) -2
-Phenylhydrazine can be easily and selectively produced by an equimolar reaction between phenylhydrazine and maleic anhydride. It may be prepared in advance and used, or it may be prepared in situ by adding phenylhydrazine and maleic anhydride during the preparation of the adhesive composition. In the latter case, maleic anhydride is equimolar or more to phenylhydrazine, preferably 1 to
It is preferable to use 1.5 times the molar amount. 1- (2-Carboxyacryloyl) -2-phenylhydrazine is derived from having an olefinic double bond and a terminal carboxyl group in the molecule, and has two effects of a polymerization accelerator and an adhesion improver. ..

1- (2-carboxyacryloyl) -2
-Phenylhydrazine shows a particularly pronounced effect in combination with 0-benzoixulfimide. 0-Benzoxulfimide is 0.1 to 5% by weight based on the total composition.
It is preferable to use. It should be noted that polymerization accelerators such as amines, amides or imides (for example, benzoxulfimide) are important because they accelerate the curing speed of the adhesive composition: filling composition loses its efficacy even when stored for a long time. In addition, it has the characteristic of good storage stability. Of these, 0-benzoxulfimide is known as a curing accelerator for anaerobic adhesives, but if it is added alone to a polymerizable acrylate ester containing an organic peroxide, a normal adhesion rate is obtained. Only the above-mentioned substances can be obtained, and when they coexist, a more excellent effect is exhibited.

As the organic peroxide, known ones can be used as appropriate, and representative examples thereof include diacyl peroxides, dialkyl peroxides, ketone peroxides, peroxyesters and the like. Particularly useful organic peroxides include organic hydroperoxides such as cumene hydroperoxide and t-butyl hydroperoxide. Of the above, cumene hydroperoxide is particularly desirable. The above organic peroxide is generally used in an amount of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, based on the entire composition.

As the photoinitiator, an appropriately known photoinitiator which invents a radical by ultraviolet rays is used. Specific examples include benzoin, benzoin methyl ether, benzoin ethyl ether, α-methylbenzoin, α-phenylbenzoin and other benzoin compounds, 1-hydroxycyclohexyl phenyl ketone, 2,2-dimethoxy-2-phenylacetophenone, diethoxy. Acetophenone, 2-methyl-1- (methyltheophenyl) -2-
(4-morpholinyl) -1-1 propanone etc. are mentioned. The photoinitiator is used in an amount of 0.01 to 10% by weight, preferably 0.1 to about 5% by weight, based on the entire composition.

The curable composition of the present invention can also be prepared as a two-component composition. It is also possible to employ a method of using the composition of the polymerization initiator as the first component and the other as the second component, and applying the respective components to the surfaces to be bonded to bond them. When used on an inert surface or between two surfaces with fairly wide gaps, it is desirable to use a suitable primer.

The UV-curable anaerobic adhesive composition of the present invention has extremely fast curing properties and good storage stability, and can withstand long-term storage. Further, due to the polyfunctionality of the polymerization accelerator, the polymerization accelerator reacts and is effectively incorporated into the adhesive molecule to have high adhesive strength, and also has excellent heat resistance, water resistance, oil resistance and weather resistance.

Next, the present invention will be described with reference to Examples and Comparative Examples.

Example 1 1- (2-Carboxyacryloyl) -2-phenylhydrazine was synthesized by reacting phenylhydrazine and maleic anhydride in equimolar amounts in chloroform. IR The following UV-curable anaerobic adhesive composition was prepared using (2-carboxyacryloyl) -2-phenylhydrazine. The amounts used are shown in parts by weight.

Polymerizable acrylate ester 100 2,2-dimethoxy-2-phenylacetophenone 2.00-benzixulfimide 1 cumene hydroperoxide 0.5 1- (2-carboxyacryloyl) -2-phenylhydrazine 0.1 Stabilizer 0.02

The above components were dissolved by heating and stirring at 50 ° C. for 4 hours to obtain a uniform solution. The completed adhesive composition was put in a glass test tube and put in a drying oven at 80 ° C. to carry out a heat acceleration test. If gelation does not occur at 80 ° C. for 2 hours, it can be considered that it corresponds to a shelf life of about 1 year at room temperature. A fitting test piece (steel pin 6φ × 40 mm, collar inner diameter 6φ × 15 mm, clearance 1/100 mm) was used to measure the anaerobic curing property. As the initial set time, the degreased fitting test piece adhesive composition was applied, fixed and then left at 25 ° C., and the time until the shaft could not be easily moved by hand was measured. Mating strength is 2 at 25 ° C
After 4 hours, the compression rate was measured at 10 mm / min. Also,
UV curing characteristics are 4Kw high pressure mercury lamp (150mW / cm
⁽² × 20 seconds), and the shear adhesive strength of the glass / glass was measured by irradiating with ultraviolet rays.

As Comparative Example 1, an experiment was conducted under the same conditions except that 1-acetyl-2-phenylhydrazine was used in place of 1- (2-carboxyacryloyl) -2-phenylhydrazine of Example 1. The results are shown in Table 1.

[0021]

[Table 1]

Example 2 The following UV curable anaerobic composition was prepared. The amounts used are shown in parts by weight. Dimethacrylate 50 2-Hydroxyethyl Methacrylate 500-Benzoxulfimide 0.5 Cumene hydroperoxide 0.5 1- (2-Carboxyacryloyl) -2-phenylhydrazine 0.1 1-Hydroxycyclohexyl phenyl ketone 2.0 Stabilizer 0.02

Comparative Example 2 1- (2-carpoxyacryloyl) -2-of Example 2
A composition was prepared in the same manner except that 0.5 parts by weight of 1,2,3,4-tetrahydroquinone was used instead of phenylhydrazine.

The resulting composition was irradiated with ultraviolet rays using a 4 Kw high pressure mercury lamp (150 mW / cm ² × 10 seconds),
The surface curability and the shear adhesive strength of glass / glass were adjusted. Further, the anaerobic curing property was examined in the same manner as in Example 1.
The results are shown in Table 2.

[0025]

[Table 2]

Example 3 The following UV curable anaerobic composition was prepared. The amounts used are all parts by weight. Dimethacrylate 50 2-Hydroxyethyl Methacrylate 500-Benzoxulfimide 0.5 Cumene hydroperoxide 0.5 Phenylhydrazine 0.05 Maleic anhydride 0.025-0.1 1 -Hydroxycyclohexyl phenyl ketone 2.0 Stabilizer 0.02 An experiment was conducted under the same conditions as in Example 1. The results are shown in Table 3.

[0027]

[Table 3]

Claims (2)

[Claims] 1. A polymerizable acrylate ester having 1-
(2-Carboxyacryloyl) -2-phenylhydrazine, an organic peroxide, and a photoinitiator are blended, and an ultraviolet-curable anaerobic adhesive composition having fast curing property. 2. The ultraviolet-curable anaerobic adhesive composition according to claim 1, which contains 0-benzoxulfimide.