WO2004099284A1

WO2004099284A1 - Anaerobic curing composition

Info

Publication number: WO2004099284A1
Application number: PCT/JP2004/006131
Authority: WO
Inventors: Aki Kusuyama
Original assignee: Three Bond Co., Ltd.
Priority date: 2003-05-09
Filing date: 2004-04-28
Publication date: 2004-11-18
Also published as: JP2004331879A

Abstract

An anaerobic curing composition consisting of (a) 100 parts by weight of a compound having at least one radical-polymerizable functional group in the molecule, (b) 0.1 to 5 parts by weight of an organic peroxide, (c) 30 to 2000 parts by weight of a compound having at least one glycidyl group in the molecule, and (d) 0.1 to 10 parts by weight of an amine compound per 100 parts by weight of the total amount of the components (a) and (c). The anaerobic curing composition retains fast-curing properties and ease of adhesion process and is reduced in outgassing as compared with those of the prior art.

Description

4 006131

Description 缣 Technical field of air-curable composition>

The present invention relates to an anaerobic curable composition mainly used as an adhesive for electronic components, and more particularly to an anaerobic curable composition that generates less gas than conventional ones. Background technology>

The anaerobic curable composition contains a (meth) acrylate monomer as a main component and is kept in a liquid state without being gelled while in contact with oxygen in the air or the like. It has the property of hardening rapidly when it is removed, and by utilizing such properties, the composition can be used for bonding, fixing, fitting of components such as screws and bolts, bonding of components, bonding between flange surfaces, sealing,に Used for filling burrows generated in structural parts. When faster curing is required, it is used in combination with a curing accelerator such as a primer.

Anaerobic curable compositions have rapid curability at room temperature and have stable physical properties even after curing, so that their use in the electric field has increased significantly. Particularly in the motor field, an anaerobic curable adhesive composition used in combination with a curing accelerator is used for adhesion between a bearing and its shaft, and for fitting and bonding around the shaft due to its productivity.

In recent years, electronic equipment has been required to have higher precision, and there is a concern that gas generated from members may adversely affect components of the electronic equipment. In particular, the gas generated from the adhesive, that is, the art gas, is more likely to be generated than other materials used, and the amount of effort is not so small. However, at present, the anaerobic curable adhesive composition generates an extremely large amount of outgas, and it is becoming impossible to satisfy the requirements for use in electronic devices.

In particular, in a hard disk drive (HDD), which is an external storage device used for a computer, a video deck, and the like, the magnetic recording plate (magnetic disk) As the capacity of magnetic disks has increased year by year and the magnetic recording density has increased, the distance between the magnetic head and the magnetic disk that reads the data has become extremely small. For this reason, if an art gas from the adhesive adheres to the magnetic disk or the magnetic head, a read / write failure occurs and the function of the HDD cannot be exhibited.

Therefore, when applying an anaerobic curable adhesive to parts where the generation of art gas is a problem, such as HDDs, baking for a certain time at a temperature of about 90 ° C or more after using the adhesive should be performed. However, a technique is used in which the exhaust gas generated from the adhesive is expelled in advance. However, very low outgassing requires a very long baking step, and outgassing cannot be completely eliminated. In addition, even after the baking process, there was a problem that further outgassing occurred at high temperatures, and there was a limit to the reduction of outgassing due to baking.

The present invention overcomes the above-mentioned conventional problems.For example, the generation of art gas at a high temperature after a baking process at about 90 ° C. for 1 hour after bonding of parts is compared with the case of using a conventional anaerobic curable composition. An object of the present invention is to provide an anaerobic curable composition which is reduced to about one tenth in comparison with the present invention.

That is, the present invention provides: (a) a compound having at least one or more radical polymerizable functional groups in a molecule: 100 parts by weight; (b) an organic peroxide: 0.1 to 5 parts by weight; ) Compound having at least one glycidyl group in the molecule: 30 to 200 parts by weight, (d) amine compound: 100 parts by weight based on the total amount of components (a) and (c) An anaerobic curable composition comprising 0.1 to 10 parts by weight. BEST MODE FOR CARRYING OUT THE INVENTION>

The compound (a) having at least one or more radically polymerizable functional groups in the molecule used in the present invention is a compound having a butyl group such as acrylic acid or methacrylic acid in the molecule, preferably at the terminal of the molecule. Yes, monomer, oligomer, polymer Is mentioned.

More specifically, the polymerizable monomer may be, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, 2-ethyl hexylhexyl (meth) acrylate, phenyl (meth). Monoesters such as acrylate and benzinole (meta) acrylate; hydroxyalkyl esters such as 2-hydroxyshethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; ethylene glycol dia Polyesters such as acrylate, polyethylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropanetri (meth) acrylate, and pentaerythritol tetraacrylate, but are not limited to these. Not something to be done What is usually used in the field of anaerobic adhesives can be used. These polymerizable monomers can be used alone or as a mixture of two or more. Examples of the polymerizable oligomer include a curable resin having a malate group, a fumarate group, an aryl group, a (meth) acrylate group, an isocyanate-modified acryloligomer, an epoxy-modified acrylyl oligomer, a polyester acrylyl oligomer, and a polyether acrylate. Clinole oligomers and the like, and these oligomers can be used alone or as a mixture of two or more.

As the polymerizable polymer, a polymerizable unsaturated polymer such as an unsaturated polyester resin and an unsaturated acryl resin can be used.

These monomers, oligomers and polymers having polymerizability can be used together for the purpose of adjusting the viscosity of the anaerobic curable composition or adjusting the physical properties of the cured product.

The organic peroxide (b) used in the present invention is conventionally used in anaerobic curable compositions, and is not particularly limited. For example, cumenehide mouth baroxide, t-pentinoleide mouth peroxide, ρ-menthanehydride dropoxide, methinoleethynoletone ketone peroxide, cyclohexane peroxide, dicumyl peroxide, diiso Hydroperoxides such as propylbenzene hydroperoxide, etc., ketone peroxides, diarylperoxide Organic peroxides such as oxides and peroxyesters, and the like can be mentioned.

These organic peroxides can be used alone or as a mixture of two or more. The compounding amount of the component (b) is 0.1 to 5 parts by weight, preferably 0.5 to 4 parts by weight based on 100 parts by weight of the component (a). In this case, if it is less than 0.1 part by weight, it is insufficient to cause a polymerization reaction, and if it is more than 5 parts by weight, the storage stability of the thermosetting composition is reduced.

The component (c) used in the present invention is a compound having at least one glycidyl group in the molecule. The glycidyl group is also called an oxysilane ring or ethylene oxide, and a compound having a glycidyl group is sometimes simply called an epoxy resin. A typical example of the component (c) is an epoxy resin containing an average of two or more epoxy groups per molecule. For example, bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin , Glycidyl dimer ester type epoxy resin, polyalkylene ether type epoxy resin, phenol novolak type epoxy resin, orthocresol nopolak type epoxy resin, biphenyl type epoxy resin, dicyclopentadiene type epoxy resin, naphthol type epoxy resin Resin, naphthalene type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, diglycidyl epoxy resin, glycidylamine type epoxy resin, etc., and these may be used alone or in combination of two or more. May be.

Epoxy resins containing only one glycidyl group in the molecule are usually low molecular weight compounds, and are called reactive diluents for epoxy resins, and are used to adjust viscosity, adjust physical properties of cured products, and adjust curing speed. To be added.

The component (c) is blended in an amount of 30 to 200 parts by weight, preferably 30 to 100 parts by weight, based on 100 parts by weight of the component (a). If the amount is less than 300 parts by weight, the amount of art gas generated during curing increases, and if it is more than 200 parts by weight, the anaerobic curability deteriorates.

The component (d) is an amine compound. Component (d) acts as a curing agent for component (c). Examples of the amine compounds include heterocyclic compounds such as 1,2,3,4-tetrahydroquinoline and 1,2,3,4-tetrahydroquinaldine. Secondary amines, quinoline, methylquinoline, quinaldine, and quinoxaline phenazine Grade 3 Amin, N, N —Aromatic tertiary amines such as dimethylanisidine, N, N-dimethylaniline, 1,2,4-triazonole, oxazonole, oxaziazono / re, thiadiazonole, benzotriazonole, hydroxybenzotriazonole Benzoxazonole, 1,2,3 benzothiadiazole, azonole compounds such as 31-mercaptobenzotrizonole, 2-ethinolay 4-methinoreimidazonole, 1-benzylimidazole 2-methylimidazole, Imidazole compounds such as 1-isopuchi / ray 2-methylimidazole; There are many compounds that cure the component (c) in addition to the above-mentioned amine compounds, but the storage stability of the components (a) and (b) is impaired if the compounds are other than the above-mentioned amine compounds. Not suitable for formulation. The above-mentioned amine compounds are preferably used because the storage stability is not impaired even if they are blended.

The mixing ratio of the component (d) is 0.1 to 10 parts by weight with respect to 100 parts by weight of the total amount of the component (a) and the component (c). If the compounding ratio of the curing agent is less than 0.1 part by weight, there is no effect as a curing agent, and if it exceeds 10 parts by weight, the storage stability deteriorates. However, when it is desired to add more than 10 parts by weight, for example, to further improve the curability, the component (d) is not added to the present composition, but becomes two-part when mixed when used. It is also possible. In this case, the amount of the component (d) exceeding 10 parts by weight may be separately mixed, or the entire component (d) may be separately mixed.

In addition to the above components, a component that promotes polymerization of component (a), that is, anaerobic curability, can be added to the present composition. Examples of the polymerization accelerator include o-benzoxyl humide, a mercaptan compound, and a hydrazine compound. Examples of the mercaptan compound include straight-chain mercaptans such as n-dodecyl mercaptan, ethyl mercaptan, and butyl mercaptan. As the hydrazine compound,

1-acetinolate 2-pheninolehydrazine, 1-acetinolene 2- (p-trinore) hydrazine, 1-benzoinole-1--2-pheninolehydrazine, 1- (1,1,1,, 1-trinoole) mouth 2 _Feninolehydrazin, 1,5-dipheninolecanolepo 'hydrazine, 1forminole 2 1Feninolehydrazine, 1acetinole 1-(p-promofenole) Hydrazine, 1-acetinole 2 _ ( p—Trofe Examples include drazine, 1-acetinol-one (2'-feninoleethynolehi-drazin), ethinole-nore-basazate, N-aminominole-hodanine, p-ditrophene-hydrazine, and ρ-tris-ruphonylhydrazide. The addition amount of these polymerization accelerators is preferably 0 to 0.5 part by weight based on 100 parts by weight of the component (a).

The present invention can further use various additives. For example, in order to obtain storage stability, a radical absorbent such as benzoquinone, hydroquinone, or hydroquinone monomethinoleate, ethylenediamine tetraacetic acid or its 2-sodium salt, oxalic acid, acetylaceton, o-- Metal chelating agents such as aminophenol may be added. These additives for improving the storage stability are preferably 0 to 1 part by weight based on 100 parts by weight of the component (a).

In addition, a thickener, a filler, a plasticizer, a colorant, and the like can be used as needed to adjust the properties of the anaerobic curable resin and the properties of the cured product.

When the anaerobic curable composition of the present invention is used, a curing accelerator can be used to accelerate anaerobic curability. The curing accelerator is obtained by dissolving a metal complex useful for improving anaerobic curability in an organic solvent, and is generally called a primer. The solvent is volatilized by applying it to the adherend in advance, and the metal complex adheres to the surface of the adherend, which has the effect of accelerating the anaerobic curing of the anaerobic adhesive to be applied later. As a component of the curing accelerator to be used, various copper complexes typified by copper 2-ethylhexanoate and copper naphthenate, and vanadium are generally used, but any metal complex that improves anaerobic curability can be used. Can be used.

Since the composition of the present invention has anaerobic curability, air or oxygen is cut off by applying and bonding or fitting to an adherend, and the composition is cured and adhered. This is due to the fact that the components (a) and (b) harden and develop an adhesive force. (C) The component is not cured at this point, but is cured by heating in the baking step, and the entire composition is completely cured. Then, a cured product that hardly generates outgas can be obtained.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. It is not limited to these. All the compositions in the table are parts by weight.

[Examples 1 and 2, Comparative Examples 1 to 5]

As the materials used in the examples, an acrylyl monomer mixture (1: 1 mixture of BP-2EM (Kyoeisha Chemical) and light ester HO (Kyoeisha Chemical)) was used as the component (a). With respect to 100 parts by weight, 2 parts by weight of cumene hydroperoxide as a component (b), 1 part by weight of o-benzoituxulamide as a polymerization accelerator, and 1 part by weight of a component (c), the following Table 1 The amount of Epicot 828 (oiled shell epoxy) and Epicot 807 (oiled shell epoxy) shown in 11 were blended. Further, as the component (d), an adhesive was prepared using 5 parts by weight of 1-benzyl-1-methylimidazole with respect to 100 parts by weight of the component (a). In Comparative Examples, adhesives were prepared by changing the composition as shown in Tables 12 and 13 below. The test piece used in the set time test and the adhesive strength test was made of SPCC_SD, 100 mm x 25 mm (JISG3141), and 0.5 parts of 2-ethylhexane was used as a primer in 100 parts of acetoneton. What melt | dissolved the copper oxide The thing which apply | coated and dried beforehand was used.

Approximately 0.06 g of each of the compositions obtained above was dropped on the test piece, and the test pieces were overlaid. Similarly, the test pieces were overlapped at the ends of 1 cm, baked at 90 ° C for 1 hour, and the tensile strength was measured at room temperature. For outgas measurement, weigh 20 mg of each sample, conduct continuous measurement at 90 ° C for 3 hours using TGZDTA 220, a heat loss measuring device manufactured by Seiko Instruments Inc., and measure the first hour. As the king time, the weight loss was measured 2 hours after the completion of baking. table 1

Table 1 _ 2

Comparative Example 1 Comparative Example 2 Comparative Example 3 Specific Acryl Monomer Mixture 100 100 100 Cumene Halo Dropperoxide 2 2 2 Polymerization Accelerator 1 1 1 Epicoat 828 0 20 0 Epicoat 807 0 0 10

1 1 Benzino 1 2-Metinorei Midazono 5 5 5 Set time (sec) 15 16 15 Hard strength (MPa) 1 3 1 5 1 3 Outgas volume (%) 5. 6 2. 3 3.5

As is clear from Table 1, the composition of the present invention shows a remarkable decrease in the amount of art gas generated as compared with Comparative Example 1 which is a conventional thermosetting adhesive to which the component (c) was not added. Can be Also, the set time and strength are satisfactory. As a matter of course, as in Comparative Example 4 and Comparative Example 6, the composition without the component (a) and the component Z or the component (b) did not result in curing.

As described above, the present invention has the quick curing property unique to the anaerobic curable composition and the easiness of the bonding step, and can drastically reduce the amount of outgas generated. Therefore, the present composition can be used in locations where art gas, such as HDD, is problematic when generated. Although the present invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

This application is based on a Japanese patent application filed on May 9, 2003 (Japanese Patent Application No. 2003-131837), the contents of which are incorporated herein by reference.

Claims

The scope of the claims

1. (a) Compound having at least one or more radically polymerizable functional groups in the molecule: 100 parts by weight, (b) Organic peroxide: 0.1 to 5 parts by weight, (c) In the molecule Compound having at least one glycidyl group: 30 to 200 parts by weight, (d) amine compound: 0.1 to 1 part by weight based on 100 parts by weight of the total of component (a) and component (c) An anaerobic curable composition comprising 0 parts by weight.

2. The anaerobic curable composition according to claim 1, comprising 0.5 to 4 parts by weight of the component (b) based on 100 parts by weight of the component (a).

3. The anaerobic curable composition according to claim 1, wherein the component (c) is contained in an amount of 30 to 100 parts by weight based on 100 parts by weight of the component (a).

4. The anaerobic curable composition according to claim 1, wherein the component (c) is an epoxy resin having an average of two or more epoxy groups per molecule.