JPS61101579A - Photocurable anaerobic adhesive composition - Google Patents

Abstract

PURPOSE:To improve interfacial adhesion, by incorporating a particular phosphorus compd. with a photocurable anaerobic adhesive compsn. comprising a (meth) acrylate monomer, org. peroxide, and photosensitizer. CONSTITUTION:A phosphorus compd. selected from among those of formula I or II (wherein R1 is -H, -CH3, -C2H5; R2 is -CH2-, -C2H4-, -CH2CH2CH2-, the formula III, the formula IV; m is 1-10; n is 1, 2) is added to a photocurable anaerobic adhesive compsn. comprising an anaerobically polymerizable monomer selected from among a methacrylate or acrylate monomer, an org. peroxide, and a photosensitizer. If necessary, a polymn. accelerator, polymn. inhibitor, colorant, thixotropic agent, filler, etc., may be added to said adhesive compsn.

Description

Detailed Description of the Invention (a) Purpose of the Invention [Field of Industrial Application] A chemical composition is a composition that does not harden while in contact with air or oxygen and is shielded from light and is stable for a long period of time. It is a curable composition that can be easily polymerized and cured by placing it between two adjacent surfaces, for example, to block air and irradiating it with light, generally ultraviolet light.

[Conventional technology]

This type of photocurable anaerobic composition contains an anaerobically polymerizable acrylic ester monomer and/or methacrylic ester monomer (hereinafter referred to as anaerobically polymerizable monomer) as a main component. Conventionally, monomers containing an organic peroxide and a photosensitizer as a polymerization initiator have been known. When such a conventional photocurable anaerobic adhesive composition is used for purposes such as adhesion, sealing, and fixing, the composition is applied, and the parts that are in contact with oxygen are cured by irradiation with ultraviolet rays.
We try to polymerize and harden the parts that are not exposed to ultraviolet rays anaerobically, but when we measure the tensile shear adhesive strength and the mating compressive shear adhesive strength after curing, we find that sufficient strength cannot be obtained. was there.

[Problems to be Solved by the Invention] One object of the present inventors is to solve the above-mentioned problems in conventional photocurable anaerobic adhesive compositions and provide an adhesive composition with improved interfacial adhesive strength. .

(B) Structure of the Invention [Means for Solving Problems] As a result of searching for means for improving the interfacial adhesion of a photocurable anaerobic composition, the present inventors discovered a specific structure as described above. We have completed the present invention by discovering the fact that a phosphorus compound having a The phosphorus compound to be
It is represented by the above formula (I) or (It), and specific examples thereof include the following.

Compounds represented by formula [I] where n is 1: 2-acryloyloxyethyl phosphate 7ate, 2-methacryloyloxyether phosphate, 2-methacryloyloxyisopropyl phosphate, etc.

Compounds represented by formula [l] where n is 2: bis(2-methacryloyloxyethyl) phosphate, bis(2-acryloyloxyethyl) phos-7ate, bis(2-methacryloyloxypropyl) phos-7ate, etc.

Compound represented by formula (It) where n is 1 = 1-chloromethyl 2-methacryloyloxyethyl phosphate, 1
-chloromethyl 2-acryloyloxyethyl phosphate, etc.

Compounds represented by formula (n) where n is 2: bis(1-chloromethyl 2-methacryloyloxyethyl) phosphate, bis(1-chloromethyl 2-acryloyloxyethyl) phosphate, bis(1-chloromethyl 2-acryloyloxyethyl) phosphate oxypropyl) phosphate, etc.

The preferred blending amount of the phosphorus compound is 0.1 to 10 parts by weight per 100 parts by weight of the total amount of each component excluding the phosphorus compound from all the components constituting the photocurable anaerobic adhesive composition. be.

[Anaerobically polymerizable monomer]

The anaerobically polymerizable monomers used in the present invention are acrylic ester and/or methacrylic ester monomers [hereinafter collectively referred to as (meth)acrylic esters] due to the coexistence of organic oxides described below. Any material may be used as long as it can be polymerized anaerobically.

An example of this is as follows.

[1] A monomer represented by the general formula % (1) or a reaction product of this monomer and an incyanated metal.

However, in the formula, R3 represents hydrogen or a methyl group, and R4 is -
CH, -CH,, -CH, -CH2-CH, or CH
.

-CH-CH3, in which hydrogen at an arbitrary position is eliminated to form a hand for bonding to an OH group and/or a halogen atom, and n is an integer of 1 to 6.

Specific examples of the monomer represented by the general formula [1] are listed below. In addition, in this specification, acrylate and methacrylate may be collectively referred to as (meth)acrylate.

2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 1,2-dihydroxyethyl (meth)acrylate, 2-hydroxy-
3-chloropropyl (meth)acrylate, etc.

[2] General formula %formula% Monomers shown in

However, R5 is the same as the above general formula [1], and also is hydrogen, -
CH,, -C2H,, -CH,OH or -C1-12-
0-C-C-CH2, horse represents hydrogen, -OH80 or -CH2-O-C-C-cH2, R8 represents hydrogen, 8゛chlorine, methyl group or ethyl group, m represents An integer of 1 to 8 is shown, n is an integer of 1 to 20, and p is 0 or 1.

Specific examples of the monomers represented by the general formula [2] are listed below.

Diethylene glycol dimethacrylate, triethylene glycol diacrylate, triethylene glycol dimethacrylate, tetraethylene glycol dimethacrylate, 1,2-propylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, di(pent-methylene glycol) dimethacrylate, Tetraethylene glycol diacrylate, tetraethylene glycol di(chloro-acrylate), di-glycerol diacrylate, glycerin trimethacrylate, trimethylolpropane trimethacrylate, di-glycerol tetramethacrylate, 6,9-bis(1゜1-dimethyl- 2-hydroxy)-2,4,8°10-tetraoxaspiro(S,S)undecane dimethacrylate, etc.

[3] General formula % Formula % However, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, R1° represents an alkylene group having 2 to 4 carbon atoms,
m represents an integer of 2 to 8.

Specific examples of the monomer represented by the general formula [5] are listed below.

2.2-bis(4-methacryloxyjethoxyphenyl)propane, 2.2-bis(4-methacryloxytriethoxyphenyl)propane, 2.2-bis(4-methacryloxytetraethoxyphenyl)propane, 2, 2-
Bis(4-methacryloxypentaethoxyphenyl)propane, 2,2-bis(4-methacryloxyhexaethoxyphenyl)propane, 2,2-bis(4-methacryloxyhexaethoxyphenyl)furopane, 2,2-bis( 4-methacryloxyoctaethoxyphenyl)propane, 2.2-bis(4-methacryloxydipropoxyphenyl)propane, 2.2-bis(4-methacryloxytriethoxyphenyl)propane, 2゜2-bis(4
-methacryloxyoctapropoxyphenyl)furopane, 2. 2-his(4-methacryloxydibutoxyphenyl)propane, 2.2-bis(4-methacryloxytributoxyphenyl)furopane, 2. 2-His (4-
Methacryloxyoctabutoxyphenyl)propane, 2
．． 2-bis(4-acryloxyjethoxyphenyl)furopane, 2.2-bis(4-7acryloxydibutoxyphenyl)propane, 2(4-methacryloxyjethoxyphenyl)-2(4-methacryloxytri ethoxyphenyl)propane, 2(4-methacryloxydipropoxyphenyl)-2(4methacryloxytriethoxyphenyl)furopane, 2,2-bis(4-αethylacryloxyjethoxyphenyl)propane, 2,2- Bis(α-propylacryloxyjetoxyphenyl)propane, 2
(4-αethyl acryloxyjetoxyphenyl)-2
(4-methacryloxyjethoxyphenyl)propane, etc.

[4] General formula A monomer indicated by .

However, RlI represents H, CH, or C, H, and B,
2 is -CH2-, -C,H,-, C8H,- or -CH
,-('H-CH.

, n represents O and an integer from 1 to 10.

Specific examples of the monomer represented by the general formula [4] are listed below.

Dicyclopentenyl (meth)acrylate, dicyclopentenyloxymethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, etc.

It is preferable that the above-mentioned anaerobically polymerizable monomers be pure products, but they may be of industrial grade containing trace amounts of polymerization inhibitors, stabilizers, and the like.

[Organic peroxide]

The organic peroxide used in the present invention acts as a polymerization initiator for anaerobically polymerizable monomers and imparts anaerobic curing properties to the composition, and includes, for example, benzoyl peroxide, methyl ethyl ketone peroxide, and cyclohexanone peroxide. Examples include oxide, cumene hydroperoxide, ditertiary butyl peroxide, tertiary butyl perbenzoate, lauroyl peroxide, dicumyl peroxide, and the like. The type and amount of the added amount is already good (as is known, it only needs to be a catalytic stoichiometric amount that is sufficient to act as a polymerization initiator and impart anaerobic curing properties to the composition, and the amount that is commonly used). That's enough.

-4゜[Photosensitizer] In the present invention, for example, benzoin, benzoin ethyl ether, benzoin ibutyl ether, benzoin octyl ether, hensyl, diacetyl, methylanthraquinone, acetophenone, benzophenone, diphenyl disulfide, dithiocyano(-mate) , α−
Chlormethylnaphthalene, anthracene, iron chloride, benzyl dimethyl ketal, etc. are used as photosensitizers.

The amount added is preferably 0.01 parts to 20 parts per 100 parts (parts by weight, same hereinafter) of the composition to which it is added.
part, more preferably in the range of 0.1 to 10 parts.

Desired [Specially Added Components] In addition to the above-mentioned components, various substances may be added to the composition of the present invention for various purposes.

For example, an appropriate amount of a polymerization accelerator may be added and mixed, and examples of the polymerization accelerator include 1. 2. 5゜4-Tetrahydroquinoline, ortho-sulfobenzoic acid imide, triethylamine, N,N-dimethylaniline, etc. are used, and the amount added varies depending on the type of polymerization accelerator, etc., and cannot be definitively determined, but examples are shown below. and 1. for 100 parts of (meth)acrylic ester monomer. 2. 3.
0.1 to 5 parts of 4-tetrahydroquinoline, ortho-
Preferably, 0.2 to 2 parts of sulfobenzoic acid imide and 0.1 to 1 part of triethylamine are used.

In addition, polymerization inhibitors such as oxalic acid, dinitrone resorcinol, and quinones are added to improve stability, dyes and pigments are added for coloring, thixotropic agents are added to give thixotropic properties, and thixotropic agents are used to increase viscosity and weight. Fillers such as silica can be added for different purposes.

The composition according to the present invention can be easily prepared by mixing and dissolving the components described above at room temperature or under heating.

It can be used in the same manner as the agent composition, and its curing can be easily achieved by applying means commonly employed for the composition.

[Example, comparative example]

Next, the present invention will be explained in detail based on Examples and Comparative Examples.

Examples 1 to 9 and Comparative Examples 1 to 3 A composition having the type and composition t (parts) of each component shown in Table 1 was prepared in Test 7 (Q, 6 x 25 x 100 sm
The exposed composition was photocured under the following predetermined conditions, and after curing at room temperature for 24 hours, the tensile shear strength was measured according to JIS K-6850.

Photo-curing conditions: (Photo-curing device used) Ushio Inc. Uniqui Air UV-4
000 (Lamp output) 80W/cIL (Lamp irradiation distance) 103 (Lamp irradiation time) 30 seconds. However, Examples 4 to 6 and Comparative Example 2 were 120 seconds.

As a result, it was confirmed that there was no surface tack on the composition in the portion of the test piece that protruded from the joint and was in contact with air, and was well cured. Table 1 shows the tensile shear strength.
As described above, the compositions of each example were significantly superior to the compositions of each comparative example, and the effect of improving interfacial adhesion by blending the phosphorus compound specified in the present invention was extremely remarkable. be.

(c) Effects of the invention When the composition of the present invention is used as an adhesive, the parts that are in contact with oxygen are irradiated with light, and the parts that are cut off from contact with oxygen are anaerobically treated. Both of these are excellent in that they cure easily and quickly, exhibiting adhesive strength and high C/fitting compressive shear strength, and are light-curing types that have significantly improved interfacial adhesive strength compared to conventional products. It is an anaerobic adhesive composition.

Claims (1)

[Scope of Claims] 1. One or more anaerobically polymerizable monomers selected from the group consisting of methacrylic acid ester monomers and acrylic acid ester monomers, an organic peroxide, and A photocurable anaerobic adhesive composition comprising a photosensitizer and one or more phosphorus compounds selected from the group consisting of compounds represented by the following formula [I] or [II]. thing. [I]▲There are mathematical formulas, chemical formulas, tables, etc.▼ [II]▲There are mathematical formulas, chemical formulas, tables, etc.▼ (The meanings of the abbreviations in the above formula are as follows. R_1: -H, -CH_3 or - C_2H_5. R_2: -CH_2-, -C_2H_4-, -CH_2
CH_2CH_2-, ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼. m: an integer from 1 to 10. n: 1 or 2. )