JPH0366781A - Anaerobically curable tacky agent composition - Google Patents

Abstract

PURPOSE:To obtain the title composition showing tacky properties in bonding, temporarily bondable to a material to be pasted, then showing firm bond strength by pressurization, comprising a resin containing an ethylenic unsaturated group on the side chain, a microcapsulated peroxide and a specific metallic compound. CONSTITUTION:The objective composition comprising (A) a resin containing an ethylenic unsaturated group on the side chain prepared by reacting (i) a tertiary amino group-containing rubber-like polymer optionally with (ii) a cyclic acid anhydride and (iii) a monomer containing an ethylenic unsaturated group and an epoxy group or aziridinyl group, (B) a microcapsulated peroxide and (C) one or more compounds of metal selected from Ca, Ba, Zr, V, Mn, Co, copper, lead, Li, Mo, Sr, Ce and zinc and/or (D) a tertiary amine.

Description

[Detailed Description of the Invention] [Objective of the Invention] (Industrial Field of Application) The present invention has adhesive properties during bonding, can temporarily adhere to an adherend, and then crushes the microcapsules by applying pressure. The present invention relates to an anaerobically curable adhesive composition suitable as a so-called pressure-sensitive adhesive, which exhibits strong adhesive strength when cured.

(Prior Art) Conventionally, as an anaerobic curable adhesive composition, one in which a rubber-like adhesive polymer is blended with a bireactive oligomer or monomer and an organic hydroperoxide has been known (Japanese Unexamined Patent Application Publication No. 59-1999). -199784 Publication, JP-A-60
(See Japanese Patent Laid-Open No. 60-6773, Japanese Patent Application Laid-open No. 11568-1982, Japanese Patent Laid-open No. 13868-1986, etc.). However, in these compositions.

For adding reactive oligomers or monomers.

The cohesive force decreases, and during the period from adhesion to pressure curing, especially when applying pressure, it often causes displacement or peeling. In order to achieve this, it was sometimes necessary to mechanically temporarily fasten the material. Additionally, in these compositions.

When used as an adhesive sheet or adhesive tape, it has drawbacks such as difficulty in long-term storage because it is blocked from oxygen and the curing reaction proceeds.

In addition, 1. Using a rubber-like adhesive polymer that has been given reactivity by introducing an unsaturated group into the side chain (
JP-A-59-199785, etc.) are also known, but in order to increase the curability, it is necessary to add monoreactive oligomers or monomers, and a decrease in cohesive force is unavoidable.

On the other hand, if the amount of reactive oligomer or monomer added is reduced in order to improve the adhesive properties before curing, the curability will decrease and the adhesive strength after curing will decrease. in this way.

An anaerobic curable adhesive composition that has sufficiently excellent adhesive properties before curing and adhesive strength after curing has not been developed.

(Problems to be Solved by the Invention) The present invention solves the above-mentioned problems in conventional anaerobic curable adhesive compositions, such as poor balance between adhesive properties before curing and adhesive strength after curing. Anaerobic curing improves the shortcomings and has excellent adhesive properties before curing, especially cohesive force, and adhesive strength after curing, has high curability, and can be stored for a long time without curing even in oxygen-blocked conditions. The present invention provides a sticky adhesive composition.

[Structure of the invention]

(Means for Solving the Problems) The present invention provides a rubbery polymer (a) having a tertiary amino group.
, optionally a cyclic acid anhydride (b), and a resin having an ethylenically unsaturated group in the side chain obtained by reacting a monomer (C) having an ethylenically unsaturated group and an epoxy group or an aziridinyl group ( A), microencapsulated peroxide (B), calcium compound barium compound,
Zirconium compounds, vanadium compounds, manganese compounds, cobalt compounds, copper compounds, lead compounds, iron compounds,
1 selected from lithium compounds, molybdenum compounds, strontium compounds, cerium compounds and zinc compounds
species or two or more metal compounds (C) and/or
This is an anaerobic curable adhesive composition consisting of a tertiary amine (D).

In the present invention, the rubbery polymer (a) having a tertiary amino group is an acrylic resin having a tertiary amino group, and a homopolymer of a monomer having a tertiary amino group,
These include copolymers of these monomers, and copolymers of these monomers with other monomers such as alkyl (meth)acrylates, vinyl acetate, vinyl propionate, vinyl ether, styrene, and (meth)acrylonitrile.Tertiary Monomers having an amino group include 4 dimethylaminoethyl (meth)acrylate, diethyla-noethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, vinylpyrrolidone, vinylcaprolactam, vinylcarbazole crystal, vinylimidazole, divinylethylene urea, etc. As an alkyl (meth)acrylate.

Alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, and octyl (meth)acrylate. Also,
In addition to the above monomers, hydroxyl groups are used to improve adhesion and to use tertiary amino groups and ε as starting points for introducing ethylenically unsaturated groups into the side chains.

A monomer having a functional group such as a -class amino group or a secondary amino group can also be used. Examples of these monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate.

Examples include (N--alkyl)agonoethyl (meth)acrylate.

In the present invention, the cyclic acid anhydride ('b) is an intramolecular anhydride of a polycarboxylic acid, such as a saturated or unsaturated aliphatic polycarboxylic anhydride, an alicyclic polycarboxylic anhydride, an aromatic Group polycarboxylic acid anhydrides, etc., or partially saturated or unsaturated hydrocarbon groups.

Some are substituted with aromatic ring groups, halogen atoms, heterocyclic groups, etc. Specific examples of these include succinic anhydride, phthalic anhydride, maleic anhydride, itaconic anhydride, glutaric anhydride, and dodecenyl succinic anhydride. acid.

Chlorendic anhydride, pyromellitic anhydride, trimellitic anhydride, cyclopentanetetracarboxylic dianhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, tetramethylene maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride acid, endomethyl L/tetrahydrophthalic anhydride, methylendomethylenetetrahydrophthalic anhydride, 5- (2,5
-dioxotetrahydroxyfuryl)-3-methyl-3
-Cyclohexene-1,2-dicarboxylic anhydride, methylnadisocic anhydride, benzophenonetetracarboxylic anhydride, ethylene glycol bis(anhydrotrimellitate).

Examples include glycerol tris (anhydrotrimellitate). Among these, it is preferable to use dicarboxylic acid or tricarboxylic acid anhydrides that do not form a crosslinked structure.

In the present invention, the monomer (C) having an ethylenically unsaturated group and an epoxy group or an aziridinyl group includes:
Glycidyl (meth)acrylate, glycidyl cinnamate, allyl glycidyl ether, vinylcyclohexene monoepoxide, 1,3-butadiene monoepoxide, etc. having epoxy groups, 2-(1-aziridinyl)ethyl(meth)acrylate), 2-(1-aziridinyl)butyl(meth)acrylate, 2-(1-
Some have an aziridinyl group such as aziridinyl)propyl(meth)acrylate, and these may be substituted with a saturated or unsaturated hydrocarbon group, an aromatic ring group, a halogen atom, a heterocyclic group, etc.

The rubbery polymer (a), the cyclic acid anhydride (b), and the monomer (C) are reacted to obtain a resin (A) having an ethylenically unsaturated group in the side chain. The reaction is carried out in the presence or absence of a suitable solvent. At this time, the tertiary amino group itself acts as a catalyst for the reaction, so the reaction proceeds without a catalyst. , N-diethylaniline, N,N-dimethylaniline and the like can also be used as catalysts. Furthermore, in order to keep the ethylenically unsaturated groups present during this reaction stable, it is possible to carry out the reaction with the addition of a radical polymerization inhibitor such as hydroquinone, hydroquinone monomethyl ether, tert-butylcatechol, or p-benzoquinone. can.

In the reaction, first, the tertiary amino group of the rubbery polymer (a) reacts with the epoxy group or aziridinyl group of the monomer (C), and then the secondary hydroxyl group or amino group generated by this reaction reacts with the cyclic acid. The anhydride I+yJ(b) reacts with the acid anhydride group to produce a carboxyl group. Furthermore, this carboxyl group reacts with the epoxy group or aziridinyl group of the monomer (C) to produce a hydroxyl group or an aziridinyl group, and the same reaction as above can proceed in sequence, resulting in a rubber-like polymer. By adjusting the amount of cyclic acid anhydride (b) and monomer (C) reacted with respect to the amount of (a), a desired number of ethylenically unsaturated groups can be added to the rubbery polymer (a). A slightly longer side chain with a length of can be introduced.

When the cyclic acid anhydride (b) is a dicarboxylic acid anhydride, 0 to 9 mol of the cyclic acid anhydride (b) and the monomer (c
) in a proportion of 1 to 10 mol, and also cyclic acid anhydride (b
It is preferable to react the monomer (C) at a ratio of approximately 1 mole more than that of the monomer (C). When the cyclic acid anhydride (b) is a tricarboxylic acid, 0 to 9 mol of the cyclic acid anhydride (b) and 1 to 9 mol of the monomer (c) per 1 mol of the tertiary amino group of the rubbery polymer (a) are used. In a proportion of 19 moles, also
Monomer (c) per n mole of cyclic acid anhydride (b)
) is preferably reacted in a proportion of approximately n+l to 2n+1 moles. When the amount of monomer (c) reacted with respect to 1 mole of tertiary amino groups of rubbery polymer (a) is less than 1 mole, the number of ethylenically unsaturated groups in the resulting resin (A) is small. In some cases, sufficient reactivity cannot be imparted to the resin (A), and conversely, the cyclic acid anhydride (b)
When the amount exceeds 9 moles, unreacted cyclic acid anhydride (b) and monomer (c) remain and are not bonded to the rubbery polymer (a).

There is a tendency for more reaction products between the cyclic acid anhydride (b) and the monomer (c) to be produced. The resulting resin (A) is:

Since the resin (A) itself has sufficient curability, it has sufficient curability and is suitable for use with reactive oligomers and monomers. Even without the use of adhesive, it exhibits sufficient adhesive strength after curing. Moreover, since it has an ethylenically unsaturated group in its side chain, the adhesive properties, especially the cohesive force, of the rubbery polymer fa) are maintained, and the resulting resin (A) has excellent adhesive properties before curing. As a result, the resin (A) obtained has a sufficiently excellent balance between adhesive properties before curing and adhesive strength after curing.

In the present invention, peroxides include tert-butyl hydroperoxide, 1.1,3.3-tetramethylbutyl hydroperoxide, p-menthane hydroperoxide, cumene hydroperoxide, methyl ethyl ketone peroxide, p- Cymen hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, cyclohexanone peroxide, methylcyclohexanone peroxide, 3.3. Hydroperoxides such as s-trimethylhexanone peroxide, di-tert-butyl peroxide, te
rt-Butyl rubber oxide 1 Examples include peroxide ides such as dicumyl peroxide, benzoyl peroxide, and acetyl peroxide. Peroxide in E.

2 is preferably used in an amount of 0.1 to 15 parts by weight based on 100 parts by weight of the resin (A) having an ethylenically unsaturated group in its side chain.

There are no particular limitations on the method for micro-encapsulating the peroxide, as disclosed in Japanese Patent Publication No. 38-19574.

Japanese Patent Publication No. 42-446, Japanese Patent Publication No. 771-771, Japanese Patent Publication No. 2882-1982, Japanese Patent Publication No. 422883, and Japanese Patent Publication No. 115371-1971.

Interfacial polymerization method described in JP-A No. 60-60173, etc., JP-A No. 36-9168, USP 34272
In 5 in situ polymerization method described in JP 50, BP 1236498, etc., USP 3787327, USP 3551346, USP 3574133
In-liquid curing coating method described in publications, etc., USP 280
No. 0457, USP2800458, USP
No. 3531418, USP No. 3577515,
Comaservation method (phase separation method) described in BP1117i78 Publication tJsP3523906 Publication, υ
Microcapsules can be formed by the interfacial precipitation method described in 5P3660304 and the like, the spray drying method described in 15P3830750, and the like. Among these methods, the thickness of the microcapsule wall can be freely controlled, the thickness of the macrocapsule wall can be made uniform, and the strength of the microcapsule wall can be increased. Microcapsules are preferably formed by an interfacial polymerization method using Voluria as the microcapsule wall, or a composite coacervation method using gelatin and gum arabic as the microcapsule wall.

A method for microencapsulating peroxide using an interfacial polymerization method using Voluria as the microcapsule wall is as follows:
A solution in which a polyisocyanate compound and the above peroxide are dissolved in a hydrophobic solvent is dispersed in an aqueous solution in which a dispersant is dissolved, a water-soluble polyamine is added to the resulting dispersion, and the mixture is stirred at room temperature to disperse. This is a method to form Volurian walls on the surface of the material. As polyisocyanate compounds,
There are no particular restrictions.

2.4-tolylene diisocyanate, 2.6-tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate hexamethylene diisocyanate-1, isophorone diisocyanate, lysine diisocyanate, dimeryl diisocyanate 1, hydrogenated tolylene diisocyanate, etc. , or a mixture thereof. The hydrophobic solvent is not particularly limited and may be any solvent as long as it is substantially incompatible with water, such as benzene, toluene, xylene, cyclohexane, hexane, ligroin, methyl acetate, ethyl acetate, and dibutyl phthalate.

Examples include methyl isobutyl ketone.

The above polyisocyanate compound usually contains 1 hydrophobic solvent, 1
It is added in a proportion of 0.1 to 50 parts by weight per 00 parts by weight. In addition, 1 the above peroxide is 1 usually a hydrophobic solvent 100
It is added at a ratio of 10 to 100 parts by weight. Examples of dispersants include gelatin or modified products thereof, gum arabic, sodium alginate, polyvinyl alcohol, polyvinyl birolide dimethyl cellulose, and carboxymethyl cellulose.

Maleic anhydride copolymer, pluronisoc type surfactant, sucrose fatty acid ester, sorbitan fatty acid ester,
Alkyl quaternary ammonium salts such as alkylbenzene sulfonate, alkylnaphthalene sulfonate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl ether, alkyltrimethylammonium chloride, etc., or mixtures thereof can be used as appropriate. These dispersants are usually used in a proportion of 0.01 to 50 parts by weight per 100 parts by weight of water, although they vary depending on the type. A solution in which a polyisocyanate compound and a peroxide are dissolved in a hydrophobic solvent is added at a ratio of 1 to 80 parts by weight to 100 parts by weight of an aqueous solution in which 9 dispersant is dissolved, and dispersed by stirring. It will be done. By adjusting the stirring speed, the particle size of the hydrophobic solvent solution can be adjusted to a desired size in the range of 10 to 500 μm. Examples of the water-soluble polyamines include ethylenediamine, hexamethylenediamine, octamethylene diamine, triethylenetetramine, p-phenylenetetramine, piperazine, diethylenetriamine, tetraethylenepentamine, amine adducts of epoxy resins, and the like. Mixtures of these can be mentioned. These water-soluble polyamines are added to an aqueous solution in which a dispersant is dissolved in water, and react with the polyisocyanate compound to form the polyuria walls of the microcapsules. The particle size of the resulting microcapsules is about 10 to 500 μm. When amino groups remain on the microcapsule walls, the microcapsule walls can be reinforced by reacting the remaining amino groups with a water-soluble polyaldehyde compound, a water-soluble polyepoxy compound, or the like. Examples of water-soluble polyaldehyde compounds include glyoxal and malondialdehyde.

Succindialdehyde, maleidialdehyde 1 glutardialdehyde, dialdehyde benzene, etc.
The water-soluble polyepoxy compounds include various water-soluble polyepoxy compounds used as water-soluble epoxy resins. If aldehyde groups or epoxy groups remain on the thus reinforced microcapsule walls, they can be further reinforced with polyamine or aminoalkoxysilane. As the polyamine, the same polyamines as those mentioned above can be used. The amino group of the aminoalkoxysilane reacts with the remaining aldehyde group or epoxy group, and the alkoxy group condenses to form a polysiloxane bond. Such aminoalkoxysilanes include T-aminopropyltrimethoxysilane, T-aminopropyltriethoxysilane, N-(2-aminoethyl)-γ-aminopropyltrimethoxysilane, N-(2-aminoethyl) −
r-aminopropylmethyldimethoxysilane, γ-(diethylenetriax))propyltrimethoxysilane, T
-Ureidopropyltriethoxysilane, etc. By reinforcing in this way, the strength of the microcapsule wall can be freely controlled. The thus obtained dispersion containing the microencapsulated peroxide (B) is filtered, washed with water, methanol, or ethanol, and dried. B) is obtained.

On the other hand, a method for microcapsulating peroxide by a complex coacervation method using gelatin and gum arabic as the microcapsule wall is to use a solution of peroxide dissolved in a hydrophobic solvent, and an anion such as sodium dodecyl sulfate. A bi-dispersed peroxide solution is obtained by dispersing a gelatin aqueous solution containing a surfactant as an emulsifier, further dispersing the resulting dispersion in a gum arabic aqueous solution, and adjusting the pH to below the isoelectric point of gelatin with an acid such as acetic acid. A film made of gelatin and gum arabic is formed around a hydrophobic solvent solution of the substance, and after the gelatin is incubated at a temperature below the set point of the gelatin, an aqueous solution of aldehyde such as formaldehyde is added to adjust the pH to 8.5 or higher. By insolubilizing gelatin, a dispersion of microencapsulated peroxide (B) is obtained, and the obtained dispersion is centrifuged, then sprayed and dried to obtain microencapsulated peroxide (B). This is a method to obtain B).

In the present invention, a calcium compound, a barium compound,
Zirconium compounds, vanadium compounds, manganese compounds, cobalt compounds, copper compounds, lead compounds, iron compounds,
Lithium compounds, molybdenum compounds.

One or more metal compounds selected from strontium compounds, cerium compounds, and zinc compounds (C)
Examples include calcium, barium, zirconium, vanadium, manganese, cobalt, i, and lead.

iron, lithium, molybdenum, strontium, cerium, zinc laurate, naphthenate, octylate,
Oleate, octenoate, rosin salt.

Fatty acid salts, resinates such as acetylacetate salts.

One or more types selected from chelate compounds and the like. The metal compound (C) is usually in a proportion of 100% by weight of peroxide in the microencapsulated peroxide (B).
It is used as the metal in the metal compound (C) in a proportion of 0.01 to 10 parts by weight.

In the present invention, the tertiary amine (D) is not particularly limited and may be N,N-dimethylbenzylamine.

Triethylamine, tributylamine, N,N-diethylaniline, N,N-dimethylaniline, N-phenyldiethanolamine, N-phenyldiisopropanolamine 1 dimethyl-ph luidine.

Triethanolane, etc. can be used.

Tertiary 7-mine (I) is usually used in a proportion of 1.0% per 100 parts by weight of peroxide in microencapsulated peroxide (B).・Used at a ratio of 1 part to 100 densities.

Improves adhesive properties before curing. Particularly, in order to increase the cohesive force, a polyisocyanate can be further added to the adhesive composition of the present invention, and the resin (A) can be partially crosslinked. This method uses hydroxyl groups in the main chain rubbery polymer (a),
It is particularly effective when it has a -class amino group or a secondary amino group. Examples of such polyisocyanates include (hydrogenated) 1-lylene diisocyanate, (hydrogenated) 4.
4-diphenylmethane diisocyanate, hexamethylene diisocyanate, etc. can be used.

To make the adhesive strength even stronger after curing.

A monomer or oligomer having an ethylenically unsaturated group such as a (meth)acryloyl group can be further added to the pressure-sensitive adhesive composition of the present invention. Such monomers and oligomers include styrene, alkyl (meth)acrylates, (meth)acrylic acid, polyhydric alcohol poly(meth)acrylates, epoxy poly(meth)acrylates, oligoester poly(meth)acrylates, and polyhydric alcohols. I/Tampolymeta)acrylate, diallyl phthalate, diallyl isophthalate, etc., as well as hydroxyl group, -
unsaturated oligo obtained by reacting a low-molecular compound having a primary amino group, a secondary amino group or a tertiary amino group, a cyclic acid anhydride, and a monomer having an ethylenically unsaturated group and an epoxy group or an aziridinyl group. - Stelles or unsaturated oligoamides can be used. The amount of these monomers and oligomers used is 60% by weight or less based on the total solid content of the adhesive composition of the present invention. 60% by weight
If it exceeds 100%, the adhesive properties before curing, especially the cohesive strength, will be significantly inferior.

The pressure-sensitive adhesive composition of the present invention may optionally contain pigments, dyes, and inorganic fillers within a range that does not impair its performance.

Organic solvents, metal powders such as silver powder, copper powder, nickel powder, etc.

Tackifiers such as carbon black, grapha, silica, xylene resins and rosin resins, silane coupling agents, etc. can be added.

The pressure-sensitive adhesive composition of the present invention has peelability properties such as silicone-treated paper or cloth, paper or cloth processed with a low-adhesion resin such as polyethylene terephthalate film laminated paper, metal foil 1 plastic film, etc. It is coated on a film, sheet, or tape with a high temperature, and if necessary, the organic solvent is removed by drying, and it is made into a one-sided or single-sided adhesive sheet or tape. In addition, for reinforcement and impact mitigation, it may be lined with a non-woven fabric such as rayon or nylon, or a fabric such as cheesecloth, or these fabrics may be used as a core material by impregnating them with the adhesive composition of the present invention. You can also do it.

The double-sided adhesive sheet or tape obtained in this way is sandwiched between two adherends of the same or different types, and after temporary adhesion due to its good adhesiveness, the microcapsules are crushed by applying pressure, and the adhesive When the composition is cured, the adherends can be firmly adhered to each other. Also 1 single-sided adhesive sheet or tape.

After temporary adhesion to the adherend due to its good adhesive properties.

By applying pressure, the microcapsules are crushed and the adhesive composition is cured, allowing it to be firmly adhered to the adherend.

(Example) The present invention will be explained below with reference to Examples. In the examples, 1 part ε represents parts by weight, and 2% represents % by weight.

Example 1 Butyl acrylate 86.4 parts Vinyl acetate 6.8 parts Dimethylaminopropyl methacrylamide 6.8 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 233 parts 80°C
The upper 67 parts of the mixture having the above composition were added dropwise to 167 parts of the mixture having the above composition heated to , and after the dropping was completed.

Heat under reflux for 12 hours, cool, and add hydroquinone to 0°0
5 parts were added to obtain a solution (solid content: 30%) of a rubbery polymer having tertiary amino groups.

Solution 2 of the obtained rubbery polymer having tertiary amino groups
60 parts of hexahydrophthalic anhydride, 9 parts of glycidyl methacrylate, and 0.3 parts of hydroquinone were mixed and reacted at 80°C for 12 hours.
1 part was added to obtain a solution (solid content: 30%) of a resin having an ethylenically unsaturated group in a slightly long side chain.

While maintaining 1 part of polyvinyl alcohol and 100 parts of water at 30°C and stirring with a stirring blade rotating at a speed of 225 revolutions per minute, 5 parts of benzoyl peroxide and 5 parts of tolylene diisocyanate are dissolved in 10 parts of xylene. Add and disperse the solution, and after 5 minutes add 5 minutes of tetraethylene pen.
Add 1 part of tolylene diisocyanate and continue stirring for 2 hours.

A dispersion of benzoyl peroxide microcapsules having walls formed by the reaction of tetraethylene pentamine, polyvinyl alcohol and water was obtained. 122 parts of the obtained microcapsule dispersion.

Add 2 parts of glutaraldehyde and stir for 2 hours.

Next, 2 parts of N-(2-aminoethyl)-r-acnobrobyltrimethoxysilane are added until the pH of 1 dispersion is about 1.
Aqueous ammonia was added to the solution to give a concentration of 1%, and stirring was continued for 6 hours. The microcapsules were then filtered out, washed with ethanol, and dried with hot air at 50°C.

Microencapsulated benzoyl peroxide was obtained. The obtained microcapsules contained 20% benzoyl peroxide, and the average particle diameter of the microcapsules was 40 μm.

100 parts of the obtained solution of the resin having an ethylenically unsaturated group in its slightly long side chain, 7.5 parts of the obtained microencapsulated benzoyl peroxide, 0.075 part of cobalt naphthenate, and N-phenyldiethanol. 1F 0.3F 5 parts were uniformly mixed and applied onto a silicone-treated polyethylene terephthalate film to a dry thickness of 60 μm, and dried at 60°C for 3 minutes to obtain an adhesive sheet. Ta.

Regarding the obtained adhesive sheet, the peel adhesion force immediately after the adhesive sheet preparation and before pressure curing, the peel adhesion force before pressure curing after 2 months of making the adhesive sheet) 11, the holding force before pressure curing, and the pressure The results of measuring the shear adhesive strength after curing are shown in the table. Note that the measurements were performed as follows.

■ Peeling adhesive strength before pressure curing Immediately after preparation and after being left at room temperature for 2 months after preparation, a polyethylene terephthalate sheet with a thickness of 50 μm is pasted on the adhesive surface of the adhesive sheet, cut into 25 mm width pieces, and then polyethylene The terephthalate film was peeled off, the resulting adhesive surface was attached to a stainless steel plate (SUS304) polished with #280 sandpaper, and left for 30 minutes.
Peeling speed 300mm/under conditions of 5℃ and 65% relative humidity.
The 180 degree peel adhesion strength was measured in minutes. During the measurements, sufficient care was taken not to destroy the microcapsules.

■ Holding power before pressure curing A polyethylene terephthalate sheet with a thickness of 50 μm is pasted on the adhesive surface of the obtained adhesive sheet, cut into 2 pieces of 25 mm width and 100 mm length, and the polyethylene terephthalate film is first peeled off. , A part of the resulting adhesive surface measuring 25 mm vertically and 25 mm horizontally was attached to a stainless steel plate (SUS 304) polished with #280 sandpaper, and the adhesive sheet fell from the stainless steel plate at 40°C and under a load of 1 kg. The time (seconds) it took to do so was measured. As with the measurement of peel adhesion, sufficient care was taken not to destroy the microcapsules during the measurement.

■Shear adhesive strength after pressure curing Place the resulting adhesive sheet on one end of each of two aluminum plates measuring 50 mm long, 10 mm wide, and 0.5 mm thick!
The adhesive side of the pieces cut into 10 mm x 10 mm width pieces was attached, the polyethylene terephthalate film was peeled off, the resulting adhesive sides were attached so that they overlapped, and pressure was applied at 10 kg/am'' using a pressure roll.

After being left at room temperature for one week, the shear strength was measured at a tensile rate of 5 mm/min at 25° C. and 65% relative humidity.

Example 2 Butyl acrylate 80.0 parts Vinyl acetate 6°7 parts Dimethylaminopropyl methacrylate ξ 13.3 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 233 parts A mixture of the above combinations was used in Example 1 and The reaction was carried out in the same manner to obtain a solution (solid content: 30%) of a rubbery polymer having a tertiary amino group.

Solution 2 of the obtained rubbery polymer having tertiary amino groups
13 parts, hexahydrophthalic anhydride 15 parts.

After mixing 21 parts of glycidyl methacrylate and 0.3 parts of hydroquinone and reacting in the same manner as in Example 1, 84 parts of ethyl acetate was added to prepare a solution of a resin having an ethylenically unsaturated group in a slightly long side chain ( Solid content: 30%) was obtained.

100 parts of the obtained solution of the resin having an ethylenically unsaturated group in its slightly long side chain, 7.5 parts of the microencapsulated benzoyl peroxide obtained in Example 1, and 10% acidic butyl phosphorus of molybdenum acetylacetonate. -0.3 part of the -to solution and 0.375 part of N-phenyldiethanolamine were uniformly mixed to obtain a pressure-sensitive adhesive sheet in the same manner as in Example 1, and the measured results are shown in the table.

Example 3 Butyl acrylate 88.0 parts Dimethylaminoethyl methacrylate 12.0 parts Azobisisobutyronitrile 0° 2 parts Ethyl acetate 233 parts Above Mi
The mixture was reacted in the same manner as in Example 1 to obtain a solution (solid content: 30%) of a rubbery polymer having tertiary amino groups.

Solution 2 of the obtained rubbery polymer having tertiary amino groups
13 parts, hexahydrophthalic anhydride 15 parts.

After mixing 21 parts of glycidyl methacrylate and 0.3 parts of hydroquinone and reacting in the same manner as in Example 1, 84 parts of ethyl acetate was added to prepare a solution of a resin having an ethylenically unsaturated group in a slightly long side chain ( Solid content: 30%) was obtained.

100 parts of the obtained solution of the resin having an ethylenically unsaturated group in a slightly long side chain, 7.5 parts of microencapsulated penzoyl peroxide obtained in Example 1, 0.075 parts of cobalt naphthenate, and 0.375 parts of N-phenyldiethanolamine mixed with 1"I-;
An adhesive sheet was obtained in the same manner as in Example 1.

The measured results are shown in the table.

Example 4 Butyl acrylate 1-94.0 parts Dimethylaminoethyl methacrylate 6.0 parts Azobisisobutyronitrile 0.2 parts Ethyl acetate 233 parts The above dark blue mixture was reacted in the same manner as in Example 1. A solution (solid content: 30%) of a rubbery polymer having grade amino groups was obtained.

Solution 2 of the obtained rubbery polymer having tertiary amino groups
60 parts of hexahydrophthalic anhydride, 13 parts of glycidyl methacrylate, and 0.3 parts of hydroquinone were mixed and reacted in the same manner as in Example 1. Then, 51 parts of ethyl acetate was added, and ethylene was added to the slightly longer side chain. A solution (solid content: 30%) of a resin having a sexually unsaturated group was obtained.

100 parts of the resulting solution of the resin having an ethylenically unsaturated group in its slightly long side chain;
0.3 parts of a 10% acidic Pudylphosphate solution of vanadium acetylacetonate and 0.375 parts of N-phenyldiethanolamine were uniformly mixed to obtain an adhesive sheet in the same manner as in Example I, and the measured results are shown in the table. .

Example 5 Butyl acrylate 79.1 parts Vinyl acetate 6.6 parts Dimethylaminoethyl methacrylate 14.3 parts Abbisisobutyronitrile 0.2 parts Ethyl acetate 233 parts The above mixture was prepared in the same manner as in Example 1. The reaction was carried out to obtain a solution (solid content: 30%) of a rubbery polymer having tertiary amino groups.

Obtained solution 2 of rubbery polymer having tertiary abrasive groups
13 parts, hexahydrophthalic anhydride 15 parts.

After mixing 21 parts of glycidyl methacrylate and 0.3 parts of hydroquinone and reacting in the same manner as in Example 1, 84 parts of ethyl acetate was added to prepare a solution of a resin having an ethylenically unsaturated group in a slightly long side chain ( Solid content: 30%) was obtained.

100 parts of the obtained solution of the resin having an ethylenically unsaturated group in a slightly long side chain, 7.5 parts of the microencapsulated benzoyl peroxide obtained in Example 1, 0,075 parts of cobal naphthenate, and 0.375 parts of N-phenyldiethanolamine were mixed uniformly, and a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1.

The measured results are shown in the table.

Example 6 Butyl acrylate 88.0 parts Vinyl acetate 5.5 parts Dimethylaminoethyl methacrylate 1.3 parts 2-hydroxyethyl methacrylate 5.2 parts Azobisisobutyronitrile 0.2 parts Ethyl acid 233 parts The mixture was reacted in the same manner as in Example 1 to form a solution of a rubbery polymer having tertiary amino groups and hydroxyl groups (solid content 30%).
I got it.

237 parts of the obtained rubbery polymer solution having tertiary amino groups and hydroxyl groups, 15 parts of hexahydrophthalic anhydride, 14 parts of glycidyl methacrylate, and 0.3 parts of hydroquinone were mixed and reacted in the same manner as in Example 1. After that, 67 parts of ethyl acetate was added.

A solution (solid content: 30%) of a resin having an ethylenically unsaturated group in a rather long side chain was obtained.

100 parts of the obtained solution of the resin having an ethylenically unsaturated group in a slightly long side chain, 7.5 parts of the microencapsulated benzoyl peroxide obtained in Example 1, 0.075 parts of cobalt naphthenate, and N - 0.375 parts of phenyldiethanolamine was mixed uniformly, and a pressure-sensitive adhesive sheet was obtained in the same manner as in Example 1.

The measured results are shown in the table.

[Effects of the Invention] In the adhesive composition of the present invention, the polymer itself has anaerobic curability, and as shown in Table 1, the peel adhesive strength before curing is 150.
0g/25mm or more, the holding force is 600 seconds or more, and the shear adhesive strength after curing is 30kg/cm or more, and both the adhesive properties before curing and the adhesive strength after curing are excellent.In addition, microencapsulation By using this peroxide, the peel adhesion strength before pressure curing hardly changes even after 2 months, resulting in extremely excellent storage stability.

As described above, the present invention has high adhesiveness and can be temporarily bonded to the adherend during bonding.1 Mechanical temporary fixing is unnecessary, and after curing, it exhibits strong adhesive strength, and the adhesive properties before curing are high. Excellent balance between adhesive strength and adhesive strength after curing.

It has now become possible to obtain an anaerobically curable adhesive composition that has excellent storage stability even when formed into an adhesive sheet or tape.

Claims (1)

[Claims] 1. A rubbery polymer (a) having a tertiary amino group, optionally a cyclic acid anhydride (b), and a monomer (c) having an ethylenically unsaturated group and an epoxy group or an aziridinyl group are reacted. Resin (A) having an ethylenically unsaturated group in the obtained side chain, microencapsulated peroxide (B), calcium compound, barium compound, zirconium compound, vanadium compound, manganese compound,
One or more metal compounds selected from cobalt compounds, copper compounds, lead compounds, iron compounds, lithium compounds, molybdenum compounds, strontium compounds, cerium compounds, and zinc compounds (C) and/or tertiary amines (D ) An anaerobic curable adhesive composition.