JPS5984964A - Adhesive composition - Google Patents

Abstract

PURPOSE:To provide the titled composition having excellent adhesivity to zinc- treated substrate, and composed of two liquid components, wherein a polymerization initiator is added to one of the liquid, a redox-type reducing component is added to the other liquid, and a specific acrylic monomer composition, a polymer or an elastomer is added to at least one of the liquid components. CONSTITUTION:The objective two-pack type adhesive composition is obtained by (a) adding a polymerization initiator (A) to one of the liquid components, (b) adding a redox-type reducing component (B) decomposing said polymerization initiator and starting the polymerization to the other component, and (c) adding (C) a monomer component composed of (i) 100pts.wt. of a polymerizable (meth) acrylate monomer, (ii) 0.2-30pts.wt. of the compound of formula (R1 is H or CH; R2 and R3 are 1-6C alkyl; n is 1-6) and (iii) 0.2-30pts.wt. of a phosphoric acid ester monomer, and (D) 5-150pts.wt. of a polymer and/or elastomer soluble in the component (C). The amounts of the components (A) and (B) are 0.1- 15pts.wt. and 0.1-15pts.wt. per 100pts.wt. of the component (C).

Description

DETAILED DESCRIPTION OF THE INVENTION This invention relates to adhesive compositions that have excellent adhesion to zinc-treated substrates.

More specifically, the present invention relates to an acrylic adhesive composition that has excellent adhesion to various substrates and also has excellent adhesion to zinc-treated substrates.

Galvanized steel sheets and other galvanized steel sheets have been widely used for roofing, wall materials, etc. since ancient times as materials with excellent surface corrosion resistance, but the quality has improved due to the development of new zinc treatment methods.
Along with this, they have come to be widely used in many fields such as automobiles and home appliances.

Under these circumstances, the demand for adhesives for these zinc-treated substrates is increasing, but at present there are few adhesives that can completely satisfy the demand. A particular problem is the adhesion to zinc-treated surfaces, and in recent new zinc treatment methods, efforts are being made to maintain adhesion, but this is still not sufficient.

Acrylic structural adhesives, commonly referred to as SGA or second generation acrylic, have many advantages such as fast curing at room temperature, strong adhesive properties, adhesion to oil surfaces, durability, and a variety of applicable adherends. It is an adhesive that has excellent characteristics and has applications in a wide range of fields such as automobiles, vehicles, electricity, and architecture.It generally forms a redox system with a polymerization initiator in one liquid and a polymerization initiator in the other. Acrylic or methacrylic monomers that contain a reducing component and can be polymerized into at least one of the two liquids, and adhesive compositions containing the monomers are described, for example, in Japanese Patent Publication No. 4526/1983 and Japanese Patent Publication No. 53/1983. No. 24103,
It is disclosed in Japanese Patent Publication No. 53-41699, Japanese Patent Publication No. 54-28178, Japanese Patent Publication No. 55-1957, Japanese Patent Publication No. 57-13594, etc.

Although such adhesives are excellent adhesives with the above-mentioned properties, they generally have the drawback of poor adhesion to zinc-treated substrates, and their application to applications related to adhesion of these substrates has been limited. is becoming difficult.

Therefore, with the ever-increasing demand for zinc-treated substrates, it would be highly desirable to have improved acrylic structural adhesives that have effective adhesion to these substrates.

JP-A No. 56-28259 has been disclosed as an adhesive that improves adhesion to zinc-treated substrates, and the specification describes an acrylonitrile-butadiene-styrene polymer and an organic sulfonyl chloride. It is described that a composition in which the compound is dissolved in a polymerizable vinyl monomer and cured by heat or an accelerator provides excellent adhesion to zinc-treated coatings.

Although the use of this composition would improve adhesion to zinc-treated coatings, the practical use of such compositions would necessitate the use of compositions containing environmentally hazardous low molecular weight organic sulfonyl chlorides with pungent odors. It has some drawbacks in terms of aspects. Further, as the polymer used, only acrylonitrile-butadiene-styrene polymer is described.

In view of these circumstances, the present invention was developed as a result of intensive research aimed at obtaining a composition that does not contain the above-mentioned harmful substances and has improved adhesion to zinc-treated substrates. (R1 is hydrogen or a methyl group, R2 and R3 are each an alkyl group having 1 to 6 carbon atoms, and n is an integer of 1 to 6.) By coexisting with a phosphoric acid ester-based rice product having a group of
The present inventors have discovered that it is possible to obtain a composition that provides excellent adhesion to zinc-treated substrates and also has excellent adhesion to various other substrates, leading to the completion of this invention. be.

The adhesive composition of this invention consists essentially of the following components.

One liquid contains a polymerization initiator, the other liquid contains a reducing component that decomposes the polymerization initiator and starts polymerization, and at least one of the liquids contains a polymerizable acrylic monomer and/or methacrylic monomer. and the acrylic monomer and/or
Or, in a substantially two-component acrylic adhesive composition comprising a polymer and/or elastomer soluble in a methacrylic monomer, (1) an acrylic monomer and a methacrylic monomer, (2) Structural formula (R1 is hydrogen or a methyl group, R2 and R3 have 1 to 1 carbon atoms)
6 alkyl group, n is an integer of 1 to 6 t) 2 to 30 parts by weight of the compound represented by (t) and (3) a phosphoric acid ester monomer I having a copolymerizable unsaturated group in the molecule. 2 to 30 parts by weight of the body shell and (4) 5 to 5 parts of a polymer and/or elastomer dissolved in the monomer of (1) above.
150 parts by weight, and further, based on the total amount of (1) to (3) above 100 parts by weight, (5) 1 to 15 parts by weight of the polymerization initiator and (6) the polymerization initiator of (5) above. 1 to 15 parts by weight of a reducing component forming a redox system.

The composition of the present invention is essentially a two-liquid system, in which the polymerization initiator and the reducing component are separated into separate liquids, and one or both of them contain an acrylic monomer and/or a methacrylic monomer. , a compound having the structural formula (A), a phosphate monomer having a copolymerizable unsaturated group in the molecule, a polymer and/or an elastomer, and other additives. When these two liquids are brought into contact or mixed during use, they react and harden. However, although the composition of the present invention is essentially a two-component system, as long as the polymerization initiator is separately blended into one solution and the reducing component is blended into the other solution before use, each component to be blended can be used. Since these are brought into contact or mixed during use, it is not necessarily necessary to prepare a two-component system, but it is of course possible to prepare a multi-component system containing three or more components, and such an embodiment is also included in the scope of the present invention. shall be included within the scope.

The adhesive composition of the present invention will be explained in more detail below.

Acrylic monomers and methacrylic monomers used in this invention include acrylic acid, methacrylic acid,
and esterified products thereof, such as methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, 2-ethylhexyl acrylate,
Alkyl acrylates such as lauryl acrylate; Alkyl methacrylates such as methyl acrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, dichlorohexyl acrylate, benzyl acrylate,
Tetridrofurfuryl acrylate, 2-acetoxyethyl acrylate, 2-ethoxyedyl acrylate, 2-phenoxyethyl acrylate, 2-hydroxyethino(acrylate, 2-hydroxypropyl acrylate, glycidyl acrylate, 3-chloro-2-
Monoacrylates such as hydroxypropyl acrylate, ethylene glycol monoacrylate, diethylene glycol monoacrylate, polyethylene glycol monoacrylate, propylene glycol monoacrylate, polypropylene glycol monoacrylate, 2-dicyclopentenoxyethyl acrylate:
Cyclohexyl methacrylate, hensyl methacrylate, tetrahydrofurfuryl methacrylate, 2-acetoxyethyl methacrylate, 2-ethoxyethyl methacrylate, 2-phenoxyethyl methacrylate, 2
-Human “roxyethyl methacrylate, 2-hydroquine zolobyl methacrylate, glycidyl methacrylate), J
-Chloro-2-hydroquine zolobyl methacrylate, ethylene glycol monomethacrylate, diethylene glycol monomethacrylate, carpitol methacrylate, polyethylene glycol monomethacrylate, noropylene glycol monomethacrylate, polypropylene glycol monomethacrylate, 2-dicyclopentenoxyethyl methacrylate, etc. monomethacrylate; ethylene glycol diacrylate, diethylene glycol diacrylate, polyethylene glycol diacrylate), 1,4-butylene glycol diacrylate,
Polyhydric acrylates such as bisphenol A diacrylate, 1,1.1-)rimethylo, -rzoronothontriacrylate; ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, 1,4-ethylene glycol dimethacrylate, bisphenol A dimethacrylate, 1.1.1- ) polyhydric methacrylate such as limethylolpropane trimethacrylate: by reaction of acrylic acid or methacrylic acid with an epoxy compound,! Epoxy preacrylate or epoxy polymethacrylate obtained by the reaction of hydroxyalkyl acrylate or hydroxyalkyl methacrylate with an isocyanate compound; Urethane polyacrylate or urethane polymethacrylate obtained by the reaction of acrylic acid or methacrylic acid with glycols and polybasic acid Polyester polyacrylate or polyester polymethacrylate obtained from; 2-acryloyloxyethyl acid succinate,
2-methacryloyloxyethyl acid succinate, 2-acryloyloxyethyl acid phthalate,
Examples include, but are not limited to, acrylates or methacrylates having a carboxyl group in the molecule, such as 2-methacryloyloxyethyl acid phthalate.

These acrylic monomers and/or methacrylic monomers may be used alone or in combination of two or more.

The above-mentioned acrylic monomer and/or methacrylic monomer?
- Among the ft-type compounds, acrylic acid and methacrylic acid have an effect as adhesion promoters, and are sometimes added to enhance adhesion to various adherends other than zinc-treated substrates, but in large amounts. If added, it may cause problems such as rusting on metals and toxicity, so it is preferable to keep the blending amount to 10% by weight or less based on the total amount of the acrylic monomer and/or methacrylic monomer.

This invention requires the use of a compound represented by the structural formula. Here, the structural formula (
In A), R1 represents hydrogen or a methyl group, R2 and R3 represent an alkyl group having 1 to 6 carbon atoms, and n represents an integer of 1 to 6.

These compounds include dimethylamine methyl acrylate, diethyl. 2-(diethylamino)ethyl acrylate, dibutylaminomethyl acrylate, dibutylaminomethyl acrylate, 3-(sohexylamino)propyl acrylate, 6
-C&(t-butyl)[amino]hexyl acrylate, 2-(X)methylamine)ethyl methacrylate, 2
-(diethylamino)ethyl methacrylate and the like.

The preferred blending amount of the compound represented by the structural formula is 10% of the total amount of the acrylic monomer and/or methacrylic monomer.
If the amount is less than 0.2 parts by weight, the effect on adhesion to the zinc-treated substrate will be poor, and if the amount exceeds 30 parts by weight, This is not preferable because it deteriorates the compatibility with the polymer or elastomer contained in the composition. Particularly preferably 0.5 to 1
The range is 5 parts by weight.

Furthermore, the present invention requires the use of a phosphoric acid ester monomer (hereinafter referred to as a phosphoric acid ester monomer) having a copolymerizable unsaturated group in the molecule.

Typical examples of these phosphate monomers include monoacryloxyethyl phosphate, bisacryloxyethyl phosphate, trisacryloxyethyl phosphate, monoacryloxypropyl phosphate, and bisacryloxypropyl phosphate. phate, trisacryloxypropylphosphate, monoacryloxyethyl-bis-3-chloro-2-hydroxypropyl phosphate, monomethacryloxyethyl 7-phosphate, monomethacryloxy-1-chloromethyl-ethyl phosphate, Bis-methacryloxyethyl phosphate, tris-methacryloxyethyl phosphate, monomethacryloxyethyl-bis-3-chloro-2-
Examples include hydroxypropyl phosphate.

The preferred blending amount of these phosphate ester monomers is Ai
0.2 to 30 parts by weight based on 100 parts by weight of the total amount of the asiacryl monomer/or methacrylic monomer j,
If the amount is in the range of 0.5 to 15 parts by weight or exceeds 30 parts by weight, the compatibility with the 7+91)mer or elastomer in the composition will be poor, which is not favorable.

In the composition of this invention, acrylic monomer and/or
Alternatively, it is necessary to coexist both the compound represented by the structural formula (A) and the above-mentioned phosphoric acid ester monomer together with the methacrylic monomer.

The blending ratio of the compound represented by the structural formula (A) and the phosphate ester base material may be appropriately selected depending on the raw materials used, the intended use, the material of the adherend, the required adhesive performance, etc.

In addition, in this invention, if necessary, a compound having a polymerizable unsaturated group such as styrene, vinyl acetate, noaryl phthalate, or spirane resin having a spiroacetal structure may be blended to further modify or reduce costs. etc. can also be done.

The compound having these polymerizable unsaturated groups is preferably blended in an amount of 50 parts by weight or less based on 100 parts by weight of the total amount of the acrylic monomer and/or methacrylic monomer. 50
Additions in excess of parts by weight are undesirable because they may significantly retard the curing time of the composition of the present invention or may provide a very brittle cured product.

Does it dissolve in the acrylic monomer and/or methacrylic monomer used in this invention? Examples of reamers and elastomers include polymethyl methacrylate homopolymers or copolymers of methyl methacrylate and other monomers, polyethyl acrylate homopolymers or copolymers of ethyl acrylate and other monomers, and acrylonitrile-butatsuene-styrene copolymers. Polymer, styrene-butadiene rubber, acrylonitrile-butadiene rubber, chlorozolene rubber, natural rubber, epichlorohydrin rubber,
Examples include soluble nylon, polyurethane, vinyl chloride-vinyl acetate copolymer, chlorosulfonated polyethylene, and salt-accumulated polyethylene.

These polymers and/or elastomers are blended for the purpose of controlling the viscosity of the composition, improving physical properties after curing, increasing adhesive strength, etc.If they meet these purposes, they may be included in the above list. It is not limited.

These polymers and/or elastomers may be used alone or in combination of two or more.

The amount to be blended depends on the type of polymer or nidistomer used.
It is preferable to use 50 parts by weight in order to achieve the above object. Particularly preferred polymers and/or elastomers that provide toughness and adhesive properties include synthetic rubbers such as acrylonitrile-butadiene rubber and styrene-butadiene rubber, and acrylonitrile-butadiene-styrene copolymers. Examples include.

The polymerization initiator blended in this invention is methyl ethyl ketone J? - Ketone 9 like oxide
- Oxides, diacyl 2- and mono-oxides such as benzoyl peroxide, hydro- and mono-oxides such as cumene hydroperoxide, dialkyl 4-oxides such as nocumyl oxide, l-butylperhenzoate, etc. Perester, neuisopropyl peroxydicar? Although any of them can be used, hydroperoxide is particularly preferred in terms of stability, ease of handling, curing speed, etc.

The amount of these polymerization initiators is 0 to 100 parts by weight of the total amount of the acrylic monomer and/or methacrylic monomer, the compound represented by the structural formula (A), and the phosphate monomer.
．． It is preferably used in a range of 1 to 15 parts by weight, and 0.
Particularly preferred is 5 to 10 parts by weight. 0. If the amount of IM is less than 15 parts by weight, sufficient free radicals will not be generated to initiate polymerization.Although it is possible to add more than 15 parts by weight, there are few advantages and the storage stability of the composition may be reduced. It may also interfere with sexuality.

The reducing component 7 that forms a redox system with the secondary group initiator includes tertiary amines such as N,N-dimethylaniline, N,N-dimethyl-p-)luidine, and acetylacetone banacle. Metal complexes of acetylacetone, metal salts of naphthenic acid, thiourea compounds such as trimethylthiourea, amine-aldehyde condensates, etc. alone,
< can be used in combination, but it is necessary to select a combination that works effectively with the polymerization initiator used above. These reducing components are 0.1 to 15 parts by weight based on 100 parts by weight of the acrylic monomer and/or methacrylic η1 monomer, the compound represented by the structural formula (A), and the phosphate monomer. The range is preferably <, 0.5 to 10
A range of 1 part by weight is particularly preferred.

As in the case of the polymerization initiator, the reducing component is 0. If the amount of IM is less than 15 parts by weight, sufficient free radicals will not be generated to initiate polymerization.Although it is possible to add more than 15 parts by weight, there are few advantages, and conversely, the storage stability of the composition will be affected. It may also cause problems.

The compositions of this invention are prepared as essentially two-component systems. When one of these two liquids is used as liquid A and the other as liquid B, if a polymerization initiator is blended in liquid A, the reducing component will be blended in liquid B. Hereinafter, the liquid containing the polymerization initiator will be referred to as liquid A, and the liquid containing the reducing component will be referred to as liquid B.

The acrylic jl'-fi and/or methacrylic monomer, polymer and/or elastomer may be blended in either the A liquid or the B liquid, or may be blended in both.

The compound represented by the structural formula (A) and the phosphoric acid ester monomer may be blended in the A solution containing the initiator, as long as the stability of the system is maintained and the compound acts effectively. It may be added to the B solution containing the reducing component. It is also possible to mix it into both liquids A and B. It is also possible to mix the compound represented by the structural formula (4) in the A liquid and the phosphate ester monomer in the B liquid, and vice versa.

That is, it is an essential requirement of this invention that the compound represented by the structural formula (A) and the phosphoric acid ester monomer coexist at the time when the liquids A and B are brought into contact or mixed during use. As long as this requirement is met, the A18 liquids can be mixed in various combinations as described above.

In addition, since the compositions of the present invention are brought into contact or mixed together at the time of use, the composition does not necessarily have to be a two-component system as described above, but can be prepared by adding A containing a polymerization initiator before use. As long as the liquid and the B liquid containing the reducing component are separated, it is natural that G can be used as a multi-component system with three or more liquids.
It may also be made in bulk.

In this invention, both the compound represented by structural formula IA) and the phosphoric acid ester monomer are not used, or
Alternatively, if only one of the two is used, there will be no or very weak adhesion to the zinc-treated substrate. Only when both are blended in such a way that they coexist, it is possible to significantly improve J&T properties on zinc-treated substrates.

Thus, the composition of the invention does not compromise the excellent properties and handling properties of acrylic structural adhesives, does not contain irritating compounds that are harmful to the environment, and eliminates the need for zinc treatments, which have often been problematic to date. Adhesion to substrates can be significantly improved.

Furthermore, since the composition of the present invention is a composition that can use a wide variety of polymers and/or elastomers, it has applicability to various purposes, such as (1) hardness and softness after curing. (2) The shrinkage rate during curing can be adjusted to a desired value depending on the application and the properties of the adherend; (3) Products with less thermal deterioration can be obtained. , '(4) There is a wide selection range of preferred formulations considering solubility or compatibility with the monomers used to be blended together, and (5) It is easy to consider cost aspects, and the formulation is appropriately selected. It is an excellent composition that can be used when selected.

The addition of the compound represented by the structural formula (A) and the phosphate ester monomer does not impair the adhesion to adherends other than zinc-treated substrates and the properties as an acrylic structural adhesive. , on the contrary, it is effective not only for adhesion between zinc-treated substrates, but also for adhesion between zinc-treated substrates and materials other than zinc-treated substrates, and for adhesion between materials other than zinc-treated substrates.

There are two methods for using the composition of this invention. First, by applying liquid A and liquid B to the surfaces of separate adherends to be bonded, and then bringing both surfaces together, 1) h
This is a separate coating method in which both the X and B liquids are brought into contact and cured. The second is a mixing method in which both AB and A liquids are mixed in advance immediately before use, and then applied to an adherend and pasted together.

In the separate coating method, it is also possible to apply a thin layer of either liquid A or liquid B to one of the surfaces of the adherend as zolaimer. In this case, methanol or acetone may be used as the liquid for Zolaimer.

In the adhesive composition of the present invention, in addition to the above-mentioned components, it is of course possible to further contain commonly used fillers, colorants, extenders, and other additives.

The adhesive composition of the present invention will be explained below using Examples and Comparative Examples. All parts herein refer to parts by weight unless otherwise specified.

Examples 1 to 8 Preparation of Solution A 25 parts of acrylonitrile-butadiene copolymer 2M (manufactured by Nippon Zeon Co., Ltd., trade name) Squid-1072) was made into wire with a rubber roll, cut into small pieces, and mixed in 75 parts of methyl methacrylate. Stir and dissolve at 50C for 6 hours, and make a 425t column.
A pace solution (1) of s was obtained.

To 100 parts of this paste solution (I) were added ethylene glycol dimethacrylate, cumene oxide, and a compound represented by the structural formula (4) such as 2-(dimethylamino)ethyl methacrylate or 2-(diethylamino). ) Monomethacryloxyethyl phosphate and bisacryloxyethyl phosphate as ethyl methacrylate and phosphate ester single deposits may be added with monomethacryloxy-1-chloromethyl-ethyl phosphate in the weight proportions shown in Table 1. By stirring and mixing, solutions A (A-1 to A-8) in Examples 1 to 8 were prepared.

Preparation of Solution B Solution B (B-1) in Examples 1 to 8 was prepared by dissolving 3 parts of trimethylthiourea in 27 parts of acetone.

Adhesion test An adhesion test was conducted using both solutions A and B above.

Galvanized iron plate (hot-dip galvanized steel plate, JIS G
-3302) cut into a size of 25 cm x 100 cylinders was used.

Solution B was applied thinly to one of the adherends with a brush, and the solvent was evaporated. Apply liquid A in a bead shape to the other side, stick the coated surfaces of both adherends together, temporarily fix with cellophane tape, and after curing for 20tZ' for 24 hours, pull at speeds of 1 and 5.
The tensile shear adhesive strength was measured at tm/min. The results are shown in Table 1. In addition, each tensile shear adhesive strength is shown as the average value of the measured values of 5 test pieces. The same applies to the following Examples and Comparative Examples.

Inkstone weight Example 9 and Comparative Examples 1 to 4 Meccrylic acid, ethylene glycol dimethacrylate, cumene hydroperoxide and a compound represented by structural formula (A) were added to 100 parts of the paste solution (I) prepared in Example 1. 2-(diethylamino)ethyl methacrylate and monomethacryloxyethyl phosphate as a phosphoric acid ester monomer were added in the weight ratios (parts) shown in Table 2, and the mixture was thoroughly stirred to prepare Example 9 and Comparative Examples 1 to 4. Each A solution (A-9 to A-13) was prepared.

Using B-1 prepared in Example 1 as liquid B, the tensile shear strength of the adhesive to a galvanized iron plate was measured in the same manner as in Example 1. The results are shown in Table 2.

Example 9 shows that excellent adhesion to a galvanized iron plate can be imparted by coexisting the compound represented by the structural formula (A) with a Nisder phosphate monomer. On the other hand, systems in which the compound represented by structural formula (A) and the phosphate monomer are not present at the same time, as in Comparative Examples 1 to 3, do not have adhesive properties to galvanized iron plates. .

In addition, as in Comparative Example 4, even if the amount of methacrylic acid as an adhesion promoter is increased by It can be seen that there is no effect on adhesion.

Example 10 and Comparative Example 5 were dissolved in 65 parts of full methacrylate to prepare a paste solution ω) having a rubber content of 35 g. In addition, methacrylic acid, ethylene glycol dimethacrylate, paraffin wax (melting point 62-64 tl'), cumene hydroperoxide, and 2-(diethylamino)ethyl methacrylate and monomethacryloxyethyl phosphate are added in the weight proportions shown in Table 3 ( Example 10 and Comparative Example 5
Each of A solutions (A-14 to A-17) in ~7 was prepared.

B-1 prepared in Example 1 was used as liquid B, and the tensile shear adhesive strength to a galvanized iron plate was measured in the same manner as in Example 1. The results are shown in Table 3.

It can be seen that the adhesive strength in Example 10 is significantly superior to those in Comparative Examples 5 to 7.

Example 11 and Comparative Examples 8 to 10 Acrylonitrile-butadiene-styrene copolymer (product name Prendex 101, manufactured by Ube Scicon Co., Ltd.) 3
0 parts was dissolved in 70 parts of methyl methacrylate. To this paste solution q
Each liquid A (A-18 to A-2 in Example 11 and Comparative Examples 8 to 10)
1) was prepared.

B-1 prepared in Example 1 was used as liquid B, and the tensile shear adhesive strength to a galvanized iron plate was measured in the same manner as in Example 1. The results are shown in Table 4.

It can be seen that the adhesive strength in Example 11 is significantly superior to those in Comparative Examples 8 to 10.

The results in Tables 2 to 4 show that even if the blended polymer or elastomer changes, the coexistence of the compound represented by structural formula (A) and the phosphoric acid ester monomer significantly improves the adhesion to galvanized steel sheets. It shows that there is.

Example 12 6 parts of methacrylic acid, 6 parts of 2-(diethylamine)ethyl methacrylate, and 10 parts of trimethylthiourea were added to 100 parts of the base solution (1) prepared in Example 1 to prepare solution A (
A-22) was prepared.

In addition, 6 parts of methacrylic acid to 100 parts of base solution (1),
Add 6 parts of monomethacryloxyethyl phos-7ate and 8 parts of cumeno idrol oxide to make solution B (B-2).
was prepared.

After mixing AB and A in a ratio of 1:1, the mixture was applied in a bead shape to one of the galvanized iron plates to be joined.

It was immediately attached to the other galvanized iron plate and temporarily fixed with sellotape. When the tensile shear adhesive strength was measured after 24 hours at room temperature using the method shown in Example 1, it was found to be 130K.
f/crn2, indicating good adhesion.

Example 13 and Comparative Examples 11 to 13 2 parts of benzoyl peroxide to 1 part of methylene chloride
A solution (A-23) was prepared by dissolving the solution in 8 parts.

Methacrylic acid, base solution (1) prepared in Example 1
Ethylene glycol dimethacrylate, N,N-methyl-p-)luidine, 2-(diethylamino)ethyl methacrylate, and monomethacryloxyethyl phosphate were added in the proportions (parts) shown in Table 5. Example 13 and Each B solution (B-3
-B-6) were prepared.

Solution A was boiled with a brush on one surface of the auxiliary lead-drawn iron plate to evaporate the solvent. Apply liquid B in a bead shape to the other surface, apply both adherends, stick them together, bring both liquids AB into contact, and temporarily fix with cellophane tape. In the same manner as in Example 1, the tensile shear adhesive strength of the galvanized iron plate was measured. The results are shown in Table 5.

The adhesive strength in Example 13 is significantly superior to those in Comparative Examples 11-13.

Example 14 A-9 prepared in Example 9 was used as liquid A, a solution (B-7) prepared by dissolving 4 parts of trimethylthiourea in 26 parts of acetone was added as liquid B, and 0.5% acetylacetone vanadyl was further added to B-7. A galvanized iron plate (hot-dip galvanized type, 1
．． 6 x 25
JISH-8610-MFZn3 on X100 copper steel plate
(manufactured by Nippon Testno and Nell Co., Ltd.)
, "Nude steel sheet (electrogalvanized surface treated steel sheet, 1.2
X25XIQQmm, manufactured by Nippon Steel Corporation) was adhered, and the tensile shear adhesive strength of 201Z' was measured after curing for 24 hours using the method shown in Example 1. The results are shown in Table 6.

Table 6 The results above demonstrate that this adhesive system has excellent adhesion not only to galvanized steel sheets, but also to other zinc-treated substrates.

Example 15 The galvanized iron plate bonded in Example 14 was immersed in water at 20C.
It was immersed in water and tested for water resistance.

Further, a constant temperature and humidity test was also conducted under heating and humid conditions, in which the specimen was exposed for one month under conditions of 50G and a relative humidity (RH) of 95 to 100 degrees. Table 7 shows the measurement results of each tensile shear adhesive strength.

Table 7 The above results show that the composition according to the invention has excellent durability in joining galvanized iron sheets and can be used under severe conditions.

Claims (1)

[Claims] One liquid contains a polymerization initiator, the other liquid contains a reducing component that decomposes the polymerization initiator and starts polymerization, and at least one of the liquids contains an acrylic monomer that can be polymerized. and/or a substantially two-component acrylic adhesive composition comprising a methacrylic monomer and a polymer and/or a nystomer that dissolves in the acrylic monomer and/or methacrylic monomer. (1) With respect to 100 parts by weight of at least one polymerizable monomer selected from the group consisting of acrylic monomers and methacrylic monomers, (2) structural formula (R4 is hydrogen or methyl group, R2 and R3 have 1 to 1 carbon atoms
(3) a phosphoric acid ester monomer having a copolymerizable unsaturated group in the molecule. and (4) 5 to 150 parts by weight of a polymer and/or elastomer dissolved in the monomer of (1) above.
For 100 parts by weight of the total amount of (1) to (3) above, (
5) 0.1 to 15 parts by weight of M intermediate initiator and (6) the above (5)
0.1 of the reducing component that forms a redox system with the polymerization initiator
An adhesive composition characterized in that it contains 2 parts of 15-15 geki.