JPH0798921B2 - Adhesion method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION (a) Purpose of the Invention (Industrial field of application) The present invention fixes an adherend within a remarkably short time (provisional) without performing a special operation such as heating or high-frequency heating. The present invention relates to an adhesive method which can be stopped) and which can obtain a sufficient adhesive strength after a certain period of time.

(Prior Art) In recent years, bonding with an adhesive has been widely performed in various industrial fields, homes, and the like. Among them, synthetic resin water-based emulsion adhesives have various advantages over organic solvent-based adhesives, such as no air pollution, excellent safety and hygiene, easy handling, and resource saving. In addition, it is used in a wide range of fields, centering on the adhesion of porous adherends such as wood, paper and cloth. However, the water-based emulsion adhesive has a fatal defect that the initial adhesive force is extremely slow to develop due to poor drying property due to the medium being water.

In order to improve these drawbacks, methods of increasing the solid content in the emulsion, using an organic solvent in combination, or applying heat have been proposed. However, none of these methods can be said to be satisfactory because the curing is insufficient or special equipment is required.

In addition, a two-component type, in which the main agent and the curing agent are applied to separate adherends and then the adherends are adhered to each other, a separate application type adhesive has been proposed. This has the disadvantage that the entire bonding operation takes time, and when the adherend is large, a large space is required to dry the adherend coated with the curing agent.

(Problems to be Solved by the Invention) In view of the above-mentioned drawbacks of the conventional bonding method using an adhesive, the present invention temporarily fixes in a short time after bonding the adherends without using another device or the like. The present invention is intended to provide an adhesive method which can achieve sufficient adhesive performance when a certain time has elapsed after laminating.

(B) Structure of the Invention (Means for Solving Problems) The inventors of the present invention have conducted various studies to solve the above problems, and as a result, have synthesized a specific room temperature anionic polymerization curable adhesive and a synthetic adhesive. Two types of adhesives are used in combination with a synthetic resin water-based emulsion type adhesive in which an anionic polymerization accelerator is added to a resin water-based emulsion, and the above two types of adhesives are used at the adhesive interface of the adherend to be bonded. The objects can be easily achieved by applying them separately so that they do not mix with each other and do not overlap with each other (however, they do not prevent mixing or overlapping with each other). It was made.

That is, the bonding method of the present invention comprises (A) the general formula (In the formula, R is an alkyl group having 1 to 16 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, a haloalkyl group having 1 to 16 carbon atoms, a cyanoalkyl group having 2 to 16 carbon atoms, Aralkyl group having 6 to 12 carbon atoms, acyloxyalkyl group having 2 to 16 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, or total carbon number 6 to 12 aryl groups), and an anionic polymerization curable adhesive with water at room temperature containing at least one anionically polymerizable compound selected from α-cyanoacrylate compounds, and (B) a synthetic resin. 2 with synthetic resin water-based emulsion type adhesive which added anionic polymerization accelerator to water-based emulsion
It is necessary to use two kinds of adhesives and apply the two kinds of adhesives described above to the adhesion surfaces of both adherends to be adhered separately so that they do not mix with each other and do not overlap each other. This is a characteristic method.

The two types of adhesives, namely, the room temperature anionic polymerization curable adhesive (A) and the synthetic resin aqueous emulsion type adhesive (B) described in the present specification, are separately applied so as not to be mixed with each other and not to be overlapped. , It is not applied in the strict sense of only applying it so as not to mix at all and not overlap at all. In other words, the application refers to application with as little mixing as possible and without overlapping, and does not prevent partial mixing or overlapping during application.

The adhesive (B) used in the bonding method of the present invention is a synthetic resin aqueous emulsion type adhesive obtained by adding an anionic polymerization accelerator to a generally known synthetic resin aqueous emulsion for adhesives. B) is novel in that an anionic polymerization accelerator is added, and exhibits excellent effects when used in the bonding method of the present invention.

As described above, the adhesive used in the bonding method of the present invention is a synthetic resin water-based emulsion type adhesive (B), instead of adding the anionic polymerization accelerator to the room temperature anionic polymerization curable adhesive (A) as in the conventional case. When the anionic polymerization accelerator is added to the room temperature anionic polymerization curable adhesive (A), its storage stability or pot life may be shortened, and Unexpectedly, the addition of an anionic polymerization accelerator to the synthetic resin aqueous emulsion type adhesive (B) is superior to that of the room temperature anionic polymerization curable adhesive (A) when using the adhesion method. It was found that the effect of shortening the set time (temporary fixing time) can be obtained. In this case, the anionic polymerization accelerator added to the aqueous emulsion acts on the room temperature anionic polymerization-curable adhesive (A) by permeation, diffusion, etc. to accelerate the polymerization and curing of the adhesive (A). That is, the temporary fixing effect can be exerted promptly.

Specific examples of the α-cyanoacrylate compound represented by the general formula (I) used in the adhesive (A) in the bonding method of the present invention include, for example, methyl-α-cyanoacrylate, ethyl-α-cyanoacrylate, Propyl-α-cyanoacrylate, butyl-α-cyanoacrylate, 2-methoxymethyl-α-cyanoacrylate, 2-methoxyethyl-α-cyanoacrylate,
2-ethoxymethyl-α-cyanoacrylate, 2-ethoxyethyl-α-cyanoacrylate, 2-propoxyethyl-α-cyanoacrylate, 2-butoxyethyl-α-cyanoacrylate, tetrahydrofurfuryl-α-cyanoacrylate, allyl -Α-cyanoacrylate, propargyl-α-cyanoacrylate, 2-
Chlorethyl-α-cyanoacrylate, 2- (2,2,2
-Trifluoroethoxy) ethyl-α-cyanoacrylate and the like.

The room temperature anionic polymerization-curable adhesive (A) in the bonding method of the present invention contains at least one of the α-cyanoacrylate compounds represented by the general formula (I). , In some cases general formula (In the formula, R ¹ and R ² are each a hydrogen atom and have 1 to 5 carbon atoms.
Is an alkyl group, an aryl group, an aralkyl group having a total carbon number of 6 to 12, or a halogen atom, and R ¹ and R ² may be the same or different. R ³ is a hydrogen atom or a methyl group. X and Y are cyano groups, respectively, and the total number of carbon atoms is 2
12 carboxylic acid ester group, ethyl sulfone group, phenyl sulfone group, formyl group, acetyl group, benzoyl group, amide group, diethylphosphonyl group or phenyl group, wherein X and Y may be the same or different. Good. ).

The 1,1-disubstituted diene compound represented by can be used in combination.

Specific examples of the 1,1-disubstituted diene compound represented by the general formula (II) include 1-cyano-1-carbomethoxybutadiene-1,3,1-cyano-1-carbethoxybutadiene- 1,3,1-cyano-1-carbo-n-propoxybutadiene-1,3, 1,1-dicarboethoxybutadiene-1,3 and the like can be mentioned.

In the preparation of the adhesive (A) in the bonding method of the present invention, one kind may be selected from the α-cyanoacrylate compounds represented by the general formula (I) and used, or two or more kinds may be selected. They may be used as a mixture thereof, or, as described above, these compounds may be used in combination with the 1,1-di-substituted diene compound represented by the general formula (II).
Further, the adhesive (A) may optionally contain SO ₂ , carboxylic acids, phosphoric acids, sulfonic acids; storage stabilizers such as hydroquinone and hydroquinone monomethyl ether; acrylic rubber, acrylic ester (co) polymers. , Thickeners such as polyesters and polyurethanes; gelling agents (eg gelling agents as described in JP-A-54-107993); plasticizers such as phthalates and phosphates Further, a colorant, a curing accelerator (for example, lactone compound, cyclalaurine compound, crown compound, etc.), an organic solvent and the like can be added within a range not significantly impairing the adhesive performance.

The synthetic resin aqueous emulsion used in the synthetic resin aqueous emulsion type adhesive (B) in the bonding method of the present invention refers to a generally known aqueous dispersion of a polymer, specifically, vinyl acetate, ethylene, Polymer obtained from one type or a copolymerizable two or more types of unsaturated monomers selected from styrene, styrene derivatives, butadiene, acrylonitrile, chloroprene, acrylic acid ester, methacrylic acid ester, vinyl chloride, vinylidene chloride, etc. Alternatively, an aqueous dispersion of a copolymer, and an unsaturated monomer having a hydroxyl group, an unsaturated monomer having a carboxyl group or an unsaturated monomer having an amide group (for example, acrylamide This includes an aqueous dispersion of a copolymer obtained by copolymerizing at least one of (1).

Here, the monomer having a hydroxyl group is allyl alcohol, 2-hydroxyethyl methacrylate, 2-
Hydroxyethyl acrylate, 2-hydroxypropyl methacrylate, 2-hydroxypropyl acrylate, monoallyl ether of polyhydric alcohol, N-methylol acrylamide, N-methylol methacrylamide and the like, and the monomer having a carboxyl group , Unsaturated acids such as acrylic acid, methacrylic acid, itaconic acid, fumaric acid, crotonic acid, half ester of maleic acid, half ester of itaconic acid, half ester of fumaric acid, maleic acid. These synthetic resin aqueous emulsions may be used alone or in combination of two or more. If necessary for various purposes, a synthetic resin aqueous emulsion may be added to a filler such as clay, talc, calcium carbonate, titanium white, or zinc white, or a film-forming aid such as butyl carbitol or butyl carbitol acetate, or dibutyl phthalate. , Plasticizers such as dioctyl phthalate, tackifiers such as rosin, terpene phenol, petroleum resin, various surfactants used for wetting, dispersing, defoaming, thickening agents, thixotropic agents, various antifreezing agents, etc. You may add and use an additive in the range which does not impair the objective of this invention.

Further, as the anionic polymerization accelerator in the present invention,
Examples include tertiary amine compounds, lactone compounds, crown compounds, N, N-dicyclohexylcarbodiimide, succinamide, ethylenethiourea, and 1,2,6 hexatriol.

As the tertiary amine compound, any aliphatic, alicyclic, aromatic-substituted aliphatic or aromatic tertiary amine compound can be used, and N, N-dimethylaniline, N, N-diethylaniline, N- Ethyl-N-methylaniline, N, N-2,4,6
-Pentamethylaniline, 4-bromo-N, N-dimethylaniline, 4-tert-butyl-N, N-dimethylaniline, N, N-dimethyl-p-toluidine, N, N-diethyl-
p-toluidine, N, N-dimethyl-m-toluidine, N, N
-Dimethyl-o-toluidine, N, N-diethyl-m-toluidine, N, N-dimethyl-1,4-phenylenediamine,
N, N-diethyl-1,4-phenylenediamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N-butyldiethanolamine, phenylethylethanolamine, β-dimethylaminoethylacetate, β-dimethylamino There is ethylbenzene. Further, a compound in which the amine compound has a reactive silicon functional group, for example, (N, N-dimethyl-3-aminopropyl) trimethoxysilane, (N, N-diethyl-3-aminopropyl) trimethoxysilane, (N, N-dipropyl-3-aminopropyl) triethoxysilane, (N, N
-Dibutyl-3-aminopropyl) triethoxysilane, (N, N-dimethyl-3-aminopropyl) trimethylsilane, (N, N-diethyl-3-aminobutyl) triethylsilane, N, N-dimethylaminophenyltri There are methoxysilane, N, N-dimethylaminophenyltriethoxysilane, N, N-diethylaminophenyltrimethoxysilane, N, N-diethylaminophenyltriethoxysilane, N, N-dimethylaminophenyltrimethylsilane and the like. Further, the compounds described in the section of amines and tertiary amines (pages 319 to 325) of "Handbook of Organic Compound Identification" Volume 3 (1967) of Chemical Rubber can be used. .

As the lactone compound, γ-butyrolactone, β-
Propiolactone, 5-ethyl-γ-butyrolactone,
Examples include ε-caprolactone and coumarin.

The crown compounds include 15-crown-5, 18-crown-6, dibenzo-18-crown-6 and dibenzo-24.
-Crown-8, dicyclohexyl-18-crown-
6, dicyclohexyl-24-crown-8, dithia-15
-There is a crown, etc.

The compounds used as these anionic polymerization accelerators are 1
One type may be used alone, or two or more types may be used appropriately.

The amount added is 0.05 to 50% by weight, preferably 0.5 to 10% by weight, based on the evaporation residue of the synthetic resin aqueous emulsion.
If the amount added is too small, the adhesive (A) cannot be polymerized and cured sufficiently quickly during bonding, and the time required for temporary fixing cannot be effectively shortened. If it is too large, the adhesive strength is reduced.

The bonding method of the present invention uses two kinds of adhesives, the adhesive (A) and the adhesive (B) prepared as described above, at the bonding interface of both adherends to be bonded. Adhesion is performed by applying the two kinds of adhesives separately so that the two kinds of adhesives do not mix with each other as much as possible and do not overlap with each other (but do not prevent mixing or overlapping of some of them). Let

As described above, there are various modes for separately applying the two kinds of adhesives so that they are not mixed with each other as much as possible and do not overlap each other. FIGS. 1 to 9 show examples of the modes. Is.

In the embodiment shown in FIGS. 1 to 5, both the adhesive (A) and the adhesive (B) are mixed on the surface of one adherend 1 of both adherends, and both adhesives are mixed. After applying so as not to overlap with each other, the adhering surface of the other adherend 2 is overlapped on this and adhering is performed.

Further, in the example of the mode shown in FIGS. 6 to 8, the adhesive agent (A) or the adhesive agent (B) is separately applied to the respective adhesive surfaces of the adherends 1 and 2, and the adherends of both adherends are adhered to each other. Even when the adhesive surfaces are overlapped, the adhesive (A) application surface and the adhesive (B) application surface are applied so that they do not overlap each other, and then the adhesion surfaces of both adherends are overlapped to perform adhesion. .

Further, in the embodiment shown in FIG. 9, first, in the step a, the adhesive (B) is applied to a relatively narrow area of the lower surface corresponding to the adhesive surface of the adherend 1, and then the adhesive is applied in the step b. The adherend 2 is overlaid on the lower surface of the adherend 1 applied in (B). Next, in step c, another adhesive (A) is applied to the gap around the applied adhesive (B) between the adherends of the adherends 1 and 2 to complete the adhesion.

(Examples, etc.) Next, adhesive preparation examples, examples and comparative examples will be described in more detail. "Parts" described in these examples means "parts by weight".

Adhesive Preparation Examples A _{1 to} A ₆ Various adhesives A _{1 to} A ₆ having various compositions shown in Table A were prepared.

Various adhesive B ₁ .about.B ₁₈ consisting of various compositions shown in the adhesive preparation Example B ₁ .about.B ₁₈ Table B were prepared.

The adhesive of Adhesive Preparation Example B ₁₈ is a control example in which no anionic polymerization accelerator was added.

Example 1-29 Comparative Example 1-2 above adhesive Preparation A ₁ to A _6, and adhesives Preparation B ₁ .about.B ₁₈
Adhesion tests were carried out using various adhesives prepared in 1 above in various combinations as shown in Table 1. The mode of application of the adhesive at that time was as shown in Table 1, respectively. Moreover, each test method was as follows.

(1) Set time (temporary fixing time) Using two plywood boards (length 100 mm x width 25 mm x thickness 3 mm), apply each adhesive shown in Table 1 in the application mode shown in Table 1 and apply immediately. After combining (the lap area of both plates is 25 mm ×
25mm), the time required to withstand a static load of 1kg was measured and used as the set time (temporary fixing time).

Note to Table 1: The total coating area (mm ² ) of the adhesives (A) and (B) in the coating method shown in each figure was as follows.

As is clear from the results shown in Table 1, in each of the examples, temporary fixing could be performed in a significantly short time.

On the other hand, in the case where the synthetic resin water-based emulsion adhesive alone was used for adhesion (Comparative Example 1), it took a long time for temporary fixing. Also, in the case of using only the adhesive (A) for adhesion (Comparative Example 2), it took a long time for temporary fixing as in the case of using only the synthetic resin aqueous emulsion adhesive.

(C) Effects of the Invention In the bonding method of the present invention, since the adhesive (A) is polymerized and cured more quickly by the action of the anionic polymerization accelerator added to the adhesive (B), a special device or the like is used. It can be temporarily fixed by an extremely short-time bonding operation without using it, and since the adhesive (B) dries with the diffusion of water to form an adhesive layer, it is mainly used for adhesion of porous adherends. , Can give excellent adhesion performance.

[Brief description of drawings]

FIGS. 1 to 9 show examples of application modes of the adhesive (A) and the adhesive (B) when carrying out the bonding method of the present invention, and 1 and 2 are both bonded to each other. The adherend is shown.

Claims (2)

[Claims] 1. A general formula (A) (In the formula, R is an alkyl group having 1 to 16 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms, a haloalkyl group having 1 to 16 carbon atoms, a cyanoalkyl group having 2 to 16 carbon atoms, Aralkyl group having 6 to 12 carbon atoms, acyloxyalkyl group having 2 to 16 carbon atoms, cycloalkyl group having 3 to 16 carbon atoms, alkenyl group having 2 to 16 carbon atoms, or total carbon number 6 to 12 aryl groups), and a room temperature anionic polymerization curable adhesive containing water containing at least one anionically polymerizable compound selected from α-cyanoacrylate compounds represented by the formula (B) synthetic resin. Two kinds of adhesives, a synthetic resin water-based emulsion type adhesive obtained by adding an anionic polymerization accelerator to an aqueous emulsion, are used, and the above-mentioned two kinds of adhesives are attached to each other at the adhesive interface of both adherends to be adhered to each other. Do not mix Bonding method for causing non-overlapping manner separately applied to perform bonding One. 2. A group of anionic polymerization accelerators consisting of tertiary amine compounds, lactone compounds, crown compounds, N, N-dicyclohexylcarbodiimide, succinamide, ethylenethiourea, 1,2,6-hexanetriol. The adhesion method according to claim 1, which is at least one anionic polymerization accelerator selected from the group consisting of: