JPH078976B2 - 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 in a short time (temporary fixing) without applying a special treatment such as heating, pressurization, or ultraviolet irradiation. ), And moreover, it provides a sufficient adhesive strength after a certain period of time.

(Prior Art) Bonding with an adhesive is widely performed in various industrial fields, households, etc. In recent years, the requirement for the bonding is not only adhesive performance but also non-toxic, non-flammability, bonding There are various demands such as speeding up of work, simplification, shortening of compression time after laminating, and adhesion performance to adherends not only for general adherends but also for porous and uneven surfaces. However, a bonding method capable of simultaneously satisfying these various requirements is known.

For example, adhesives used industrially include hot melt adhesives, rubber-based solvent adhesives, UV curable adhesives,
Two-component acrylic adhesives, α-cyanoacrylate adhesives, etc. are excellent adhesives and are used for adhesion of adherends in various fields such as paper packaging, electrical parts, precision equipment, construction, civil engineering, household products, etc. Has been done. However, each of these adhesives has various problems.

That is, the hot-melt adhesive requires a heating applicator in order to be used by being heated and melted at a high temperature, and the adhesive force after deposition is rapidly reduced as the softening temperature of the adhesive is approached, Further, there is a limitation on the type of adherend that can exert the adhesive force.

Rubber-based solvent-based adhesives require a large amount of solvent to be volatilized and removed by the time between application of the adhesive and pasting.The waiting time is long and adhesion takes time, and odor, toxicity and There are drawbacks such as the danger of ignition.

The ultraviolet curable adhesive requires an ultraviolet ray generator and can be applied only to bonding transparent parts and the like.

The two-component acrylic adhesive requires a two-liquid weighing and mixing device, and the bonding work becomes complicated.

The α-cyanoacrylate adhesive does not need to be heated, mixed, or irradiated with ultraviolet rays, and can be cured and adhered at room temperature in a short time. However, this adhesive has low impact adhesive strength and peel adhesive strength, and the adhesive performance is poor in reliability. In addition, it has poor adhesion to porous adherends such as wood, cloth, and concrete, and to the adhered surface having irregularities.

There are attempts to improve the above-mentioned drawbacks by adding various modifiers such as a thickener, a plasticizer, and a curing accelerator to the α-sinoacrylate-based adhesive, or by incorporating a primer. Not enough results.

The 1,1-di-substituted diene compound-based adhesive also has excellent performance of curing in a short time like the above α-cyanoacrylate-based adhesive, but is inferior in adhesive performance to a porous adherend or an uneven surface. It has the same drawbacks as the α-cyanoacrylate adhesive.

(Problems to be Solved by the Invention) In view of the above-mentioned drawbacks of conventional adhesives and bonding methods, the present invention temporarily fixes in a short time without using any other device after bonding the adherends. If a certain period of time elapses after laminating, sufficient adhesion performance, particularly sufficient peeling strength and impact adhesion strength can be obtained, and in addition to ordinary adherends, it can be applied to porous adherends and surfaces. It is an object of the present invention to provide a bonding method that can exhibit sufficient bonding performance even on an uneven adherend and is therefore applicable to adhesion of adherends in a wide variety of fields.

(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, used two specific types of adhesives in combination. In addition, the above-mentioned 2 is applied to the bonding interface of the adherend to be bonded.
The purpose could be easily achieved by applying different kinds of adhesives to each other so as not to mix with each other as much as possible and not to overlap with each other to perform the adhesion.

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 6 to 12 carbon atoms, or total carbon number An aryl group of 6-12, and an α-cyanoacrylate compound represented by (In the formula, R ¹ and R ² are each a hydrogen atom and have 1 to 5 carbon atoms.
Represents 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.
Represents a carboxylic acid ester group, an ethyl sulfone group, a phenyl sulfone group, a formyl group, an acetyl group, a benzoyl group, an amide group, a diethylphosphonyl group, or a phenyl group, wherein X and Y are the same or different. May be. ) A room temperature anionic polymerization-curable contact agent containing at least one anionically polymerizable compound selected from the group consisting of 1,1-disubstituted diene compounds represented by At least one room temperature moisture-curable compound selected from the group consisting of a polyisocyanate compound having at least two in the molecule and an organosilicon compound having at least two silicon atoms to which a hydrolyzable group is bonded in the molecule. Two kinds of adhesives, which are the main component of room temperature and moisture curable adhesive, are used, and the above two kinds of adhesives are not mixed with each other as much as possible at the adhesion interface of both adherends to be adhered, and they are overlapped with each other. It is a method characterized in that it is applied separately so that it does not occur (however, it does not prevent mixing or overlapping with a part) and adhesion is performed.

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, tetrahydrofurfurin-α-cyanoacrylate, allyl -Α-cyanoacrylate, propargyl-α-cyanoacrylate, 2-
Chloroethyl-α-cyanoacrylate 2- (2,2,2-
Examples include trifluoroethoxy) ethyl-α-cyanoacrylate.

Specific examples of the 1,1-disubstituted diene compound represented by the general formula (II) used in the adhesive (A) in the adhesive method of the present invention include 1-cyano-1-carbomethoxybutadiene-1. , 3-, 1-Cyano-1-carboethoxybutadiene-1,3,1-cyano-1-carbon
-Propoxy butadiene-1,3, 1,1-dicarboethoxy butadiene-1,3 and the like.

For the preparation of the adhesive (A) in the bonding method of the present invention, the α-cyanoacrylate compound represented by the general formula (I) and the 1,1-disubstituted diene compound represented by the general formula (II) are used. You can choose one from
Two or more kinds may be selected and used as a mixture thereof.
Further, the adhesive (A) includes, as required, 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 A colorant, a curing accelerator, an organic solvent and the like may be further added.

The organic isocyanate compound having at least two isocyanate groups in the molecule, which is used in the adhesive (B) in the bonding method of the present invention, is an isocyanate-terminated polyurethane or organic polythiol obtained by reacting an organic polyhydroxy compound with an organic polyisocyanate. Isocyanate-terminated polyurethanes obtained by reacting a compound with an organic polyisocyanate can be mentioned.

Examples of the organic polyhydroxy compound as the raw material include the following compounds.

(A) Lactone polyol and alkylene oxide adduct thereof: (b) Polyester polyol and alkyne oxide adduct thereof: (c) Polyoxyalkylene polyol, polyoxycycloalkylene polyol and alkylene oxide adduct thereof: (d) Polyalkanol Amines and their alkylene oxide adducts: (e) Polyamines derived from polyamines by adding alkylene oxides to polyamines: (f) Non-reducing sugars, sugar derivatives and their alkylene oxide adducts: (g) Aromatic Alkylene oxide adduct of amine-phenol-aldehyde ternary condensation product: (h) Polyphenol alkylene oxide adduct: (i) Polytetramethylene glycol: (j) Castor oil Such polyfunctional glyceride: (k) Polyhydroxy group-containing vinyl polymer: (l) Polyhydroxypolysulfide polymer: (m) 5000-75000 prepared by reacting a lactone polyester with a polyol such as bisphenol A. Hydroxyl-terminated long-chain lactone polyester having a molecular weight within the range of: (n) Hydroxy group-containing polybutadiene, diene (co) acrylonitrile-butydiene copolymer, etc.
Polymer: Examples of the organic polythiol compound as a raw material thereof include pentaerythritol thioglycolate, mercaptoethyl adipate, and the like, and commercially available products thereof include Thiocol LP-3 and Thiocol LP-8 (the above are Torreol).・ Tiocor's product name), Epomate QX-1
0, Epomate QX-11 (the above is a trade name of Yuka Shell Epoxy Co., Ltd.), and polythiol DION 3-800 LC (trade name of Diamond Shamrock Co.).

Examples of the organic polyisocyanate as the raw material include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzidine diisocyanate and naphthalene. -1,5-diisocyanate, hexamethylene diisocyanate, 4,4 ', 4 "-triphenylmethane triisocyanate, decamethylene diisocyanate, polyphenylmethylene polyisocyanate (manufactured by acting phosgene on aniline-formaldehyde condensate) , Dianisidine diisocyanate, xylene diisocyanate, bis- (2-isocyanatoethyl) -fumarate, bis- (2-isocyanatoethyl) -cyclohex-4-cene-1,2- Carboxylate, bis - (2-isocyanatoethyl) carbonate, and "An'naren (Annalen), 562, 122135 ( 194
9) include organic polyisocyanates as disclosed by Siefken.

The organic silicon compound having at least two silicon atoms to which a hydrolyzable group is bonded, which is used in the adhesive (B) in the bonding method of the present invention, has a general formula: (In the formula, Z is a hydrolyzable group, R ⁴ is a group other than a hydrolyzable group, and n is an integer of 0 to 2.) A compound having at least two "functional silicon functional groups" in the molecule.

Specific examples of the hydrolyzable group Z in the general formula (III) include, for example, acetooxy group, octanoyloxy group, benzoyloxy group-containing acyloxy group; dimethylketoxime group, methylethylketoxime group, diethylketoxime group and the like. Ketoxime group; alkoxy group such as methoxy group, ethoxy group, propoxy group; alkenyloxy group such as isopropenyloxy group, 1-ethyl-2-methylvinyloxy group; dimethylamino group, diethylamino group, butylamino group, cyclohexyl Examples thereof include amino groups such as amino groups; aminoxy groups such as dimethylaminoxy group and diethylaminoxy group; amide groups such as N-methylacetamide group, N-ethylacetamide group, N-methylbenzamide group and the like.

The group R ⁴ within the hydrolyzable group in the general formula (III) is, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group or a butyl group; a cyclopentyl group,
Cycloalkyl group such as cyclohexyl group; alkenyl group such as vinyl group, allyl group; aryl group such as phenyl group, tolyl group, naphthyl group; aralkyl group such as 2-phenylethyl group; And iminoalkyl groups such as, and groups in which some or all of the hydrogen atoms of each of these groups are substituted with halogen atoms such as chlorine atoms.

Specific examples of the organosilicon compound having at least two hydrolyzable group-bonded silicon atoms in the molecule include the following compounds.

(A) Room temperature curable silicone compound obtained by reacting silanol-terminated polydiol with a siloxane compound having a reactive silicon functional group represented by the general formula (III) in the molecule: (b) A compound having a group capable of reacting with an isocyanate group in the molecule and a reactive silicon functional group represented by the general formula (III), and a polyisocyanate similar to that used as the main component in the adhesive (B). Room temperature curable silicon-terminated compounds obtained by reacting with a compound (see Japanese Patent Publication No. 46-30711, etc.): (c) Isocyanate group in the molecule and the above general formula (II
A compound having a reactive silicon functional group represented by I), and an organic polyhydroxy compound or an organic polythiol compound similar to those used as a raw material for producing the organic polyisocyanate compound as the main component of the adhesive (B). Room-temperature curable silicon-terminated compound obtained by reacting with: (d) Various kinds of polyoxyalkylene polyether compounds having an allyl group at the molecular end are added to the above-mentioned general formula (III)
A silicon-modified polyoxyalkylene polyether compound obtained by the addition reaction of a compound having a reactive silicon functional group represented by --SH or hydrogen having a hydrogen bonded directly to silicon: (e) Others, for example, Japanese Patent Publication No. Sho 49 Compounds containing terminal reactive silicon functional group as described in JP-A-32673: In order to prepare the adhesive (B) in the method of the present invention, the above-mentioned organic polyisocyanate compound and organic silicone compound are more suitable. Select one compound to use, or 2
It is possible to select one kind or more and use it as a mixture to form an adhesive as it is. If necessary, the adhesive may be a plasticizer such as phthalate ester; a filler such as calcium carbonate or carbon black; a curing accelerator such as an organotin compound; an adhesiveness-imparting agent such as a silane compound; Anti-sagging agents such as silica; dehydrating agents such as molecular sieves; other antioxidants, ultraviolet absorbers, coloring agents and the like can be added.

Further, in the adhesive (B) using an organic polyisocyanate compound, Japanese Patent Publication Nos. 43-12510 and 57-16126 are used.
No. 48-20639, No. 55-35407, and JP-A-60-19.
As disclosed in Japanese Patent No. 5177, a ketimine compound which hydrolyzes to form a polyamino compound, a polyimino compound or an amino alcohol, an enamine compound or an oxazoline compound can be used in combination, and an isocyanate of an organic polyisocyanate compound can be used. The group can be used by appropriately blocking it with phenols, oximes and the like.

Further, in the adhesive (B) containing an organic silicone compound as a main component, an organosiloxane and a silane compound having a reactive silicone functional group represented by the general formula (III) are reacted in advance to form an organic silicone compound. Instead, the raw material organosiloxane and the silane compound having a reactive silicone functional group can be blended as they are to prepare the adhesive (B).

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 between the adhered surfaces of the adherends 1 and 2 around the applied adhesive (B) to complete the adhesion.

(Examples, etc.) Next, the adhesive preparation agent, 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 ₅ consisting of a variety of compositions shown in the adhesive preparation Example B ₁ .about.B ₅ Table B were prepared.

Examples 1 to 19 Comparative Examples 1 to 2 Adhesion tests were conducted using the various adhesives prepared in the above adhesive preparation examples A and B 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 matching (the lap area of both plates is 25m x 25m
m), the time required to withstand a static load of 1 kg was measured and used as the set time (temporary fixing time).

(2) Impact resistance Two mild steel plates (length 100 mm x width 25 mm x thickness 1.6 mm) are used, and the adhesives shown in Table 1 are applied in respective modes,
Immediately, both plates were pasted in a cross shape (the wrap area of both plates was 25 m × 25 mm). After curing for 7 days at 20 ℃, 2
It was dropped from a height of m onto the concrete surface and observed whether it peeled off. The evaluation was based on the following preparations.

◯: It does not peel off after 5 drop tests.

×: peeled off in one drop test.

(3) Peeling test Two mild steel plates (length 200 mm x width 25 mm x thickness 0.5 mm) were used, each adhesive shown in Table 1 was applied in each mode, and immediately laminated (lap of both plates Area is 170mm × 25m
m). After curing by leaving it at 20 ° C. for 7 days, the peel strength was measured.

As is clear from the results in Table 1, in each of the examples, both impact resistance and peeling strength were good, and the set time was 2 to 5 minutes, so that temporary temporary fixing was possible. On the other hand, Comparative Example 1 using only the adhesive (A)
On the other hand, the impact resistance and the peel strength were extremely poor. Also,
In Comparative Example 2 using only the adhesive (B), the impact resistance and the peel strength were excellent, but it took 1 hour and 30 minutes before temporary fixing.

(C) Effects of the Invention In the bonding method of the present invention, the adhesive (A) is rapidly cured by the moisture of the adherend, the set time (time required for temporary fixing) is short, and the adhesive (B ) Easily reacts with moisture such as moisture in the air at room temperature stoichiometrically and cures, so that not only general adherends, but also adherends with multi-faceted surfaces such as fibers and uneven adhesive surfaces It also exhibits excellent adhesion performance to the body, and in particular, can provide adhesion excellent in water resistance, peeling resistance, impact resistance and heat aging resistance.

[Brief description of drawings]

1 to 9 show examples of modes of applying the adhesive (A) and the adhesive (B) when carrying out the bonding method of the present invention. Show the body.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-63-66276 (JP, A) JP-A-63-46282 (JP, A) JP-A-53-66945 (JP, A) JP-A-58- 89674 (JP, A) JP 56-135570 (JP, A) JP 53-40027 (JP, A) JP 38-19845 (JP, B1)

Claims (1)

[Claims] 1. (A) 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 having 6 to 12 carbon atoms or total carbon number of 6
~ 12 aryl groups. ) An α-cyanoacrylate compound represented by (In the formula, R ¹ and R ² are each a hydrogen atom and have 1 to 5 carbon atoms.
Represents 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.
Represents a carboxylic acid ester group, an ethyl sulfone group, a phenyl sulfone group, a formyl group, an acetyl group, a benzoyl group, an amide group, a diethylphosphonyl group, or a phenyl group, wherein X and Y are the same or different. May be. ) A room temperature anionic polymerization-curable contact agent containing at least one anionically polymerizable compound selected from the group consisting of 1,1-disubstituted diene compounds represented by At least one room temperature moisture-curable compound selected from the group consisting of a polyisocyanate compound having at least two in the molecule and an organosilicon compound having at least two silicon atoms to which a hydrolyzable group is bonded in the molecule. Two kinds of adhesives, which are the main component of room temperature and moisture curable adhesive, are used, and the above two kinds of adhesives are not mixed with each other as much as possible at the adhesion interface of both adherends to be adhered, and they are overlapped with each other. A bonding method characterized in that the adhesives are applied separately so that they do not become mixed (but do not prevent mixing or overlapping in some parts).