JPS6366276A - Bonding and adhesive - Google Patents

Abstract

PURPOSE:To enable fixing of materials to be bonded in a short time without requiring a specific treatment, by using a specific adhesive of normal- temperature anionic polymerization curing type and a specific adhesive of normal-temperature moisture-curing type in such a way that both the adhesives are neither mutually blended nor superimposed. CONSTITUTION:Two kinds of adhesives of (A) an adhesive of normal- temperature anionic polymerization curing type with water consisting essentially of an alpha-cyanoacrylate compound shown by formula I (R is 1-16C alkyl, etc.) and/or a 1,1-disubstituted diene compound shown by formula II (R<1> and R<2> are H, 1-5C alkyl, etc.; R<3> is H or CH3: X and Y are cyano, amido, etc.) and (B) an adhesive of normal-temperature moisture-curing type obtained by adding an anionic polymerization initiator to a main component consisting of a polyisocyanate compound containing two or more isocyanate groups in the molecule and/or a moisture-curing compound of organosilicon compound containing two or more silicons bonded to hydrolyzable groups in the molecule are used in such a way that both the adhesives are neither mutually bonded nor superimposed.

Description

Detailed Description of the Invention (a) Purpose of the Invention (Field of Industrial Application) The present invention is capable of fixing (temporarily) adhering Vc for a short period of time without special treatment such as heating, pressurization, or ultraviolet irradiation. (Prior art) Adhesive bonding is widely used in various industrial fields and households, but in recent years, requirements for adhesives include not only adhesive performance but also non-toxicity, non-flammability, and adhesive properties. There are various demands such as speeding up work, simplifying W15, shortening the pressing time after bonding, and adhesion performance not only for general adherends but also for porous and uneven adherends.However, There is no known bonding method that can satisfy these binding requirements at the same time.

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

That is, hot-melt adhesives require a heating application device because they are heated to high temperatures and melted before use, and the adhesive strength after adhesion rapidly decreases as it approaches the softening temperature of the adhesive. There are restrictions on the types of adherends that can exhibit adhesive strength.

Rubber-based solvent-based adhesives require a large amount of solvent to be volatilized and removed after the adhesive is applied and before bonding, and the waiting time is long, resulting in long bonding times. There are drawbacks such as the risk of ignition.

Ultraviolet curing adhesives require an ultraviolet generator and can only be used to bond transparent parts.

Two-component acrylic adhesives require a two-component lid and mixing device, making the bonding work complicated.

The α-cyanoacrylate adhesive does not require heating, mixing, ultraviolet irradiation, etc., and can be cured and bonded at room temperature in a short time. However, this adhesive has low impact adhesive strength and peel adhesive strength, and its adhesive performance is unreliable. Poor adhesion to porous adherends such as warped wood, cloth, and concrete, and to uneven adherend surfaces.

α-cyanoacrylate adhesive, thickener, plasticizer,
There have been attempts to improve the above drawbacks by adding various modifiers such as curing accelerators, or by using primers in combination.
In both cases, sufficient results cannot be obtained.

1.1-Disubstituted diene compound thread adhesive also has excellent Lfc performance of curing in a short time like the α-cyanoacrylate adhesive described above, but it has poor adhesion performance to porous adherends and uneven surfaces. It has the same drawbacks as α-cyanoacrylate adhesives in that it is inferior.

(Problems to be Solved by the Invention) In view of the above-mentioned shortcomings of conventional adhesives and bonding methods, the present invention provides an adhesive method that can be used in a short period of time without using any other equipment after bonding adherends together. It can be temporarily fixed, and after a certain period of time has passed after lamination, sufficient adhesive performance, especially sufficient peel-resistant adhesive strength and impact adhesive strength, can be obtained. It is intended to provide sufficient adhesion even to adherends or adherends with uneven surfaces.

(b) Structure of the Invention (Means for Solving the Problems) As a result of various studies to solve the above-mentioned problems, the present inventors have developed a specific room-temperature anionic polymerizable adhesive and an anionic polymerizable adhesive. Two types of adhesives are used in combination, including a specific room-temperature, moisture-curing adhesive containing an accelerator, and the two types of adhesives are mutually applied to the adhesive interface of the adherend to be bonded. By applying the adhesives separately and adhering them so that they do not mix or overlap as much as possible, this purpose could be easily accomplished.

That is, the adhesion method of the present invention is based on (4) general formula (wherein,
R is an alkyl group having 1 to 16 carbon atoms, and the total number of carbon atoms is 2 to 1.
6 alkoxyalkyl group, haloalkyl group having 1 to 16 carbon atoms, cyanoalkyl group having 2 to 16 total carbon atoms, aralkyl group having 6 to 12 total carbon atoms, total carbon number 2 to 16
, an acyloxyalkyl group having 3 to 16 carbon atoms, an alkenyl group having 2 to 16 carbon atoms in total, or an aryl group having 6 to 12 carbon atoms in total. ), and an α-cyanoacrylate compound represented by the general formula (wherein R and R are each a hydrogen atom and have 1 to 5 carbon atoms)
is an alkyl group, an aryl group, an aralkyl group having 6 to 12 carbon atoms in total, or a halogen atom, and R and R may be the same or different. R is a hydrogen atom or a methyl group. X and Y are each a cyano group, and the total number of carbon atoms is 2
~12 carboxylic acid ester groups, ethylsulfone groups, phenylsulfone groups, formyl groups, acetyl groups, benzoyl groups, amide groups, diethylphosphonyl groups, or phenyl groups, and X and Y may be the same or different. It's okay. ) 1,1-di-substituted diene compound ↓ 1,1-disubstituted diene compound ↓ 1,1-disubstituted diene compound ↓ 1,1-disubstituted diene compound ↓ 1,1-disubstituted diene compound; At least one moisture-curable compound selected from the group consisting of polyisocyanate compounds having at least two groups in the molecule, and organic silicon compounds having at least two silicon atoms bonded to hydrolyzable groups in the molecule. A two-glaze type adhesive is used, which is a room-temperature, moisture-curing type adhesive which is made mainly of This method is characterized in that the adhesives are applied separately so as not to mix with each other and to prevent them from overlapping each other (does not prevent them from mixing or overlapping in some areas) to effect adhesion.

The adhesive (B) used in the bonding method of the present invention is a polyisocyanate compound having at least two isocyanate groups in the molecule, and an organic silicon compound having at least two silicon atoms to which a hydrolyzable group is bonded. This adhesive is a room temperature moisture curing type adhesive which contains at least one moisture curing compound koji selected from the group consisting of koji as a main component and further contains an anionic polymerization accelerator. and,
This adhesive (B) is novel in that it contains an anionic promoter, and exhibits excellent effects when used in the bonding method of the present invention.

As described above, in the adhesive used in the bonding method of the present invention, the anionic 1-accelerator is not added to the room temperature anionic polymerization curable adhesive (G), but is added to the room temperature moisture curable adhesive (B). The reason is that if an anionic polymerization accelerator is added to an anionic polymerization-curing adhesive at room temperature, its storage stability or usable life will be shortened, so it should be added to the adhesive (B). After applying the inner adhesive and bonding, the anionic polymerization accelerator added to the room temperature moisture curable adhesive (B) is added to prevent permeation, diffusion, etc. 4) to accelerate the polymerization and hardening of the adhesive, thereby quickly exhibiting the temporary fixing effect.

Specific examples of the α-cyanoacrylate compound represented by the general formula (1) used in the adhesive (4) in the adhesive method of the present invention include 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-propoquinethyl-α-cyanoacrylate, 2-butoxyethyl-α-cyanoacrylate, tetrahydrofurfuryl-α-cyanoacrylate, Allyl-α-cyanoacrylate, Propargyl-α-cyanoacrylate, 2-
Chlorethyl-α-cyanoacrylate), 2-(2,2
, 2-) trifluoroethoxy) ether-α-cyanoacrylate, etc.

Specific examples of the 1,1-j-substituted diene thread compound represented by the general formula (IIl) used in the adhesive in the adhesive method of the present invention include, for example, 1-cyano-1-carbomethoxybutadiene-1, Examples include 3,1-cyano-1-carpoethoxyptasoene-1,3, l-cyano-1-carbo n-propoxybutadiene-1,3,1,1-dicarboethoxybutadiene-1,3. .

Preparation 1c of adhesive (4) in the adhesive method of the present invention is as follows.

One type may be selected and used, or two or more types may be selected and used as a mixture. In addition, the adhesive (
For 4), if necessary, include SO2, caldic acids, phosphoric acids, sulfonic acids: M storage stabilizers such as hydroquinone and hydroquinone monomethyl ether; acrylic rubber, acrylic ester (co)! Thickeners such as coalescent 1jl, polyesters, and polyurethanes; Gluing agents (for example, gluing agents such as those described in JP-A-54-107993): Phthalate esters, phosphate esters, etc. A plasticizer; further K can be mixed with a coloring agent, a curing accelerator, an organic solvent, etc.

The organic isocyanate compound having at least two isocyanate groups in the molecule used in the adhesive (E) in the adhesive method of the present invention is an isocyanate-terminated polyurethane obtained by reacting an organic polyhydroxy compound and an organic polyisocyanate. , isocyanate-terminated polyurethane obtained by reacting an organic polythiol compound and an organic polyisocyanate.

Examples of organic polyhydroxy compounds used as raw materials include the following compounds1: (a) Lactone polyol and its alkylene oxide adduct; (b) Polyester polyol and its alkyne oxide adduct; (e) Poly Oxyalkylene polyols, polyoxycycloalkylene polyols and their alkylene oxide adducts: (d) Polyalkanolamines and their alkylene oxide adducts: (e) 7I? Polyols derived from cypolyamines by adding alkylene oxides to polyamines: (f) Acyclic amines, sugar derivatives and their alkylene oxide adducts: Excellent) Aromatic amine-phenol-aldehyde ternary condensation Alkylene oxide adduct of product: (h) z Alkylene oxide adduct of liphenol: (1) Polytetramethylene glycol: (j)
Polyfunctional glyceride such as oil: (k) Polyhydroxy group-containing vinyl polymer: (1) Polyhydroxy polysulfide 1-combined lactone polyester is reacted with a polyol such as bisphenol A etc. by phosdan reaction! 7 Prepared 5 000-7500
Hydroxyl-terminated long-chain lactone polyester having a molecular weight within the range of 0: (n) Diene yarn (co-) such as polybutadiene containing hydroxyl groups, acronitrile-butidiene monomer, etc.
Polymer: Organic polythiol compounds used as raw materials include, for example, pentaerythritol thioglycolate, mercazoton ethyl adipate, and commercially available products include Thiokol LP-3 and Thiokol LP-3.
For 8C and above, Tone Thiokol (product name), Epome)
QX-10,
-800LC (Diamond Jamrock product name)
etc. can be mentioned.

In addition, examples of the organic polyisocyanate as a raw material include m-phenylene diisocyanate, p-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-)lylene diisocyanate, 4,4'-diphenylmethane diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate, hexamethylene diisocyanate), 4,4',4''-triphenylmethane triisocyanate, decamethylene diisocyanate, polyphenylmethylene polyisocyanate (aniline-formaldehyde condensate with phosdan) dianisidine diisocyanate, xylene diisocyanate, bis-(2-isocyanatoethyl)-fumarate, bis-(2-isocyanatoethyl)-cyclobek-4-cene-1,2-dical xylate, -(2-・ethyl isocyanate)
Carbonate, and 1 Annalen
562.122135 (1949), such as those disclosed by Mr. Siefken (1949).

The organic silicon compound having at least two silicon atoms to which a hydrolyzable group is bonded in the molecule used in the adhesive (B) in the adhesive method of the present invention has the general formula % formula % () (in the formula, zth :11.Hydrolyzable group, R4
is a group other than a hydrolyzable group, and n is an integer of O to 2. ) (Hereinafter, this may be referred to as a "reactive silicone functional group") ] Compounds having at least two groups in the molecule are mentioned.

Specific examples of the hydrolyzable group Z in the general formula (I [ Ketoxime groups such as groups: methoxy group,
Alkoxy groups such as ethoxy group and zolopoxy group; isopropenyloxy group.

Alkenyloxy groups such as 1-ethyl-2-methylvinyloxy; amine groups such as dimethylamino, diethylamino, butylamino, and cyclohexylamino groups; aminoxy groups such as dimethylaminoxy and diethylaminoxy; N- Examples include amide groups such as methylacetamide group, N-ethylacetamide group, and N-methylbenzamide group.

In addition, as the group R other than the hydrolyzable group in the general formula (III), for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; basis,
Alkenyl groups such as allyl groups; aryl groups such as phenyl, tolyl, and naphthyl groups; iminoalkyl groups such as aralkyl groups such as 2-phenylethyl; and some or all of the hydrogen atoms in these groups. is substituted with a norogne atom such as a chlorine atom.

Specific examples of organosilicon compounds having at least two silicon atoms to which hydrolyzable groups are bonded include the following compounds.

(a) Room-temperature-curable silicone compound obtained by reacting a silanol-terminated polydiorganosiloxane with a silane compound having a reactive silicone functional group represented by the general formula (III) in one molecule: (b) Molecule A compound having a group capable of reacting with an isocyanate group and a reactive silicone functional group represented by the above general formula (I[l), and a polyisocyanate similar to that used as the main component in the above adhesive ω). A room temperature-curable silicon-terminated compound obtained by reacting with a compound (
(3) a compound having an isocyanate group and a reactive silicone functional group represented by the general formula (2) in the molecule;
A room temperature-curable silicon-terminated compound obtained by reacting the same organic polyhydroxy compound or organic polythiol compound as used as a raw material for producing the organic polyisocyanate compound, which is the main component of B). A silicon-modified polyester obtained by adding a compound having a reactive silicon functional group represented by the general formula (l [I) and having a -8R group or a hydrogen directly bonded to silicon to a compound having a group having Oxyalkylene polyether compound: (e) Other compounds containing terminal reactive silicone functional groups, such as those described in Japanese Patent Publication No. 49-32678, etc.: The adhesive (B) in the method of the present invention further contains an anion. A polymerization accelerator is added.

Examples of the anionic polymerization accelerator include tertiary amine compounds, lactone compounds, cylacrown compounds, crown compounds, N,N-dicyclohexylcardiimide, succinic acid amide, and ethylenethiourea.

As the tertiary amine compounds, any aliphatic, alicyclic, aromatic substituted aliphatic, or aromatic tertiary amine compound can be used. Specific examples include N,N-dimethylaniline, N,N-diethylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl-p-)luidine, N,N-dimethyl-m-toluidine. , N,N-diethyl-m-)luidine, N,N-bis(2-hydroxypropyl)-p-1 luidine, triphenylamine,
Examples include N,N-dimethylethanolamine, N,N-diethylethanolamine, N-butylgetanolamine, phenylethylethanolamine, β-dimethylaminoethyl acetate, and β-dimethylaminoethylbenzene.

Further, as the tertiary amine compounds, r91) compounds in which the above-mentioned tertiary amine compound is endowed with a reactive silicone functional group represented by the above-mentioned general formula (Ill) can also be used. For example, (N,N-dimethyl-
3-aminopropyl)trimethoxysilane, (N,N-
diethyl-3-aminopropyl)trimethoxysilane,
(N,N-dipropyl-3-aminopropyl)triethoxysilane, (N,N-diptyl-3-aminozolobyl)triethoxysilane, (N,N-dimethyl-3-aminopropyl)trimethylsilane, (N,N -diethyl-
3-aminobutyl)triethylsilane, N,N-dimethylaminophenyltrimethoxysilane, N,N-dimethylaminophenyltriethoxysilane, N,N-diethylaminophenyltrimethoxysilane, N,N
- & ethylaminophenyltriethoxysilane, N,
N-dimethylaminophenyltrimethylsilane, etc.
It can be used as a tertiary amine compound for anionic polymerization promoters.

Furthermore, as the tertiary amine compound, TheChe
r Hand published by mical Rubber Co.
book ofTables for Organic
Compound Identification
J Volume 3 (1967) Tertiary amines section (319-
Various tertiary amines, such as those described on page 325), can also be used.

Examples of the lactone compounds include γ-butyrolactone, β-propiolactone, 5-ethyl-γ-butyrolactone, ε-caprolactone, and coumarin.

As the silacrown compound, for example, 1-(3
-aminopropyl)-1-methylcylacone-11-crown-4,1-vinyl-1-methylcylacrow-5,
l-vinyl-1-methylsilacrown-6,1,1-
dimethylcysi 11-crown-4,1,1-somethylcylar 14-crown-5,1,1-dimethylcysi-1 Fucrown-6,1,1-dimethylcysi-2
0-crown roof etc.

Examples of the crown compound include 15-crown-5,18-crown-6, dipenzo-18-crown-6, dibenzo-24-crown-8, dicyclohexyl-18-crown-6゜dicyclohexyl-24 -crown-8, dithia-15-crown, etc.

The above-mentioned compounds used as anionic polymerization accelerators may be used alone or in combination of two or more. The amount added is 0 to adhesive (B).
．． 05-50% by weight, preferably 0.5-40% by weight. If the amount added is too small, the adhesive (A
) cannot be rapidly cured by light, and the time required for temporary fixing cannot be effectively shortened, and if the amount is too large, the adhesive strength will be reduced.

To prepare the adhesive (B)' in the method of the present invention, one of the above-mentioned organic polyisocyanate compounds and organic silicon compounds may be selected and used, or two or more may be selected and used as a mixture. and add anion 1 to this
The adhesive (B) can be prepared by adding the entire polymerization accelerator.

In addition, the adhesive may include, if necessary, a plasticizer such as a phthalate ester; a filler such as calcium carbonate or carbon black; a curing accelerator such as an organic tin compound; an adhesion imparting agent such as a silane compound: Anti-sagging agents such as fumed silica; dehydrating agents such as molecular sieve; other antioxidants, ultraviolet absorbers, colorants, etc. can be blended.

In addition, adhesives using organic polyisocyanate compounds (
In B), Japanese Patent Publication No. 43-12510, No. 57-
No. 16126, No. 48-20639, No. 55-354
As disclosed in No. 07 and JP-A-60-195177, ketimine compounds, enamine compounds, or oxazoline compounds that are hydrolyzed to produce polyamino compounds, polyimino compounds, amino alcohols, etc. can be used in combination. It can be used as an organic polyisocyanate compound suitably blocked with isocyanate-based phenols, oximes, etc.

Furthermore, an adhesive (B
), organosiloxant of the general formula ([1
) is reacted in advance to form an organosilicon compound, and the raw organosiloxane and the silane compound having a reactive silicone functional group are mixed together as they are. An adhesive (B) can be prepared.

The bonding method of the present invention uses two types of adhesives, adhesive (A) and adhesive (B) prepared as described above, and applies them to the adhesive interface of the inner adherend to be bonded. Adhesives of Class 22I are applied separately and bonded so that the two types of adhesives do not mix with each other as much as possible and do not overlap each other (but do not prevent them from mixing or overlapping in some areas). Let's do Nk.

As described above, there are various ways to apply adhesives for two vertebrates separately so as not to mix them with each other and avoid overlapping them, and Figures 1 to 9 show examples of these ways. It is something.

In the embodiments shown in FIGS. 1 to 5, both the adhesive (A) and the adhesive (B) are mixed on the surface of one of the inner adherends 1, and the inner adhesive is mixed. After 9 layers are applied so as not to overlap, the adhesive surface of the other adherend 2 is laid over this layer for bonding.

In addition, in the embodiments shown in FIGS. 6 to 8, adhesive (A) or adhesive (B
) separately, and in such a way that even when the adhesive surfaces of the inner adherends are overlapped, the applied surface of adhesive (A) and the applied surface of adhesive CB) do not overlap each other, and then both branches are bonded. Overlap the adhesive surfaces of the body and perform the adhesive bonding.

Furthermore, in the embodiment shown in FIG. 9, the adhesive (B) is first applied to a relatively narrow area on the lower surface of the adherend 1 corresponding to the bonding surface in step a, and then the adhesive (B) is applied in step b. The adherend 2 is placed on the lower surface of the adherend 1 to which (B) has been applied. Next, in step C, another adhesive (A)' is applied to the gap around the applied adhesive (B) between the adhesive surfaces of adherend 1 and adherend 2 to completely complete the adhesion.

(Examples, etc.) Next, adhesive preparation examples, examples, and comparative examples will be explained in further detail. "Parts" in these examples mean "parts by weight."

Adhesive n Preparation Examples A1 to A6 Various adhesives A1 to A6 having various compositions shown below
was prepared.

Table A Notes for Table A: *1...Cemedine Co., Ltd. trade name, ethyl-α-cyanoacrylate adhesive Adhesive Preparation Examples B1 to B16 Adhesives consisting of various compositions shown in the table below (without shaving) B
) Pace compositions b1 to b5 were prepared.

Table b (2Q) Representation notes: *l...Product name of Kaneshiro Chemical Industry Co., Ltd., H3 (CH2O)2slCH2cH2cH2o-terminated propylene oxide 1 combination*2...Sanyo Chemical Co., Ltd. product Name, tolylene diisocyanate adduct of polyether polyol *3...Takeda Pharmaceutical Co., Ltd. product name, tolylene diisocyanate adduct of polyether polyol *4...Product name of Nippon Aerosil Co., Ltd., fumed silica *5. ...Equimolar solution of dioctyl phthalate Using various paste compositions shown in Table BVc
Adhesives B1 to B and 6 were prepared by adding various anionic polymerization promoters in combination as shown.

Notes to Table B: *...Comparative Example Examples 1 to 29 Comparative Examples 1 to 4 The various adhesives made from PT in the adhesive preparation examples A and B above were combined in various ways as shown in Table 1. An adhesion test was conducted using At that time, the adhesive fabric mode is the first
It was recommended to show each in the table. In addition, each test method was as follows.

(1) Set time (temporary fixing time) Plywood C length 100
Using two sheets (mm x width 25fi x thickness 31m), each adhesive shown in Table 1 was applied in the application mode shown in Table 1, and after immediately bonding, the lap area of both boards was 25cm
25 m), the total time required to withstand a static load of 1 Yu was measured and defined as set time C (temporary fixing time).

(2) Use two impact-resistant mild steel plates (length: 100cm x width: 25cm x thickness: 1.6cm), apply the adhesive shown in Table 1 in the respective manner, and immediately glue both plates together. The lap area of both C plates pasted together is 25 tmrr x 25 m).

After being left to cure at 20°C for 7 days, it was dropped from a height of 2 m onto a concrete surface and observed whether it would peel off or not. The evaluation was based on the following criteria.

○...No peeling after 5 drop tests.

×...Cannot be peeled off in one drop test.

(3) Peeling test mild steel plate (length 200w x width 25cm x thickness 0.5 + m
), each adhesive shown in Table 1 was applied in the respective manner, and the sheets were immediately bonded together (the lap area of both sheets was 170 w x 25 wn). After curing for 7 days at 20°C, the heating strength was increased by 6111.

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

As is clear from the results in Table 1, in each of the Examples, temporary fixing could be achieved in a very short time, and the impact resistance and peel strength of the adhesive were also excellent.

On the other hand, when using a room temperature moisture curing adhesive using water without adding a VC anion polymerization accelerator for adhesive (B) (Comparative Example 1), temporary fixing took a relatively long time (
In addition, when only an anionic polymerizable curing agent was used as a substitute for adhesive (B) (Comparative Example 2), the temporary fixing time was as short as 10 seconds. The impact resistance and peel strength of the adhesive were extremely poor.

In addition, when bonding was done using only adhesive (A) (Comparative Example 3), it took a relatively long time for temporary fixing (240 seconds).
, impact resistance and peel strength were also poor.

Furthermore, when bonding was performed using only the adhesive (B) (Comparative Example 4), it took 1 hour and 30 minutes for temporary fixing VC.

(c) Advantages of the Invention In the adhesive method of the present invention, the adhesive (A) is rapidly cured by moisture in the adherend, and is further cured by the action of the anionic promoter added to the adhesive (8). Because it polymerizes and hardens quickly, the set time (time required for temporary fixing) is extremely short, and the adhesive (B) cures by reacting with moisture in the air in a chemistry-like manner. It exhibits excellent adhesion not only to membrane adherends, but also to porous adherends such as fibrous adherends and uneven adherends, and has particularly good water resistance, peeling resistance, and impact resistance. and can provide adhesion with excellent heat aging resistance.

[Brief explanation of the drawing]

Figures 1 to 9 illustrate examples of how adhesives (A) and (B) are applied when carrying out the adhesive method of the present invention, and 1 and 2 are in contact with each other. Both schools are shown. Figure 1 Figure 2 Figure 3 Figure 9 Procedural amendment August 27, 1988 Commissioner of the Japan Patent Office Black 1) Mr. Akiyu 1. Indication of the case 1986 Patent Application No. 154154 2. Title of the invention Adhesive method and adhesive 3, Relationship with the case of the person making the amendment Patent applicant name Cemedine Co., Ltd. 6 Subject of amendment (1) “Detailed description of the invention column” of document a 7 Contents of amendment (Attachment ) /'-〉, total 3. ．． 1---- Details of the amendment (1) "Compounds having an allyl group at the end of the molecule" on page 20, line 8 of the specification are changed to "various types of polyoxyalkylene polyether compounds having an allyl group at the end of the molecule" correct. (2) “Special Public Service 1973-32” on page 20, lines 14-15.
678 Publication” and “Special Publication No. 49-32673”
I am corrected. Procedural amendment November 27, 1988 Commissioner of the Patent Office Black 1) Mr. Yu Aki ■, Indication of the case Patent Application No. 154154 of 1988 2, Name of the invention Adhesive method and adhesive 3, Person making the amendment Case and Relationship between Patent applicant name Cemedine Co., Ltd. 6, subject of amendment (1) "Detailed description of the invention" column 7 of the specification, contents of the amendment\-~su ψ f7\ Contents of the amendment (1) Description No. The entire text of page 10, line 18 to page 11, line 10 is corrected as follows. In this way, in the adhesive used in the adhesive method of the present invention, the anionic polymerization accelerator is added to the room temperature moisture curable adhesive (B). If added to (A), there is a risk of shortening its storage stability or usable life, and if the adhesive method of the present invention is used, contrary to expectations, anionic polymerization accelerators may be added to room temperature moisture-curing adhesives. This is because it was found that adding it to (B) had a better effect of shortening the set time (temporary fixing time).In this case, adding it to the room temperature moisture curing adhesive (B) The anionic polymerization accelerator that has been kept acts on the room temperature anionic polymerization curing adhesive (A) by permeation, diffusion, etc., accelerates the polymerization and curing of the adhesive (A), and quickly achieves the temporary fixing effect. (2) The entire text of page 13, lines 10-11 is corrected as follows. "In addition, colorants and curing accelerators (such as lactone compounds, silacrown compounds, crown compounds, etc.)
, organic solvents, etc. may be blended within a range that does not significantly impair adhesive performance. ” Procedural amendment August 1988 [” Commissioner of the Japan Patent Office Kunio Ogawa 1. Indication of the case Patent Application No. 154154 of 1988 2. Method of adhering the name of the invention 3. Person making the amendment Related Patent applicant name Cemedine Co., Ltd. 6 "Title of the invention", "Claims column" and "Detailed description of the invention column" of the specification to be amended Contents of the amendment (1) Invention of the specification The name will be corrected to "adhesion method". (2) The entire scope of the claims in the specification shall be amended as stated in Attachment 2. (3) The statement "and the adhesive used therein" on page 4, line 10 of the specification is deleted. (4) "Adhesive and bonding method" in the first line of page 7 of the specification is corrected to "bonding method using adhesive." (5) The statement "and the adhesive used therein" on page 7, line 9 of the specification is deleted. (6) “Toluidine, N, N” on page 21, line 10 of the specification
-diethyl-" is corrected to "toluidine, N,N-dimethyl-o-)luidine, N,N-diethyl-". (7) On page 15, line 16 of the specification, ``Mercaptone ``remarkably'' is amended to ``or''. Attachment 2, Claim 1) (A) General formula % Formula % (wherein R is an alkyl group having 1 to 16 carbon atoms, an alkoxyalkyl group having 2 to 16 total carbon atoms, and 1 to 1 carbon atoms) 16
haloalkyl group, cyanoalkyl group having 2 to 16 total carbon atoms, aralkyl group having 6 to 12 total carbon atoms, acyloxyalkyl group having 2 to 16 total carbon atoms, acyloxyalkyl group having 3 to 16 total carbon atoms.
A cycloalkyl group, an alkenyl group having 2 to 16 carbon atoms in total, or an aryl group having 6 to 12 carbon atoms in total. ), and an α-cyanoacrylate compound represented by the general formula (wherein R1 and R2 each have a hydrogen atom and a carbon number of 1
-5 alkyl group, aryl group, aralkyl group having 6 to 12 carbon atoms in total, or halodane atom, and R and R may be the same or different. R is a hydrogen atom or a methyl group. and Ap, X and Y may be the same or different. ) Anionic polymerization-curing adhesive at room temperature with moisture, the main component being at least one ayu-1 polymeric compound selected from the group consisting of 1,1--,'-substituted diene compounds represented by ( B) At least one type of moisture selected from the group consisting of polyisocyanate compounds having at least two isocyanate groups in the molecule and organosilicon compounds having at least two silicon atoms bonded to hydrolyzable groups in the molecule. A room-temperature, moisture-curing adhesive containing a curable compound as a main component and an anionic polymerization accelerator added thereto is used, and the above two adhesives are applied to the adhesive interface between the two adherends. A bonding layer characterized by applying different types of adhesives separately so that they do not mix with each other and do not overlap each other (however, this does not prevent them from mixing or forming in some parts). Method. 2) The anionic polymerization accelerator is selected from the group consisting of tertiary amine compounds, lactone compounds, silacrown compounds, crown compounds, N,N-nocyclohexylcarbodiimide, succinic acid amide, and ethylene thiourine. %. The method of lamination according to claim 1, wherein the method is one selected or a mixture of two or more selected.

Claims (1)

[Claims] 1) (A) General formula ▲ Numerical formulas, chemical formulas, tables, etc. , carbon number is 1-16
haloalkyl group, cyanoalkyl group having 2 to 16 total carbon atoms, aralkyl group having 6 to 12 total carbon atoms, acyloxyalkyl group having 2 to 16 total carbon atoms, acyloxyalkyl group having 3 to 16 total carbon atoms.
a cycloalkyl group, an alkenyl group having 2 to 16 carbon atoms in total, or an aryl group having 6 to 12 carbon atoms in total. ), and the general formula ▲ mathematical formula, chemical formula, table, etc. Aryl group, total number of carbon atoms is 6-1
2 is an aralkyl group 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 each a cyano group, a carboxylic acid ester group having a total carbon number of 2 to 12,
Ethylsulfone group, phenylsulfone group, formyl group,
It is an acetyl group, a benzoyl group, an amide group, a diethylphosphonyl group, or a phenyl group, and X and Y may be the same or different. ). An adhesive that cures at room temperature by anionic polymerization with moisture, the main component of which is at least one anionic polymerizable compound selected from the group consisting of 1,1-disubstituted diene compounds; The main component is at least one moisture-curable compound selected from the group consisting of a polyisocyanate compound having two silicon atoms, and an organic silicon compound having at least two silicon atoms bonded to a hydrolyzable group in the molecule. In addition, two types of adhesives are used: a room-temperature, moisture-curing type adhesive to which an anionic polymerization accelerator is added, and the two types of adhesives are not mixed with each other as much as possible at the bonding interface of both adherends to be bonded. An adhesive method characterized in that the adhesive is applied separately so as not to overlap with each other (but not to prevent mixing or overlapping in some parts). 2) The anionic polymerization accelerator is one selected from the group consisting of tertiary amine compounds, lactone compounds, silacrown compounds, crown compounds, N,N-dicyclohexylcarbodiimide, succinic acid amide, and ethylenethiourea, or Claim 1 which is a mixture of two or more types
Adhesion method described in section. 3) At least one type of moisture selected from the group consisting of polyisocyanate compounds having at least two isocyanate groups in the molecule and organosilicon compounds having at least two silicon atoms bonded to hydrolyzable groups in the molecule. A room-temperature, moisture-curing adhesive that has a curable compound as its main component and an anionic polymerization accelerator added to it.