JPS6346282A - Adhesive - Google Patents

Abstract

PURPOSE:To obtain a room temperature and moisture curing adhesive, consisting essentially of a specific moisture curing compound, e.g. a polyisocyanate compound, etc., and anionic polymerization accelerator added thereto, rapidly curable by moisture of an adherend and capable of well bonding to even adherends with unevennesses. CONSTITUTION:An adhesive obtained by adding (B) an anionic polymerization accelerator, preferably a tertiary amine compound, lactone compound, silacrown compound, etc., to (A) at least one moisture curing compound selected from the group of polyisocyanate compounds having at least 2 isocyanate groups in the molecule and organosilicon compounds having at least 2 Si atoms linked to a hydrolyzable group, e.g. a compound having >=2 groups expressed by the formula (Z is hydrolyzable group; R<4> is a group other than Z; n is 0-2) in the molecule as a principal component.

Description

Detailed Description of the Invention (1) Purpose of the Invention (Field of Industrial Application) The present invention is capable of fixing (temporary) adherends in a short time without special treatments such as heating, pressurization, or ultraviolet irradiation. The present invention relates to an adhesive that is suitable for bonding that can be stopped (stopped) and that has sufficient bonding strength after a certain period of time has elapsed.

(Prior art) Bonding with adhesives is widely used in various industrial fields and households, but in recent years, demands for adhesives include not only N-contact performance but also non-toxicity, non-flammability, WC There are various demands such as speeding up and simplifying the bonding process, shortening the pressing time after bonding, and adhesion performance not only for general adherends but also for porous and uneven adherends. However, 1) There is no known adhesive that can simultaneously satisfy these requirements. For example, adhesives used industrially include hot melt adhesives, 1 rubber-based solvent-based acrylate adhesives, etc. As an excellent adhesive, it is used to bond adherends in various fields such as paper packaging, electrical parts, precision instruments, architecture, civil engineering, and household goods. 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 limits to the types of adherends that can exhibit adhesive strength.

Rubber-based solvent-based adhesives require an adhesive applicator to volatilize and remove a large amount of solvent before bonding, and the waiting time is long! & It takes time to see. Disadvantages include odor, toxicity and flammability due to solvent volatilization.

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

Two-component acrylic adhesives require a device for weighing and mixing the two components, 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. In addition, it has poor adhesion to porous adherends such as wood, cloth, concrete, and uneven 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-di-substituted diene compound adhesives also have an excellent ability to cure in a short time like the α-cyanoacrylate adhesives mentioned above, but they have poor adhesion performance to porous adherends and uneven surfaces. In this respect, it has the same drawbacks as α-cyanoacrylate adhesives.

(Problems to be Solved by the Invention) In view of the above-mentioned shortcomings of conventional adhesives and bonding methods, the present invention provides temporary bonding in a short time without using any other equipment after bonding adherends. After a certain period of time has elapsed after lamination, sufficient adhesion performance S, especially sufficient peel adhesion strength and impact adhesion strength, can be obtained. Provides an adhesive that can exhibit sufficient adhesion performance even for certain adherends and is suitable for use in adhesive methods that can be applied to bonding adherends in a wide range of fields. This is what I am trying to do.

(b) Compilation of the invention (means for solving the problems) The inventors of the present invention have repeatedly conducted research in order to solve the above-mentioned problems, and as a result, they have arrived at the adhesive of the present invention. be.

The first adhesive of the present invention is selected from the group consisting of a polyisocyanate compound having at least two trapping isocyanate groups in the molecule, and an organosilicon compound having at least two silicon atoms to which a hydrolyzable group is bonded in the molecule. It is a room temperature moisture curing type adhesive which contains at least one selected moisture curing compound as a main component and further contains an anionic polymerization accelerator. This adhesive is novel in that it contains an anionic polymerization accelerator.

The second adhesive of the present invention has a general formula (wherein R is an alkyl group having 1 to 16 carbon atoms, an alkoxyalkyl group having 2 to 16 carbon atoms in total, and 1 to 16 carbon atoms).
haloalkyl group, cyanoalkyl group having 2 to 16 total carbon atoms, 7ralkyl 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 groups, aryl groups, aralkyl groups having 6 to 12 carbon atoms in total, or halogen atoms. R1 and R2 may be the same or different. R is a hydrogen atom or a methyl group. X and Y are each a cyano group, a Cal I7 acid ester group having 2 to 12 carbon atoms in total, an ethylsulfone group, a phenylsulfone group, a formyl group, an acetyl group,
X and Y may be the same or different; CB) an anionically polymerizable adhesive at room temperature with moisture, the main component of which is at least one anionically polymerizable compound selected from the group consisting of 1,1-disubstituted diene compounds represented by Do you have at least two inside? At least one compound selected from the group consisting of a lysocyanate compound and an organic silicon compound having at least two silicon atoms to which a hydrolyzable group is bonded in the molecule.
2. A room-temperature moisture-curing adhesive containing a moisture-curing compound as a main component and an anionic polymerization accelerator added thereto.
This is an adhesive consisting of a combination of adhesives of type a.

Since the above-mentioned room-temperature moisture-curing adhesive which is the first adhesive of the present invention and the room-temperature moisture-curing adhesive CB) which is the above-mentioned second adhesive of the present invention are the same, the following In the explanation, this adhesive is referred to as "room temperature moisture curing adhesive C".
B) J, or simply "Adhesive 0)".

Accordingly, the room temperature moisture curing adhesive CB in the present invention
) is novel in that an anionic polymerization accelerator is added, and this adhesive CB) is similar to the room-temperature Ayuoff 1 and polymerization type adhesive (4) in the second adhesive of the present invention. By using it in combination with a room temperature anionic polymerization type adhesive, it is possible to perform soaked adhesion as described below.

In the present invention, the reason why the anionic polymerization accelerator is added to the room-temperature, moisture-curing adhesive ω) is that the anionic polymerization accelerator is originally added to the room-temperature anionic polymerization-curing adhesive, such as an adhesive. Although it is supposed to act on the adhesive, adding it to the same adhesive may shorten its storage stability or usable life, but in some cases it immediately becomes dull and becomes completely unusable. In addition, according to the research of the present inventors, two types of adhesives are available: a room temperature moisture curing adhesive such as Adhesive (Adhesive Medium) and a room temperature moisture curing adhesive such as Adhesive (1). For example, apply the second part to the adhesive interface of the two-wave garment to be bonded.
If you use a method of adhesion by applying different types of adhesives separately so that they do not mix as much as possible and do not mix as much as possible (however, do not prevent them from mixing or overlapping in some areas), it is possible to This is because it has been found that when an anionic polymerization accelerator is added to a room-temperature, moisture-curing adhesive, an excellent shortening effect on set time (temporary fixing time) can be seen. In this case, the anionic polymerization accelerator added to the room-temperature, moisture-curing adhesive 03) acts on the room-temperature anionic polymerization-curing adhesive through permeation, diffusion, etc., and causes the adhesive to cure (4). It accelerates polymerization and hardening and quickly exhibits a temporary fixing effect.

The general formula (
Specific examples of the α-cyanoacrylate compound represented by 1) 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-propoxyethyl-
α-cyanoacrylate, 2-butoxyethyl-α-cyanoacrylate, tetrahydrofurfuryl-α-cyanoacrylate, allyl-α-cyanoacrylate, globalgyl α-cyanoacrylate, 2-chloroethyl-α-cyanoacrylate, 2-(2 ,2,2-)
Examples include (lifluoroethoxy)ethyl-α-cyanoacrylate.

The general formula (
Specific examples of the 1,1-disubstituted diene compound represented by U) include 1-cyano-1-carmethoxybutadiene-1,3,1-cyano-1-carmethoxybutadiene-1, Examples include 3,1-cyano-1-car & n-propoxybutadiene-1,3,1,1-nocargoethoxybutadiene-1,3.

In preparing the adhesive (A) in the present invention, the general formula (
One type may be selected and used from the α-cyanoacrylate type compound represented by 1) and the 1,1-disubstituted diene type compound represented by the general formula (11), or two or more types may be selected and used. It may also be used as a mixture. moreover,
If necessary, the adhesive (adhesive body) may contain SO□, carboxylic acids, phosphoric acids, sulfonic acids; storage stabilizers such as hydroquinone, hydroquinone monomethyl ether; acrylic rubber, acrylic acid esters) polymers, polyesters, Thickeners such as I diurethanes; gluing agents (for example, the more gluing agents described in JP-A-54-107993); plasticizers such as phthalate esters and phosphate esters; Coloring agents, curing accelerators (for example, lactone compounds, silacrown compounds, crown compounds, etc.), organic solvents, etc. can be blended within ranges that do not significantly impair adhesive performance.

As the organic isocyanate compound having at least two isocyanate groups in the molecule used in the adhesive of the present invention, insyanate compound obtained by the reaction of an organic polyhydroxy compound and an organic polyisocyanate is used.
Examples include isocyanate-terminated polyurethane, isocyanate-terminated polyurethane obtained by reaction of an organic polythiol compound and an organic polyisocyanate, and the like.

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

(,) Lactone polyol and its fullkylene oxide adduct: (b) Polyester polyol and its alkyne oxide adduct: (c) Polyoxyalkylene polyol, ? Lyoxycycloalkylene polyols and their alkylene oxide adducts: (d) Polyalkanolamines and their alkylene oxide adducts; (e) Polyols derived from polyamines by adding alkylene oxides to polyamines: (f) Non-polyols Cyclic sugars, sugar derivatives, and their alkylene oxide adducts: (g) Alkylene oxide adducts of aromatic amine-phenol-aldehyde ternary condensation products: 弽) Alkylene oxide adducts of polyphenols: (1) Polytetra Methylene glycol: (J)
Polyfunctional glycerides such as castor oil / vinyl polymers containing hydroxyl groups: (1) Polyhydroxy polysulfide polymers: (c) Prepared by reacting lactone polyesters with polyols such as bisphenol A and phosgene. 5000~75000
hydroxyl-terminated long-chain lactone polyesters having a molecular weight within the range of: (n) polybutanoene containing hydroxyl groups;
Diene-based products such as acronitrile-butidiene copolymer (
Co)polymer: Examples of organic polythiol compounds used as raw materials include pentaerythritol thioglycolate, mercapto V ethyl adipate, and commercially available products include Thiokol LP-3 and Thiokol L.
P-8 (the above are trade names of Torre Thiokol Co., Ltd.), Epomate QX-10, Epomate QX-1t (the above are trade names of Yuka Shell Epoxy Co., Ltd.), ? Lithiol DION
3-800LC (trade name of Diamond Jamrock Co.) and the like.

Examples of organic polyisocyanates used as raw materials include m-phenylene diisocyanate, p-phenylene diisocyanate, 2.4-)lylene diisocyanate, 2,6-lylene diisocyanate, 4.4'-
diphenylmethane diisocyanate, benzidine diisocyanate, naphthalene-1,5-diisocyanate,
hexamethylene diisosyphne), 4.4', 4'
-) Riphenylmethane triisocyanate, decamethylene diisocyanate, polyphenylmethylene diisocyanate (manufactured by reacting aniline-formaldehyde condensate with phosgene), dianisidine diisocyanate, xylene diisocyanate, bis-(2-isocyanatoethyl)- fumarate, bis-(2-isocyanatoethyl)-cyclobek-4-cene-1,2-cica/L/gexylate, bis-(2-isocyanatoethyl)cargenate, and 1-annalene (Annal@
Examples include organic polyisocyanates such as those disclosed by Mr. Siefken (5lefk*n) in 562.122135 (1949).

The organosilicon compound having at least two silicon atoms to which a hydrolyzable group is bonded in the molecule used in the adhesive (B) of the present invention has the general formula (where 4 is a hydrolyzable group and , R4 is a group other than a hydrolyzable group, and n is an integer from O to 2. Examples include compounds having at least two of them.

Specific examples of the hydrolyzable group 2 in the general formula (III) include acyloxy groups such as acetoxy, octanoyloxy, and benzoyloxy; dimethylketoxime, methylethylketoxime, diethylketoxime, and the like. Ketoxime group; methoxy group,
Ethoxy group! Alkoxy groups such as lopoxy groups; alkenyloxy groups such as ingropenyloxy groups and 1-ethyl-2-methylvinyloxy groups; amine groups such as dimethylamino groups, diethylamino groups, butylamino groups, and cyclohexylamino groups; trimethyl Aminoxy groups such as aminoxy group and diethylaminoxy group; N-methylacetamide group,
Examples include amide groups such as N-ethylacetamido group and N-methylbenzamide group.

In addition, as the group R other than the hydrolyzable group in the general formula (1), for example, an alkyl group such as a methyl group, an ethyl group, a globyl group, a butyl group; a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group; Examples include alkenyl groups such as vinyl and allyl groups; aryl groups such as phenyl, tolyl and naphthyl; aralkyl groups such as 2-phenylethyl; and atom-substituted groups.

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 above general formula (l[l) in the molecule: (b) A compound having a group capable of reacting with an isocyanate group and a reactive silicone functional group represented by the general formula (III) in the molecule, and a polyisocyanate similar to that used as the main component in the adhesive (6) described above. Room-temperature curable silicon-terminated compound obtained by reacting with a compound (see Japanese Patent Publication No. 46-30711, etc.): (c) An isocyanate group in the molecule and the above -E formula Cl1l
) and an organic polyhydroxy compound or an organic polythiol compound similar to that used as a raw material for producing the organic polyisocyanate compound which is the main component of the adhesive (B). Room-temperature curable silicon-terminated compound obtained by reacting: (b) Various polyoxyalkylene polyether compounds having an allyl group at the molecular terminal are reacted with the general formula (I[I)
It has a reactive silicon functional group represented by -8H
Silicon-modified preoxyalkylene polyether compound obtained by addition reaction of a compound having hydrogen directly bonded to a group or silicon: (e) Other terminal reactivity as described in Japanese Patent Publication No. 49-32673, etc. Silicon functional group-containing compound: An anionic polymerization accelerator is further added to the adhesive 03) in the present invention.

Examples of the anionic polymerization accelerator include tertiary amine compounds, lactone compounds, cylacrown compounds, crown compounds, N,N-dicyclohexylcal-diimide, 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-noethyl-p-)luidine, N,N-dimethyl-m-toluidine, NlN-dimethyl-0-)luidine, N,N-diethyl-m-)luidine, N,N-bis(2-hydroxypropyl)-p-toluidine, triphenylamine, N,N-trimethylethanolamine, N , N-diethylethanolamine, N
-butyljethanolamine, phenylethylethanolamine, β-dimethylamine ethyl acetate, β-
Trimethylaminoethylbenzene, etc. are included.

Further, as the tertiary amine compounds, compounds obtained by adding a reactive silicon functional group represented by the above-mentioned general formula (III) to the above-mentioned tertiary amine compound can also be used. For example, (NtN-dimethyl-3-aminozolopyl)trimethoxysilane, (N,N-diethyl-3-aminozolopyl)trimethoxysilane, (N,N-digrol-3-aminoglopyl)triethoxy7rane, (N
-N-diptyl-3-aminozolopyl)triethoxysilane, (N,N-dimethyl-3-aminozolopyl)trimethylsilane, (N,N-diethyl-3-aminobutyl)triethylsilane, N,N-dimethylaminophenyl triethylsilane Methodisilane, N,N-trimethylaminophenyltriethoxysilane, N,N-diethylaminophenyltriethoxysilane, N,N-diethylaminophenyltriethoxysilane, N-N-dimethylaminophenyltrimethylsilane, etc. also promote anionic polymerization. It can be used as a tertiary amine compound for pharmaceuticals.

Furthermore, as the tertiary amine compound, TheChe
“Handb” published by mical Rubber Co.
ook ofTable@s for Organic
Compound Identification
J Volume 3 (1967), Tertiary amines section (319
Various tertiary amines, such as those described on pages 325 to 325, can also be used.

Examples of the lactone compounds include γ-butyrolactone, β-gloviolactone, 5-ethyl-γ-butyrolactone, I-cabrolactone, and coumarin.

Examples of the cylacracune compound include 1-(3
-aminozolopyl)-1-methylcyla-11-crown-4,1-vinyl-1-methylcylacrown-5,
1-vinyl-1-methylsilacrown-6,1,1-
Dimethylsaidi-11-crown-4,1,1-dimethylcychie 14-crown-5,1,1-dimethylcycee 1 Fucrown-6,1,1-dimethylcycee 2
0-crown roof, etc.

Examples of the crown compound include 15-crown-5,1B-crown-6, dipenzo-18-crown-6, dipenzo-24-crown-8, dicyclohexyl-18-crown-6, dicyclohexyl- 24-
Examples include crown-8, dithia-15-crown, and the like.

The compounds used as the above-mentioned anionic promoters may be used alone or in combination of two or more. The amount added is 0 to adhesive (6).
．． 0.05 to 50% by weight, preferably 0.5 to 40% by weight. If the amount added is too small, the adhesive (4
) cannot be polymerized and cured sufficiently quickly, and the time required for temporary fixing cannot be effectively shortened, and if the amount is too large, the adhesive strength will be reduced.

In order to polish the adhesive ω) in the present invention, a suitable compound 1a is selected from among the above-mentioned organic polyisocyanate compounds and organic silicon compounds, or 28 or more are selected and used as a mixture, and an anion is added to this. It can be an adhesive CB) to which a polymerization accelerator is added. In addition, the adhesive may include a plasticizer such as a phthalate ester; a filler such as calcium carbonate or carden black; a curing accelerator such as an organic tin compound; an adhesive agent such as a silane compound; Anti-sag agents such as silica; dehydrating agents such as molecular sheep; other antioxidants, ultraviolet absorbers, colorants, etc. can be blended.

Also, organic? Adhesive C using a lysocyanate compound
In B), Japanese Patent Publication No. 43-12510, No. 57-
No. 16126, No. 48-20639, No. 55-354
07 and JP-A-60-195177, hydrolyzed? riamino compound, I
A ketimine compound, an enamine compound, or an oxazoline compound that produces a liimino compound or an amino alcohol can be used in combination, and an organic polyisocyanate compound whose isocyanate group can be appropriately blocked with phenols, oximes, etc. can be used. can.

Furthermore, an adhesive (B
), an organosiloxant of formula (II
Instead of reacting the silane compound having a reactive silicone functional group represented by I) in advance to form an organosilico compound and blending it, the raw organosiloxane and the silane compound having a reactive silicone functional group are blended as they are. ◇ A preferred embodiment in which adhesion is carried out using adhesives of two colors: the adhesive (4) of the present invention prepared as described above and the adhesive (). As mentioned above, apply the Class 281 adhesive to the bonding interface of the two-wave adherends to be bonded in such a way that the Class 28 adhesives do not mix with each other as much as possible and do not overlap each other (K (however). This is a method in which adhesives of type 2a are applied separately without interfering with each other (not interfering with mixing or overlapping in some parts), and are applied separately to achieve adhesion. There are various modes of application, and FIGS. 1 to 9 show examples of these modes.

In the embodiment shown in FIGS. 1 to 5, both the adhesive layer and the adhesive (B) are applied to the surface of one of the adherends 1 of the two wave adherends, and a nine-layer adhesive is mixed with a solid adhesive. After applying the adhesive so as not to cause the adhesion to occur, the adhesion surface of the other adherend 2 is placed on top of this and adhesion is performed.

In addition, in the embodiments shown in FIGS. 6 to 8, the adhesive (A) or the adhesive (6
) separately, and even when the adhesive surfaces of both corrugated bodies are overlapped, the adhesive is applied to the surface to which adhesive (4) is applied.

Furthermore, in the embodiment shown in FIG. 9, the adhesive (B) is applied to a relatively narrow area on the lower surface of the adherend 1 corresponding to the bonding surface in step C, 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 CB) has been applied. Next, in step C, another adhesive (
4) is applied to complete the adhesion.

(Examples, etc.) Next, adhesive preparation examples, adhesion examples, and comparative adhesion examples will be given for further details. "Part" in these examples means "1 part by weight"
means.

Adhesive Preparation Examples A1-A.

Various adhesives A1 to A, consisting of various compositions shown in Table A.
was prepared.

Table A Note 1 to Table A...Product name of Cemedine Co., Ltd., ethyl-α-cyanoacrylate adhesive Adhesive Preparation Example 13t-13sa First, adhesive CB consisting of various compositions shown in Table bK below.
) Prepare a pace composition bs-bs for

Table b Representation notes: *1...Product name of Kanebuchi Chemical Co., Ltd., sulpropylene oxide polymer with H (CH30)2SICH2CH2CH2〇-terminal group*2...Product name of Sanyo Chemical Co., Ltd., poly Tolylene diisocyanate adduct of ether polyol *3...Trade name of Takeda Pharmaceutical Co., Ltd. /Tolylene diisocyanate adduct of IJ ether polyol *4...Name of Nippon Aerosil Co., Ltd.'s black product name, fumed silica *5...・Did you understand that it is an equimolar amount of nooctyl phthalate?
ll! Adhesives B1 to B16 were prepared by using the paste compositions shown in Table B and adding various combinations of Ayu1F1 adhesion accelerators as shown in Table B.

Notes to Table B: *... Comparative Adhesion Examples 1 to 29 Comparative Adhesion Examples 1 to 4 Various adhesives prepared in the above adhesive preparation examples A1 to A6 and B1 to B111 were used as shown in Table 1. Adhesion tests were conducted using various combinations. The application mode of the adhesive at that time was as shown in Table 1.

In addition, each trial method was as follows.

(1) Set time (temporary fixing time) Plywood (length 100
After applying each adhesive shown in Table 1 in the application mode shown in Table 1, and immediately laminating them together (the lap area of both boards is 25 cm ■X 25
m), measure the time it takes to withstand a static load of 1 m,
Set time (temporary fixing time).

(2) Impact-resistant mild steel plate (length 100w x width 25m x thickness 1.6 tea
), the adhesive shown in Table 1 was applied in each manner, and the two boards were immediately pasted together in a cross shape (
The lap area of both plates is 25 w 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.

○: Not peeled off after 5 drop tests.

X: Cannot be peeled off in one drop test.

(3) Peeling test mild steel plate (length 200 = X size 25 m x thickness 0.5
Using two sheets of M), each adhesive shown in Table 1 was applied in the respective manner, and the sheets were immediately bonded together (the lap area of the drawing board was 170 glue x 25 wg). After curing at 20° C. for 7 days, peel strength was measured.

Notes to Table 1: The total applied surface &(,,'') 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 below, in each bonding example, temporary fixing was possible in a very short period of time, and the impact resistance and peel strength of the bond were also excellent. iOn the other hand, instead of adhesive (13), anionic polymerization promoter
Room-temperature, moisture-curing adhesive using moisture without adding an r-adhesive agent.
When using a staining agent (comparative adhesion example 1), temporary fixing is required.
J took a relatively long time (120 seconds).
In addition, instead of the adhesive (B), anionic polymerizable curing
- When only adhesive is used (comparative adhesive example 2), temporary fixing
The bonding time was short at 10 seconds, but the impact resistance of the adhesive was
2 and the peel strength was extremely poor.
1 Also, when bonding is done using only adhesive (comparative
5. Temporary bonding K requires a relatively long time for soft bonding example 3).
(240 seconds), impact resistance and peel strength
Inferior.

Furthermore, when bonding was performed using only the N-contact agent 53) (Comparative Adhesion Example 4), it took 1 hour and 30 minutes for temporary fixing. k(C)
Effect of invention h
Adhesive 03) of the present invention and room temperature anion polymerization curing adhesive 1, especially the adhesive of the present invention, are used in combination to prevent the solid adhesives from mixing as much as possible, and n) to avoid overlapping. Apply the room-temperature anion polymerizable adhesive 1 to form an adhesive.In particular, the adhesive 1 of the present invention is rapidly cured by the moisture of the adherend, and the anionic polymer added to the adhesive (B) 1. Due to the action of the accelerator, the adhesive (8) polymerizes and hardens quickly, so the adhesive time (time required for temporary fixing) is significantly shortened. Because it reacts and hardens logically, -
It exhibits excellent adhesion not only to shells and leather adherents, but also to porous substrates such as fibrous substrates and adherends with irregularities, and has excellent water resistance, sub-peelability, and impact resistance. It is possible to provide adhesion with excellent properties and heat aging properties.

[Brief explanation of the drawing]

Figures 1 to 9 illustrate the application machine side of adhesive (A) and adhesive (B) when bonding 1 is performed using the adhesive of the present invention, and 1 and 2 are shown. shows both adherends that are attached to each other. Figure 1 Figure 2 Figure 3 Figure 4 Figure 8 Figure 5 Figure 6 Date Figure 7 Figure 8

Claims (1)

[Scope of Claims] 1) A compound 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 comprising at least one moisture-curable compound as a main component and further containing an anionic polymerization accelerator. 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 28 or more
Adhesives listed in section. 3) (A) General formula ▲ Numerical formula, chemical formula, table, etc. ▼ (In the formula, R is an alkyl group having 1 to 16 carbon atoms, an alkoxyalkyl group having a total number of carbon atoms of 2 to 16, and a carbon number of 1 to 16. 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. ) at least one selected from the group consisting of 1,1-disubstituted diene compounds represented by
(B) A polyisocyanate compound having at least two isocyanate groups in the molecule, and a silicon atom to which a hydrolyzable group is bonded. At least one selected from the group consisting of organic silicon compounds having at least two in the molecule
2. A room-temperature moisture-curing adhesive containing a moisture-curing compound as a main component and an anionic polymerization accelerator added thereto.
An adhesive consisting of a combination of different types of adhesives. 4) The anionic polymerization accelerator is one selected from the group consisting of tertiary amine compounds, lactone compounds, silacrown compounds, crown compounds, N,N-synchrohexylcarbodiimide, succinic acid amide, and ethylenethiourea. or a mixture of two or more types.
Adhesives listed in section.