JPS6121171A - Rapidly curable water-based adhesive and adhesion - Google Patents

Abstract

PURPOSE:The title adhesive that is composed of the first solution containing a water-suluble polymer bearing acetoacetyl groups in the molecule and the second solutin containing polyethyleneimine, thus being suitable for use in wood and tiles, developing satisfactorily strong final adhesion after pressing for a short time and standing aging. CONSTITUTION:The objective adhesive is obtained by using (A), as the first solution, an aqueous solution or emulsion of a polymer containing acetoacetyl groups in the molecule such as acetoacetylated polyvinyl alcohol of 0.5-20mol% of acetoacetylation dgree as a solution of 5-50wt% concentration, and/or an aqueous emulsion such as an emulsion of acetoacetylated copolymer and (B), as the scond solution, a polyethyleneimine, e.g., of the formula (R1-R3 are H, CH2NH2NH2).

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application 1] The present invention relates to a two-component separate coating fast-curing water-based adhesive and a two-component separate coating adhesive method.

More specifically, for example, when bonding two pieces of wood at room temperature, the first liquid is applied to one side of one piece of wood, the second liquid is applied to one side of another piece of wood, and the coated surfaces are immediately brought into close contact. This invention relates to a two-component separate application type fast-curing water-based adhesive and a two-component separate application adhesive method, which eliminates the need for a light press after a few minutes and which adheres to a wooden frame after a few hours.

[Conventional technology] Conventionally, polyvinyl acetate emulsion, urea resin, rubber glue, epoxy resin, incyanate compound, etc. have been used as adhesives for wood and straight boards, but with the exception of contact-type rubber glue, Both of these adhesives have poor adhesive start-up (initial adhesion), and contact type rubber adhesives also
Because it contains organic solvents, there is a danger of toxicity and fire, especially when used in closed areas such as factories, and it also has the disadvantage of being stiff and prone to aging. It was hoped that it would appear.

[Summary of the Invention 1 As a result of intensive research, the present inventor has invented an adhesive that solves all of these problems.

That is, the first invention of the present invention is based on the following (0 and (b)).
This is a two-component, quick-curing, water-based adhesive that can be applied separately.

(to) A first solution consisting of an aqueous solution or an aqueous emulsion of a polymer compound having an acetoacetyl group in the molecule.(ii) A second solution consisting of polyethyleneimine.

Moreover, the second aspect of the present invention is a two-component, separately applied, fast-curing water-based adhesive consisting of the following (c) and (c).

(c) Aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule and /*
or an aqueous emulsion; and 2) a second liquid comprising polyethyleneimine and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups.

Further, the third aspect of the present invention is a two-component, separately applied, fast-curing water-based adhesive consisting of the following (e) and (f).

(e) An aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule and/or
*or a first liquid consisting of an aqueous emulsion and a crosslinking agent that crosslinks crosslinking groups other than the acetoacetyl group, and (v) a second liquid consisting of polyethyleneimine.

Further, the fourth invention of the present invention is the second invention used in each of the above inventions.
This is a two-liquid separate application bonding method characterized by separately applying a first liquid and a second liquid of a separate liquid application type water-based adhesive to the adhesive surface of an object to be adhered, and then bringing the adhesive surfaces into contact with each other.

[Example 1 First, the first invention of the present invention will be explained.

A polymer compound having an acetoacetyl group in its molecule and polyethyleneimine form a crosslinked structure and rapidly gel through the reaction mechanism shown in the following formula, although it is only a guess. When an aqueous solution and/or emulsion of a molecular compound and polyethyleneimine are separately applied to the surface of an object to be adhered, and the applied surfaces are brought into close contact with each other to cause a gelation reaction, strong adhesion can be achieved for a short period of time. It will be held in

The present invention is characterized in that the gelation reaction and adhesion are carried out simultaneously.

In other words, since the gelled product obtained by reacting two compounds in advance no longer exhibits adhesive properties, the adhesive of the present invention can be used in combination with an aqueous solution of a polymeric compound having an acetoacetyl group in the molecule and/or insects or insects. It must be a two-component adhesive consisting of an aqueous emulsion and polyethyleneimine.

Furthermore, since this gelation reaction is carried out in an aqueous medium, the two-liquid separate application type adhesive of the present invention is an aqueous solution or aqueous emulsion type adhesive, that is, an aqueous adhesive.

The aqueous medium used in the present invention is water or a mixture of water and a polar solvent. Among the first liquids used in the present invention, as an aqueous solution of a polymer compound having 7-7 cetyl groups in the molecule, water-soluble polymer compounds such as polyvinyl alcohol, hydroxyalkyl cellulose, and starch are acetoacetylated. Aqueous solutions of acetoacetylated polyvinyl alcohol, acetoacetylated hydroxyalkylcellulose, acetoacetylated starch, etc. are used.

In addition, among the first liquid used in the present invention, the aqueous emulsion of a polymer compound having an acetoacetyl group in the molecule includes a monomer containing an acetoacetyl group and an a, β ethylenic monomer. Examples include an emulsion copolymerized acetoacetylated copolymer emulsion and a polymer emulsion using the above-mentioned polymer compound having an acetoacetyl group in the molecule as an emulsifier.

Next, a water-soluble polymer compound having an acetoacetyl group in the molecule will be explained.

As an example, acetoacetylated polyvinyl alcohol is prepared by reacting polyvinyl alcohol with diketene in a known manner. For example, if polyvinyl alcohol is dispersed in an acetic acid solvent,
There is a method in which diketene is added to this, and a method in which polyvinyl alcohol is dissolved in a solvent such as dimethyl formaldehyde or dioxane in advance and diketene is added thereto. It can also be obtained by directly contacting polyvinyl alcohol with diketene gas or liquid diketene.

The polyvinyl alcohol used has a degree of polymerization of 200 to 3000° and a degree of saponification of 3o, which is obtained by saponifying polyvinyl acetate.
~100 mol% polyvinyl alcohol or its derivatives,
Alternatively, a saponified product of a copolymer of vinyl acetate and a monomer copolymerizable with vinyl acetate, preferably a water-soluble one.

Among the acetoacetylated polyvinyl alcohols obtained as described above, those used in the present invention are preferably 5-50% aqueous solutions having a degree of acetoacetylation of 0.5-20 mol%. Acetoacetylated hydroxyalkyl cellulose and acetoacetylated starch are also produced in the same manner.

Next, an aqueous emulsion of a polymer compound having an acetoacetyl group in the molecule will be explained.

Monomers containing acetoacetyl groups, such as allyl acetoacetate, vinyl acediacetate, 2-acetoacetoxyethyl acrylate, 2-7cetoacetoxyethyl methacrylate, 2-7cetoacetoxybrobyl acrylate, 2-7cetoacetoxyp Tetrabiru methacrylate, etc., and a, β ethylenic monomers, such as vinyl acetate, vinyl esters such as vinyl esters of saturated fatty acids branched at the a-position, methyl acrylate-Y or methyl methacrylate E, such as methyl (meth)acrylate. 1. (meth)acrylates such as ethyl (meth)acrylate, butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, monovinyl monomers such as styrene, acrylonitrile, ethylene, vinyl chloride, etc. An aqueous emulsion of a polymer compound having an acetoacetyl group in the molecule can be obtained by emulsion copolymerization with the following. It also includes an aqueous polymer emulsion obtained by emulsion polymerization using acetoacetylated polyvinyl alcohol as an emulsifier.

The appropriate concentration of the aqueous emulsion is usually 10 to 60%.

The polyethyleneimine of the second liquid used in the present invention has the general formula (where R1, R2, and R3 are H or CH2Cl128
112, X, y are integers), and the molecular weight is 300
It is about 100,000.

Low molecular weight liquids are light when used as they are, but high molecular weight ones are preferably used as a 1-40% aqueous solution.

Next, the vJ2 invention and the third invention of the present invention will be explained in Ill.

That is, the second invention provides (c) a first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group and a crosslinking group other than an acetoacetyl group in the molecule; This is a two-component, quick-curing water-based adhesive that uses a second component that is composed of a crosslinking agent that crosslinks crosslinking groups other than acetyl groups.

The third invention also provides (e) crosslinking an aqueous solution and/or aqueous emulsion of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule, and the crosslinking group other than the acetoacetyl group. This is a two-component, quick-curing water-based adhesive that uses a first component fi made of a crosslinking agent and a second component made of polyethyleneimine.

In the above two inventions, the crosslinking agent that crosslinks crosslinking groups other than the acetoacetyl group contained in the molecule of the polymer compound is blended in the w&2 solution in the second invention. This is because if it is added to the first liquid (c), a crosslinking reaction with the crosslinking group will proceed and gelation will occur.

However, if the reaction between the crosslinking group and the crosslinking agent is slow, or if the crosslinking agent is mixed immediately before use, the crosslinking agent can be mixed in the first liquid (e) as in the third invention.

Next, a case will be described in which an isocyanate compound is used as a typical crosslinking agent and a hydroxyl group is used as a typical crosslinking group.

Using the first liquid and the second liquid (1) to adhere the objects to be adhered,
A rapid adhesive force is generated due to the gelation reaction between the acetoacetyl group and polyethyleneimine, and then, in this adhered state, the reaction between the isocyan winter-F compound and the reactive group progresses, resulting in water resistance and heat resistance. This results in excellent adhesion.

The reaction fi structure is estimated as follows.

[Margin 1 below] Adhesion by these two types of reactions is one of the features of #2 and the third invention.

In addition to the acetoacetyl group, the polymer compound of @1 liquid (c) or (e) in the second and third inventions has a crosslinking group such as a hydroxy group, a carboxyl group, a chlor atom, a methylol group, an acid amide group, an amide group, etc. It has a group.

As the aqueous solution of such a polymer compound, an aqueous solution of acetoacetylated polyvinyl alcohol, carboxy-modified acetoacetylated polyvinyl alcohol, acetoacetylated starch, acetoacetylated hydroxyalkyl cellulose, etc. is used.

In addition, as an aqueous emulsion of a polymer compound, a monomer containing an acetoacetyl group, such as allyl acetate, vinyl acetate, 2-7cetoacetoxyethyl (meth)acrylate, 2-7cetoacetoxypropyl (meth)acrylate etc., and a and β ethylenic monomers, such as vinyl esters such as vinyl acetate, (meth)acrylates such as methyl (meth)acrylate, monovinyl monomers such as styrene, acrylonitrile, and ethylene, and have a crosslinking group. Monomers, such as unsaturated carboxylic acids such as (meth)acrylic acid, ritonic acid, itaconic acid, maleic acid, 2-hydroxyethyl (meth)acrylate, acrylamide, N-/tyrolacrylamide, N,N- An aqueous emulsion obtained by emulsion copolymerization of dimethyl acrylamide, glycidyl methacrylate, etc. is suitable.

Polymer emulsion resins using a polymer compound having an acetoacetyl group in the molecule as an emulsifier include vinyl acetate resin, vinyl acetate-ethylene copolymer resin, acrylic ester resin emulsion, etc. using acetoacetylated polyvinyl alcohol as an emulsifier. is suitable.

Examples of the crosslinking agent used in the second and third inventions include isocyanate F compounds such as tolylene diisocyanate (TDI), methylene bis-diphenyl diisocyanate (MDI) ζhexamethylene diisocyanate, and pheasylene diisocyanate, and polyepoxides of polyols. polyepoxide compounds, methylolated melamine,
Initial condensates of methylolated urea and divalent or trivalent metal salts are used.

Next, the fourth invention will be explained.

The fourth invention is a method of bonding using the two-component, separately applied, fast-curing water-based adhesive of the first, second and third inventions. That is, the first liquid is applied to the surface to be bonded, such as a surface of wood, and the second liquid is applied to another surface to be bonded, such as a straight board, and both surfaces are immediately bonded. When they are brought together and pressed together,
The acetoacetyl group and polyethyleneimine undergo a rapid gelation reaction, and the bond becomes quite strong within 1 to 5 minutes at room temperature, so the bonding method involves releasing the pressure or curing the adhesive. The amount of adhesive applied is 18th!1
0-200g/m2 (solid content), second liquid 1-50g/m
” (as polyethyleneimine) is suitable.

Generally, with water-based adhesives, sufficient final adhesive strength cannot be achieved at room temperature unless the adhesive is pressed for a considerable period of time, but the fast-curing water-based adhesive of the present invention requires only a short period of time to obtain sufficient final adhesive strength after being left unused. The final adhesive strength is improved.

In this case, the important thing is to apply the two liquids separately without mixing them.

This is because the reaction between acetoacetyl groups and polyethyleneimine is very fast, so if they are mixed and applied, they will gel during mixing, and the gelled product will not exhibit adhesive properties.

When using the two-component, separately applied, fast-curing water-based adhesive of the second and third inventions, after the primary adhesion is performed by the reaction between the acetoacetyl group and polyethyleneimine, it is then cross-linked with other cross-linking groups. Secondary adhesion occurs as a result of a reaction between the crosslinking agent and the crosslinking group, but in this case as well, it is sufficient to perform a slight compression and then leave it to cure.However, depending on the purpose, the crosslinking agent and crosslinking group By selecting these, desired performance such as water resistance and heat resistance can be achieved.

Conventional adhesives using isocyanate compounds have poor initial adhesion and require a long time to press, resulting in extremely low work efficiency, but when isocyanate compounds are used in the second and third inventions, Because the initial adhesion is extremely excellent, a very light adhesive force can be obtained by simply leaving it after a short time of pressing, reducing work time, and the adhesive strength itself is also higher than that of conventional incyanate adhesives. The clothes are excellent.

The adhesive of the present invention has flexibility, toughness,
In order to impart elasticity, plywood resin emulsion and synthetic rubber latex are appropriately used together.

In addition, fillers such as calcium carbonate, plasticizers, preservatives,
The process is completed by adding colorants, surfactants, viscosity modifiers, etc. as appropriate.

The two-component quick-curing water-based adhesive of the present invention can be applied to fibrous materials such as wood, plywood, particle board, hardboard, slate board, silica board, mortar, tiles, and other inorganic materials, melamine decorative board. Suitable for high-speed bonding of plastic materials such as Bakelite, Styrofoam, and paper materials such as cardboard, paperboard, and kraft paper.

The present invention will be explained below with reference to Examples and Comparative Examples.

Example 1 I1 was prepared by mixing the following components.

15% aqueous solution of acetoacetylated polyvinyl alcohol, which is obtained by adding 6.0 mol% of acetoacetyl groups to polyvinyl alcohol with a degree of polymerization of 100 and a degree of saponification of 99 mol%. Vinyl acetate resin emulsion A 1 20 with a concentration of 50%, manufactured by Manufacturer Co., Ltd. Next, the following components were mixed to prepare a second solution.

20% aqueous solution of polyethylene imiso with a degree of polymerization of 70,000 100 parts by weight 20%
Zirconium ammonium carbonate aqueous solution 2 Example 2 The following components were mixed to prepare a first solution.

30% aqueous solution of acetoacetylated polyvinyl alcohol with 7.6 mol% of acetoacetyl groups added to polyvinyl alcohol with a degree of polymerization of 5001 and a degree of saponification of 88 mol%9 100 parts by weight of calcium carbonate 20.

The following components were used as the second vL.

Polyethylene with a polymerization degree of 500 min Example 3 A first liquid was prepared by mixing the following components.

100 parts by weight of a 20% aqueous solution of acetoacetylated polyvinyl alcohol, which is obtained by adding 3.0 mol% of acetoacetyl groups to polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 99 mol%. The ingredients were used as a second liquid.

Polyethylene with a polymerization degree of 100,000 Miso 5% aqueous solution Example 4 1st w1. with the following ingredients. Closed.

Movinyl 149 (polymerization degree 5001) /Polyvinyl with a chemical degree of 99 mol% 6.0 mole acetate in alcohol Acetylated acetoacetate polyvinyl alcohol 40% vinyl acetate as emulsifier resin emulsion layer) A second liquid was prepared with the following ingredients.

Polyethylene with a polymerization degree of 100,000 Miso 5% aqueous solution Example 5 The following components were used as a first liquid.

Polymerization degree 800, saponification degree 99 mol% 7 to polyvinyl alcohol 9.1 mol% of cetoacetyl group Added acetoacetylation 20% of polyvinyl alcohol aqueous solution A second liquid was prepared with the following ingredients.

Polyethylene with a degree of polymerization of 500 min Example 6 The first g was prepared by mixing the following ingredients.

10% water 11 100 parts by weight of acetoacetylated hydroxyethyl cellulose obtained by adding 6.0 mol % of acetoacetyl groups to hydroxyethyl cellulose with a degree of polymerization of 1 F 0 and an average number of moles of ethylene oxide added of 2.0 〇- 503Q/1 The following components were mixed to prepare m second liquid.

20% aqueous solution of polyethylene imiso with a degree of polymerization of 70,000 100 parts by weight 20%
Zirconium carbonate ammonium aqueous solution 2 Example 7 The following components were mixed to prepare a first solution.

A 40% aqueous solution of acetoacetylated starch prepared by adding 3 mol% of 7cetoacetyl groups to oxidized starch. Ioo parts by weight Neil 80 50 30 // Calcium carbonate 20 ti A second liquid was prepared with the following ingredients.

Polyethylene with a polymerization degree of 100,000 Imine 5% aqueous solution Example 8 1st m was prepared by mixing each of the following components.

Using polyvinyl alcohol as an emulsifier, 2-7cetoacetyl? Emulsion 5 100fillS with a concentration of 40% obtained by emulsion polymerization of diethyl methacrylate/butyl methacrylate/methyl methacrylate (weight ratio: 151 50/35)
Movinyl^l150 1Q //The following ingredients were added to make the second liquid.

Polyethyleneimine with a degree of polymerization of 500 Example 9 A first liquid was prepared with the following ingredients.

100 parts by weight of 50% emulsion polymerized by emulsion polymerization of 2-7cetoacetoxyethyl acrylate/vinyl acetate (weight ratio: 13/8) using polyvinyl alcohol as an emulsifier. And so.

Polyethylene with a polymerization degree of 100,000 Min 5% aqueous solution Example 10 A first liquid was prepared by mixing the following components.

Degree of polymerization: 1001 Degree of saponification: 99 mol% of polyvinyl alcohol, 6.0 mol% of cetoacetyl group Added acetoacetylation 15% of polyvinyl alcohol Water-soluble [100 parts by weight Movinyl ^D-50 [Hoechst combination Specially made 50% vinyl acetate resin emulsion a] 20〃 Next, the following components were mixed to prepare a second liquid.

20% aqueous solution of polyethylene imitate with a degree of polymerization of 70,000 100 parts by weight Tetraethylene glycol dicrycidyl ether 5 Example 11 The following components were mixed to prepare a first liquid.

30% aqueous solution of acetoacetylated polyvinyl alcohol prepared by adding 7.6 mol% of acetoacetyl groups to polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% 100 parts by weight Movinyl^D-502011 20% aluminum chloride 5 A second liquid was prepared with the following ingredients.

Example 1 of 5% aqueous solution of polyethyleneimine with a degree of polymerization of 100,000
2 The following components were mixed to prepare the first liquid.

20% aqueous solution of acetoacetylated polyvinyl alcohol with 3.0 mol% of acetoacetyl groups added to polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 99 mol% 100 parts by weight Movinyl^D-5020// Methylene bis-diphenyl diisocyanate (MDI) 2 //The following components were used as a second solution.

Polyethylene with a polymerization degree of 500 min Example 13 A first liquid was prepared with the following ingredients.

15% aqueous solution of acetoacetylated polyvinyl alcohol with 6.0 mol% acetyl groups added to polyvinyl alcohol with a degree of polymerization of 100 and a degree of saponification of 99 mol% 100 parts by weight Movinyl^D-5020 // 20% chloride Aluminum aqueous solution 5 Methylene bis-diphenyl diincyanate (old H) 2 The following components were used as the second @.

Polyethylene with a polymerization degree of 70,000 Mitsu 20% aqueous solution Comparative example 1 The following ingredients were used as an adhesive.

Vinyl acetate resin emulsion 1 with a concentration of 50% using polyvinyl alcohol (specially manufactured by Hekytos Hei) as an emulsifier Comparative example 2 The following components were mixed to prepare an adhesive.

15% aqueous solution of acetoacetylated polyvinyl alcohol used in Example 1 100 parts by weight Movinyl^D-5020// Table 1 shows the formulation of the vil liquid and second liquid in the example and the formulation of the adhesive in the comparative example. As shown.

Comparative Test Using the fast-curing water-based adhesive consisting of the first and second liquids obtained in Examples 1 to 13 and the adhesives of Comparative Examples 1 and 2, JIS
The adhesive strength was measured according to the method shown in K 6852 "Test method for compressive shear bond strength of adhesives".

The test results are shown in Table 2.

The outline of the test method was as follows.

(Regular f'll) Apply tAl solution to one adhesive surface of two pieces of bar material of 25 mm x 30 mm (imine content), both sides were closely bonded together, and immediately pressed at 5 kgf/cm2.

Then, the pressure was released after each of the pressing times shown in Table 2, and the compressive shear adhesive strength was measured after curing for 5 minutes and after curing for 24 hours.

(Water Resistance) After the above-mentioned curing, the adhesive test piece was immersed in room temperature water for 3 hours, and the pressing shear adhesive strength was immediately measured.

(It heat) After the above-mentioned curing, the adhesive test piece was left in a thermostat at 70° C. for 3 hours, and the compressive shear adhesive strength was immediately measured.

Margin 1 below E (Regarding normal adhesive strength) Comparative Example 1 is a woodworking adhesive (JIS Type 1 No. 1 passed product), but in order to produce an adhesive strength of 100 kgf/am2 or more, the pressing time is 10 minutes x A curing time of 24 hours is required.

Further, in order to obtain an initial adhesive force of 10 kgt/cva2 or more, a short pressing time (at least 5 minutes) is required.

On the other hand, in Examples 1 to 13, the pressing time was 2 minutes x the curing time was 24 hours, and the pressure was 100 kgf/cm2.
It shows an initial adhesion force of 10 kgf/am'' or more when the pressing time is 1 minute x the curing time is 5 minutes.

Comparative Example 2 is an example in which the second liquid was not used in Example 1, but its adhesive performance was extremely poor.

(Regarding Water Resistant Adhesive Strength) In the case of Comparative Example 1, even under the conditions of 10 minutes of pressing time and 24 hours of curing time, the JIS standard of 40 kgf/ce+'' could not be achieved.

On the other hand, in Examples 1 to 13, the pressure was 50 kgf/cm or more in 10 minutes of pressing time x 24 hours of curing time,
Example 1.6.10.11.1 in particular using a crosslinking agent
2.13, the performance far exceeded the JIS standard.

(Regarding heat-resistant adhesive strength) Compared to the comparative examples, all of the examples showed superior adhesive performance. For those using a cross-linking agent in combination with and (, the pressing time is 1
100kgf/cI for 0 minutes x 24 hours of curing time
It exhibited an adhesion strength of over 11".

Procedural amendment (voluntary) August 17, 1980 Manabu Shiga, Commissioner of the Patent Office To the enemy 1. Indication of the case 1983 Patent application No. 141884 2. Name of the invention Fast-curing water-based adhesive and adhesive method 3. Make amendments Patent applicant address: 4-10-33 Akasaka, Minato-ku, Tokyo Name: Hiroaki Takama, 4th generation representative of Hoechst Synthesis Co., Ltd. Address: 540 Address: + is in front of Soraichi Makoji 9-chome Target of V1175 amendment for bolt draw f (1) “Claims” column of the specification ■ Contents of amendment in column 6 of “Detailed description of the invention” of the specification (+) “Claims” column of the specification " shall be amended as shown in the attached document "Amended Scope of Claims."

■ Correct "gelling" on page 7, line 10 of the specification to "gelling".

■ "Allyl acetate, vinyl acetate" on page 16, line 16 is corrected to "allyl acetoacetate, vinyl acetoacetate."

(4) Delete "100 parts by weight" on page 26, line 17.

(5) On page 29, line 5, "The following components were used to prepare the first solution." was corrected to "The following components were mixed to prepare the first solution."

(6) Left part of Table 2 on page 33 ” and correct it.

Cover” 1! A two-component quick-curing water-based adhesive consisting of (() and (b) below).

(a) # consisting of an aqueous solution and/or aqueous emulsion of a polymer compound having an acetoacetyl group in the molecule
1 liquid.

(b) A second liquid consisting of polyethyleneimine.

2. A two-component, separately applied, fast-curing water-based adhesive consisting of (c) and (c) below.

(c) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule.

B) A second liquid comprising polyethyleneimine and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups.

3. The two-liquid separate coating type fast curing according to claim 2, wherein the crosslinking group other than the acetoacetyl group in (c) is a crosslinking group that reacts with an isocyanate compound, and the crosslinking agent in (c) is an isocyanate compound. Water-based adhesive.

4 A two-component, quick-curing water-based adhesive consisting of (e) and (f) below.

(e) An aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule and/or
*Or a first liquid consisting of an aqueous emulsion and a crosslinking agent that crosslinks crosslinking groups other than the acetoacetyl group.

(f) Second liquid consisting of polyethyleneimine.

5. The two-component, separately applied, fast-curing water-based adhesive according to claim 4, wherein the crosslinking group other than the acetoacetyl group in (e) is a group that is an isocyanate compound, and is isocyanate A.

6. The first of a set of adhesives selected from the following three sets of two-component separate application type fast-curing water-based adhesives: P), (B), (C), (E) and (F). A two-liquid separate coating and bonding method, characterized in that the liquid and the second liquid are separately applied to the bonding surface of an object to be bonded, and then the bonding surfaces are brought into contact.

(g) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group in its molecule.

(b) A second liquid consisting of polyethyleneimine.

(c) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in its molecule.

B) A second liquid comprising polyethyleneimine and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups.

(e) An aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule and/or
*Or a first liquid consisting of an aqueous emulsion and a crosslinking agent that crosslinks crosslinking groups other than the acetoacetyl group.

(f) Second liquid consisting of polyethyleneimine. ” or later
Top-4=

Claims (1)

[Scope of Claims] 1. A two-component, separately applied, fast-curing water-based adhesive consisting of the following (a) and (b). (a) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group in its molecule. (b) A second liquid consisting of polyethyleneimine. 2. A two-liquid, separately applied, fast-curing water-based adhesive consisting of (c) and (d) below. (c) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule. (d) A second liquid comprising polyethyleneimine and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups. 3. The two-component separate coating type quick-coating method according to claim 2, wherein the crosslinking group other than the acetoacetyl group in (c) is a crosslinking group that reacts with an isocyanate compound, and the crosslinking agent in (d) is an isocyanate compound. Curing water-based adhesive. 4. A two-component, quick-curing water-based adhesive consisting of (e) and (f) below. (e) An aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule and/or
Alternatively, a first liquid comprising an aqueous emulsion and a crosslinking agent that crosslinks crosslinking groups other than the acetoacetyl group. (f) A second liquid consisting of polyethyleneimine. 5. The two-component, separately applied, fast-curing water-based adhesive according to claim 4, wherein the crosslinking group other than the acetoacetyl group in (e) is an isocyanate compound. 6 One set of adhesive selected from the following three sets of two-component separate application fast-curing water-based adhesives: (a) and (b), (c) and (d), (e) and (f). A two-liquid separate coating and adhesion method characterized by separately applying a first liquid and a second liquid to an adhesive surface of an object to be adhered, and then bringing the adhesive surfaces into contact. (a) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group in its molecule. (b) A second liquid consisting of polyethyleneimine. (c) A first liquid consisting of an aqueous solution and/or an aqueous emulsion of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in its molecule. (d) A second liquid comprising polyethyleneimine and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups. (e) An aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than the acetoacetyl group in the molecule and/or
Or a first liquid consisting of an aqueous emulsion and a crosslinking agent that crosslinks crosslinking groups other than the acetoacetyl group. (f) A second liquid consisting of polyethyleneimine.