JPS6178883A - Instantaneously setting water-base adhesive and bonding by using same - Google Patents

Abstract

PURPOSE:To obtain the titled adhesive showing an improvement in terms of toxicity, fire hazard, and aging properties, by the combined use of the first liquid comprising an aqueous solution of a high-molecular compound containing acetoacetyl groups in a molecule, and the second liquid comprising an aqueous solution of a hydrazine compound. CONSTITUTION:A two-pack water-base adhesive (I) comprising liquids (a) and (b) as follows: (a) The first liquid comprising an aqueous solution and/or an aqueous emulsion of a high-molecular compound containing acetoacetyl groups in a molecule. (b) The second liquid comprising an aqueous solution of a hydra zine compound. Alternately, a two-pack water-base adhesive (II) comprising liquid (c) and (d) as follows: (c) The first liquid comprising an aqueous solution and/or an aqueous emulsion of a high-molecular compound containing acetoacetyl groups and other crosslinkable groups. (d) The second liquid compris ing an aqueous solution of a hydrazine compound and a crosslinking agent which crosslinks the crosslinkable group other than the acetoacetyl group.

Description

[Detailed description of the invention] This invention relates to a two-liquid separate coating and adhesion 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 coating type instant curing water-based adhesive and a two-component separate coating bonding method, which eliminates the need for pressurization after a few minutes and which adheres to the point of breaking into water after a few hours.

Traditionally, polyvinyl acetate, urea glue, rubber glue, epoxy resin, and insium compound have been used as adhesives for wood and slate boards, but with the exception of contact-type rubber glue. All of these adhesives have poor adhesive start-up (initial adhesion), and contact-type rubber adhesives also contain organic solvents, which pose a risk of toxicity and fire, especially when used in closed areas such as factories. It also has the disadvantage of being stiff and easily aged, so there has been a desire for a water-based adhesive with high initial adhesion.

As a result of intensive research, the present inventors have invented an adhesive that solves all of these problems.

That is, the first invention of the present invention provides the following C) and (B).
2a is an instant curing water-based adhesive that can be applied separately.

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

(b) A second liquid consisting of an aqueous solution of a hydrazine compound.

Moreover, the second invention of the present invention is a 2-fill coating type instant curing water-based adhesive consisting of the following (c) and (c).

Q9 Aqueous solution of a polymer compound having an acetoacetyl group and a crosslinking group other than acetoacetyl group in the molecule and/*
(2) a second liquid comprising an aqueous solution of a hydrazine compound and a crosslinking agent for crosslinking 9A crosslinking groups other than the acetoacetyl group;

Moreover, the third invention of the present invention is a 2a separate coating type instant 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 a 77t77tyl group in the molecule and/or
or (1a) comprising an aqueous emulsion, a crosslinking agent that crosslinks a crosslinking group other than the 7-ceto-heptyl group, and (2) a second liquid comprising an aqueous solution of a hydrazine compound.

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 adhesion method characterized by separately applying the 11'll and the second liquid of the 81 separate application type water-based adhesive to the adhesive surface of the object to be adhered, and then bringing the adhesive surfaces into contact. .

First, the first invention of the present invention will be explained.

A polymer compound having an acetoacetyl group in the molecule and a hydrazine compound undergo a reaction mechanism as shown in the following formula, forming a crosslinked structure and rapidly gelling. In this case, acetoacetyl Applying an aqueous f# liquid and/or aqueous emulsion of a polymer compound having an acetyl group and an aqueous solution of a hydrazine compound to the surface of the object to be adhered,
By bringing these coated surfaces into close contact with each other to cause a delification reaction, strong adhesion can be achieved in a short period of time.

s"hurt・2" L response 8 adhesive "simultaneous 1"row'
The present invention is characterized by the fact that:

That is, since a gelled product obtained by reacting two compounds in advance no longer exhibits adhesive properties, the adhesive of the present invention is prepared by using an aqueous solution of a polymer compound having an acetoacetyl group in the molecule and/or It must be a 2ta separate application type adhesive consisting of aqueous Emulnon 1 and an aqueous solution of a hydrazine compound.

Furthermore, since this delification reaction is carried out in an aqueous medium, the 281 separate coating type adhesive of the present invention is a water-based soluble A* and water-based emulsion type adhesive, that is, a water-based 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 an acetoacetyl group in the molecule, a water-soluble polymer compound such as polyvinyl alcohol, hydroxyfurkylcellulose, starch, etc. is 77-doe acetylated. Aqueous solutions of acetoacetylated polyvinyl alcohol, acetoacetylated hydroxyfurkylcellulose, 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 its molecule contains a monomer containing an acetoacetyl group and an a, β ethylenic monomer. Emulsion-copolymerized aceto7-7 tylated copolymer emulsicone and polymer emulsicone using a polymer compound having a 77F7 cetyl group in the molecule as an emulsifier may be mentioned.

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

As an example, acedoheptatylated polyvinyl alcohol can be obtained by reacting polyvinyl alcohol with polyvinyl alcohol by a known method. Examples include a method in which polyvinyl alcohol is dispersed in an acetic acid solvent and noketene is added to this, or a method in which polyvinyl alcohol is previously dissolved in a solution such as trimethylformaldehyde or nooxane and noketene is added to this. and so on. It can also be obtained by directly contacting polyvinyl alcohol with noketene gas or liquid noketene.

The polyvinyl alcohol used has a polymerization degree of 200 to 3000 and a saponification degree of 30, which is obtained by tenizing 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 acetoacetylated hydroxyl, preferably a 5-50% aqueous solution with a degree of acetoacetylation of 0.5-20 mol%. Alkyl cellulose and acetoacetyl Hokuto powder are also produced in the same manner.

Next, an aqueous emulsion of a polymer compound having 7ceto-7tyl groups in the molecule will be explained.

Monomers containing a 7ceto7 heptyl group, such as allyl 7cetoacetate, vinyl acetoacetate, 2-7cetoacetate,
Setoxyethyl acrylate, 2-7 setoxyethyl methacrylate, 2-7 heptadoxypropyl acrylate, 2-7 setacetoxypropyl methacrylate, etc., and a, β ethylenic monomer, such as vinyl acetate, α Vinyl esters such as vinyl esters of saturated fatty acids branched at position, methyl acrylate or methyl tacrylate.
ri) acrylate, (meth)acrylate such as Z-ethylhexyl (meth)acrylate, nonyl (meth)acrylate, styrene, 7-crianitrile, ethylene,
By emulsion copolymerizing with a monovinyl monomer such as hinyl chloride, an aqueous bicarbonate of a polymer compound having an acetoacetyl group in the molecule can be obtained. Also included is a polymer aqueous emulsion polymerized by emulsion polymerization using aceto7-7-tylated polyvinyl alcohol as an emulsifier.

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

The @2+11 hydrazine compounds used in the present invention include hydrazine, hydrazone hittride, inorganic salts of hydrazine such as hydrochloric acid, sulfuric acid, nitric acid, nitrous acid, phosphoric acid, thiocyanic acid, and carbonic acid, and organic salts such as formic acid and oxalic acid. L
Monosubstituted forms of hydracune with methyl, ethyl, propyl, butyl, allyl, asymmetric disubstituted forms such as 1,1-tmethyl, 1.1-tmethyl, 4-n-butyl-methyl, and 1,2-tmethyl , 1,2-methyl, 1,2-diinpropyl, and other symmetrical disubstituted compounds.

Particularly suitable hydrazine compounds are carbohydranod,
Cheryl acid nohydrazide, malonic acid nohydrazide, succinic acid nohydrazide%7 nopic acid nohydrazide, cepatic acid nohydrazide, dodecanoic acid nohydrazide, isoheptalic acid nohydrazide, terephthalic acid nohydrazide, glycolic acid nohydrazide, polyacrylic acid hydrazide, etc. It is.

These hydrazine compounds are used in aqueous solution.

The concentration of the aqueous solution is usually 0.1 to 50%.

Next, the second and third aspects of the present invention will be explained.

That is, the $2 invention provides (c) an aqueous solution of a polymer compound having a 77-doad acetyl group and a crosslinking group other than an acetoacetyl group in the molecule; and/or an aqueous solution of a hydrazine compound. and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups.

The third invention also provides (e) an aqueous Wl solution and C//* or an aqueous emulnolayer of a polymer compound having a 7cetoacetyl group and a crosslinking group other than an acetoacetyl group in the molecule; This is a two-part, separately applied, instant-curing water-based adhesive using an eleventh liquid consisting of a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups, and a second liquid consisting of an aqueous solution of a hehydrazine compound.

In the above two inventions, the crosslinking agent that crosslinks the crosslinking groups other than the acetoacetyl group contained in the molecule of the polymer compound is added to the second liquid in the second invention. This is because if it is added to No. 181 (c), the crosslinking reaction with the crosslinking group will progress and gelation will occur.

However, if the reaction between the crosslinking group and the crosslinking agent is slow, or if it is blended immediately before use, the crosslinking agent can be blended in the first step (e) as in the Is3 invention.

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

Previously, when the objects to be bonded are bonded using the first liquid and the second liquid,
First, rapid adhesion occurs due to the gelation reaction between the acetoacetyl group and the hydrazine compound, and then the reaction between the isocyanate compound and the reactive group progresses in this bonded state, resulting in an adhesion with excellent water resistance and heat resistance. It will be done.

The reaction mechanism is as follows (estimated).

This adhesion due to the reaction of 2fllls is one of the features of the second and third inventions.

In addition to the acetoacetyl group, the polymer compound of No. 1711 (c) or (e) in the second and third inventions has a hydroxyl group, a carboxyl group, a lyal atom, a /tyrol group, an acid 7-mido group, and an amine 7 group. It has a crosslinking group such as.

As the aqueous solution of such a polymer compound, aqueous solutions such as acetoacetylated polyvinyl alcohol, carboxy-modified 77-domain acetylated polyvinyl alcohol, acetoacetylated starch, and acetoacetylated hydroxyfurkyl cellulose are used.

In addition, as an aqueous emulsion of a polymer compound, a monomer containing an acetoacetyl group, such as 7lylacetate, vinyl acetate, 2-7ceto7cetoxyethyl (meth)7acrylate, 2-7ceto7cetoxyprobyl (meth) Acrylates, a, β-ethylenic monomers, such as vinyl esters such as vinyl acetate, acrylates such as methyl (meth) 7-acrylate, monovinyl monomers such as styrene, acriminitrile, and ethylene. , monomers with crosslinking groups, such as unsaturated carboxylic acids such as acrylic acid, crotonic acid, itafonic acid, maleic acid, 2-hydroquinethyl (meth)acrylic V-), acrylamide, N- An aqueous emulsion obtained by emulsion copolymerization of methylacryl 7mide, N,N-methylacryl 7mide, etc. is suitable.

Polymer emulgenes that use a polymer compound with an acetoacetyl group in the molecule as an emulsifier include vinyl acetate resin made by reducing 1L of acetoacetylated polyvinyl alcohol, vinyl acetate-ethylene copolymer resin, and acrylic acid ester! J'll Emaruno 5N and the like are suitable.

Examples of crosslinking agents used in the second upstream t53 invention include tolylene diisocyanate (TDI), methylene bisno phenyl noisocyanate (801), hexylymethlene diisocyanate, quizylene diisocyanate, and hydrogenated methylene bisno phenyl isocyanate. etc./
Polyepoxide compounds such as cyanate compounds and polyol polyepoxides, and 1. Initial condensates of d-thylated melamine, methylolated urea, and divalent or trivalent metal salts are used.

Next, the fourth invention will be explained.The 49th invention is a method of bonding using a separately applied instant curing water-based adhesive in 2)l of the first, second and tA3 inventions. That is, the 11th
Apply No. 11 to the surface to be bonded, such as a surface such as wood, and apply the second liquid to the other surface to be bonded, such as a slate board, and immediately bring both sides together. When brought into contact with each other and compressed, the acetoacetyl group and the hydrazine compound rapidly undergo a reaction.
This bonding method allows the adhesive to bond with considerable strength within 1 to 5 minutes at room temperature, so the pressure can be released and the adhesive is left to cure. The amount of adhesive applied is 10-200 g/s of the first liquid.
(solid content), second liquid 0.1 to 5%/+s' (as hydrazine compound) is suitable.

- Generally, water-based post-adhesives cannot achieve sufficient final bond strength unless IF tightening is performed for a considerable period of time at room temperature, but the instant curing water-based adhesive of the present invention only requires 11iSI11 pressure tightening at room temperature. So, free fi! ! Sufficient final adhesive strength can be achieved after birth.

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

This is because the reaction between the acetoacetyl group and the hydrazine compound is very fast, so if they are mixed and applied, they will form during the mixing, and the hydrazine compound will not exhibit adhesive properties.

m 2 j; and when using the two-component separate application type instant-curing water-based contact layer cutting of the third invention, after the first layer is corrected by the reaction between the acetoacetyl group and the hydrazine compound, A reaction occurs between the crosslinking group and the crosslinking agent, resulting in secondary adhesion, but in this case too, only a slight amount of pressure is applied and the rest is left as is. All you need is a crosslinking agent and a crosslinking group depending on the purpose! ! By increasing the temperature, 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.However, when isocyanate compounds are used in the second and third inventions, Because the initial adhesion is extremely excellent, a large adhesive force can be obtained by simply leaving it for a short time after pressing, reducing work time, and the adhesive strength itself is significantly higher than that of conventional insifnate adhesives. Excellent.

The adhesive of the present invention has flexibility, toughness,
In order to impart elasticity, plywood memory (fat emulsion or synthetic rubber latex can be used in combination as appropriate).

In addition, fillers such as calcium carbonate, plasticizers, preservatives,
A coloring agent, a surfactant, a viscosity regulator, etc. can be added as appropriate.

The instant curing water-based adhesive of the present invention can be applied to wood, plywood, particle board, fibrous materials such as 7%-board, 5FPi materials such as slate boards, silica boards, mortar, tiles, and melamine. Decorative board, Bakelite,
Suitable for high-speed bonding of plastic materials such as Styrofoam, paper materials such as cardboard, paperboard, and Kraft paper.

Hereinafter, the present invention will be explained with reference to Examples and Comparative Examples.

Actual opening 1 A first solution was prepared by mixing the following six components.

Polyvinyl furfur with a degree of polymerization of 100 and a degree of saponification of 99 mol % was added with 6.0 mol % of 7-17-hythyl groups to form a 15% aqueous solution of polyvinyl furfur with an acetoacetyl ratio of 100 parts movinyl 8 D-50. [Polyvinyl acetate emulsion J 20 with a concentration of 50% manufactured by Hoechst Synthesis M] Next, add 1illL of the following tIS2 oil.

59g carbohydrazide aqueous solution Example 2 Mix the following ingredients and make the first liquid lll11! Shita.

30% aqueous solution of acetoacetylated polyvinyl alcohol with 7.13 mol% of acetoacetyl groups added to polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% 100 parts by weight 50% formic acid in water? Il 2 # 2nd with the following ingredients? It was set as ll.

0.5% isophthalic acid tunohydranide aqueous solution implementation 3 A first liquid was prepared by mixing the following components.

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 80 to 50 300 050% phosphoric acid aqueous solution 2 Next, the following components were mixed to prepare a second solution.

10% 7 Novic Acid Cividra S! Aqueous solution 100 parts by weight Aluminum chloride solution 5 ri Fire Example 4 The following components were mixed to prepare a first solution.

*Acetate used in Example 1 Acetylated polyvinyl alcohol −le The second one with the following ingredients? It was set as Il.

10967 Novic acid hydranide aqueous solution Example 5 The following components were mixed to make 7!4 of the first wL.

20% aqueous solution of acetoacetylated polyvinyl alcohol with 9.1 mol% of 7-cetyl groups added to polyvinyl alcohol with a degree of polymerization of 100 and a degree of saponification of 99 mol%.
Elementary 5 #5
0%'J N R Water # ill Z n No. 21i1 was prepared with the following ingredients.

0.5% isophthalic acid water f# liquid Example 6 No. 11 was prepared by mixing the following components.

IO% aqueous solution of acetoacetylated droxyethylcellulose, which has 6.0 mol% of acetoacetyl groups added to hydroxyethylcellulose with a degree of polymerization of 170 and an average molar addition of ethylene oxide of 2.0 100 parts by weight to Movinyl 80 50 30 7150% formic acid aqueous solution 2 nWhat are the following ingredients? 3-) was used as the second liquid.

5% carbohydranod aqueous solution Example 7 A first liquid was prepared by mixing the following components.

1 part by weight of 40% aqueous solution of acetoacetylated starch (= L
To Neil 〇-50 3Q.

50% formic acid aqueous solution 2 nThe following ingredients were used as a second solution.

10967 Nopinic acid nohydranide aqueous solution'P. Example 8 A first liquid was prepared by mixing the following components.

Polyvinyl alcohol 21. As a chemical cutting, emulsion polymerization of 2-7cetoacethine ethyl methacrylate/butyl methacrylate/methyl methacrylate (weight ratio: 157 50/15) with a degree of 40% of Emulno 1 100 weights 1 part Movinyl 80 to 50 , 10/.

uric acid 5
950% phosphoric acid aqueous solution 2 rt
A second solution was prepared by adding the following ingredients.

0.5% Isophthalic acid nohydranide water soluble 1i1 100 parts by weight 20%
Aluminum chloride aqueous solution 5 Example 9 The following components were mixed to prepare No. 11.

Emaruno 1 with a concentration of 50% obtained by emulsion polymerization of 2-7cetoacetoquine ethyl acrylate/vinyl acetate (weight ratio: 13/87) using polyvinyl alcohol as an emulsifier 100 weight 11 parts 5 Q 9
6 Formic acid water 78 liquids 2 The following ingredients were used as the second liquid.

IQ%7 Nopinic acid nohydrofnod aqueous solution Example 10 A first liquid was prepared by mixing the following components.

15% of acetoacetylated polyvinyl alcohol with a degree of polymerization of 100 and a degree of saponification of 99 mol% and 6.0 mol% of 7 cetoacetyl groups added with Fl + 5. Water-soluble 100 ffii part movinyl 80-50 [manufactured by Hoechst Synthesis ■] Vinyl acetate emulsion with a concentration of 50% 20 50% phosphoric acid aqueous solution 2 Next, mix the following components and make the second liquid pa! ! did.

5% carbohydrazide aqueous solution 100 parts by weight Teto-2 ethylene glycol noglin norether 5 Example II The following components were mixed to prepare a first liquid.

Acetoacetylated polyvinyl alcohol with a degree of polymerization of 500 and a degree of saponification of 88 mol% to which 7.6 mol% of 7-cetoacetyl groups have been added 30% aqueous solution 100 parts I part movinyl 8D-5020N 50% phosphoric acid aqueous solution O, 2〃 20% aluminum chloride 5〃The following ingredients were used as a second liquid.

10 Zoro 7 Novin PIl Kuhydranod Aqueous Solution Example 12 Mix the following components to make the first one i1! ! Added 3.0 mol% of 7cetoacetyl groups to the prepared polyvinyl alcohol with a degree of saponification of 500 and 99 mol%. 20% of 7cetoacenalized polyvinyl alcohol, 78 parts water, 100 parts by weight, 50 20 # 20% phosphoric acid aqueous solution 2 / 1,000 bisno phenylneuson 7) (801) 2 # iT+2 with the following ingredients! And so.

(1.5% isophthalic acid nohydranide aqueous solution')! , Example 13 The following components were mixed to prepare a first liquid.

15% of acetoacetylated polyvinyl alcohol with a degree of polymerization of 100 and a degree of saponification of 99 mol% to which 6.0 mol% of 7-cetyl groups have been added 15% water 100 parts by weight of water 100 parts by weight Movinyl^D-50209 50% phosphorus Acid aqueous solution 2920% aluminum water Ig solution 5tr Menalenbis-nophenylnoinane) CMDI) 2/1 The following ingredients were used as the second solution.

5% carbohydranod aqueous solution Comparative example 1 The following ingredients were used as an adhesive.

To Movinyl 〇-50 [Polyvinyl alcohol manufactured by Hekytos Synthesis ■] Polyvinyl acetate emulnolan 1° with an emulsifier binding concentration of 50% Comparative Example 2 The following components were mixed to prepare an adhesive.

30% aqueous solution of acetoacetylated polyvinyl alfur used in Example 2 100 parts by weight 50% formic acid solution 2 1i in Example
The composition of No. 11 and the second liquid and the composition of the adhesive of the comparative example are the first
As shown in the table.

Using the instant curing adhesive consisting of the 11th and 2nd liquids obtained in Comparative Test Examples 1 to 13 and the adhesive of Comparative Example 1 and 2, JIS K-
The adhesive strength was measured according to the method described in ``Compression Shear Bond Strength Test Method for 6852r Adhesive''.

The test results are shown in Table 2.

The outline of the test method was as follows.

(Adhesive strength development property) 2511!1X 30+smX 10mm Two pieces of bar material. Apply 100g/m" of the first liquid to one adhesive part, and apply 5g/L of the second liquid to the other side, and stick both sides together. Immediately after bonding, they were pressed together for 5 kgf/6N1' for 1 minute, and the compression shear bond strength was measured immediately after depressurization.

(Normal state) After pressing for 5 kHz/cm' x 4 minutes, the pressure was released, and the compressive shear bond strength was measured after curing for 72 hours (in a 20'CX65% atmosphere).

(Water resistance) After curing as described in ^11, the adhesive test piece was immersed in room temperature water at 3 o'clock, and immediately after that, the compressive shear bond strength was measured 1. Ta.

(Heat Resistance) After curing as described above, the adhesive test piece was left at a constant temperature of 60° C. for 24 hours, and the compressive shear bond strength was immediately measured.

(Set time) One end face of the above two pieces of bar material (10m+*X 30+s
After applying 100g/m2 of the first liquid on the surface of m) and 50g/m2 of the second liquid on the other side, the two sides were adhered together and immediately 2kg was applied.
Clamp with a load of

After a predetermined time, release the pressure, apply a load of 5 kg to this test piece, and check whether the test piece is adhered.

The am time of adhesion is the set time.

[Margin J (Regarding Seven Throat Time) Comparative Example 1.2 requires a long time of 2 to 10 minutes, whereas Examples 1 to 13 can be fixed in a very short time of 5 to 30 seconds.

(Regarding adhesive strength development) Compared to Comparative Example 1.2, Examples 1 to 13 had approximately 5 times to 20
Exhibits double the adhesive strength.

(Always!! Regarding adhesive strength) In contrast to Comparative Examples 1.2, Examples j to 13 all had adhesive strength of 1.
00 kgf/cm" or more, indicating sufficient adhesive strength.

(Regarding water-resistant adhesive strength) In the case of Comparative Example 1.2, I'1 II 4 minutes when clamping x 1 when curing
Under the harsh conditions of 72 hours, the JIS standard 40
kgf/cm' cannot be indicated.

On the other hand, in Examples 1 to 13, the pressing time was 4 minutes
Example 3.8.10.11 Showing 40 kgf/cm' or more after 111172 hours of curing, especially using a crosslinking agent
．． 12.13 showed performance far superior to the JIS standard.

(Regarding heat-resistant adhesive strength) Compared to the comparative examples, all of the examples showed superior adhesive performance.

Patent applicant: Hekytos Synthesis Co., Ltd. - β continuation -? 111 Original body: (spontaneous) 1980/10/20 1 "lY < Cattle indication 1988 Patent Application No. 202197 2 Name of invention Instant hardening water-based adhesive cutting and bonding method 3 Person making correction 7F, matter Relationship with Patent applicant: 11 Address: 4-10-33 Akasaka, Minato-ku, Tokyo Name: Hoechst Gosei Co., Ltd. Name: (6522) Patent attorney: Asahi Naso Tai7ke Telephone: (06) 943-8922 (Main) GoPi5
7 Mountains 11: No. 1:) (1) Contents of column 6 oil 1 of "Detailed explanation of the invention" in Akira Ou 1 re (2) Page 32, line 2! -5z/z", I to I'5
0z/, v2. Correct it with l.

(3) Same as above: 2rE 4th line 1 good thing” is corrected to “strength”.

(4) 4α Correct the entire Table 1 as shown.

Below margin -1 ・11; Pull...I l:5 Direct injection 2-&Regular body is corrected as follows.

[Margin 1 below

Claims (1)

[Scope of Claims] 1. A two-component, separately applied, instant-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 an aqueous solution of a hydrazine compound. 2. A two-component, separately applied, instant-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 an aqueous solution of a hydrazine compound and a crosslinking agent that crosslinks crosslinking groups other than acetoacetyl groups. 3. The two-component separate coating type instantaneous material 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, separately applied, instant-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 an aqueous solution of a hydrazine compound. 5. The two-component separately applied instant curing water-based adhesive according to claim 4, wherein the crosslinking group other than the acetoacetyl group in (e) is a crosslinking group that reacts with an isocyanate compound, and the crosslinking agent is an isocyanate compound. . 6 One set of adhesive selected from the following three sets of two-component separate application instant 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 an aqueous solution of a hydrazine compound. (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 an aqueous solution of a hydrazine compound 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 an aqueous solution of a hydrazine compound.