JPH0324511B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a fast-curing adhesive composition for two-component separate application adhesives. For more details, see A.
As the liquid, an aqueous solution of a polymer compound having imide groups in the molecule, or an aqueous dispersion obtained by mixing rubber latex and/or synthetic resin latex with this aqueous solution is used, and as liquid B, a specific compound substantially having aldehyde groups is used. A two-component non-mixable solution consisting of two AB components, using a water and/or lower aliphatic alcohol solution in which a dialdehyde compound or a hydrate thereof is dissolved, or a dialdehyde compound or a hydrate thereof is dissolved together with a water and/or lower aliphatic alcohol solution. The present invention relates to a type of adhesive composition. When adhering this composition, one surface to be bonded is coated with liquid A, the other side is coated with liquid B, and then the two surfaces are bonded together and pressure bonded. The object of the present invention is to provide a two-component separate application type adhesive composition that is capable of fast-curing adhesion with excellent initial adhesive strength that reaches considerable strength in minutes. Recently, in the wood industry, etc., attempts have been made to continuously mass-produce materials using conveyor systems, and there is a demand for adhesives that have a fast bonding speed. Cyanoacrylate-based instant adhesives may be used for this purpose, but
It is expensive and impractical. In addition, as a two-component separate application type fast-curing adhesive, urea resin adhesive A
Products in which component B is made by mixing a strong acid such as phosphoric acid with an aqueous solution of a polymer compound such as polyvinyl alcohol (PVA) have been on the market for quite some time. However, this strong acid has the drawback of accelerating the aging of the urea resin system and deteriorating the strength of the wood itself, so it is not widely used. The present inventor previously discovered that a mixed aqueous solution of a polymer compound having an imide group in its molecule and a dialdehyde compound such as glyoxal has a molecular weight of 70 to 90%, like glue.
proposed a gel composition that becomes a sol when heated to ℃ and becomes a gel when cooled to 40 to 50 ℃ (Japanese Patent Application Laid-Open No.
No. 54-30244). These heat-reversible gel compositions can be used in a similar way to glue and can also be used for adhesive purposes, but not only do they need to be heated to 70 to 90 degrees Celsius before use, but they also require mixing with rubber latex or synthetic resin emulsion. It was difficult to clean, and it had the disadvantage of poor water resistance if left as is. Therefore, the present inventor did not mix a polymer compound having an imide group in its molecule and a dialdehyde compound, but created a two-component system in which each component was an aqueous solution, and separately applied it to both surfaces to be bonded. It was discovered that when applied and bonded together at room temperature, it soon gels and can be used as a fast-curing adhesive (Japanese Patent Laid-Open No. 56-90867). By doing this, it was difficult to mix other ingredients such as rubber latex and synthetic resin emulsion with gel compositions, but by making it a two-component type, these can be mixed freely.
It is possible to improve the elasticity and water resistance of the cured film, and it is also possible to increase the concentration of dialdehyde compounds such as glyoxal, which increases the gel strength and initial adhesion strength compared to the above-mentioned gel compositions. It has the advantage of making the wood stronger, and since it does not contain strong acids, it does not deteriorate the wood.
In addition, from the viewpoint of energy saving, an adhesive composition that has good workability and hardens quickly even at room temperature can be obtained. However, depending on the application, the two-component quick-curing adhesive that uses the heat-reversible gel composition described above may not only have poor initial adhesive strength but also poor final adhesive strength and durability. In some cases, an aqueous solution of a dialdehyde compound, such as glyoxal, used in Solution B becomes deeply colored as its pH increases, and a gel composition with adhesive strength produced by contact mixing of the two solutions A and B also For example, by using an alkaline solubilizer in solution A, the pH of the system can be adjusted.
As the value increases, the color becomes darker, so it may be unsuitable for applications where dark coloring of the adhesive layer is not desirable. In addition, since Liquid B is water-based, it may be difficult to apply depending on the adherend due to insufficient wettability, and since it has a relatively low viscosity, it may not have sufficient adhesive strength on adherends with large suction. Furthermore, when considering how to apply liquid B to an adherend, there are various problems that require further improvement, such as slow drying during application. Furthermore, it would be desirable in terms of storage and transportation if a solid powdered aldehyde compound from which liquid B can be prepared immediately before use could be used. The purpose of the present invention is to solve these problems, and as a result of intensive research, the inventor has
As a component of liquid B, a compound selected from among compounds that substantially have an aldehyde group or a compound that exists as a hydrate thereof when dissolved in water has an adhesion property as well as a water-soluble dialdehyde compound. There are compounds that can take advantage of the rapid formation of strong gels, and at least one of these, and also such compounds, together with a water-soluble dialdehyde compound, can be used in B.
By using it as a liquid component and dissolving it in water and/or lower aliphatic alcohol,
The present invention was achieved based on the finding that a two-component fast-curing adhesive can be obtained that can improve each of the above-mentioned problems as desired. The requirements of the present invention thus obtained are as follows. That is, in the present invention, liquid A contains an imide group (

An aqueous solution of a synthetic polymer compound having the structure [formula], or 1 part by weight of this aqueous solution as a solid content, is mixed with rubber latex and/or a synthetic resin emulsion within a range of up to 10 parts by weight as a solid content. Using the aqueous dispersion obtained as liquid B, a compound substantially having an aldehyde group or a compound existing as a hydrate thereof when dissolved in water, i.e. (a) a water-soluble monoaldehyde compound, (b) paraformaldehyde; (c) water-soluble dialdehyde starch;
and (d) water and/or in which at least one compound selected from the group consisting of 2,3-dihydroxy-1,4-dioxane is dissolved, or such a compound and a water-soluble dialdehyde compound are dissolved together. Using a lower aliphatic alcohol solution,
This is a two-component, non-mixable, fast-curing adhesive composition for two-component separate application type adhesive, characterized by comprising the above-mentioned two components A and B. The present invention will be explained in detail below. A of the present invention
Used for liquids, tomid group (

Suitable synthetic polymer compounds having the structure [formula] include those having a maleimide group in the molecule, such as a multicomponent copolymer of α,β-unsaturated compounds and maleimide. There is. In a multicomponent copolymer having a maleimide group in the molecule, using an unsaturated compound capable of forming a carboxyl group such as maleic anhydride as a component of the copolymer makes the copolymer water-soluble, and It is also useful and preferred for improving adhesive performance.
These polymer compounds can be used in the present invention by dissolving them in water as they are, or by adding a basic substance to make them water-solubilized to form an aqueous solution. These multicomponent copolymers include vinyl acetate-
Maleic anhydride - maleimide, styrene - maleic anhydride - maleimide, isobutylene -
Examples include maleic anhydride-maleimide, ethylene-maleic anhydride-maleimide, vinyl methyl ether-maleic anhydride-maleimide, vinylpyrrolidone-maleic anhydride-maleimide, and partially imidized maleic anhydride-added polybutadiene. These may be used alone or in combination of two or more. It is also possible to react a copolymer such as styrene-maleic anhydride or isobutylene-maleic anhydride with ammonia to convert a part of the maleic anhydride in the molecule into maleimide, which can also be used in the present invention. Aqueous solutions of these synthetic polymer compounds are usually 5
(wt%, the same applies hereafter) to 50% aqueous solution. If necessary, it can be quickly and uniformly dissolved by heating to about 60 to 80°C. Basic substances used for solubilization as required include alkali metal hydroxides, ammonium hydroxide, alkali metal carbonates, ammonium carbonate, ammonium phosphate, alkaline weak acid salts such as borax, and alkaline earth metals. These include metal hydroxides, or water-soluble basic organic compounds such as ethanolamines and morpholine. Solution A of the present invention consists of adding rubber latex and/or
Alternatively, a synthetic resin emulsion can be mixed and used. Even when such a mixed solution A is used, a gel with adhesive strength, which is an essential feature of the present invention, is rapidly formed upon contact and mixing with components in solution B. This mixture is useful to improve the elasticity, water resistance, and other adhesion properties of the coating as needed, and allows the mixture to have film-forming and adhesive properties without gelling or significant separation during mixing. is preferable. Rubber latexes include styrene-butadiene synthetic rubber, acrylonitrile-
Water-based latexes such as butadiene-based synthetic rubber, chloroprene-based synthetic rubber, or natural rubber, and carboxyl-modified rubber latexes thereof are suitable. As a synthetic resin emulsion, vinyl acetate,
Such as homopolymer emulsion or ethylene-vinyl acetate copolymer mainly composed of vinyl monomers such as acrylic esters and methacrylic esters,
Polymer emulsions of these monomers are suitable. These rubber latexes and synthetic resin emulsions may be used alone or in a mixture of two or more types, and these usually have a solid content of 40 to 40.
Use 60%. This rubber latex or synthetic resin emulsion has a solid content of 10 parts by weight of an aqueous solution of a polymer compound having an imide group in its molecule.
It is preferable to mix within a range of parts by weight as the upper limit. If the mixing amount is too large, the gel strength of the gel that is rapidly formed by contact mixing of the polymer compound having an imide group in the molecule in the A solution and the aldehyde compound in the B solution will be insufficient. It does not exhibit the desired rapid curing properties, cannot exhibit initial adhesive strength, and has insufficient final adhesive strength. Further, a filler can be added to the A liquid as necessary for the purpose of increasing the volume and strengthening the liquid. Examples of the filler include calcium carbonate, kaolin, baryta, wood flour, and plant shell powder, and an appropriate amount is added depending on the purpose. In addition to the above-mentioned liquid A in the present invention,
If necessary, plasticizers, colorants, and other compounding agents that are commonly used may be added without any problem, and furthermore, if the usable time can be taken into consideration when bonding, a crosslinking agent may be added. On the other hand, when dissolved in water, the B solution of the present invention has
That is, when dissolved in the water contained in liquid B, or when contacted with liquid A and dissolved in the water contained in liquid A, it exists substantially as a compound having an aldehyde group or a hydrate thereof. Among the compounds suitable for the purpose of the present invention, water-soluble monoaldehyde compounds, paraformaldehyde,
Dissolved in water-soluble dialdehyde starch and at least one compound selected from the group consisting of 2,3-dihydroxy-1,4-dioxane, or disclosed in JP-A-56-90867. A water and/or lower aliphatic alcohol solution containing a water-soluble dialdehyde compound dissolved therein is used. Examples of the monoaldehyde compound used as a component of liquid B of the present invention include formaldehyde, acetaldehyde, etc., which are soluble in water and/or lower alcohols. In formaldehyde aqueous solutions, formaldehyde is said to exist as methylene glycol, which is a hydrated monomer, and polyoxymethylene glycol, which is a hydrated polymer.The industrial product is called formalin, and it also contains methanol due to the manufacturing process. It is common to do so. The concentration of this monoaldehyde compound in liquid B used in the present invention is usually 1 to 37% by weight. Paraformaldehyde used as a component of liquid B of the present invention is said to have the molecular structure of polymethylene glycol as a hydrate of a linear polymer of formaldehyde, and is in powder form and is mixed with water and/or lower Soluble in aliphatic alcohols.
The B solution of the present invention is usually used as a 1 to 30% by weight solution. The dialdehyde starch used as a component of liquid B of the present invention is a white powder, and is a high-molecular polyaldehyde in which the constituent units of starch are replaced with dialdehyde. Its chemical structure is as follows It is mainly composed of chain polymers having structural units such as (n...indicates the degree of polymerization). This dialdehyde starch is dissolved in water using a solubilizing agent such as acidic sodium sulfite or borax, and is usually used as a 5 to 40% by weight aqueous solution or a methanol/water mixed solution for the B solution of the present invention. It will be done. 2,3-dihydroxy-1,4-dioxane used as a component of liquid B of the present invention is a white powder that is soluble in water and/or lower aliphatic alcohol. This compound quickly dissolves in water, and when made into an aqueous solution, reversibly reverts to glyoxal, which is a dialdehyde compound, and ethylene glycol, so it can essentially be treated as powdered glyoxal. The B solution of the present invention is usually used in the form of a 5-30% by weight solution. The B liquid of the present invention may be appropriately selected from the above depending on the desired performance, or may be a mixture of two or more of these, or may further include:
In the combination system with the dialdehyde compound disclosed in JP-A No. 56-90867 (hereinafter, these are abbreviated as aldehyde compounds), this book is made into a solution dissolved in water and/or lower aliphatic alcohol. Make it the B liquid of the invention. As the lower aliphatic alcohol used in the B liquid of the present invention, one having good volatility, such as one having 1 to 5 carbon atoms in the molecule, is suitable. For example, methyl alcohol; ethyl alcohol; n- or iso-propyl alcohol; n-, sec-, iso-, tert-
Butyl alcohol; n-, sec-, iso-, tert-
Examples include amyl alcohol. B of the present invention
In the liquid form, these lower aliphatic alcohols may be used alone, as a mixture of two or more, or as a mixed solvent system of these and water. This B solution can also be used as an aqueous solution or an aqueous dispersion in which a cross-linking agent that forms a cross-bond with a functional group such as a carboxyl group of a polymer compound contained in A solution is added and mixed. I can do it. Thus, when the two components are applied separately and bonded together, it is possible to generate this crosslinking bond in parallel with the gelation caused by the aldehyde compound, and it is possible to create a crosslinking bond that can be mixed without reacting with the aldehyde compound. agent is appropriate. Effective examples of such crosslinking agents include hydrophilic polyepoxy compounds such as polyepoxides of polyols. If a crosslinking agent is mixed with the aldehyde compound, it will not only have quick curing properties due to gel formation, but also improve water resistance and heat resistance after curing due to crosslinking. Further, the B liquid in the present invention may contain a colorant, a surfactant, a viscosity modifier, etc., as appropriate, as long as they do not impair the effects of the aldehyde compound. The separately applied adhesive composition consisting of two parts A and B obtained by the present invention is used for adhesion by applying part A to one surface to be adhered, such as wood, and then applying part B to one side of the adherend, such as wood. When applied to the other surface to be bonded, and the two surfaces are closely bonded and pressed together, considerable initial bond strength can be obtained within 30 seconds to several minutes at room temperature. The pressure can be released over time, and if left as is to cure, the final adhesive strength will be sufficiently high. In addition, machining such as cutting can be performed shortly after depressurization. Generally, adhesives in aqueous medium do not have sufficient final adhesive strength at room temperature unless they are compressed and pressed for quite a long time, but the adhesive composition of the present invention has fast curing properties. Therefore, even if the clamping/pressing is performed for a short time, it is possible to achieve a bond with sufficient final adhesive strength after being left and cured. Further, in the adhesive composition of the present invention, the B liquid may be applied in advance and left to dry, or the A liquid may be applied to the other surface later and the adhesive composition is closely bonded to achieve the desired adhesion. It can also be used with workability similar to that of a one-component adhesive. Therefore, when the adhesive composition of the present invention is used in woodworking, etc., it is possible to create a continuous conveyor system. Furthermore, in the fast-curing adhesive composition of the present invention consisting of two components A and B, the B component is as shown below.
A compound that substantially has an aldehyde group or a hydrate thereof when dissolved in water, namely (a) a water-soluble monoaldehyde compound (hereinafter referred to as monoaldehyde), (b) paraformaldehyde, (c) at least one compound selected from the group consisting of water-soluble dialdehyde starch (hereinafter referred to as dialdehyde starch) and 2,3-dihydroxy-1,4-dioxane (hereinafter referred to as dihydroxydioxane); The present invention uses a solution of water and/or lower aliphatic alcohol (hereinafter referred to as alcohol) in which such a compound and a water-soluble dialdehyde compound (hereinafter referred to as dialdehyde) are dissolved or dissolved together. Compared to the case (disclosed in JP-A-56-90867) in which an aqueous solution containing dialdehyde was used as liquid B (hereinafter referred to as conventional liquid B), which was previously invented by the inventor of
A fast curing adhesive composition is obtained having various improved characteristics as described below. That is, when monoaldehyde or paraformaldehyde is used as the B liquid component, the gel composition produced in the adhesive layer is nearly colorless, and the degree of coloring of the adhesive layer maintains the hue of the formulation itself, and is different from dialdehyde. The mixed B liquid also has the characteristic that it can be made relatively light in color, although it depends on the mixing ratio. However, when an aqueous solution containing mainly dialdehyde, that is, the conventional B solution, is used, the adhesive layer becomes colored in a hue close to yellowish brown, making it unsuitable for use depending on the purpose of adhesion. Adhesives containing monoaldehyde or paraformaldehyde as the B liquid component also have the characteristic of providing adhesive strength with greater durability than adhesives using conventional B liquids. In addition, when dialdehyde starch is used as the B liquid component, since it is a high-molecular polyaldehyde, the B liquid can have a relatively high viscosity. It has an excellent feature of exhibiting stronger adhesive strength than conventional adhesives using liquid B, which can only be prepared with low viscosity. The reason for this is that when a low-viscosity liquid B is applied to an adherend with large suction, the suction is large and the liquid B component works effectively to generate a gel composition with adhesive strength on the surface of the adherend. Unfortunately,
It is thought that by using liquid B with a high viscosity, suction can be reduced and it will work effectively. In addition, as liquid B of the present invention, an alcoholic solution of paraformaldehyde and dihydroxydioxane, or a water-alcohol mixed solvent solution of monoaldehyde, paraformaldehyde, dialdehyde starch, and dihydroxydioxane, and furthermore, these used in the present invention. When the above-mentioned alcoholic solution containing an aldehyde compound and a dialdehyde is used, the adhesive composition of the present invention dries quickly after being applied to the adherend. When you intend to apply it on the garment,
It has the characteristic of being able to extremely improve workability. When the surface to which Liquid B has been applied and dried is closely bonded to the surface to which Liquid A has been applied, which has been applied to another surface to be bonded, the moisture in Liquid A will work effectively. , a gel composition with adhesive strength can be produced from the B liquid component and the A liquid component, and desired adhesion can be achieved. As described above, the B liquid of the present invention can also be used as an alcoholic solution, and the solvent can be appropriately selected depending on the desired workability during adhesion, so the conventional B liquid can be used as an aqueous solution. In contrast, the adhesive composition of the present invention consisting of two liquids A and B exhibits better effects due to the properties of liquid B. Furthermore, paraformaldehyde, dialdehyde starch, and dihydroxydioxane are used as aldehyde compounds for the components of liquid B of the present invention.
Since it is normally in the form of a solid powder, preparing a solution immediately before use makes it easier to store and transport, and it is easier to handle than dialdehydes such as glyoxal, which are usually only supplied as an aqueous solution. It is convenient and has the advantage of reducing and rationalizing costs. As described above, the two-component, non-mixable, fast-curing adhesive composition of the present invention, consisting of two components A and B, for two-component separate application type adhesives is significantly superior to conventional adhesive compositions. It is a fast-curing adhesive that is effective. The adhesive composition of the present invention can be applied to various wood materials such as wood, chipboard, hardboard, inorganic materials such as slate boards, silicon boards, and plastics such as melamine resin decorative boards, Bakelite boards, and expanded polystyrene boards. Can be used to bond paper materials such as base materials, corrugated paper, paperboard, and kraft paper. Therefore, flat panels, decorative plywood, prefabricated panels, laminated wood, etc. can be bonded together, edges attached, tenons, dowels, tomes, hooks, square wood, etc.
For other wood industries such as assembly and furniture assembly,
It can also be used for paper processing such as cardboard, interleaf paper, paper tubes, paper containers, and bag making, speeding up and saving labor, and can be bonded even at room temperature, contributing to shortening bonding work time and saving energy. The adhesive composition of the present invention will be specifically explained below using Examples. However, the present invention is not limited to these Examples. Example 1 (a to d) and Comparative Examples 1 to 2 An isobutylene-maleic anhydride copolymer (trade name Isoban 04 manufactured by Clarei Soprene Chemical Co., Ltd.) was heated to 180°C in an ammonia atmosphere,
An isobutylene-maleimide-maleic anhydride copolymer (molar ratio 2:1:1) was obtained. A container containing 48 parts by weight of this isobutylene-maleimide-maleic anhydride copolymer (hereinafter abbreviated as acid imide copolymer), 7.6 parts by weight of industrial 25% ammonia water as a solubilizer, and 104 parts by weight of water. The mixture was heated to a liquid temperature of 85°C and stirred for 2 hours to uniformly dissolve the mixture, thereby preparing an acid imide copolymer aqueous solution (solid content 31%). Add polyvinyl acetate emulsion adhesive (trade name: Bond) to 130 parts by weight of this aqueous solution.
Add 200 parts by weight of CH18, solid content 41% (manufactured by Konin Co., Ltd.) and 60 parts by weight of heavy calcium carbonate (trade name BF-100, manufactured by Bihoku Funka Kogyo Co., Ltd.) as a filler, and stir and mix thoroughly. A viscous liquid with a solid content of 46.7% was prepared and was designated as liquid A. The mixing ratio of the solid content of the acid imide copolymer aqueous solution and the solid content of the polyvinyl acetate emulsion adhesive in this A solution is about 1:2. On the other hand, a 37% by weight aqueous solution of formaldehyde alone or 15% by weight of glyoxal in this aqueous solution.
Mixed aqueous solutions were prepared by mixing the aqueous solutions in the proportions shown in Table 1, and these were used as Solution B of Example 1 (a to d). Moreover, Comparative Example 1 is shown in which the B solution is a 15% by weight aqueous solution of glyoxal alone. Using these two liquids A and B, the adhesive strength was measured in accordance with JIS K-6852 "Testing method for compressive shear adhesive strength of adhesives". The test used birch wood as the adherend.
Apply liquid A to the adhesive surface of one of two test pieces of size 25 x 30 x 10 (each mm) (application amount approximately 200 g/m ² ),
Liquid B was applied to the adhesive surface of the other test piece (application amount: about 40 g/m ² ), both sides were closely bonded together, and immediately pressed together (pressing pressure: about 5 kg/cm ² ). Then, the pressure was released after each of the pressing times shown in Table 1, and the compressive shear adhesive strength was measured after curing for 5 minutes and after curing for 72 hours. Note that the bonding operation, curing, and measurement in this test were all carried out in an atmosphere at 20°C. Separately, for comparison, a case was shown as Comparative Example 2 in which an adhesive test piece was prepared using only the above-mentioned liquid A without using liquid B, and the compressive shear adhesive strength was measured. The results of these measurements are shown in Table 1.

[Table] The results shown in Table 1 are based on the results of Example 1 (a to
d) had better initial and final adhesive strength than the case without using B liquid (Comparative Example 2), and compared to Comparative Example 1 in which glyoxal alone aqueous solution was used as B liquid,
The initial adhesive strength (after 5 minutes of curing time) was about the same,
Furthermore, the final adhesive strength (after 72 hours of curing time) was also shown to be similar. Further, in this case, the adhesive layer of Comparative Example 1 had a yellowish brown color, but the degree of coloring of the adhesive layer of Examples 1 (a to d) of the present invention was relatively light milky white to pale yellow. Examples 2 to 5 and Comparative Example 3 To 80 parts by weight of an acid imide copolymer aqueous solution (solid content 31%) obtained in the same manner as in Example 1, 20 parts by weight of heavy calcium carbonate (BF-100) as a filler was added. A viscous liquid with a solid content of 44.8% was prepared by stirring and mixing thoroughly, and this was designated as liquid A. On the other hand, a 37% by weight aqueous solution of formaldehyde (Example 2), 20% by weight of powdered paraformaldehyde (95% active ingredient), methyl alcohol:water (1:
1) Solution dissolved in 80% by weight of mixed solvent (Example 3), 40% by weight of dialdehyde starch (trade name: Cultus, manufactured by Nippon Carlito Co., Ltd.), 8% by weight of borax as a solubilizer, 52% by weight of water. An aqueous solution (Example 4) and a 30% by weight methanol solution of 2,3-dihydroxy-1,4-dioxane (Example 5) were prepared by heating and dissolving them at a temperature of 80°C in a container. These were designated as B solutions of Examples 2 to 5, respectively. Using these two liquids A and B, and using birch wood as the adherend in the same manner as in Example 1, liquid A was mixed with approximately 200%
g/m ² , approximately 40 g/m ² of liquid B was applied, and both sides were closely bonded to prepare an adhesive test piece. The compressive shear adhesive strength was measured. Table 2 shows the results. Comparative Example 3 shows the measurement results of an adhesive test piece prepared by applying only liquid A at a rate of about 200 g/m ² without using liquid B at all.

[Table] In Table 2, the adhesive compositions of Examples 2 to 5 of the present invention consisting of two liquids A and B had a lower Excellent adhesive strength was obtained by pressing for a short time, and the desired rapid curing properties were exhibited. Example 6 and Comparative Example 4 Solution A was prepared in the same manner as in Example 1, while Solution B contained 20 parts by weight of powdered paraformaldehyde (95% active ingredient), methyl alcohol:water (1:
1) A 20% by weight alcoholic aqueous solution (Example 6) dissolved in 80 parts by weight of a mixed solvent and a 15% by weight glyoxal aqueous solution (Comparative Example 4) were prepared as a comparison. Using the adhesive composition consisting of these two components A and B, and using birch wood as the adherend, each adhesive test piece was prepared in the same manner as the adhesive strength test conducted in Example 1. (approx. 200g/m ² of liquid A, approx. 200g/m 2 of liquid B)
40 g/m ² ), and the compressive shear adhesive strength was measured. Using the same adherend, adhesive test pieces obtained under each bonding condition shown in Table 3 were left in a dryer at 60°C for 30 days, then left at room temperature for 24 hours, cooled to room temperature, and then compressed and sheared. The adhesive strength was measured and used as a durability test. The results of these measurements are shown in Table 3.

[Table] Table 3 shows that Example 6, in which the paraformaldehyde solution of the present invention was used as liquid B, had adhesive strength that was more durable than that in Comparative Example 4, in which a 15% by weight aqueous solution of glyoxal was used as liquid B. This shows that it is possible to obtain Further, in this case, the adhesive layer of Comparative Example 4 had a yellowish brown color, but the adhesive layer of Example 6 of the present invention had a milky white color based on the calcium carbonate filler. Example 7 (e to h) and Comparative Example 5 Styrene-butadiene copolymer rubber latex (trade name KS-
207, solid content 48%, manufactured by Sumitomo Nogatatsu Co., Ltd.)
168 parts by weight and 69 parts by weight of heavy calcium carbonate (BF-100) as a filler were added and thoroughly stirred and mixed to prepare a viscous liquid with a solid content of 50.2%, which was designated as Solution A. The mixing ratio of the solid content of the acid imide copolymer aqueous solution and the solid content of the styrene-butadiene copolymer rubber latex in this liquid A is about 1:1.6. On the other hand, dialdehyde starch (trade name Caldas, manufactured by Nippon Carlito Co., Ltd.) was prepared into an aqueous solution with each concentration (wt%) shown in Table 4, and this was used as Solution B of Example 7 (e to h). . Using the adhesive composition consisting of these two components A and B, and using birch wood as the adherend, each adhesive test piece was prepared in the same manner as the adhesive strength test conducted in Example 1. The compressive shear adhesive strength was measured. Separately, for comparison, an adhesive test piece was prepared using only the above-mentioned liquid A without using liquid B, and the compressive shear adhesive strength was measured as comparative example 5. The results of these measurements are shown in Table 4.

【table】

[Table] This Table 4 shows that the adhesive compositions consisting of two parts A and B of Example 7 (e to h) of the present invention had a dialdehyde starch concentration of 5% by weight in an aqueous solution [viscosity
10cps (30℃)] to 40% by weight aqueous solution [viscosity 1000cps
(30°C)], the results show that higher adhesive strength values were obtained compared to Comparative Example 5, which did not use liquid B. Further, the degree of coloring of Examples 7 (e to h) of the present invention was milky white (e) to yellowish brown (h). Example 8 (i to l) and Comparative Example 6 A solution prepared in the same manner as in Example 7 was used, and as a B solution, 40 parts by weight of dialdehyde starch (trade name Caldas) and borax as a solubilizer were used. A 40% by weight aqueous solution of dialdehyde starch was prepared by heating and dissolving 8 parts by weight of water and 52 parts by weight of water in a container, and this aqueous solution and a 40% by weight aqueous solution of glyoxal. The mixed aqueous solution mixed in the ratio shown in the table was used as the B solution of Example 8 (i to l), and the following test was conducted. For comparison, Comparative Example 6 is shown in which a 40% by weight aqueous solution of glyoxal alone was used as liquid B. Using this adhesive composition consisting of two parts A and B,
Size 20 x 30 x 10 (each mm) on one side as an adherend
using birch wood, and the other side has a size of 20 x 30 x 10 (each mm).
Using particle board, apply approx. A liquid to the birch wood.
200 g/m ² was applied, and approximately 40 g/m ² of liquid B was applied to the end surface of the particle board, and an adhesive test piece was prepared in the same manner as the adhesive strength test method conducted in Example 1. Then, the compressive shear adhesive strength was measured. The results of these measurements are shown in Table 5.

【table】

[Table] Table 5 shows the 40% by weight aqueous solution of dialdehyde starch of Example 8 (i to l) of the present invention alone or
Furthermore, when using liquid B [viscosity 1000 to 50 cps (30°C)] containing a 40% by weight aqueous solution of glyoxal, a 40% by weight aqueous solution of glyoxal alone in Comparative Example 6 [viscosity 10 cps (30°C)] was used. This shows that higher adhesive strength can be obtained than when using This shows that the B solution of the present invention used in Example 8 (i to l) is
This is thought to be because it has a viscosity of 1000 cps to 50 cps (30°C), and there is little suction against the end surface of particle board. Example 9 and Comparative Example 7 Solution A was prepared in the same manner as in Example 7, while Solution B was prepared using a 30% by weight methanol solution of 2,3-dihydroxy-1,4-dioxane (Example 9) and as a comparison. A 30% by weight aqueous solution of glyoxal (Comparative Example 7) was prepared. Using the same method as the adhesive strength test conducted in Example 1, birch wood with a size of 25 x 30 x 10 (each mm) was used as the adherend on one side,
On the other side, a melamine resin decorative board (product name Decora, manufactured by Sumitomo Bakelite Co., Ltd.) with a size of 25 x 30 x 1.2 (each mm) was used, and approximately 200 g/m ² of liquid A was applied to the birch wood. Approximately 40g of liquid B on the melamine resin decorative board
After drying the B ^solution for the respective times shown in Table 6, they were immediately bonded together and pressed together to prepare an adhesive test piece, and then the compressive shear adhesive strength was measured. These results are shown in Table 6.

【table】

[Table] Since the B liquid of the present invention used in Example 9 uses methanol as the solvent, it rides better on the melamine resin decorative board and is easier to apply than the case where the aqueous solvent B liquid of Comparative Example 7 is used. , and the drying was extremely fast, reaching a dry state 1 minute after application, which was convenient for forming a dry application surface of liquid B. On the other hand, the one to which the water-based liquid B of Comparative Example 7 was applied was still undried and wet 5 minutes after application, became semi-dry after 30 minutes, and gradually became dry in about an hour. Ta. Thus, in Example 9 based on the present invention, compared to Comparative Example 7 using an aqueous B liquid, the surface to which the B liquid was applied had good wettability and it was easy to uniformly apply the B liquid. Moreover, it dries extremely quickly, and the adhesive strength developed in adhesion after being left for several days shows that a value comparable to that of Comparative Example 7 can be obtained by pressing for a short time.

Claims (1)

[Scope of Claims] 1 As liquid A, an aqueous solution of a synthetic polymer compound having an imide group (structure [formula]) in the molecule, or 1 part by weight of the solid content of this aqueous solution, rubber latex and/or synthetic Using an aqueous dispersion obtained by mixing a resin emulsion with an upper limit of 10 parts by weight as a solid content, as liquid B, a compound having substantially aldehyde groups or its hydration when dissolved in water. (a) water-soluble monoaldehyde compounds, (b) paraformaldehyde, (c) water-soluble dialdehyde starch,
and (d) at least one compound selected from the group consisting of 2,3-dihydroxy-1,4-dioxane is dissolved, or such a compound and a water-soluble dialdehyde compound are both dissolved in water and/or or using a lower aliphatic alcohol solution,
A two-component non-mixable fast-curing adhesive composition for two-component separate application type adhesive, characterized by comprising the above-mentioned two components A and B.