KR870000700B1 - Adhesives including mciro capsule - Google Patents

Abstract

Microcapsule-contg. adhesive(I) of chemical reaction or solvent- activated hardening type is prepd. Thus, very fine liq. particles of at least one component of the (I) is dispersed in aq. soln. of aminoplast components and acid catalyst is added so that aminoplast prepolymers undergoes polycondensation. A modifying agent(II) is added to aq. dispersion during polymerization so that microcapsules are formed which enclose at least one component of (I) within the membrance consisting substantially of the (II)-modified aminoplast. The microcapsules are collected, dried, and dispersed in other components which form the (I) with microcapsules.

Description

Adhesives Containing Microcapsules

The present invention relates to adhesives containing microcapsules, and more particularly, to adhesives containing microcapsules, either in chemical reaction form or in activated form by a solvent. In more detail, the present invention relates to an adhesive containing a microcapsule and a medium, and a method for preparing the adhesive, wherein the microcapsule is composed of at least one base material and the microcap constituting the adhesive. It consists mainly of aminoplas pretreated with modifiers, which is a thin film of the schoon, and the media consists of other components that make up the adhesive, the microcapsule is dispersed in the media, and the adhesive is chemically reactive. Or a solvent-activated type, and the manufacturing method comprises a microcapsule composed mainly of a thin film material mainly containing an aminoplast treated with a control agent and a base material of at least one component constituting the adhesive, and other components constituting the adhesive. To a process of dispersing.

Adhesives are classified into four groups according to their curing methods.

1) Solvent-evaporative adhesive: After use of the adhesive, all the previously contained media such as solvent or water are lost from the used adhesive by evaporation from the adhered end or absorbed by the adhered material, whereby the thin film of adhesive formed It shows the maximum strength.

2) Chemically Responsive Adhesive: The cured adhesive thin film is formed by chemical reaction between resin and curing agent or chemical reaction between monomer (or oligomer) and catalyst by mixing two different components of adhesive. One contains a resin or a monomer, and the other contains a curing agent or a catalyst.

3) Solvent-activated adhesive: Apply adhesive to the surface of the object to be bonded to form a dried adhesive film on the surface, spray the solvent on it to reactivate the applied thin film surface, and then reactivate the other object to be bonded. The adhesion is completed by placing on the phase.

4) Hot Melt Adhesive: Apply the melted adhesive to the surface of the object to be bonded and cool the object treated as above to complete the adhesion.

Chemically reactive adhesives consist of two separate components that are to be mixed immediately before use, so this type of adhesive must be discarded for use inconvenient, limited in operating time after mixing the two components and the remaining mixture of the two components. Has the drawbacks, such as the need to do.

On the other hand, solvent-activated adhesives have problems such as environmental pollution, industrial hygiene and stability. This is because a large amount of organic solvent needs to be used.

In order to solve the above drawbacks of the conventional adhesives, attempts have been made to capsulate the components of the adhesive and microcapsules having a gelatin or polyamide thin film have been proposed. However, the thin film walls of the proposed microcapsule are generally semipermeable or have microscopic pores, so that the adhesive component contained therein is easily extracted from the microcapsule, and the thin film for organic solvents such as alcohols, ketones and esters The poor resistance of the walls has led to the same drawbacks, such as the extraction of the contents of the microcapsule by such solvents.

In particular, the following two conditions are required for the use of microcapsules in adhesives where solvent-resistance is particularly required.

(1) Thin film walls of microcapsule are to have particularly good solvent resistance.

(2) The microcapsule itself is to be excellent in pressure-sensitivity such that it is easily ruptured by a small increment of the applied pressure. Therefore, it is very difficult to actually use such an adhesive including microcapsules.

In other words, in order to enhance the solvent-resistance of the microcapsule, the method of depositing the microcapsule on the base material to activate the surface of the microcapsule, and the method of contacting the surface with an alpha-cyanoacrylate intermediate, and the microcap A method has been attempted to coat a microcapsule with a material resistant to medium so as to disperse the shoe in an adhesive to form a two-layered microcapsule. According to this method, however, the pressure required to rupture the microcapsule in use is so great that the microcapsule treated as above cannot be used as a component of the adhesive.

It is an object of the present invention to provide an adhesive containing a microcapsule excellent in solvent-resistance and pressure-resistance, and this adhesive solves the drawbacks of conventional adhesives, chemically reactive and solvent-activated, and uses an excess adhesive component. Convenient and easy to use at the time of use without need.

According to a first aspect of the present invention, an adhesive containing a microcapsule and a medium is provided. The microcapsule is a thin film material of a microcapsule and a base material, which is at least one component constituting the adhesive, and is pretreated with an amino agent. It is mainly composed of a flask, and the medium is composed of other components constituting the adhesive, the microcapsule is dispersed in the medium, and the adhesive is chemically reactive or solvent activated.

As a second aspect of the present invention, there is provided a method for preparing a chemically reactive or solvent-activated adhesive containing microcapsules, which method comprises forming an aminoplast with fine liquid particles that are at least one component of the adhesive. Disperses in the aqueous component of the component and adds an acid catalyst to the aqueous component, thereby polycondensing the prepolymers of the component forming the aminoplast, and then adjusting the additive in the aqueous component in the copper or finished groove where the polycondensation is completed. Forming a microcapsule to capsulate at least one of the components in the thin film consisting mainly of the aminoplastable controlled by the modulator, collecting and drying the microcapsules thus formed, and forming an adhesive. Dispersing the microcapsule in other ingredients It is configured.

The present invention is characterized in that it is a chemically reactive or solvent-activated adhesive containing microcapsule, wherein the microcapsule is (1) at least one adhesive component and the base material to be capsulated in the microcapsule (2). A thin film of microcapsule, consisting primarily of aminoplas pretreated with a regulator, contained in a system consisting mainly of other components of the adhesive.

In other words, the adhesives containing microcapsules, which are chemically reactive or solvent-activated, according to the invention, when they are chemically reactive, ie the components of the adhesive consist mainly of resins and curing agents, for example, or as monomers, oligomers and catalysts In this case, as the component, a curing agent or a catalyst (preferably a small amount is preferable) is dispersed in a resin or a monomer and an oligomer to take the form of an adhesive containing a capsulated microcapsule.

In addition, when the component is a multi-component system such as consisting mainly of monomers, catalysts and curing agents, the microcapsules containing catalysts or both catalysts and curing agents prevent the reaction between the catalyst and monomers and between the curing agent and monomers. In order to disperse in the monomer.

In this regard, two or more components which do not interact may be capsulated separately, but such two or more components may be capsulated simultaneously, and the catalyst or curing agent may be capsulated in a form dissolved in a solvent. Can be.

On the other hand, the adhesive containing the microcapsule of the present invention may take another form, and in the case of the solvent activated form, the adhesive containing the resin to be applied on the surface of the substance to be bonded (hereinafter referred to as the "resin solution") It takes the form of an adhesive containing microcapsule, capulized with a solvent necessary for dissolving and activating the resin to form the adhesive thin film to be dispersed. Therefore, according to the present invention, the problem with the conventional solvent activation type adhesive caused by the use of a large amount of solvent, because it is necessary to capsulate only the minimum amount of solvent necessary for activating the resin, Can be solved.

An important point when capturing at least a kind of adhesive component is that both the solvent-resistant and pressure-sensitive of the thin film wall forming the microcapsule must be excellent.

In order to obtain a material for forming a thin film wall having the above characteristics, the inventors have found that aminoplasts pretreated with a modifier are suitable as the material. As used herein, the term “aminoplast” refers to melamine-formaldehyde prepolymer, urea-formaldehyde prepolymer-meramine-thiourea-formaldehyde prepolymer and melamine-thiourea-formaldehyde prepolymer or melamine-formaldehyde prepolymer and thiourea- A resin obtained by polycondensing at least one prepolymer selected from the group consisting of a mixed prepolymer containing formaldehyde prepolymer in the presence of a water-soluble cationic urea resin and an anionic surfactant.

The thin film material of the microcapsule according to the present invention includes an aminoplast prepared by a polycondensation reaction in the presence of a regulator.

The microcapsules formed from the treated aminoplastes are superior in solvent-resistance and free-flexibility compared to the microcapsules formed from the untreated aminoplasties, while the microcapsules formed from the treated aminoplastes have excellent pressure-sensitivity. Indicates.

Modulators used for this purpose include phenolic compounds such as phenol, resorcinol, catechol, hydroquinone, cresol, xylenol and salginine, and polyalkylene polyamine compounds such as hexamethylenetetramine and triethylenetriamine. Can be enumerated.

In order to form the microcapsule of the present invention, fine liquid particles of the adhesive component to be capsulated are dispersed in an aqueous solution in which an aminoplast prepolymer, a water-soluble cationic urea resin and an anionic surfactant are dissolved, and thus prepared. Acid catalysts such as low molecular weight carboxylic acids such as formic acid, acetic acid and citric acid; Inorganic acids or aqueous solutions such as hydrochloric acid, nitric acid and phosphoric acid, wherein the salts are acidic; Or an easily hydrolyzable salt such as aluminum sulfate, titanium oxychloride, magnesium chloride, ammonium chloride, ammonium nitrate, ammonium sulfate, and ammonium acetate, and the like, and then the water-soluble cationic urea resin and anionic surfactant A high molecular weight hydrophobic thin film wall that completely encapsulates each fine liquid particle of the adhesive component by polycondensing the prepolymer and the water-soluble cationic urea while inducing complex-coacervation by dispersing in the aqueous solution of the flask. Micro-capsulization is achieved by forming and dispersing it in the system.

When the above-mentioned regulator is added to the system during the polycondensation process, a capwool-type thin film wall including the aminoplast treated with the regulator as described above is formed. The amount of modifier is preferably 0.1 to 30% by weight, preferably 0.5 to 20% by weight relative to the prepolymer and the modifier is added as its aqueous solution at a concentration of 0.02 to 5% by weight. Related to this, the water-soluble cationic urea resins used for the production of complex salt-coreservation and for the preparation of the aminoplasts described above are materials obtained by introducing a cationic modifying group into the urea-formaldehyde resin, ie For example polycondensation products of urea-formaldehyde prepolymers with polyalkylenepolyamines, guanidans, diaminoethanols, dicyandiamides, diethylaminoethanol and guanylureas.

Examples of the anionic surfactants include substances having lipophilic groups and anionic-hydrophilic groups in the molecule, such as salts of fatty acids, sulfate esters of higher alcohols, and alkylarylsulfonate salts, for example sodium is also decylbenzenesulfonate. Is used.

In the present invention, in the polycondensation forming the microcapsule, two kinds of materials having different charges coexist with the prepolymer. One of the two materials is a water-soluble cationic urea resin, and the other is an anionic interface. Active agent. This important aspect results in a stabilized aqueous dispersion containing microcapsules of uniform quality.

Since the microcapsule of the present invention can be easily separated from the dispersion used in the preparation thereof and dried, the microcapshoeul can be processed in a free-flowing powder state after preparation, and thus the microcapsule has excellent solvent resistance and adhesives. It can be used advantageously for adhesive formation by disperse | distributing uniformly to the other components of.

The following describes in detail the adhesive containing the microcapsule according to the present invention when the adhesive is in (1) chemical reaction form and (2) in solvent activated form.

(1) Adhesives in chemical reaction form: In order to prepare an adhesive in chemical reaction form, that is, an adhesive containing a resin, an adhesive monomer or oligomer, a reaction inhibitor and a curing agent, any one of these components may be used in microcapsules. Is capululized in, and the microcapsule is dispersed in a mixture of other ingredients.

As a component to be capululated in the microcapsule, a small amount of components, such as a reaction inhibitor or a curing agent, is generally adopted. There are two or more kinds of components to capsulate in the microcapsule, and two or more components may be capsulated together or individual components may be capsulated separately.

As the resin for adhesion, a copolymer of poly (acrylic acid), poly (methacrylic acid), epoxy resin, polyester, polyamide, polyurethane and lower alkyl acrylate or lower alkyl methacrylate, dicarboxylic acid, diol and lower Copolymers of alkyl acrylates or lower alkyl methacrylates, epoxidized poly (lower alkyl acrylates) epoxidized poly (lower alkyl methacrylates), low molecular silicone resins, natural rubber, neoprene rubber, poly (vinylacetate) and polystyrene Can be enumerated.

A microcapsule containing an initiator or a curing agent required for the reaction is dispersed in at least one resin selected from the above resins and a monomer or oligomer for an adhesive, or dispersed in a solution prepared by dissolving them in an organic solvent.

Examples of the reaction initiator include dibutyl-tin dilaurate, tin caprylate, or a solution obtained by dissolving organic oxides such as benzoyl peroxide and dibutyl peroxide in an organic solvent. Examples of the curing agent include N, N-dimethylaniline, N, N -Dimethyl toluidine etc. are mentioned.

When using an adhesive containing a chemically capped microcapsule, it is applied to either surface of the object to be bonded, and then the other object to be adhered to the first object is laminated on the first object to be pressed onto the coating surface of the first object. Pressure is applied to the object thus stacked from the object side.

Then, the microcapsule is easily overheated so that the contents of the microcapsule can be freely contacted with other components applied to the surface of the first object, whereby curing proceeds to achieve strong adhesion between the two objects. Adhesives containing microcapsules in the form of chemical reactions can be used on the surface of an object by any of several methods, such as painting, spraying, or brushing.

(2) Solvent-activated adhesive: To prepare a solvent-activated adhesive, a microcapsule containing an organic solvent for activating the resin constituting the adhesive thin film is dispersed in the resin solution constituting the adhesive thin film.

As the organic solvent which can be capululized, almost all solvents generally used are suitable for use, and hexane, heptane, benzene, toluene, xylene, carbon tetrachloride, trichloroethylene and tetrachlorethylene can be listed.

Examples of the resin activated with the solvent include neoprene rubber, butyl rubber, styrene-butadiene rubber, natural rubber, polystyrene, poly (vinylacetate), methylcellulose, ethylcellulose, poly (vinyl chloride), ethylene and vinyl acetate. The copolymer of a copolymer, an acrylic resin, methacryl resin, polyamide, vinyl acetate, and a lower alkyl acrylate can be mentioned.

The solvent-activated adhesive according to the present invention comprises the above-mentioned microcapsule containing a solvent as a base material, which base material is dispersed in a resin solution constituting an adhesive thin film and a resin.

In the case of using a solvent-activated adhesive, the adhesive is applied to the surface of one of the two objects to be bonded, the adhesive thus dried is dried, and the object having the applied surface is applied while applying pressure to the first object. It is placed on the other side of the microcapsule, thereby overheating by pressure, so that the solvent can freely activate the resin component of the coating surface to achieve good adhesion. Adhesives containing microcapsules in solvent activated form can also be used on the surface of any object to be adhered to another object by methods such as painting, spraying, brushing, and the like.

Since the microcapsule used in the present invention can be easily ruptured even under a pressure of less than 10 kg / cm 2, the above adhesion of the two objects by lamination and pressure can be easily performed.

The adhesive containing microcapsules according to the invention thus has the advantage that it is used in a wide range of adhesive applications.

The present invention will be described in more detail with reference to the following examples.

However, the present invention is not limited to the embodiments described below, and those skilled in the art can easily learn the main features of the present invention from the above description, and can be used for various purposes without departing from the spirit and scope of the present invention. Depending on the state, various changes and modulations of the present invention can be achieved.

Example 1

1-1 Preparation of Two Prepolymers

A 2% aqueous sodium hydroxide solution was added to adjust the pH of 162 g of formaldehyde 37% aqueous solution (hereinafter referred to as formalin) to 9, and then 63 g of melamine was mixed and the mixture was reacted at 70 ° C while stirring. Immediately after confirming that the melamine was completely dissolved in the reaction mixture, 225 g of water was added to the reaction mixture, and the reaction mixture was stirred for 3 minutes to express the melamine-formaldehyde resin copolymer (hereinafter referred to as M4F prepolymer. An aqueous solution of melamine means (1: 4).

Separately, triethanol amine was added to adjust the pH of formalin 146 g to 8.5, and then mixed with 60 g of urea, and the mixture was reacted at 70 ° C. for 1 hour to express urea-formaldehyde resin prepolymer (hereinafter referred to as U1.8F prepolymer). An aqueous solution of was prepared.

1-2: Preparation of Cationic Urea Resin

162 g of formalin and 60 g of urea were mixed, the mixture was stirred, triethanolamine was added to adjust the pH to 8.8, and the reaction mixture was reacted at 70 ° C. for 30 minutes with stirring. 24 g of water and 3 g of tetraethylenepentamine were added to 40 g of the reaction mixture, and the reaction mixture was adjusted to 3.0 by adding 15% aqueous hydrochloric acid solution while stirring at 70 ° C., and the reaction was carried out for 1 hour. As the reaction proceeded, the pH of the reaction mixture decreased, so that an aqueous 10% sodium hydroxide solution was added to the reaction mixture to adjust its pH to 3.0 and the reaction was carried out at a low temperature of 55 ° C. When the viscosity of the reaction mixture reached 200 cps, sodium hydroxide 10% aqueous solution was added to neutralize the reaction mixture, and 400 g of water was added to the neutralized reaction mixture to obtain a water-soluble aqueous cationic urea solution.

1-3: Microcapshules

(나트륨도데실벤젠술포네이트, KAO-ATLAS Co., Japan 제조) 3g을 혼합하여 A-액으로 명명되는 용액을 얻었다.100 g of M4F prepolymer (see 1-1), 50 g of U1.8F prepolymer (see 1-1), 158 g of aqueous solution of water-soluble cationic urea resin (see 1-2), 62 g of water and 1 g of triethanolamine 10% aqueous citric acid solution was added to the mixture, and the pH was adjusted to 5.2.

(Sodium dodecylbenzenesulfonate, manufactured by KAO-ATLAS Co., Japan) 3 g was mixed to obtain a solution named A-liquid.

200 ml of xylene was dispersed in the A-liquid thus prepared so that the average diameter of the dispersed xylene particles was 30 to 50 micrometers.

The aqueous acid solution thus obtained was stirred gently and reacted for 1 hour while being kept at a temperature of 30 ° C. The pH was adjusted to 3.6 by adding 10% aqueous citric acid solution to this dispersion. After one more hour, a 10% aqueous citric acid solution was added to the reaction mixture to adjust its pH to 3.0, and then 200 ml of a 10% aqueous solution of resorcinol was added to the reaction mixture. After stirring for 18 hours the microcapsulization was complete.

After collecting the thus formed microcapsule, the capshoe was washed with water and dried in an air-dryer at 35 ° C. to obtain a powdery microcapsule having an average diameter of 30 to 50 micrometers.

1-4: Preparation of adhesive in solvent activated form as final product

1 part by weight of phenolic resin and 1 part by weight of coumarone resin were dissolved in a solution prepared by dissolving 100 parts by weight of masticated neoprene rubber in 500 parts by weight of toluene, and prepared in (1-3). After adding 30 parts by weight of cap wool, the entire mixture was uniformly mixed to obtain an adhesive containing micro cap wool.

Example 2-9

Eight kinds of adhesives according to the invention were obtained in the same procedure as in Example 1 except for using each of the thin film wall-forming prepolymers and the respective regulators shown in Table 1 instead of those used in Example 1.

TABLE 1

Note: ^* 1, ^* 2, ^* 3, and ^* 4 indicate the following description of each prepolymer.

Each prepolymer shown in Table 1 was prepared as follows.

Preparation of Prepolymer

^* 1: Tu 1.8F used in Example 4

Triethanolamine was added to adjust the pH of formalin 146 g to 8.5, and then mixed with 76 g of thiourea and the mixture was reacted at 70 DEG C for 1 hour to give Tu 1.8F (1 mol of thiourea: 1.8 mol of formaldehyde). ) An aqueous solution of a prepolymer was obtained.

^* 2: [MTu 4F used in Example 7

After adjusting the pH of formalin 324 g to 9.0 by adding 2% aqueous sodium hydroxide solution, it was mixed with 63 g of melamine and 38 g of thiourea, the mixture was reacted at 70 DEG C, and melamine and thiourea were completely reacted with the reaction mixture. Immediately after confirming the melting, 425 g of water was added to the reaction mixture, and the resulting solution was cooled to room temperature as it was.

^* 3 MTu 5F used in Example 8

Triethanolamine was added to adjust the pH of formalin 405 g to 8.5, and then mixed with 42 g of melamine, 25 g of thiourea and 20 g of urea, the mixture was reacted at 70 DEG C for 1 hour, and the product was cooled to room temperature.

^* 4: MU 4F used in Example 9

Triethanolamine was added to adjust the pH of formalin 324 g to 8.5, which was then mixed with 63 g of melamine and 30 g of urea and the mixture was reacted at 70 ° C. for 30 minutes. 225 g of water was added to the reaction mixture, which was then cooled to room temperature.

[Test Example 1]

The adhesives prepared in Examples 1 to 9 were applied to a poly (vinyl chloride) plate having a thickness of 0.5 mm at a ratio of 6 g / plate m 2 of the adhesive, and the coated plates were dried at 40 ° C. for 2 hours to avoid adhesiveness. A surface was obtained.

Next, another sheet of poly (vinyl chloride) having a thickness of 0.5 mm is laminated on the coated plate surface so as to form a laminate of two layers of poly (vinyl chloride) having an adhesive layer sandwiched therebetween. Or a pitch-roll adjusted to 200 kg / cm 2 to obtain a bonded object.

After the bonded object was left at room temperature for 24 hours, the adhesion between the two plates was tested. The results are described in the following Table 2, in which the test results for the adhesive bonded with the adhesive prepared in Comparative Examples 1 to 5 are described.

TABLE 2

Note for Table 2:

In Table 2, "good adhesion" means that the two plates are so firmly bonded to each other that one of the two plates cannot be detached from the other by hand, and "bad adhesion" means that one of the two plates is removed from the other. It means that it can be easily detached by hand or not adhered to each other.

Comparative Example 1

An adhesive containing microcapsule was obtained by the same procedure as in Example 1 except that no resorcinol was added as a regulator.

[Comparative Examples 2 to 4]

대신에 표 3에 기재한 제3성분중 어느 하나를 사용함으로써 실시예 1에서 A-액에 상응하는 액체를 얻고, 176g의 키실렌을 실시예 1에서와 동일한 조건하에 상기액에 분산시켰다. 이와같이 형성된 수용성 분산액의 pH가 5.0 미만으로된 경우에는 A-액에 상응하는 액의 pH를, 수산화나트륨 수용액을 가하여 5.0으로 조정하였다.The water-soluble cation of Example 1, using 100 g of M4F prepolymer prepared in the same manner as in Example 1 (1-1) and 50 g of U 1.8F prepolymer prepared in the same manner as in Example 1 (1-1) Urea resin and NEOPEIEX

Instead, the liquid corresponding to A-liquid was obtained in Example 1 by using any one of the third components listed in Table 3, and 176 g of xylene was dispersed in the liquid under the same conditions as in Example 1. When the pH of the aqueous dispersion thus formed was less than 5.0, the pH of the liquid corresponding to the A-liquid was adjusted to 5.0 by adding an aqueous sodium hydroxide solution.

Following the same procedure as in Example 1 but without adding 10% aqueous solution of resorcinol, the aqueous acid solution was reacted to obtain an aqueous acid solution of microcapsules. After collecting the microcapsule and washing with water, the washed microcapsule was air dried.

By using the microcapsule prepared in this way, in the same manner as in Example 1, an adhesive containing the microcapsule was obtained.

TABLE 3

대신에 제3성분으로 사용된 물질Water Soluble Cationic Urea Resin and NEOPELEX

Substances used as third component instead

Comparative Example 5

275 g of xylene was dispersed at 275 g in a 10% by weight aqueous solution of gelatin at an average diameter of 30 to 50 micrometers at 50 ° C., and then 275 g of arabic rubber 10% aqueous solution and 450 ml of water were added with gentle stirring, After adjusting the pH of the mixture formed as described above to 4.4, the reaction mixture was prevented as it is for 10 minutes, the mixture was cooled to 5 DEG C, 36.5 ml of 25% aqueous glutaraldehyde solution was added thereto, and the mixture was stirred for 1 hour. . The mixture was heated again to 50 ° C. and stirring continued for 30 minutes, then the mixture was cooled to room temperature to obtain a slurry of microcapsule. An adhesive containing a microcapsule was prepared in the same manner as in Example 1 by using a dried powdered microcapsule obtained by spray-drying a slurry of the microcapsule.

By testing each of the adhesives prepared in Comparative Examples 2 to 5, it was found that the organic solvent that had been capsulated from the beginning in the microcapsule was evaporated and erased from the microcapsule without leaving any residue.

Example 10

Instead of 176 g of xylene in Example 1, except that 176 g of a 5% solution of triallyl cyanuric acid ester dissolved in xylene or a 5% aqueous tert-perbenzoic acid ester dissolved in diethyl phthalate were used. By the same procedure as in Example 1, two kinds of microcapsules were prepared.

Separately, 0.5 part by weight of benzoyl peroxide and 10 parts by weight of methyl methacrylate were added to a solution prepared by dissolving 40 parts by weight of ethylene, furopropylene and 1,4-hexadiene trimer in 360 parts by weight of toluene, and the mixture was heated at 80 ° C. The reaction was carried out for 5 hours to prepare an adhesive.

4.0 parts by weight of powdered microcapsule prepared using Perbutyl Z, 6.5 parts by weight of powdered microcapsule prepared using triallyl cyanuric acid ester, and 100 parts by weight of the trimer obtained as described above. Adhesive was prepared. The adhesive thus prepared is applied to each of two lauan plates, and the coated surfaces are laminated together, and the laminated and bonded objects are preferably laminated by pressing the laminated objects under a pressure of 10 kg / cm 2 at 50 ° C. Got it. In addition, the adhesive prepared as described above, containing two kinds of microcapsules, retained its original adhesion even after one month of storage.

Example 11

In Example 2, a kind of microcapsule was prepared by the same procedure as in Example 2 except for using 224 g of diethyl phthalic acid ester containing 5% by weight of benzoyl peroxide instead of 176 g of xylene. .

Separately, 7 parts by weight of poly (methyl methacrylate) was dissolved in a mixed solvent consisting of 150 parts by weight of butyl acetate, 120 parts by weight of ethyl acetate, and 30 parts by weight of methyl isobutyl ketone, and 40 parts by weight of methyl methacrylate in the solution thus formed. Part and 1.0 part by weight of N, N-dimethyl-P-toluidine were further added to prepare a mixed solution. The mixed solution thus prepared was mixed with 6.5 parts by weight of the microcapsule prepared as described above to obtain an adhesive in a chemical reaction form.

After applying the adhesive to the mild steel plate and evaporating the solvent, place another mild steel plate on the coated surface of the first mild steel plate, and then apply a pressure of 10㎏ / ㎠ to the laminated mild steel sheet while rupturing the microcapsule. Laminated and bonded mild steel sheets were obtained, which showed strong adhesion between the component materials after 10 minutes.

REFERENCE EXAMPLE 6

In Comparative Example 5, the same microcapsulization process as in Comparative Example 5 was performed except that 224 g of diethylphthalic acid ester containing 5% by weight of benzoyl peroxide instead of 176 g of xylene was used. Obtained Capshuul.

After preparing the adhesive by mixing 6.5 parts by weight of the microcapsule thus prepared with the same solution as in Example 11, the adhesive was applied to the mild steel sheet and the solvent was evaporated. A laminate was obtained by placing another mild steel sheet on the first mild steel surface thus applied and dried and applying a pressure of 10 kg / cm 2 to the laminated mild steel sheet as in Example 11. However, the adhesion between the two plates was not satisfactory. Even when a pressure of 200 kg / cm 2 was used with the same adhesive, no improvement was found when the mild steel sheet laminate was tested again.

Example 12

By the same procedure as in Example 6, except that 180 g of a mixture with 100 parts by weight of EPON 828 (epoxy resin, manufactured by Du Pont, EPON is a registered trademark) was used instead of 176 g of xylene. Slurry of microcapsule was prepared by making microcapsule.

After collecting the microcapsule from the slurry, the microcapsule was washed with water and dried to obtain a free flowing microcapsule. Adhesive containing microcapsules by mixing a solution obtained by dissolving 100 parts by weight of N-methoxy- (methylated nylon), so-called nylon 8 in 200 parts by weight of methanol, with a free-flowing powdery microcapsule prepared as described above. Was prepared.

The adhesive thus prepared was applied onto a single lauan plate and the other one was placed thereon, and a strong adhesive of the laminated lauan plate was obtained by applying a pressure of 10 kg / cm 2 to the laminate at 70 ° C.

Even after leaving the laminate for one week at a temperature of 70 ° C. and a relative humidity of 75%, no loss of adhesion appeared between the adhesive plates.

In addition, the adhesive prepared as described above containing microcapsule could be maintained in a stable state without gelation after one month.

Claims (27)

In an adhesive containing a microcapsule, the adhesive contains a microcapsule and a solvent, wherein the microcapsule is a base material of at least one of the components constituting the adhesive and a thin film material of the microcapsule, And a microcapsule, wherein the solvent is composed of an aminoplast pretreated with a control agent, the solvent is composed of components constituting an adhesive, the microcapsule is dispersed in the solvent, and the adhesive is in a chemical reaction form or a solvent activated form. Adhesive containing shrouds. 2. The aminoplast of claim 1 wherein the aminoplast is a melamine-formaldehyde prepolymer, urea-formaldehyde prepolymer, melamine-urea-formaldehyde prepolymer and melamine-thiourea-formaldehyde prepolymer or melamine-formaldehyde prepolymer and thiourea-form And an polycondensate formed in the presence of an aqueous cationic urea resin and an anionic surfactant from at least one prepolymer selected from the group consisting of mixed prepolymers containing aldehyde prepolymers. The adhesive according to claim 1, wherein said modifier is a phenolic compound. 4. The adhesive according to claim 3, wherein the phenolic compound is selected from the group consisting of phenol, resorcinol, catechol, hydroquinone, cresol, xylenol and salginine. The adhesive of claim 1 wherein the modulator is a polyalkylene polyamine. The adhesive according to claim 5, wherein the polyalkylene polyamine is hexamethylene tetramine or triethylene tetramin. The adhesive according to claim 1, wherein the microcapsule, which is capulized with a reaction initiator or a curing agent, is dispersed in the other component mixture of the adhesive as the base material. 8. The adhesive according to claim 7, wherein the reaction initiator is dibutyl-tin dilaurate, tin caprylate, benzoyl peroxide, dibutyl peroxide. 8. The adhesive according to claim 7, wherein the curing agent is N, N-dimethylaniline or N, N-dimethyltoluidine. The microcapsule containing microcapsule as claimed in claim 1, wherein the microcapsule capululating the solvent is dispersed in the resin solution constituting the adhesive thin film as the base material for activating the resin constituting the adhesive thin film. Solvent activated form of adhesive. The adhesive according to claim 10, wherein the solvent is selected from the group consisting of benzene, toluene, xylene, hexane, heptane, carbon tetrachloride, trichloroethylene and tetrachloroethylene. In the method for producing an adhesive in a chemical reaction form or solvent activated form containing a microcapsule, at least one of the microliquid particles of the adhesive component is dispersed in an aqueous acid solution of the component forming the aminoplast, An acid catalyst is added to the dispersion, thereby polycondensing the prepolymer of the component forming the aminoblast, and adding at least one modifier to the aqueous acid solution during the polycondensation. Forming a microcapsule for capsulating the component, collecting and drying the microcapsule thus formed, and dispersing the microcapsule in a component constituting the adhesive containing the microcapsule; Contains microcapsule, characterized in that The method of manufacturing an adhesive. The method of claim 12, wherein the aminoplast is selected from melamine-formaldehyde prepolymer, urea-formaldehyde prepolymer, melamine-urea-formaldehyde prepolymer and melamine-thiourea-urea-formaldehyde prepolymer, or melamine-formaldehyde prepolymer. Adhesive resin, characterized in that the resin obtained by polycondensing in the presence of an aqueous cationic urea resin and an anionic surfactant from at least one prepolymer selected from the group consisting of mixed prepolymers containing thiourea-formaldehyde prepolymers. Manufacturing method. The method for producing an adhesive according to claim 12, wherein the regulator is a phenolic compound. 15. The method of claim 14, wherein the phenolic compound is selected from the group consisting of phenol, resorcinol, catechol, hydroquinone, cresol, xylenol and salginine. 13. The method of claim 12 wherein the modifier is a polyalkylene polyamine. The method for producing an adhesive according to claim 16, wherein the polyalkylene polyamine is hexamethylenetetramine or triethylenetetramine. 13. A method according to claim 12, wherein 0.1 to 30% by weight, preferably 0.5 to 20% by weight, of modifier is added to the preplymer of the component forming the aminoplast. The method for producing an adhesive according to claim 18, wherein the regulator is added as an aqueous solution of 0.02 to 5% by weight. 13. A method according to claim 12, characterized in that the microcapsule, which encapsulates both or both of the reaction initiator and the curing agent, is dispersed in a mixture of the adhesive other components containing the microcapsule. 21. The method of claim 20, wherein the reaction initiator is dibutyl-tin dilaurate, tin caprylate, benzoyl peroxide or dibutyl peroxide. 21. The method of claim 20, wherein the curing agent is N, N-dimethylaniline or N, N-dimethyltoluidine. 13. The microcapsule of claim 12, wherein the microcapsule, which is capulized with a solvent, is dispersed in a resin solution which will form the adhesive thin film as a base material for activating the resin which will make up the adhesive thin film. A method for producing a solvent-activated adhesive containing. The microcapsule according to claim 23, wherein the solvent for activating the resin is selected from the group consisting of benzene, toluene, xylene, hexane, heptane, carbon tetrachloride, trichloroethylene and tetrachloroethylene. The manufacturing method of the adhesive containing these. The compound according to claim 12, wherein the acid catalyst is selected from the group consisting of formic acid, acetic acid, citric acid, hydrochloric acid, nitric acid, phosphoric acid, aluminum sulfate, titanium oxychloride, magnesium chloride, ammonium chloride, ammonium nitrate, ammonium sulfate, and ammonium acetate A method for producing an adhesive containing a microcapsule, characterized in that. The resin according to claim 13, wherein the water-soluble cationic urea resin is prepared by polycondensing urea-formaldehyde prepolymer with polyalkylenepolyamine, guanidine, diaminoethanol, dicyandiamide, diethylaminoethanol or guanylurea. Method for producing an adhesive containing a microcapsule, characterized in that. The method for producing an adhesive according to claim 13, wherein the anionic surfactant is a salt of a fatty acid, a sulfate ester of a higher alcohol, or a salt of an alkylarylsulfonate.