KR100634137B1 - Process for preparing capsule-type adhesive and polymer adhesion-beads encapsulated by melamine resin - Google Patents

Abstract

Provided is a method for preparing an capsulated adhesive of a polymer adhesion bead which can be stored and transported in a powder state even at a room temperature and is excellent in the durability of particle surface. The method comprises the steps of dissolving 0.5-1 wt% of sodium dodecyl benzenesulfonate in distilled water; adding melamine and a formalin resin in a ratio of 1:1.7 to 1:2.5 by mol to the obtained solution and stirring it at 60-70 deg.C for 20-40 min; and adding a polymer adhesion bead to the obtained solution to crosslink the melamine resin and the formalin rein under an acidic condition, thereby capsulating the polymer adhesion bead. The capsulated adhesive has a size of 3-15 micrometers. Preferably the amount of the polymer adhesion bead is 75-80 wt% to 20-25 wt% of melamine and formalin resin.

Description

Process for preparing capsule-type adhesive and polymer adhesion-beads encapsulated by melamine resin

1 is a photograph of the polymer adhesive beads produced by the suspension polymerization method.

2 (A) to 2 (E) is a photograph of the shape of the capsule in the capsule adhesive prepared by Examples 1 and 2 and Comparative Examples 1 to 3.

Figure 3 is a photograph showing the change in shape of the polymer adhesive beads and the adhesive bead-capsule adhesive according to the present invention.

Figure 4 is a view showing the result of performing the bonding of the activated carbon, which is a porous body with an adhesive in the conventional solution state and the capsule adhesive according to the present invention.

FIG. 5 is a SEM photograph of the surface of the activated carbon sheet prepared in FIG. 4.

The present invention relates to an adhesive encapsulating polymer adhesive beads using a melamine resin.

Most rubber adhesives have a high viscosity at room temperature and have a glass transition temperature of -20 to -60 ° C. The adhesive agent in the state of the mucous is mainly contained in a container and sealed and stored, there is a problem that the adhesive workability is slow and smooth due to high viscosity and stickiness in use.

The present invention is to form a powder state by encapsulating in the mucous sticky polymer adhesive beads in the mucous state of the polymer film produced by a non-sticky foreign material at room temperature, so-called melamine-formalin crosslinking reaction, Its purpose is to provide a new concept of adhesive that is convenient in storage, transport, workability, and adhesive efficiency by applying the appropriate pressure to the outer wall and causing the internal material to exhibit adhesive force when used.

In the capsule adhesive of the present invention, dodecylbenzenesulfonic acid sodium salt, a particle stabilizer, is dissolved in distilled water, and then melamine and formalin are added, stirred at 60 to 70 ° C. for 20 to 40 minutes, and polymer adhesive beads are added thereto. Under acidic conditions, it is characterized by consisting of a polymer encapsulated beads through the cross-linking reaction of melamine and formalin as shown in the following scheme.

The present invention will be described in more detail as follows.

Polymer adhesive beads used in the present invention are prepared by the following method. That is, a polymer adhesive bead having a size of 30 to 100 μm using 2-ethylhexyl acrylate, styrene, and acrylic acid as a monomer and reacting at 70 ° C. for 4 hours using an initiator, an emulsifier, and a dispersant. To prepare. A photograph of the polymer adhesive beads prepared by the suspension polymerization method is shown in FIG. 1.

The capsule-type adhesive in which such polymer adhesive beads are encapsulated with a polymer membrane first dissolves sodium dodecylbenzenesulfonate salt as a particle stabilizer at about 0.5 to 1% by weight based on distilled water. If the stabilizer is more than 1% by weight or less than 0.5% by weight, it is preferable to make the above ratio since encapsulation is inhibited by foam formation by the dispersant.

Next, melamine and formalin resin are added to the solution in a molar ratio of 1: 1.7 to 1: 2.5, preferably in a ratio of 1: 1.9, and 20 to 40 at a speed of 400 to 600 rpm at 60 to 70 ° C. After stirring for a minute, the mixture is cooled at room temperature, and then the polymer adhesive beads prepared above are added.

Here, the addition amount of the polymer adhesive beads is most preferably added at 75 to 80% by weight relative to 20 to 25% by weight of melamine and formalin resin. If the melamine and formalin resin is used at less than 20% by weight, the efficiency of encapsulation is very low, and the surface thickness is low so that the shape is maintained at room temperature, but when dried at 60 ° C, the outer wall collapses. Will not. On the contrary, if it exceeds 25% by weight, the outer wall becomes too thick, and the adhesion efficiency of the inner material is lowered during the adhesive processing by the press, which is not desirable.

Next, the mixture was stirred at 400 to 600 rpm, and 0.2N HCl was added to adjust the pH to 4, which is an acidic condition. Then, a crosslinking reaction of melamine and formalin was carried out as shown in the following scheme, and then the mixture was heated at 50 to 70 ° C. for 3 to 5 hours. After the reaction, a capsule-type adhesive having a thickness of about 3 to 15 µm is produced.

The present invention will be described in more detail based on Examples and Comparative Examples as follows.

Production Example  1: polymer Adhesive beads  Produce

31.9 g of 2-ethylhexyl acrylate (Yakuri Chem, Japan), 102.65 g of water, 1.3 g of styrene (Kanto Chem, Japan), 1 g of acrylic acid (Junsei Chem, Japan) as monomers, and 2,2'-azo as an initiator 0.1 g of bis (isobutyronitrile) (Fluka, Germany), 4.9 g of Triton X-100 (Sigma-Aldrich Co., USA) as emulsifier, 1.35 g of Acrylsol ASE-60 (Rohm and Haas, USA) as dispersant The reaction mixture was reacted for 4 hours at 70 ° C. under a nitrogen stream to prepare a polymer adhesive bead in a slime state having a particle range of 30 to 100 μm.

Example  One

Melt resin (Acros organics, USA) and formalin resin (Daejung Chem, Korea) were dissolved in 0.5 wt% of dodecylbenzenesulfonate sodium salt (SDBS, Junsei, Japan), a particle stabilizer, in 99.5 wt% of distilled water. It added in the molar ratio and stirred for 30 minutes at 500 rpm at 65 degreeC. After cooling to room temperature, 20% by weight of the polymer adhesive beads prepared in Preparation Example 1 were added to 80% by weight of melamine and formalin resin, and the mixture was stirred at 500 rpm, and adjusted to pH 4 by addition of 0.2N HCl. After the crosslinking reaction of the melamine resin and formalin resin was carried out at 60 ℃ for 4 hours to prepare a capsule adhesive. The thickness of the prepared capsule adhesive was 3 to 10 탆.

Example  2

Melt resin (Acros organics, USA) and formalin resin (Daejung Chem, Korea) were dissolved in 0.5 wt% of dodecylbenzenesulfonate sodium salt (SDBS, Junsei, Japan), a particle stabilizer, in 99.5 wt% of distilled water. It added in the molar ratio and stirred for 30 minutes at 500 rpm at 65 degreeC. After cooling to room temperature, 80% by weight of the polymer adhesive beads prepared in Preparation Example 1 were added to 20% by weight of melamine and formalin resin, and the mixture was stirred at 500 rpm, and adjusted to pH 4 by addition of 0.2N HCl. After the crosslinking reaction of the melamine resin and formalin resin was carried out at 60 ℃ for 4 hours to prepare a capsule adhesive. The thickness of the prepared capsule adhesive was 10 to 15 mu m.

Comparative example  One

Melt resin (Acros organics, USA) and formalin resin (Daejung Chem, Korea) were dissolved in 0.5 wt% of dodecylbenzenesulfonate sodium salt (SDBS, Junsei, Japan), a particle stabilizer, in 99.5 wt% of distilled water. It added in the molar ratio and stirred for 30 minutes at 500 rpm at 65 degreeC. After cooling to room temperature, 88% by weight of the polymer adhesive beads prepared in Preparation Example 1 were added to 12% by weight of the melamine and formalin resin, stirred at 500 rpm, and adjusted to pH 4 by addition of 0.2N HCl. After the crosslinking reaction of the melamine resin and formalin resin was carried out at 60 ℃ for 4 hours to prepare a capsule adhesive. The thickness of the prepared capsule adhesive was 3 to 5 탆.

Comparative example  2

Melt resin (Acros organics, USA) and formalin resin (Daejung Chem, Korea) were dissolved in 0.5 wt% of dodecylbenzenesulfonate sodium salt (SDBS, Junsei, Japan), a particle stabilizer, in 99.5 wt% of distilled water. It added in the molar ratio and stirred for 30 minutes at 500 rpm at 65 degreeC. After cooling to room temperature, 85% by weight of the polymer adhesive beads prepared in Preparation Example 1 were added to 15% by weight of melamine and formalin resin, and the mixture was stirred at 500 rpm, and adjusted to pH 4 by addition of 0.2N HCl. After the crosslinking reaction of the melamine resin and formalin resin was carried out at 60 ℃ for 4 hours to prepare a capsule adhesive. The film thickness of the prepared capsule adhesive was 3 to 8 mu m.

Comparative example  3

Melt resin (Acros organics, USA) and formalin resin (Daejung Chem, Korea) were dissolved in 0.5 wt% of dodecylbenzenesulfonate sodium salt (SDBS, Junsei, Japan), a particle stabilizer, in 99.5 wt% of distilled water. It added in the molar ratio and stirred for 30 minutes at 500 rpm at 65 degreeC. After cooling at room temperature, 67% by weight of the polymer adhesive beads prepared in Preparation Example 1 were added to 33% by weight of the melamine and formalin resin, and the mixture was stirred at 500 rpm, and adjusted to pH 4 by addition of 0.2N HCl. After the crosslinking reaction of the melamine resin and formalin resin was carried out at 60 ℃ for 4 hours to prepare a capsule adhesive. The film thickness of the prepared capsule adhesive was 10-20 탆.

2 (A) to 2 (E) of the accompanying drawings are photographs of the shape of the capsule in the capsule adhesive prepared by Examples 1 to 2 and Comparative Examples 1 to 3. According to FIG. 2 (A) (Comparative Example 1), the amount of melamine resin and formalin resin is small and the capsule formation efficiency is very low. According to FIG. 2 (B) (Comparative Example 2), melamine resin and formalin The amount of the resin is larger than in the case of Comparative Example 1, the outer wall is formed and the surface thickness is low, the shape is maintained at room temperature, it can be seen that the phenomenon that the outer wall collapses when dried at 60 ℃. In addition, according to FIG. 2E (Comparative Example 3), the amount of melamine resin and formalin resin is excessive and the outer wall is so thick that the adhesion efficiency of the inner material is lowered during the adhesive processing by the press.

On the other hand, Fig. 2 (C) (Example 1) and Fig. 2 (D) (Example 2) are suitable for melamine resin and formalin resin, so that the durability of the particle surface is excellent, and the shape is excellent even when heated and dried at 70 ° C. It was found that there is no loss of internal material.

Figure 3 of the accompanying drawings is a photograph showing the change in shape of the polymer adhesive beads and the adhesive bead-capsule adhesive according to the present invention. Figure 3 (a) shows the polymer adhesive beads in the aqueous dispersion state prepared in Preparation Example 1, Figure 3 (b) and Figure 3 (c) is prepared in Preparation Example 1 on the slide glass of the microscope at room temperature, respectively 5 and 30 minutes after the sample is placed, the cohesion between polymer adhesive beads is shown. It can be seen that most of the polymer adhesive beads prepared in Preparation Example 1 had their surfaces aggregated.

On the other hand, the capsule adhesive of the polymer adhesive beads prepared in Example 1 and Example 2 of the present invention is a picture immediately after the reaction is shown in Figure 3 (d), Figure 3 (e) and Figure 3 (f) is 60 The picture after heat-processing at 70 degreeC and 70 degreeC for 24 hours is shown. According to FIG. 3 (e) and FIG. 3 (f), even after 24 hours of heating, aggregation of particles did not occur, and no change in particle form was observed.

 4 is a view showing a result of performing the bonding of the activated carbon which is a porous body with the adhesive of the conventional solution state and the capsule adhesive according to the present invention. According to FIG. 4 (A), the activated carbon is adhered by the existing adhesive. When it was made, it was found that the adhesive blocked the pores of the porous body to maintain the porosity, and when the capsule adhesive of the present invention was used as shown in FIG. 4 (B), the porosity was maintained, and the polymer adhesive beads were activated carbon having a porous body. It was found that the activated carbon sheet having the desired shape can be manufactured by performing a partially binding role.

5 is an SEM image of the surface of the activated carbon sheet prepared in FIG. 4, and when the capsule adhesive according to the present invention is used, the surface shows a porous body.

The capsule adhesive of the polymer adhesive bead according to the present invention has excellent durability of the surface of the particles, the shape is maintained even after heating and drying at 70 ℃, there is no effect of loss of the internal material.

Accordingly, the capsule adhesive according to the present invention can be stored and moved as a powder at room temperature, and can be used as an adhesive of a new concept useful in terms of workability and useful in terms of adhesive adhesion efficiency.

Using the capsule adhesive according to the present invention it is possible to produce an activated carbon sheet having a porosity of the desired form through the adhesion of activated carbon as a porous material.

Claims (3)

Dodecylbenzenesulfonic acid sodium salt, a particle stabilizer, was dissolved at about 0.5 to 1% by weight with respect to distilled water, and then melamine and formalin resin were added to the solution in a molar ratio of 1: 1.7 to 1: 2.5, and then added at 60 to 70 ° C. After stirring for 20 to 40 minutes, the polymer adhesive beads are added to the polymer, characterized in that the polymer is prepared by encapsulating the polymer adhesive beads in the size of 3 to 15㎛ through a crosslinking reaction of the melamine resin and formalin resin under acidic conditions Method for producing a capsule adhesive of adhesive beads. The method of claim 1, wherein the polymer adhesive beads are added in an amount of 75 to 80% by weight based on 20 to 25% by weight of melamine and formalin resin. The method of claim 1, wherein the crosslinking reaction is performed by adding polymer adhesive beads to the resin solution and adjusting the pH to 4 by adding 0.2N HCl while stirring them at 400 to 600 rpm for 3 to 5 hours at 50 to 70 ° C. A method for producing a capsule adhesive of polymer adhesive beads, characterized in that the reaction.

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