KR100932371B1 - Method for producing a pressure-sensitive adhesive foam composition using the above foam composition and a method for producing a pressure-sensitive adhesive product using the foam composition prepared by the above method - Google Patents

Abstract

The present invention relates to a method for producing a pressure-sensitive adhesive foam composition which can simultaneously impart adsorption and adhesiveness using the above-described foam composition, and a method for producing a pressure-sensitive adhesive product using the foam composition prepared by the above method. In the present invention, in order to make the pressure-sensitive adhesive coating in a foam coating method, in the manufacturing process of the foam cell was prepared with a foam composition different from the inner wall composition of the foam cell and the composition of the foam outer medium. The media portion of the coating layer gives sufficient adhesion to perform the adhesive function, while the inner walls of the cells formed inside the coating layer have different adhesive strengths, and have elasticity, but do not stick / deform to each other by external pressure again. Designed to be resilient, this soft property with reduced adhesiveness provides sufficient elasticity to open cells that adsorb and provide adsorptive force, while providing a foundation to give the necessary adhesion to the coating medium. The present invention relates to a method for providing a tack-adhesive product having excellent tack-adhesive power and detachable properties even at a pressure weaker than that of a conventional removable PSA.

Adhesive, Adsorbent, Pressure Sensitive Adhesive, Foam, Foam Composition, Adhesive Polymer, Coating

Description

A method for preparing adsorptive and adhesive foam layer having different composition and a method for producing a adsorptive and adhesive article by using the same}

The present invention relates to a method for producing a pressure-sensitive adhesive foam composition using the above-mentioned foam composition and to a method for manufacturing a pressure-sensitive adhesive product using the foam composition prepared by the above method, and more particularly, to the inner wall of the foam cell in the manufacturing process of the foam cell. Prepared with a foam composition of more than different composition and composition of the foam outer medium. The cells formed inside the coating layer have excellent elasticity, but the inner wall of the cell does not have the same tacky as the medium, so that the cells can be restored after deformation without being collapsed by external pressure. open cell) can provide sufficient elasticity to maximize the adsorption force and at the same time give sufficient adhesion to the coating medium, to provide a pressure-sensitive adhesive product having excellent adhesion and detachability even at a weaker pressure than conventional PSA It is about.

Adsorptive-Pressure Sensitive Adhesive (APSA) is a product that utilizes both the adsorption and adhesion characteristics.The adsorption force of the closed cell and open cell structures of the foam and the adhesion of the medium By means of using, it is possible to adhere to various adhered surfaces even at low pressure, and even when detached, it means a re-adhesive adhesive capable of maintaining the existing adhesiveness and adhesive strength while minimizing the transition of the adhesive onto the adhered surface. .

The tackifier is composed of a coating layer (1) and the material (2), the coating layer is open foam cells (4), closed foam cells (5), cells It consists of a cell wall 6 and a coating media 3 (FIG. 1).

The physical mechanism by which the adhesive adheres to the body (adhesive) 7 is as follows.

First, when the coated surface faces the substrate 7, the cohesive coating media 3 come into contact with the substrate to impart the necessary initial adhesive force (9). At this time, as the tacky adhesive area around the open cell increases, the pressure increases in the open cell 4, and the activity of the open cell as the adsorption cell begins to increase (8).

The synergistic effect of the adsorption force and the adhesive force is further reinforced by the closed cell 5. The closed foam cell 5 evenly distributes the initial pressure to the substrate to create an elastic bulky layer necessary for the effective adsorption and adhesion region to work effectively. It is possible to make a smooth coating (coating) surface on the substrate (Fig. 1), and also to secure a wide contact area even at a small pressure even in irregular adhesives, and exhibits adhesion to various deposits (Fig. 2). .

Existing pressure-sensitive adhesives increase the adhesive force in proportion to the pressure-sensitive adhesiveness and contact area of the pressure-sensitive adhesive, which has limited properties and materials, whereas the pressure-sensitive adhesive has a bulkyness characteristic of a closed cell. ), Sufficient contact area can be secured even on irregular substrates.

On the other hand, when the foam is designed with a soft polymer or a tacky polymer for adhesion to various substrates, the structure of the cells is weakened or the inner surface of the cells is tacky together with the media component, thereby adhering to the adherent substrate. After the transition easily occurs or when the adhesive pressure is applied for initial contact, this pressure deforms not only the open foam cell 4 but also the closed foam cell 5 and cannot be restored due to the adhesive performance inside the cell. As a result of the loss of the desired after-burning properties (Bulkiness) (Fig. 3) re-adhesion to various substrates is significantly reduced.

On the other hand, in the case of a simple adsorptive coating, the foam cell can be structurally stable due to the selection of a higher strength polymer and the required bulkiness can be secured. Its adhesive strength is significantly weaker than the method (Table 1), and the irregular base material having a low smoothness has a feature that is difficult to exhibit its performance, or the ductility of the adsorption cell has a disadvantage in that its function is hardly exhibited at low temperatures. In addition, in the case of a conventional adsorption type coating agent having a foam size of 100 μm or less, it is difficult to maintain the openness of the adsorption cell because the surface cell is too small to be covered with a polymer film.

Thus, the present inventors make a resilient cell wall (Resilient cell wall) (6 ') as shown in Figure 4 to overcome the disadvantages of the prior art as described above, but the adhesion of the inner wall of the cell is designed to be weaker than the adhesion of the medium Less Tacky, while the coating medium was designed with a more cohesive polymer, resulting in a foam coating with an ideal structure that results in a cohesive enhanced coating medium (3 ').

The coating agent differs from the inner wall composition of the foam cell and the composition of the foam outer medium in the manufacturing process of the foam cell, so that the coating medium is ductile and the adhesion is enhanced while the inner wall of the cells formed inside the coating layer is less tacky than the medium. In one composition, the cell morphology can be easily restored after deformation, resulting in the structure of bulky, stable foam cells and tacky media required for this tackifier. Due to this property, the adhesive coating product prepared by the coating method can be reattached and detached many times, and can be adhered only by placing on the substrate without applying pressure depending on the substrate. The present invention has been completed by confirming that the adhesive agent can be prepared.

The object of the present invention is to form a foam cell that does not collapse due to sufficient adhesiveness and sufficient ductility and elasticity while using the bulkiness of the foam so as to have strong adsorption and adhesive force, easy release property and re-adhesiveness to various substrates. It is an object of the present invention to provide a tackifier foam composition for preparing a tackifier having an open cell structure of a suitable size for adsorption.

Another object of the present invention is to provide a pressure-sensitive adhesive product and a method for producing the same using the pressure-sensitive adhesive foam composition.

In order to achieve the above object, the present invention comprises the steps of (1) preparing a mixed solution by stirring a water-based polymer, foaming agent (foaming agent), thickener, crosslinking agent and extender (extender) or flame retardant capable of forming a foam; (2) forming a primary foam composition using the mixed solution; And (3) preparing a secondary foam composition by adding a pressure-sensitive adhesive or a tackifier, a thickener, and a foam size controlling agent to the primary foam composition to prepare a secondary foam composition. It provides a method of manufacturing.

The present invention also includes coating a foam composition prepared by the above method with a knife, a bar, a comma coater, etc. to suit the purpose of the substrate, and curing the foam according to the use of the adhesive, and then attaching the release paper. Provided are methods for preparing a tack-adhesive product.

Furthermore, the present invention provides a tack-adhesive product having a strong tack-adhesive power, easy release property and re-adhesion prepared by the above method.

Hereinafter, the configuration of the present invention will be described in detail.

Preferred methods for preparing the foam compositions of the present invention include the following steps:

(1) 100 parts by weight of an aqueous polymer capable of forming a foam, 0.01 to 20 parts by weight of a foaming agent, 0.01 to 4 parts by weight of a thickener, 0.01 to 7 parts by weight of a crosslinking agent, and 0.01 to 50 parts by weight of an extender or flame retardant. Preparing a mixed solution by stirring;

(2) forming a primary foam composition such that the foam density is 0.2 to 0.5 kg / L using the mixed solution; And

(3) to 100 parts by weight of the primary foam composition, 0.01 to 50 parts by weight of a pressure-sensitive adhesive or tackifier, 0.01 to 5 parts by weight of a thickener and 0.01 to 5 parts by weight of a foam size controlling agent Preparing a secondary foam composition by stirring the foam density to 0.2-0.5 kg / L.

The foam composition of the present invention is to compensate for the difficulty of maintaining the openness of the surface cell is so small that the surface cell is covered with a polymer coating, which has a conventional adsorption composition having a foam size of 100 ㎛ or less By opening the foam size regulator as described above to increase the size of the cell to 200-250 μm, it is possible to more surely open the cell (Fig. 5). The foam compositions of the present invention thus have a foam size of approximately 50-250 μm.

In the present invention, the foamable water-based polymer is acrylic (Acrylics), poly vinyl acetate (Poly Vinyl Acetate), ethylene vinyl acetate (Ethylene Vinyl Acetate), polyurethane (Polyurethane), acrylic urethane (Acrylic Urethane) mechanical Aqueous polymers capable of mechanical or chemical foaming may be used, but are not limited thereto.

In the present invention, the polymer may be used alone or in mixture of two or more thereof.

In the present invention, the polymer may also be used in the form of an emulsion or dispersion.

In the present invention, the blowing agent alone or selected from C-14 to C-24 fatty acid salts such as lauryl sulfates and stearates, and sulfosuccinates. Mixtures of two or more may be used, but are not limited thereto.

In the present invention, the thickener may be used alone or a mixture of two or more selected from the group consisting of acrylic, starch and urethane, but is not limited thereto.

In the present invention, the crosslinking agent may be used alone or a mixture of two or more selected from the group consisting of melamine formaldehyde, isocyanates, aziridines and carbodiimides. This is not restrictive.

In the present invention, the extender may be used alone or in the form of a mixture of two or more of titanium dioxide (TiO ₂ ), talc, silica, clay, or calcium carbonate, but is not limited thereto.

In the present invention, the flame retardant may be used alone or in the form of a mixture of two or more from organic or inorganic phosphorus, halogen, inorganic (aluminum hydroxide, magnesium hydroxide, antimony oxide), melamine, and the like, but is not limited thereto.

In a preferred embodiment of the present invention, 0.01 to 1 part by weight of the dye may be further added to the mixed solution of the first step.

In the present invention, the dye may use a general organic and inorganic dyes, but is not limited thereto.

In a preferred embodiment of the present invention, 0.01 to 1 part by weight of a preservative may be further added to the mixed solution of the first step.

In the present invention, the preservative may be used isotizolin (Isothizolin) system is not limited thereto.

In a preferred embodiment of the present invention, 0.01 to 1 part by weight of a fungicide may be further added to the mixed solution of the first step.

In the present invention, the antibacterial agent may use an isothiazolin-based compound, but is not limited thereto.

In the present invention, foam forming can be performed using a mechanical foam forming apparatus. The mechanical foam forming apparatus may be known in the art, and specifically, may be a product such as Datacolor, Bombi, Hansa, and the like.

In the present invention, the pressure-sensitive adhesive or tackifier added in the third step may be used alone or a mixture of two or more selected from the group consisting of acrylic, acrylic urethane copolymer, rosin ester, and the like, but is not limited thereto.

In the present invention, the foam size adjusting agent may be used alone or a mixture of two or more selected from the group consisting of polyethylene oxide, polypropylene oxide and polydimethylsiloxane, but is not limited thereto. .

In the present invention, the material to be coated with the foam composition in order to manufacture the adsorption-adhesive product may be used as a fabric (textile), non-woven fabric, plastic foam (plastic foam), plastic sheet (plastic sheet), paper, synthetic paper, etc. It is not limited.

In the present invention, the method of coating the foam composition on the material may be performed by a knife, a bar, a comma coater, etc. according to the adhesive use, but is not limited thereto.

In the present invention, the dry curing of the coated foam composition can be carried out at 100 ~ 150 ℃ 1-3 minutes.

Adsorption adhesive product using the above-mentioned foam composition of the present invention has excellent re-adhesiveness without being transferred to the base material by excellent adsorption force and easy release property by the synergistic effect of the adsorption force and adhesive force. In addition, due to the bulkiness of the coating layer, the selection of materials is varied, so that not only a plastic sheet having a high smoothness but also a low-smooth fiber fabric, a nonwoven fabric, etc., can be treated with a pressure-sensitive adhesive of the thick film. In addition, due to this property, the product treated with this adhesive can provide sufficient contact area even in the case of non-porous substrates with high smoothness and excellent adhesion and detachment performance in various substrates than conventional PSA. Have The adsorption characteristic of this adhesive is that it can reduce the stickiness of the adhesive face and can also reduce the discomfort when touching.

Hereinafter, the configuration and effects of the present invention through the embodiments will be described in more detail. These examples are only for illustrating the present invention, but the scope of the present invention is not limited by these examples.

Example  1: Preparation of the present invention foam composition

While stirring 50 kg of acrylic emulsion (50% solids), 1.5 kg of TiO ₂ (60% solution) was added thereto, 0.25 kg of thickener (Alkali Swellable thickener) was added, and sodium sulfosuccinate (Sodium) was added. 2 kg of Sulfosuccinates (30%) and 2 kg of ammonium stearate solution (28%) were added thereto, followed by stirring at 800 RPM for 5 minutes.

1 kg of carbodiimide (40%) and 0.005 kg of isothiazolin antibacterial agent were added to the stirred solution, and the viscosity was adjusted to 3,000 to 4,000 cps (Brookfield viscometer, 20 rpm, # 4 spindle). And the mixed solution was prepared by stirring for about 10 minutes.

The mixed solution was foamed using a foam forming apparatus (Autofoam / Datacolor) so as to have a foam density of 0.27 to 0.3 g / mL.

0.5 kg of Acrysol ASE-60 while stirring the foam solution again in a mixer (300 RPM), 5 kg of an acrylic urethane-based adhesive (YST 630, 56%), polyethylene 1 kg of oxide was added and mixed (mixing), and then the foam composition of the present invention was prepared by stirring the final density of the foam to 0.3 to 0.35 g / mL.

Example  2: present invention Adhesion  Product production

In the coating composition, the foam composition prepared in Example 1 was coated with a coating knife (coating knife: 2 mm width) on the back surface of the fabric (150d X 150d) with a gap coating (gap gap; 0.4-0.5) mm). The coating water was dried and cured at 120-150 ° C. for 2 minutes, and then laminated with a release paper to prepare the present invention.

The adhesive surface of the adhesive layer coated on the fabric as described above was shown in Figure 5 by taking a photomicroscopy (Model name: Olympus DP12).

5, the smooth adhesive face and the backing property of cells of various sizes on the surface of the coating layer do not follow the bending of the woven fabric (material; 150X150 denier plain weave fabric) while maintaining an open shape without deformation. You can see that it maintains bulkiness.

Experimental Example  One: Adhesion  Test

The adhesive force of the adhesive product prepared in Example 2 was tested. The test was carried out in accordance with KSA 1107.

Stainless, glass, and acrylic were used as the adherend, that is, the measurement was performed by comparing the adhesive strength with a conventional product under each condition of Table 1 below.

Test Items Adhesion 180 ℃ Peel Adhesion (N / cm) (25 ℃) Holding force (falling time min) (60 ℃) ^{* 2} Possession Adhesive Sheet (Example 2) ^{* 5} Comparative Example (Adsorption) ^{* 3} Adhesive Sheet (Example 2) ^{* 5} Comparative Example (Adsorption) ^{* 3} Stainless steel (SUS 304) ^{* 1} 0.40 0.03 9 NA ^{* 4} Glass 0.40 0.05 9 NA acryl 0.35 0.06 8 NA Note 1: Test using UTM and test according to KSA 1107 2: Apply a load of 1kg to 25mm × 25mm 3: Adsorption sheet using foam from Japan's company (cell size ~ 90㎛) 4: NA: Not applicable Not applicable), immediate failure 5. Example 2 (Material: Sheet coated on 150 × 150 denier plain weave fabric)

As can be seen through the experimental results of Table 1, the adhesive sheet of the present invention showed a significantly improved adhesion and retention compared to the conventional adsorption sheet.

As mentioned above, specific parts of the present invention have been described in detail, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Thus, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

As described above through the above embodiments, the tackifier using the ideal foam composition of the present invention and the tackifier product manufactured using the same are actual paper, handbill, photo paper, double-sided tape, interior sheets and products, decoration sheets and products, wallpaper It is very useful when the adhesive layer does not transfer even after a certain period of time in various materials such as label paper and the like, so that a necessity of clean detachment is required or the product needs to be rebuilt elsewhere. In particular, adhesives can be processed with a single coating on fabrics and non-woven fabrics, where it is difficult to secure the smoothness and thickness of the sufficient adhesive layer by the conventional paste method. In addition, since the adhesive surface is less sticky, it can be said to have high utilization as a DIY product.

1 is a cross-sectional view showing the structure of a pressure-sensitive adhesive coating.

2 is a cross-sectional view showing a physical mechanism in which the adhesive is effectively adhered to non-porous substrates.

Figure 3 is a cross-sectional view showing the deformation after the pressure-sensitive adhesive when the foam is designed with a soft polymer or tacky polymer (tacky).

4 is a cross-sectional view of the adhesive article of the present invention having an elasticity-enhanced inner wall and an improved adhesion medium.

Figure 5 is a micrograph showing the appearance of the adhesive coating surface of the base fabric (150d X 150d) coated on the fabric according to an embodiment of the present invention.

<Description of Major Symbols in Drawing>

1: coating layer 2: material

3: coating medium 4: open foam cell

5: closed foam cell 6: cell inner wall

7: substrate 8: adsorption zone

9: adhesion area 3 ': adhesion-enhanced coating medium

4 ': modified open foam cell 5': modified closed foam cell

6 ': Cell inner wall designed to be restored due to different media and composition

Claims (18)

(1) 100 parts by weight of an aqueous polymer capable of forming a foam, 0.01 to 20 parts by weight of a foaming agent, 0.01 to 4 parts by weight of a thickener, 0.01 to 7 parts by weight of a crosslinking agent and 0.01 to 50 parts by weight of an extender or flame retardant Preparing a mixed solution; (2) forming a primary foam composition such that the foam density is 0.2 to 0.5 kg / L using the mixed solution; (3) adding the pressure-sensitive adhesive or tackifier 0.01-50 parts by weight and the thickener 0.01-5 parts by weight to the primary foam composition to vary the composition of the medium and the inner wall of the foam; And (4) foam size controlling agent (foam size controlling agent) Method of producing a pressure-sensitive adhesive foam composition comprising the step of adding 0.01 to 5 parts by weight of the foam density to 0.2 to 0.5 kg / L. According to claim 1, The foamable water-based polymer is acrylic polymer (Acrylic polymer), poly vinyl acetate (Poly Vinyl Acetate), ethylene vinyl acetate (Ethylene Vinyl Acetate), polyurethane (Polyurethane), acrylic urethane copolymer ( Acrylic Urethane copolymer) and a combination of these methods for producing a pressure-sensitive adhesive foam composition characterized in that it is selected from the group consisting of. The foam according to claim 1, wherein the blowing agent is selected from the group consisting of lauryl sulfates, stearates, sulfosuccinates and combinations thereof. Method of Preparation of the Composition. The method of claim 1, wherein the thickener is selected from the group consisting of acrylic thickeners, starch thickeners, urethane thickeners, and combinations thereof. According to claim 1, wherein the crosslinking agent is characterized in that the adhesive is characterized in that selected from the group consisting of melamine formaldehyde (Isocyanates), isocyanates (Aziridines), carbodiimides and combinations thereof Process for the preparation of the foam composition. The method of claim 1, wherein the extender is selected from the group consisting of titanium dioxide (TiO ₂ ), talc, silica, clay, calcium carbonate, and combinations thereof. The method of claim 1, wherein the flame retardant is selected from the group consisting of aluminum hydroxide, magnesium hydroxide, antimony oxide, and combinations thereof. The method of claim 1, wherein 0.01 to 1 part by weight of the dye is further added to the mixed solution of the first step. The method of claim 1, wherein 0.01 to 1 part by weight of a preservative is further added to the mixed solution of the first step. The method of claim 1, wherein 0.01 to 1 part by weight of a fungicide is further added to the mixed solution of the first step. The method of claim 1, wherein the pressure-sensitive adhesive or tackifier added in the third step is selected from the group consisting of acrylic polymers, acrylic urethane copolymers, rosin esters, and combinations thereof. . The method of claim 1, wherein the foam size adjusting agent is a pressure-sensitive adhesive foam composition, characterized in that selected from the group consisting of polyethylene oxide, polypropyreneoxide, polydimethylsiloxane, and combinations thereof. Manufacturing method. A method for producing a pressure-sensitive adhesive product, characterized in that the foam composition prepared by the method of any one of claims 1 to 12 is coated on a material, dried and cured, followed by attaching a release paper. The method of claim 13, wherein the material is fabric, nonwoven fabric, photo paper, paper, synthetic paper, wallpaper, decorative sheets, interior sheets, plastic foam or plastic. A method for producing a pressure-sensitive adhesive product, characterized in that it is a sheet (plastic sheet). The method of claim 13, wherein the method of coating the foam composition on a material is performed by using a knife, a bar, or a comma coater. A pressure-sensitive adhesive product, which is prepared by the manufacturing method of claim 13, has a strong adhesive force, easy release property and re-adhesiveness. A pressure-sensitive adhesive composition prepared by the method of any one of claims 1 to 12, wherein the composition of the inner wall constituting the foam cell in the coating medium has an abnormal foam composition different from the composition of the coating medium. 18. The adhesive composition of claim 17 wherein the foam size is between 50 and 250 μm.

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