KR102092102B1 - Eco-friendly water-soluble wall adhesive composition and manufacturing method of the same - Google Patents

Abstract

The present invention relates to an eco-friendly aqueous wall adhesive composition and to a manufacturing method thereof and, more specifically, to an aqueous wall adhesive composition comprising: 15 to 25 wt% of an ethylene vinyl acetate (EVA) copolymer; 5 to 10 wt% of polyvinyl alcohol (PVA); 15 to 25 wt% of silica sand; 25 to 35 wt% of cement; 2 to 5 wt% of a thickener; and 10 to 20 wt% of water.

Description

ECO-FRIENDLY WATER-SOLUBLE WALL ADHESIVE COMPOSITION AND MANUFACTURING METHOD OF THE SAME

The present invention relates to an environmentally friendly aqueous wall adhesive composition and a method for manufacturing the same, more specifically, 15 to 25% by weight of EVA (ethylene vinyl acetate) copolymer, 5 to 10% by weight of polyvinyl alcohol (PVA), and 15 to 25 silica sand It relates to an aqueous wall adhesive composition comprising a weight percent, 25 to 35 percent by weight of cement, 2 to 5 percent by weight of a thickener and 10 to 20 percent by weight of water.

Adhesion is a phenomenon in which two kinds of solids of the same kind or different kinds are intervened to bind, and these substances are called adhesive resins and the solids to be adhered are called adherends. There are many types of adhesive resins currently used, but they can be largely divided into oily products using organic solvents and aqueous products using water as a solvent.

In the case of oily products, adhesiveness is high, but there is a problem in that workability and stability are poor due to the generation of harmful gases. In particular, conventional wall construction adhesives include two-component epoxy and chloroprene composed of polyurethane-based bisphenol a and amide-based amides (isocyanate) and polyol (polyol), which are solvent-based adhesives. Chloroprene Rubber) A rubber-based adhesive was used.

However, recently, an aqueous acrylic adhesive has been developed and widely used in order to improve workability while meeting new environmental standards. For example, various aqueous urethane-based adhesives are described in a method of manufacturing an anionic water-based polyurethane adhesive composition in Patent Publication No. 1995-0002244, and in Patent Publication No. 10-020956, an aqueous polyurethane dispersion adhesive composite with improved heat resistance It is described with respect to, and Patent Publication No. 1998-0066934 describes a method for manufacturing an aqueous polyurethane adhesive for shoes, and Patent Publication No. 10-0262136 describes a water-resistant, removable acrylic pressure-sensitive adhesive in an acrylic system. It has been described, and Patent Publication No. 10-0430495 describes an aqueous acrylic adhesive composition for a PVC wall and a method of manufacturing the same.

However, in the case of the conventional water-based acrylic adhesive, excellent adhesive strength is exhibited under normal room temperature conditions, but when the temperature decreases, there is a disadvantage in that the adhesion between the adherend and the substrate is not well performed, resulting in a significant decrease in adhesive strength.

Patent Registration No. 10-0262136 Patent Registration No. 10-0020956

  The present invention is to solve the problems as described above, and does not use an organic solvent to ensure eco-friendly and safety, and at the same time, has excellent adhesion strength to maintain long-term adhesion durability, excellent adhesion regardless of the ambient temperature in winter and summer It is an object to provide an environmentally friendly aqueous wall adhesive composition and a method for manufacturing the same.

In order to achieve the above object, the present invention is 15 to 25% by weight of EVA (ethylene vinyl acetate) copolymer, 5 to 10% by weight of polyvinyl alcohol (PVA), 15 to 25% by weight of silica sand, 25 to 35% by weight of cement, Provided is an aqueous wall adhesive composition comprising 2 to 5% by weight of a thickener and 10 to 20% by weight of water. At this time, the composition may further include 1 to 5% by weight of activated carbon.

On the other hand, in order to achieve the above object, the present invention is a step of stirring for 20 to 30 minutes after adding PVA to distilled water of 80 ~ 90 ℃; Putting EVA copolymer in distilled water to which PVA is added and stirring for 1-2 hours; Adding silica sand and cement to the mixed solution to which the EVA copolymer is added and stirring for 30 minutes to 1 hour; And adding a thickener to the mixed solution in which the silica sand and cement are added and stirring for 30 minutes to 1 hour.

The aqueous wall adhesive composition prepared according to the present invention does not use an organic solvent to improve workability and stability, has excellent adhesion strength to maintain long-term adhesion durability, and has excellent adhesion regardless of ambient temperature.

In particular, the conventional wall adhesive compositions are made of epoxy resin as a main component, and when a fire occurs, they become a medium of fire propagation and greatly increase the fire in the building, causing damage to human beings as well as the discharge of harmful components used in the epoxy resin itself and buildings, causing air pollution. Although it was a major cause of causing the present invention, when using the present invention, it is possible to control the combustion of a building, thereby preventing human damage and air pollution.

Hereinafter, the present invention will be described in detail with reference to examples and drawings of the present invention. These examples are only provided by way of example to illustrate the present invention in more detail, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples. .

In addition, unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the art to which the present invention belongs, and in case of conflict, the present specification including definitions. The description will take precedence.

In order to clearly describe the proposed invention in the drawings, parts irrelevant to the description are omitted, and like reference numerals are assigned to similar parts throughout the specification. And, when it is said that a part "includes" a certain component, this means that other components may be further included instead of excluding other components unless otherwise specified. In addition, "part" described in the specification means one unit or block that performs a specific function.

The identification numbers (first, second, etc.) in each step are used for convenience of explanation, and the identification numbers do not describe the order of each step, and each step does not explicitly describe a specific order in the context. It may be carried out differently from the order specified above. That is, each step may be performed in the same order as specified, or may be performed substantially simultaneously, or in the opposite order.

The aqueous wall adhesive composition of the present invention is 15-25% by weight of ethylene vinyl acetate (EVA) copolymer, 5-10% by weight of polyvinyl alcohol (PVA), 15-25% by weight of silica sand, 25-35% by weight of cement, thickener It characterized in that it contains 2 to 5% by weight and 10 to 20% by weight of water. Hereinafter, each configuration will be described in detail.

The ethylene vinyl acetate (EVA) copolymer has a strong cohesive force and provides adhesion to the adhesive composition while maintaining strength to a certain degree, and can be prepared by copolymerizing ethylene monomer and vinyl acetate monomer. The ethylene monomer and the vinyl acetate monomer may be used a conventional monomer used in the art, in particular, it is preferable to copolymerize in an amount of 10 to 20% by weight of ethylene monomer and 80 to 90% by weight of vinyl acetate monomer.

It is recommended that the ethylene vinyl acetate (EVA) copolymer has a high solid content, specifically, AF7200 (Air products company) having a solid content of 72% or AF426 (Ari products company having a solid content having a carboxy function of 62%). ) Can be used. The EVA copolymer preferably has a solids content of 55% or more, and particularly, a solids content of 65-80% is preferred for improving work speed and adhesion.

In addition, the EVA (ethylene vinyl acetate) copolymer is preferably included in 15 to 25% by weight in the composition. When the content is within the above range, after short pre-drying, high adhesive strength is maintained to improve the molding effect of the final product, and workability and adhesive strength can be improved.

The polyvinyl alcohol (PVA) serves as a dispersant and at the same time, a hydroxyl group serves to improve the overall functionality of the adhesive composition. The content is preferably included in 5 to 10% by weight in the composition, and when the content is within the above range, there is an effect of further improving the heat resistance, heat resistance, and adhesion of the aqueous adhesive.

The silica sand is to serve as a filler and a supplement, the content is preferably contained in 15 to 25% by weight in the composition, if the content is less than the above range, the strength of the composition may be lowered, if it exceeds this Adhesion may deteriorate.

The silica sand may be used alone, but preferably, silica sand surface-treated with silicone oil may be used to further increase miscibility.

At this time, the silicone oil, a variety of commercially available silicone oils can be used, specifically, dimethyl silicone oil (dimethyl silicone oil), methylphenol silicone oil (methylphenol silicone oil), methyl hydrogen silicone oil (methyl hydrogen silicone oil) ), Amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, carbinol-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil, fluorine-modified silicone oil, and the like can be used.

The viscosity of the silicone oil is not particularly limited, it is preferable to use the one of 20 ~ 500cSt, the surface treatment method with silicone oil is not particularly limited. For example, after dissolving the silicone oil in a solvent such as toluene, the silica sand is dispersed in the solvent and the solvent is evaporated to attach the silicone oil to the surface of the silica sand. A dry method of attaching silicone oil to the surface and performing a predetermined heat treatment may be used.

The content of the silicone oil adhered to the surface of the silica sand is preferably 1 to 3 parts by weight compared to 100 parts by weight of the silica sand. If it is smaller than this, it is difficult to play a role in increasing the degree of miscibility, and if it is larger than this, silica sand may be aggregated.

Meanwhile, in order to further increase the miscibility and stability of the silica sands, the composition may further include 1 to 3 parts by weight of cyclodextrin compared to 100 parts by weight of silica sand. The cyclodextrin is a cyclic compound composed of a glucose group as a repeating unit, and forms a complex with additives such as silica sand and attracts and immobilizes the additives by hydrogen bonding to the outside, thereby minimizing the outflow of additives and composition Can give stability.

Various cyclodextrins commercially available may be used as the cyclodextrin, and in one embodiment, 2,3,6-tri-O-naphthoyl-beta-cyclodextrin may be used.

On the other hand, the cement is an inorganic filler, the content of which is preferably included in 25 to 35% by weight in the composition, when the content is less than the above range, the strength of the composition may be lowered, and if it exceeds this, the adhesiveness is lowered Can be.

The thickener is intended to improve flowability and workability by adjusting the viscosity of the composition, and a thickener generally used may be used without limitation. The content is preferably included in the composition in 2 to 5% by weight, and if it is smaller or more than this, the overall workability is reduced and the physical properties may be deteriorated.

Meanwhile, the composition may further include 1 to 5% by weight of activated carbon in the total composition in order to increase flame retardancy as necessary. At this time, in order to further increase the flame retardancy, the activated carbon may be a zinc-activated carbon composite. The zinc-activated carbon composite is obtained by dispersing an organometallic coupling agent and activated carbon in an aqueous medium, adding zinc chloride or zinc iodide to the dispersion, followed by drying to obtain a zinc / coupling agent / activated carbon composite, and then drying the dried composite. It can be obtained by firing.

Preferably, the activated carbon is modified by surface oxidation, for example, 1) a dry oxidation method in which oxidant gases such as water vapor, carbon dioxide, oxygen and ozone are contacted with activated carbon at high temperature, and 2) activated carbon and an oxidant (eg Hydrogen peroxide, nitric acid, sulfuric acid, etc.) There is wet oxidation in which the reagent solution reacts. Others include electrochemical oxidation, ozone treatment, annealing, microwave cooling plasma heat treatment, and the like.

의 화학식을 가지는 커플링제가 사용될 수 있으며, 상기 식에서, RO는 가수분해기 또는 기질 반응성기로, 상기 R은 탄소수 2 내지 10개이고, 상기 Z는 알루미늄, 실리콘, 티타늄, 아연 및 지르코늄으로 구성된 군에서 선택되는 1종 이상의 원소이며, 상기 R'는 지방족, 나프텐계 또는 방향족의 열가소성 작용기로서, 탄소수 10 내지 40을 가지고, Y는 비닐, 알릴, 아크릴 또는 메타크릴의 열반응성 또는 열경화성 관능기이며, n은 1 내지 3의 정수이다. 상기 유기금속계 커플링제의 사용량은 특별히 한정되지 않지만, 활성탄 중량을 기준으로, 0.1~5중량%의 양으로 사용될 수 있다. The organometallic coupling agent

Coupling agent having the formula may be used, wherein RO is a hydrolysis group or a substrate reactive group, R is 2 to 10 carbon atoms, and Z is selected from the group consisting of aluminum, silicon, titanium, zinc and zirconium. One or more elements, wherein R 'is an aliphatic, naphthenic or aromatic thermoplastic functional group, having 10 to 40 carbon atoms, Y being a heat-reactive or thermosetting functional group of vinyl, allyl, acrylic or methacryl, n being 1 to It is an integer of 3. The amount of the organometallic coupling agent is not particularly limited, but may be used in an amount of 0.1 to 5% by weight based on the weight of activated carbon.

The operating conditions and reaction conditions, such as the addition temperature of the organometallic coupling agent, the addition method, the addition rate and the stirring rate, are not particularly limited, and may be determined by ordinary knowledge and level of those skilled in the art.

On the other hand, as a modified mineral-based filler for imparting antimicrobial properties to the composition, the adhesive composition of the present invention may further comprise 1 to 5% by weight of the alkaline earth metal carbonate coated with a water-insoluble copper salt in the total composition.

The alkaline earth metal carbonate is selected from the group consisting of magnesium carbonate, magnesium calcium carbonate, calcium carbonate, or mixtures thereof, and the water-soluble copper salt is copper nitrate, copper sulfate, copper acetate, copper chloride, copper bromide, hydrates thereof, and It is selected from the group consisting of mixtures of these.

The water-soluble copper salt may be coated by a spraying method, and is preferably sprayed at a temperature of 80 to 120 ° C according to an embodiment.

Meanwhile, the aqueous wall adhesive composition of the present invention comprises: i) adding PVA to distilled water at 80 to 90 ° C. and stirring for 20 to 30 minutes; ii) adding EVA copolymer to distilled water to which PVA is added and stirring for 1 to 2 hours; iii) adding silica sand and cement to the mixed solution to which the EVA copolymer is added and stirring for 30 minutes to 1 hour; And iv) adding a thickener to the mixed solution to which the silica sand and cement are added and stirring for 30 minutes to 1 hour.

Description of each component is as described above, and when activated carbon or copper salt is added, it may be added together in step iii).

Hereinafter, examples and experimental examples of the present invention will be described. However, the scope of the present invention is not limited to the following preferred embodiments, and those skilled in the art can implement various modified forms of the contents described herein within the scope of the present invention.

<Example 1>

After heating 100 g of distilled water to 85 ° C., 30 g of PVA was added, followed by stirring at RPM 500 for 20 minutes. 30 g of EVA was added to 25 g of the PVA solution and stirred at RPM 1500 for 1 hour. When stirring was completed, 20 g of silica sand and 30 g of cement were added to the mixed solution, followed by stirring at low speed at RPM 500 for 30 minutes. Then, 3 g of a thickener was added and stirred with PM 500 for 30 minutes to prepare an adhesive composition.

<Example 2>

After heating 100 g of distilled water to 85 ° C., 30 g of PVA was added, followed by stirring at RPM 500 for 20 minutes. 30 g of EVA was added to 25 g of the PVA solution and stirred at RPM 1500 for 1 hour. When the stirring was completed, 20 g of silica sand coated with dimethyl silicone oil and 30 g of cement were added to the mixed solution, followed by stirring at low speed at RPM 500 for 30 minutes. Then, 3 g of a thickener was added and stirred with PM 500 for 30 minutes to prepare an adhesive composition.

<Comparative Example 1>

Two types of commercially available aqueous acrylic adhesive compositions were used as Comparative Example 1.

<Experimental Example>

[Adhesive strength test method]

(1) Room temperature (25 ℃ ± 2 ℃) adhesive strength

After the adhesive was applied to the slate plate with HERA, an open time was given for about 15 to 20 minutes, and then the wall specimen was pressed and adhered to the slate plate. After 2 hours, 4 hours, 24 hours, and 168 hours respectively at room temperature, the specimen was peeled off and measured at 90 °.

(2) Cold adhesion strength

After applying the adhesive to the slate plate in 10 ° C thermostat with Hera, the open time was given for about 15 to 20 minutes, and then the wall specimen was pressed and adhered to the slate plate. Then, after 2 hours, 4 hours, 24 hours, and 168 hours, respectively, in a 10 ° C. thermostat, 90 ° was peeled off.

Properties Comparative Example 1 Example 1 Example 2 23 ℃ 10 ℃ 23 ℃ 10 ℃ 23 ℃ 10 ℃
90 ° peeling
Adhesive strength
(Kgf / 25mm) 2 hours later 1.5 1.2 1.8 1.5 2.0 2.2 4 hours later 2.1 1.5 2.4 2.3 3.0 3.1 24 hours later 5.5 4.6 7.7 6.1 7.8 7.4 After 168 hours 7.4 5.6 8.4 7.1 9.2 8.7

As can be seen from the above table, the results of comparing physical properties according to Comparative Examples 1 and 1 and 2 at 23 ° C. at room temperature and 10 ° C. at low temperature were confirmed to have the best adhesive strength in Example 2.

The present invention is not limited to the specific embodiments and descriptions described above, and various modifications can be carried out by anyone having ordinary knowledge in the technical field to which the present invention pertains without departing from the gist of the present invention as claimed in the claims. And such modifications are within the protection scope of the present invention.

Claims (5)

EVA (ethylene vinyl acetate) copolymer 15-25% by weight, PVA (polyvinyl alcohol) 5-10% by weight, silica sand 15-25% by weight, cement 25-35% by weight, thickener 2-5% by weight, activated carbon 1 ~ 5% by weight and 10 ~ 20% by weight of water,
The silica sand is a silica sand surface-treated with silicone oil, wherein the silicone oil is dimethyl silicone oil, methylphenol silicone oil, methyl hydrogen silicone oil, amino-modified silicone oil, epoxy-modified silicone oil, carboxyl-modified silicone oil, Carbinol-modified silicone oil, polyether-modified silicone oil, alkyl-modified silicone oil or fluorine-modified silicone,
The viscosity of the silicone oil is 20 ~ 500cSt, the content of the silicone oil adhered to the surface of the silica sand is 1 to 3 parts by weight compared to 100 parts by weight of silica sand aqueous wall adhesive composition. delete delete delete delete