KR101796032B1 - Aqueous Inorganic Incombustible expanded Adhesive Composition and Preparation Method Thereof - Google Patents

Abstract

It is resistant to fire, has no corrosiveness to metal, and has enhanced adhesive strength. It is widely used in adhesives such as fireproof doors, sandwich panels, fire retardant boards, fumed silica boards, lightweight foam walls for fire resistance, non- There is provided a water-soluble, inorganic fire-resistant foam adhesive composition useful as a filler, such as nonflammable foam silicone, nonflammable foam gasket, nonflammable foam insulation, nonflammable foam conduit penetration filler, incombustible foam pipe penetration filler, curtain wall linear filler, and a method of making the same.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a water-soluble inorganic non-foaming foam adhesive composition,

The present invention relates to a water-soluble inorganic non-foaming foam adhesive which is resistant to fire, has no corrosiveness against metals and has enhanced adhesion, and is useful as an adhesive or filler for fireproof doors, sandwich panels, fire retardant boards, fumed silica boards, Compositions and methods for their preparation.

Recently, a characteristic feature of a large-scale fire accident is that a large amount of smoke and toxic gas generated by the combustion of the interior material in the case of fire leads to a large-scale disaster accompanied with many human casualties. Such large-scale disasters are caused by the difficulty of evacuation due to smoke and toxic gas generated in the fire due to the use of various polymeric materials.

Smoke and toxic gases are caused by the combustion of various polymer materials used as interior and exterior materials for buildings, vehicles, furniture, and home appliances. The solution is to provide fire resistance or nonflammability to polymer materials, And to minimize the damage of life and property by suppressing the fire early. In addition, since the regulations on the combustion of rubber, fiber, and paper including synthetic resin are being strengthened all over the world, the necessity of refractory or nonflammable is greatly emphasized.

For example, a fire door of a building is used as an opening or closing door of an entrance door or an emergency passage of a general house, an apartment, a factory, an office, a prefabricated building or the like, And it shall be equipped with the requirements of physical property that fire or emergency doors should not be burned or deformed by strong internal heat in case of fire.

Generally, fireproof doors made of metal are separated from each other by a front panel and a back panel in order to lighten the load, and honeycomb cores, oil, and inorganic heat insulators are inserted into the spaces so as to lighten the weight of fire doors, , So that the heat radiating effect is excellent. However, most urethane foam adhesives are used for bonding panels and honeycomb cores. These urethane foam adhesives are applicable to refractory materials with a Limiting Oxygen Index (LOI) of 17% and a limit oxygen index of more than 27% And the ignition point is low at about 50 ℃. On the other hand, there is no problem of releasing toxic gas during combustion.

In the case of sandwich panels using oil-based and core-insulating materials between the metal plate and the metal plate, a urethane foamable adhesive is used to bond the metal plate and the core. Such urethane foamable adhesive easily burns in case of fire, It is a factor that deteriorates the fire resistance performance.

Therefore, it is required to develop a nonflammable foam adhesive which is resistant to fire and does not generate toxic gas.

Disclosure of the Invention The object of the present invention is to provide a water soluble inorganic fire retardant which is resistant to fire, has no corrosiveness against metals and has enhanced adhesion and is useful as an adhesive or filler for fireproof doors, sandwich panels, fire retardant boards, fumed silica boards, A foamed adhesive composition and a process for producing the same

A water-soluble inorganic flame retardant foam adhesive composition according to one aspect of the present invention is a water-soluble inorganic flame retardant foam adhesive composition comprising a two-component adhesive containing a first component as an adhesive and a second component as an adhesive force hardening agent. Wherein the first component is selected from the group consisting of 23 to 50 wt% of a water-soluble thin film forming material, 24 to 40 wt% of a refractory inorganic composite filler, 2 to 5 wt% of reinforcing fibers, 0.3 to 1 wt% To 50% by weight of water, 0.1 to 0.3% by weight of a blowing agent, and 0.01 to 0.03% by weight of a second coupling agent. Wherein the water-soluble thin film-forming material comprises at least one of zinc oxide-containing water-soluble resin, sodium silicate, potassium silicate and water-soluble epoxy resin, and the refractory inorganic composite powder is at least one selected from the group consisting of expanded peridotite, expandable vermiculite, Cordierite Powder). Wherein the reinforcing fiber comprises at least one of a polypropylene fiber, a polyester fiber and an acrylic fiber. The first coupling agent includes at least one of a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent. Wherein the blowing agent comprises at least one of azodicarbonamide (ADC) blowing agent, 4,4-oxybisbenzenesulfonylhydrazide (OBSH) blowing agent, microspheres blowing agent and swelling agent. (E. G., A mixture) comprising at least one of a complex aluminum phosphate, a sodium fluorosilicate, a magnesium powder and a silicon dioxide fine powder. And the second component is included in an amount of 5 to 10 parts by weight based on 100 parts by weight of the entire first component.

The water-soluble inorganic flame retardant foam adhesive composition is a composition comprising 1 part selected from the group consisting of a dispersing agent, an adhesion promoter, an antioxidant, a surfactant, a defoaming agent, a crosslinking agent, a coloring agent, a curing agent, an ultraviolet light blocking agent, a UV stabilizer, an emulsifier, May further comprise additives of the species.

The water-soluble inorganic fire-retardant foam adhesive composition may further comprise a coloring composition which selectively introduces one of the coloring mixtures to produce a necessary color.

The colorant mixture may be one of iron oxide, barium chromate, ultramarine, chromium oxide, manganese dioxide, carbon black, cadmium, titanium, and zinc oxide.

According to an aspect of the present invention, there is provided a method for producing a water-soluble inorganic non-foaming foam adhesive composition, comprising the steps of: 1) heating water to 70 to 100 캜 by adding water to a reaction vessel; Step 2) The refractory inorganic filler powder is charged into a stirrer and stirred, and then a first coupling agent is further added to coat the refractory inorganic filler powder with the first coupling agent. Step 3) further adding the refractory inorganic composite powder coated with the first coupling agent to the reaction vessel of the step 1) and stirring the mixture; Step 4) further adding a water-soluble thin film-forming substance to the reaction vessel of step 3) and stirring the mixture; Step 5) further adding the reinforcing fiber to the reaction vessel of step 4) and stirring the same; Step 6) Stirring the foaming agent into a stirrer, adding a second coupling agent, and then coating; Step 7) further adding and stirring the foaming agent coated with the second coupling agent to the reaction vessel of the step 5) to prepare a first component as an adhesive; Step 8) 5 to 10 parts by weight of a second component which is an adhesion strengthening hardener containing at least one of aluminum complex phosphate, sodium fluorosilicate, magnetic powder and silicon dioxide fine powder with respect to 100 parts by weight of the first component, ) To obtain a water-soluble inorganic flame-retardant adhesive composition; Step 9) adding one of the coloring mixtures to the reaction vessel of step 8) to obtain a water-soluble inorganic flame retardant adhesive composition of the required color. The first coupling agent is contained in an amount of 0.3 to 1 wt% based on 100 wt% of the first component, and the second coupling agent is included in an amount of 0.01 to 0.03 wt%.

INDUSTRIAL APPLICABILITY According to the present invention, excellent adhesion, nonflammability, foamability and corrosion resistance to metal materials are avoided. On the other hand, high durability can be expected because of good adhesion with inorganic or organic materials. The water-soluble inorganic fire-resistant foam adhesive composition of the present invention can improve fire resistance and durability when used as an adhesive or a filler for fireproof doors, sandwich panels, fire retardant boards and fumed silica boards.

Hereinafter, the present invention will be described in detail.

The water-soluble inorganic fire-retardant foam adhesive composition of the present invention comprises an ingredient (1) which is an adhesive and an ingredient (2) which is an adhesive strength enhancing hardener. At this time, the component (2) is included in an amount of 5 to 10 parts by weight based on 100 parts by weight of the total of the component (1).

The adhesive comprises the following component (1).

Specifically, the component (1) contains 25 to 50% by weight of a water-soluble thin-film forming material, 20 to 40% by weight of a fire-resistant inorganic composite powder, 2 to 5% by weight of reinforcing fibers, 0.3 to 1% by weight of a first coupling agent, 0.1 to 0.3% by weight of a blowing agent, 0.01 to 0.03% by weight of a second coupling agent, and 0.02 to 5% by weight of a multifunctional composite additive. The multifunctional composite additive may include an organosilicon wetting agent, an adhesion promoter, a nanostructured material, and the like.

In this case, the water-soluble thin film-forming material is coated with a water-soluble inorganic flame retardant foam adhesive composition to give excellent adhesion to metal and non-metal surfaces, and forms a firm thin film on the metal surface to prevent contact between the metal surface and air, . Preferably, water glass, a water-soluble epoxy resin, or a zinc oxide-containing water-soluble resin is used. The water glass is an aqueous solution of one or more kinds of silicate materials such as sodium silicate, potassium silicate and sodium silicate potassium, and the content of the silicate material is 0.5 to 80% by weight. The zinc oxide-containing water-soluble resin may be a water-soluble epoxy resin or a water-soluble acrylic resin containing zinc oxide powder.

The water-soluble thin film-forming material is contained in an amount of 25 to 50% by weight in the component adhesive (1). If the content of the water-soluble thin film-forming material is less than the above range, there is a fear that film or thin film formation is difficult. If the content is above the range, hardening components are not sufficient in the composition, and curing is difficult.

The refractory inorganic filler powder is contained in an amount of 20 to 40% by weight of the component adhesive (1), and the thermal expansion coefficient of the water-soluble inorganic incombustible foam adhesive composition is controlled so that the adhesive has a predetermined strength and crack resistance. That is, the water-soluble inorganic non-foaming foam adhesive composition has a coefficient of thermal expansion equal to or close to the coefficient of thermal expansion of the adherend, thereby improving the adhesive strength and the durability of the adherend. If the content of the refractory inorganic composite powder is out of the above range, it is difficult to control the viscosity of the water-soluble inorganic non-inflammable foam adhesive composition, which makes it difficult to apply the composition to the adhesive agent.

The refractory inorganic composite powder may include at least one material selected from the group consisting of expanded sepiolite, expanded vermiculite, expanded pearlite, and cordierite. have. Preferably, the refractory inorganic composite powder has a particle size of 1500 to 2000 mesh.

The reinforcing fiber is added to improve the crack resistance of the water-soluble inorganic flame-retardant foam adhesive composition, and is contained in an amount of 2 to 5% by weight of the component adhesive, and polypropylene fiber, polyester fiber and acrylic fiber are possible.

The coupling agent is a compatibilizer used for improving the compatibility of the water-soluble thin film forming material and the refractory inorganic composite powder. The coupling agent may be selected from the group consisting of a silane coupling agent, a titanate coupling agent, an aluminate coupling agent, and combinations thereof. Preferably, a water soluble coupling agent is used. The coupling agent may be contained in an amount of 0.3 to 1% by weight based on the component adhesive (1). When the coupling agent is contained within the above range, the compatibility of the water-soluble thin film forming material and the refractory inorganic composite powder is improved, and the overall physical properties of the water-soluble inorganic non-fluoro foam adhesive composition are improved.

The blowing agent causes a chemical reaction during the production process to produce gas, which is dissolved in the water-soluble resin or water glass in the reactor. That is, the foaming agent reacts with a predetermined temperature or pressure condition to change its molecular structure and produces gas, which corresponds to a chemical foaming agent. Preferably, azodicarbonamide (ADC) blowing agent or 4,4-oxybisbenzenesulfonylhydrazide (OBSH) blowing agent, microspheres blowing agent, and swelling agent are used. Such a foaming agent is used in an amount of 0.1 to 0.3% by weight in the component adhesive (1). If the content of the foaming agent is too small, the foaming can not be performed smoothly. If the foaming agent is contained too much, the foaming becomes large and the foaming cell may be weakened.

Water is included as the remainder so that the (1) component adhesive satisfies 100% by weight of the total.

(1) 5 to 10 parts by weight of a curing agent of component (2) is contained in 100 parts by weight of the adhesive.

The curing agent is added to enhance the adhesion of the water-soluble inorganic non-foaming foam adhesive composition of the present invention to the metallic material to which it is applied. If the content of the curing agent is less than the above range, the effect of imparting adhesive force to the adherend is insignificant. On the other hand, if the content exceeds the above range, the viscosity of the adhesive composition becomes high and the applicability becomes poor.

If necessary, the adhesive composition of the present invention may be added with an additive. The additive constituting the present invention is not particularly limited as long as it is added for the purpose of reinforcing the desired properties for the purpose of enhancing the adhesiveness in the present invention and it is not intended to impair the purpose of the present invention as long as it is for securing basic physical properties such as viscosity, Any of these may be added within the range not exceeding the above range. For example, the additive may further include at least one additive selected from the group consisting of a dispersant, an adhesion promoter, an antioxidant, a surfactant, a defoamer, a crosslinking agent, a colorant, a curing agent, an ultraviolet screening agent, a UV stabilizer, an emulsifier, But is not limited thereto. The additive is preferably contained in an amount of 0.02 to 5% by weight of the component adhesive (1).

On the other hand, the water-soluble inorganic non-foaming foam adhesive may further include a coloring composition which exhibits the required color by selectively adding one of the coloring mixtures. At this time, the coloring agent may be selected from among iron oxide, barium chromate, ultramarine, chromium oxide, manganese dioxide, carbon black, cadmium, titanium, and zinc oxide.

Next, the method for producing the above water-soluble inorganic flame retardant foam adhesive composition will be described.

The water-soluble inorganic non-foaming foam adhesive composition of the present invention described above

Step 1) adding water to the reaction vessel and heating to 70 to 100 占 폚;

Step 2) injecting a refractory inorganic composite powder into a stirrer, stirring the mixture, and adding a coupling agent to coat the refractory inorganic composite powder with a first coupling agent;

Step 3) further adding the refractory inorganic composite filler coated with the first coupling agent to the reaction vessel of the step 1) and stirring the mixture;

Step 4) further adding a water-soluble thin film-forming substance to the reaction vessel of step 3) and stirring the mixture;

Step 5) further adding the reinforcing fiber to the reaction vessel of step 4) and stirring the same;

Step 6) Stirring the foaming agent into a stirrer, adding a second coupling agent, and then coating;

Step 7) The foaming agent coated with the second coupling agent is further added to the reaction vessel of step 5) and stirred to prepare the component (1) adhesive, and (1) .

Step 8) The method further comprises: (1) further adding and stirring (2) 5 to 10 parts by weight of the adhesion-force hardening agent to 100 parts by weight of the adhesive to the reaction vessel in the step 7) to provide a water-soluble inorganic flame retardant adhesive composition.

Step 9) adding one of the coloring mixtures to the reaction vessel in step 8) to stir the mixture to provide the required color composition.

Each step will be detailed below.

Step 1) First, water is added to the reaction vessel and heated to 70 to 100 占 폚.

Step 2) Subsequently, the refractory inorganic composite powder is put into a stirrer and stirred, and then a first coupling agent is further added to coat the refractory inorganic composite powder with the first coupling agent. This step is a step for improving the compatibility with the water-soluble thin film forming material by coating the refractory inorganic composite powder with the first coupling agent. At this time, after the refractory inorganic composite powder is charged, the stirring speed is from 450 to 550 times / minute and from 8 to 12 minutes. After the first coupling agent is charged, the stirring speed is from 700 to 900 times / .

Step 3) Next, the refractory inorganic composite powder coated with the first coupling agent is further added to the reaction vessel of the above step 1) and stirred. At this time, the agitation speed is set to 270 to 330 times / min for 25 to 35 minutes.

Step 4) Subsequently, an aqueous thin film forming material is further added to the reaction vessel of the step 3) and stirred. At this time, stirring is carried out at a rate of 450 to 550 times / minute for 25 to 35 minutes.

Step 5) Next, the reinforcing fiber is further added to the reaction vessel of step 4) and stirred. If necessary, additives can be added after addition of reinforcing fibers and stirring.

Step 6) The foaming agent is added to a stirrer and stirred, and then a second coupling agent is added thereto, followed by coating. At this time, stirring was carried out at a stirring speed of 200 times / minute for 5 minutes, and a second coupling agent was added to adjust the dispersion time to 10 minutes.

Step 7) The foaming agent is further added and stirred into the reaction vessel of step 5) to prepare the component (1) adhesive, and 100 parts by weight of the produced adhesive (1) is produced.

Step 8) (1) 5 to 10 parts by weight of the adhesive force hardening agent (2) is further added to the reaction vessel of the step 7) to 100 parts by weight of the adhesive to obtain a water-soluble inorganic flame retardant foam adhesive composition. At this time, the stirring speed is 500 rpm and the stirring is continued for 5 minutes.

Step 9) One of the coloring mixtures is added to the reaction vessel in step 8) and stirred to obtain the required color composition.

The present invention may be better understood by the following examples, which are for the purpose of illustrating the invention and are not intended to limit the scope of protection defined by the appended claims.

Example  One

400 kg of water was put into a 2000 L reaction vessel and the temperature was heated to 80-100 캜. 100 kg of expanded permafrost of 1500-2000 mesh, and 200 kg of expanded vermiculite were charged into a high-speed centrifuge, and the rotation speed was set to 450-550 times / min and dispersed for 10 minutes. Then, 3 kg of a water-soluble coupling agent, which is the first coupling agent, was put into a centrifuge and dispersed for 20 minutes at a rotation speed of 700-900 times / min.

303 kg of the refractory inorganic composite powder coated with the first coupling agent was charged into a reaction vessel, and the mixture was dispersed for 30 minutes at a rotation speed of 270-330 times / min. 274 kg of zinc oxide-containing water-soluble resin having a solid content of 48 was charged into the reaction vessel and dispersed for 30 minutes at a rotation speed of 450-550 times / minute. Then, 20 kg of polypropylene fiber was further charged into the reaction vessel and stirred for 20 minutes.

1 kg of a mixture of an organosilicon wetting agent, a dispersant and an adhesion promoter was added to the reaction vessel as a multifunctional complex additive, followed by sufficient stirring.

1.8 kg of the OBSH blowing agent was put into a centrifuge and the rotation speed was set to 200 times / minute and the treatment was performed for 5 minutes. Subsequently, 0.2 kg of the second coupling agent is added to the composite foaming agent, and the dispersion time is set to 10 minutes.

2 kg of the foaming agent coated with the second coupling agent is further charged into the reaction vessel and sufficiently stirred.

(2) 80 kg of a material containing at least one of adhesion-strengthening hardener complex aluminum phosphate, sodium fluorosilicate, magnetic powder and silicon dioxide fine powder is added and mixed for 1000 kg of the component-based adhesive of the component (1).

After agitation, it is used as an adhesive such as iron, wooden fire door filler, sandwich panel, fire retardant board and fumed silica board.

Example  2

500 kg of water was put into a 2000 L reaction vessel and the temperature was heated to 80-100 캜. 200 kg of expanding seaweeds having a size of 1500-2000 mesh was charged into a high-speed centrifuge, and the rotation speed was set to 550 times / minute and dispersed for 10 minutes. Then, 4 kg of a water-soluble coupling agent, which is the first coupling agent, was charged into a centrifuge and dispersed for 20 minutes at a rotation speed of 700-900 times / min.

204 kg of the refractory inorganic composite powder coated with the first coupling agent was charged into the reaction vessel and dispersed for 35 minutes at a rotation speed of 320 times / minute. 250 kg of water glass having a solid content of 48% was charged into the reaction vessel and dispersed for 30 minutes at a rotation speed of 500 rpm. Then 40 kg of polypropylene fibers were further charged into the reaction vessel and stirred for 25 minutes.

3 kg of an adhesion promoter and a nano-saline mixture were further added to a reaction vessel using a multifunctional complex additive and stirred sufficiently.

2.7 kg of the OBSH blowing agent was charged into a centrifuge and the rotation speed was set to 200 times / minute and the treatment was performed for 5 minutes. Subsequently, 0.3 kg of the second coupling agent is added to the composite foaming agent and the dispersion time is set to 10 minutes.

(2) a material containing at least one of 80 kg of the adhesive force hardening agent, complex aluminum phosphate, sodium fluorosilicate, magnetic powder and silicon dioxide fine powder is added to 1000 kg of the component-based adhesive, and after mixing and stirring, It is used as adhesives for wooden fire doors, sandwich panels, fire retardant boards and fumed silica boards.

Comparative Example  One

The two component systems of component (1) 1000 and component (2) 80 obtained in Example 1 were mixed and used as an adhesive.

Comparative Example  2

The two components of the component (1) 1000 and component (2) 80 obtained in Example 2 were mixed and the adhesive was used as it was.

Claims (5)

1. A water-soluble inorganic fire-retardant foam adhesive composition comprising a two-component adhesive containing a first component as an adhesive and a second component as an adhesive force-
Wherein the first component comprises 23 to 48.59 weight percent water soluble thin film forming material, 24 to 40 weight percent refractory inorganic composite fill powder, 2 to 5 weight percent reinforcing fiber, 0.3 to 1 weight percent first coupling agent, 25 To 50% by weight of water, 0.1 to 0.3% by weight of a blowing agent, and 0.01 to 0.03% by weight of a second coupling agent,
Wherein the water-soluble thin film-forming substance comprises at least one of zinc oxide-containing water-soluble resin, sodium silicate, potassium silicate and water-soluble epoxy resin,
Wherein the refractory inorganic composite powder comprises at least one of expanded peridotite, expandable vermiculite, happosite fiber and cordierite powder,
Wherein the reinforcing fiber comprises at least one of polypropylene fiber, polyester fiber and acrylic fiber,
Wherein the first coupling agent comprises at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent,
Wherein the blowing agent comprises at least one of azodicarbonamide (ADC) blowing agent, 4,4-oxybisbenzenesulfonylhydrazide (OBSH) blowing agent, microspheres blowing agent and swelling agent,
Wherein the second component comprises at least one of complex aluminum phosphate, sodium fluorosilicate, Magnatic powder and silicon dioxide fine powder,
Wherein the second component is contained in an amount of 5 to 10 parts by weight based on 100 parts by weight of the entire first component. The method according to claim 1,
The two-component adhesive
The water-soluble inorganic non-foaming foam adhesive composition may contain,
And one kind of additive selected from the group consisting of a dispersant, an adhesion promoter, an antioxidant, a surfactant, a defoaming agent, a crosslinking agent, a coloring agent, a curing agent, an ultraviolet screening agent, a UV stabilizer, an emulsifier, Soluble inorganic fire-retardant foam adhesive composition. The method according to claim 1,
The water-soluble inorganic fire-retardant foam adhesive composition according to claim 1, wherein the water-soluble inorganic fire-retardant foam adhesive composition further comprises a coloring composition which selectively introduces one of the coloring mixtures to provide a necessary color. The method of claim 3,
Wherein the colorant mixture is one of iron oxide, barium chromate, ultramarine, chromium oxide, manganese dioxide, carbon black, cadmium, titanium, and zinc oxide. Step 1) adding water to the reaction vessel and heating to 70 to 100 占 폚;
Step 2) The refractory inorganic filler powder is charged into a stirrer and stirred, and then a first coupling agent is further added to coat the refractory inorganic filler powder with the first coupling agent.
Step 3) further adding the refractory inorganic composite powder coated with the first coupling agent to the reaction vessel of the step 1) and stirring the mixture;
Step 4) further adding a water-soluble thin film-forming substance to the reaction vessel of step 3) and stirring the mixture;
Step 5) further adding the reinforcing fiber to the reaction vessel of step 4) and stirring the same;
Step 6) Stirring the foaming agent into a stirrer, adding a second coupling agent, and then coating;
Step 7) further adding and stirring the foaming agent coated with the second coupling agent to the reaction vessel of the step 5) to prepare a first component as an adhesive;
Step 8) 5 to 10 parts by weight of a second component which is an adhesion strengthening hardener containing at least one of aluminum complex phosphate, sodium fluorosilicate, magnetic powder and silicon dioxide fine powder with respect to 100 parts by weight of the first component, ) To obtain a water-soluble inorganic flame-retardant adhesive composition;
Step 9) adding one of the coloring mixtures to the reaction vessel of step 8) to obtain a water-soluble inorganic flame retardant adhesive composition of the required color,
Wherein the first coupling agent is contained in an amount of 0.3 to 1% by weight based on 100% by weight of the first component, and the second coupling agent is contained in an amount of 0.01 to 0.03% by weight.