KR102293544B1 - Method for manufacturing peelable pvb resin coat composition having flame-resistance - Google Patents

Abstract

The present invention relates to a method for producing a flame-retardant peelable coating agent comprising a PVB (Polyvinyl butyral) resin, (a) adding 1 to 10 parts by weight of a phosphorus-based flame retardant to 15 parts by weight of distilled water and stirring at 250 to 350 rpm, ( b) adding the mixture prepared in (a) to 100 parts by weight of a PVB (Polyvinyl butyral) resin, and adding a flame retardant stirring at 650 to 750 rpm for 20 to 25 minutes, (c) the composition that has undergone the step (b) Then, adding 0.1 to 10 parts by weight of a liquid dispersant based on 100 parts by weight of the PVB resin and stirring the dispersant at 350 to 450 rpm for 5 to 20 minutes, (d) 23 parts by weight of distilled water based on 100 parts by weight of the PVB resin After adding 0.5 to 20 parts by weight of a powdery thickener to the mixture to prepare a thickener aqueous solution, the thickener is added to the composition subjected to step (c) and stirred at 100 to 400 rpm for 35 to 45 minutes, (e) A mixing step of adding 1 to 10 parts by weight of a surfactant to the composition that has undergone step (d) based on 100 parts by weight of the PVB resin and stirring at 450 to 550 rpm for 5 to 20 minutes, and (f) the step (e) It relates to a method for producing a flame-retardant peelable PVB resin coating agent comprising adding 0.1 to 5 parts by weight of an antifoaming agent to the rough composition based on 100 parts by weight of the PVB resin and stirring at 250 to 350 rpm for 5 to 15 minutes.

Description

Flame-retardant peelable PVB resin coating agent manufacturing method {METHOD FOR MANUFACTURING PEELABLE PVB RESIN COAT COMPOSITION HAVING FLAME-RESISTANCE}

The present invention relates to a method for producing a flame-retardant peelable coating agent containing a PVB (Polyvinyl butyral) resin, and to a method for producing a PVB resin coating agent having excellent flame retardancy while maintaining excellent physical properties of PVB by including a phosphorus-based flame retardant will be.

PVB (Polyvinyl Butyral) is formed by the reaction of polyvinyl alcohol and butyraldehyde. It is useful in various fields due to its strong bonding strength, excellent adhesion to various material surfaces, excellent toughness, flexibility and optical transparency. this is acknowledged It has excellent acid and alkali resistance and is widely used as an automotive safety glass adhesive, coating agent, paint binder, etc. due to its strong chemical properties in general hydrocarbon solvents. Moreover, it is known as an optimal material for peelable coating that shows strong adhesion to various materials such as metal, glass, wood, weight, and fabric.

However, despite the excellent properties described above, PVB has no flame retardant performance, so it has a problem of being vulnerable to welding, ignition, etc.

For this reason, there were restrictions that it was difficult to be used in various industrial fields, so the demand for a technology that can utilize PVB resin in various industrial fields by improving flame retardancy while maintaining excellent physical properties of PVB itself continues. .

After repeated research to solve the above problems, the inventors of the present invention have completed a method for producing a PVB resin coating agent having excellent flame retardancy while maintaining the physical properties of PVB.

The present invention uses a PVB resin that has excellent tensile strength and flexibility, excellent chemical resistance, and excellent adhesion to various materials such as metal, glass, wood, and fabric, and has excellent physical properties even when mixed with components other than PVB resin An object of the present invention is to provide a method for producing this maintained PVB resin coating agent.

In particular, an object of the present invention is to provide a method for producing a PVB coating composition having improved flame retardancy properties by solving the problem that conventional PVB resins have poor flame retardancy properties.

The present invention also provides a method for producing a PVB resin coating agent that can be applied to various products and equipment for preventing fire or a fire risk for the purpose of preventing surface contamination in various industrial fields by improving the flame retardant properties of PVB resin aim to do

Furthermore, the present invention provides an optimal composition and manufacturing process that enables the components in the PVB resin coating agent to be uniformly mixed, and to exhibit the same physical properties throughout the coating composition, and to implement a stable formulation that is not easily separated over time. aim to

The present invention relates to a method for producing a flame-retardant peelable coating agent comprising a PVB (Polyvinyl butyral) resin, (a) adding 1 to 10 parts by weight of a phosphorus-based flame retardant to 15 parts by weight of distilled water and stirring at 250 to 350 rpm; (b) adding the mixture prepared in (a) to 100 parts by weight of a PVB (Polyvinyl butyral) resin, and adding a flame retardant stirring at 650 to 750 rpm for 20 to 25 minutes, (c) passing the step (b) To the composition, 0.1 to 10 parts by weight of a liquid dispersant is added based on 100 parts by weight of the PVB resin, and the dispersant is added step of stirring at 350 to 450 rpm for 5 to 20 minutes, (d) 23 parts by weight of distilled water based on 100 parts by weight of the PVB resin After adding 0.5 to 20 parts by weight of a powdery thickener to the part and mixing to prepare a thickener aqueous solution, the thickener is added to the composition subjected to step (c) and stirred at 100 to 400 rpm for 35 to 45 minutes, (e) ) A mixing step of adding 1 to 10 parts by weight of a surfactant to the composition subjected to step (d) based on 100 parts by weight of the PVB resin and stirring at 450 to 550 rpm for 5 to 20 minutes, and (f) the step (e) It includes a defoaming step of adding 0.1 to 5 parts by weight of an antifoaming agent to the composition subjected to 100 parts by weight of the PVB resin and stirring at 250 to 350 rpm for 5 to 15 minutes.

In the present invention, it may further include a dye adding step of adding 0.01 to 5 parts by weight of the dye to the composition that has undergone step (f) based on 100 parts by weight of the PVB resin.

In the present invention, the step (d) comprises the steps of: (d-1) dividing the total amount of the thickener aqueous solution into 5; (d-2) adding the thickener divided into 5 in step (d-1) to the composition subjected to step (c) every 1 to 5 minutes; (d-3) further stirring the composition subjected to step (d-2) for 10 to 40 minutes; may include.

In the present invention, the surfactant may include a glycol-based surfactant, the powdery thickener may include a clay mineral-based thickener, the dispersant may include a wetting and dispersing agent, and the antifoaming agent may include a silicone-based antifoaming agent.

In the present invention, the surfactant includes polyalkylene glycol, the powdery thickener includes an organic modified clay mineral thickener, and the dispersant includes polyoxyalkylene alkyl ether, sodium polyacrylate, sodium alkylnaphthalenesulfonate- It will include one or more selected from the group consisting of formalin condensate, sodium lignin sulfonate, and polyethylene glycol phenyl ether, and the antifoaming agent may include amorphous silica.

In the present invention, the step (e) is to be performed after performing a resting step of resting for 1 to 5 minutes in order to remove air bubbles remaining in the composition obtained in step (d), and the step (f) is , After stirring at room temperature for 3 to 10 minutes, the temperature may be raised to maintain a temperature of 30 to 35 ℃ and stirred for 2 to 5 minutes.

The present invention can produce a PVB resin coating agent that improves the flame retardant properties of the PVB resin, while maintaining excellent tensile strength, flexibility, adhesion to various materials, and chemical resistance of the PVB resin itself.

The PVB resin coating agent prepared according to the present invention has an effect that can be utilized in various industrial fields requiring flame retardant properties.

The present invention can manufacture a PVB resin coating that can be used in industrial sites that require welding or heat treatment such as construction, civil engineering, and the like.

In the present invention, the PVB resin coating agent exhibits the same physical properties throughout the coating composition, and it is possible to implement a stable coating agent formulation that is not easily separated over time.

1 to 3 are flame retardant test (UL 94) reports of PVB resin coatings prepared according to the present invention;
4 and 5 are an EPMA (Electron Probe Micro-Analysis) graph of the composition that has undergone step (b) of the present invention and a photograph of the surface after coating;
6 is a photograph of the surface after coating of the PVB resin coating agent prepared according to the present invention.

Hereinafter, each configuration of the present invention will be described in more detail so that those of ordinary skill in the art to which the present invention pertains can easily carry out, but this is only an example, and the scope of the present invention is defined by the following contents not limited.

Existing PVB resin products do not have flame retardancy, so there is a limitation in the application area of PVB resin. The present invention relates to a method for producing a PVB resin coating agent with improved flame retardant properties while maintaining excellent physical properties of PVB resin.

Specifically, the present invention relates to a method for producing a flame-retardant peelable coating agent comprising a PVB (Polyvinyl butyral) resin, (a) adding 1 to 10 parts by weight of a phosphorus-based flame retardant to 15 parts by weight of distilled water and stirring at 250 to 350 rpm step; (b) adding the mixture prepared in (a) to 100 parts by weight of a PVB (Polyvinyl butyral) resin, and adding a flame retardant stirring at 650 to 750 rpm for 20 to 25 minutes; (c) adding 0.1 to 10 parts by weight of a liquid dispersant to the composition subjected to step (b) based on 100 parts by weight of PVB resin and stirring at 350 to 450 rpm for 5 to 20 minutes; (d) 0.5 to 20 parts by weight of a powdery thickener is added to 23 parts by weight of distilled water based on 100 parts by weight of the PVB resin and mixed to prepare an aqueous thickener solution, and then put into the composition subjected to step (c) and at 100 to 400 rpm adding a thickener stirring for 35 to 45 minutes; (e) a mixing step of adding 1 to 10 parts by weight of a surfactant to the composition subjected to step (d) based on 100 parts by weight of the PVB resin and stirring at 450 to 550 rpm for 5 to 20 minutes; and (f) adding 0.1 to 5 parts by weight of an antifoaming agent to the composition that has undergone step (e) based on 100 parts by weight of the PVB resin and stirring at 250 to 350 rpm for 5 to 15 minutes.

The flame retardant is an additive added to impart flame retardancy to the resin, and in order not to deteriorate the physical properties of the PVB resin, among various flame retardants such as brominated flame retardants, phosphorus-based flame retardants, inorganic flame retardants and halogen flame retardants (excluding bromine-based), phosphorus-based flame retardants It is characterized in that only a flame retardant is added.

Specifically, when the PVB resin and the brominated flame retardant are used, there is a problem that the brominated flame retardant is not uniformly dispersed in the coating composition, and therefore, it is difficult to ensure uniform flame retardancy in the coating composition. Moreover, as the dispersibility is lowered, there is a problem in that it is difficult to be stably maintained in a single formulation, so that the applicability is poor as a liquid paint, and there is a difficulty during operation.

In addition, in the case of a halogen-based flame retardant other than an inorganic flame retardant or a brominated flame retardant, when used with a PVB resin, there is a problem in that the formulation stability of the prepared coating composition is deteriorated. In particular, there is a problem in that it is difficult to apply as a liquid paint, and there is a problem in that it is solidified when stored in a coating state, and there is a problem in that stability during long-term storage is poor.

On the other hand, when a phosphorus-based flame retardant is used, it can be uniformly dispersed in the PVB resin, and thus has an advantage of excellent flame retardancy. Moreover, as the formulation is stably maintained for a long period of time, it has excellent applicability when applied as a liquid paint, and the coating agent does not coagulate or the formulation is not separated during long-term storage, so it has excellent distribution and productivity.

When adding a phosphorus-based flame retardant, it is preferable to add an appropriate amount of the phosphorus-based flame retardant because the dispersion power, flame retardant performance, and basic properties of the PVB resin are changed depending on the amount added, and the flame retardant performance is particularly excellent.

It may further include a dye adding step of adding 0.01 to 5 parts by weight of the dye to the composition that has undergone step (f) based on 100 parts by weight of the PVB resin.

By adding the dye, a color is imparted to the coating agent, and as a peelable coating agent, it has the effect of improving the aesthetics in constituting the outer surface of the substrate.

In the present invention, the PVB resin uses a water-dispersible PVB resin, and thus, the main solvent of the composition is distilled water.

As the surfactant, a glycol-based surfactant may be used, and preferably, polyalkylene glycol may be used. By using the glycol-based surfactant, the miscibility of the aqueous composition containing the water-dispersible PVB can be greatly improved.

The thickener may be one or more selected from the group consisting of a silicate-based thickener, a cellulose-based thickener, and a urethane-based thickener.

Preferably, a clay mineral-based thickener may be used, and most preferably, an organically modified clay mineral thickener may be used. For example, you can use BYK's Optigel-WX.

On the other hand, the dispersant may include a wetting and dispersing agent, for example, polyoxyethylene alkyl ether-based dispersing agent, polysiloxane-based dispersing agent, etc. may be used, and specifically, polyoxyalkylene alkyl ether, sodium polyacrylate, alkyl Sodium naphthalene sulfonate-formalin condensate, sodium lignin sulfonate, may include one or more selected from the group consisting of polyethylene glycol phenyl ether.

Preferably, the dispersant may be added polyoxyethylene alkyl ether, for example, SUNFOL TDA-7 may be used.

As described above, when a wetting and dispersing agent is used, it has good compatibility with water-dispersed PVB, and thus has a significantly improved dispersibility in the coating composition.

The anti-foaming agent may be a silicone-based anti-foaming agent. Preferably, a silicone-based antifoaming agent may be used, and preferably, amorphous silica may be used. For example, DOW's AFE-1110, AFE-0120, etc. can be used.

In addition to this, the present invention may additionally add additives to the purpose of use of the coating composition or to reinforce the function, and the specific configuration is limited in the range that does not impair the purpose of the present invention as long as it is a component utilized in the relevant technical field can be used without

On the other hand, in the method for producing a flame retardant peelable PVB resin coating agent according to the present invention, the step (d) is, (d-1) dividing the total amount of the thickener aqueous solution into 5, (d-2) the (d-1) Adding the thickener divided into 5 in step (c) every 1 to 5 minutes to the composition subjected to step (c), (d-3) stirring the composition subjected to step (d-2) for additional 10 to 40 minutes may include.

This is to gradually increase the viscosity by adding the thickener in 5 portions. If the thickener is added at once, the viscosity of the coating composition is rapidly increased, and there is a problem that a coagulated product may be formed at a local site inside the reaction system.

Therefore, it is preferable to add the thickener in portions, and in particular, it is preferable to add the thickener in 5 portions every 1 to 5 minutes. If the time between the addition intervals is too short, there is a problem that a coagulate is formed at the local site as in the case where the thickener is added at once. There is a problem in forming a viscosity gradient from the lower end to the upper end.

In particular, such a problem needs to be prevented in that it greatly reduces formulation stability and long-term storage stability. It is not easy to turn, and after long-term storage, it is difficult to function as a coating agent, or there is a problem in that the coating operation becomes difficult.

In the flame-retardant peelable PVB resin coating preparation method according to the present invention, the step (e) is performed after performing a rest step of resting for 1 to 5 minutes in order to remove air bubbles remaining in the composition obtained in step (d). In the step (f), after stirring at room temperature for 3 to 10 minutes, the temperature is raised to maintain a temperature of 30 to 35 °C, and stirring may be performed for 2 to 5 minutes.

Although the coating composition according to the present invention is prepared to maintain the excellent tensile strength of the PVB resin, when the stirring process is performed to prepare a uniform composition, the contained air bubbles are maintained in the composition and applied to the surface to be coated and dried. When this is done, an empty space is formed by air bubbles in the coating material, which causes a problem in that the tensile strength of the coating agent decreases.

Therefore, in order to solve this problem, after performing the stirring in step (d), it is preferable to go through a resting step in order to remove visually visible bubbles. When the resting step is shorter than the above time, there is a problem that there is almost no bubble removal effect, and if it is longer than the above time, the mixing degree or reactivity between the antifoaming agent and the coating agent composition is decreased as the addition time of the antifoaming agent is too late. There is a problem that air bubbles cannot be sufficiently removed.

In step (f), after stirring at room temperature for 3 to 10 minutes, the temperature is raised to maintain a temperature of 30 to 35 ° C. and stirring for 2 to 5 minutes is preferable. It is to sufficiently mix so as to be uniformly dispersed in the interior, and after this, raising the temperature to maintain a temperature of 30 to 35 ° C. and stirring for 2 to 5 minutes further activates the reactivity of the antifoaming agent, while reducing the amount of air bubbles present in the coating composition. This is to improve the kinetic energy so that it can escape faster and more quantity.

If the stirring time at room temperature is shorter than the above time, there is a problem that the antifoaming agent is not uniformly mixed, and if it is longer than the above time, it is only to additionally perform an ineffective process even though the antifoaming agent is sufficiently uniformly mixed, There is a problem in that manufacturing efficiency is lowered.

When the temperature rise temperature is lower than the temperature range, there is a problem that there is no big difference in the speed at which the bubbles escape, and when it is higher than the temperature range, a problem in that the coating composition is cured may occur.

Therefore, while maintaining the elevated temperature, by stirring for a short time to sufficiently remove air bubbles, it is possible to finally complete the flame-retardant peelable PVB resin coating agent.

Hereinafter, the present invention will be specifically described by way of examples. However, this is only an embodiment of the present invention, and the scope of the present invention is not limited thereto.

[Production Example]

- After dissolving 15 parts by weight of distilled water and 5 parts by weight of phosphorus-based flame retardant at 300 rpm to avoid clumping, add 100 parts by weight of PVB resin and stir at 700 rpm for 20 to 25 minutes

- Add 3 parts by weight of liquid dispersant to 100 parts by weight of PVB resin at a time and stir at 400 rpm for 10 to 15 minutes

- Divide 5 parts by weight of a thickener into 100 parts by weight of PVB resin, add it every 3 minutes, and stir at 400 rpm to ensure good dispersion. After adding all the thickeners, further stir at 500 rpm for 20 minutes

- In order to evenly mix the hydrophobic thickener and the hydrophilic flame retardant, 5 parts by weight of a surfactant is added to 100 parts by weight of the PVB resin and stirred at 500 rpm for 10 to 15 minutes.

- In order to remove air bubbles remaining after standing for 3 minutes, 3 parts by weight of an antifoaming agent is added to 100 weight parts of PVB resin in a stationary state, and then dispersed slowly at 300 rpm for 10 minutes to remove air bubbles.

- After the bubbles are removed, 1 part by weight of a coloring pigment is added to 100 parts by weight of PVB resin for visual effect, and the composition is completed by stirring at 200 rpm for 10 minutes until all the colors of the mixture change.

[Experimental Example 1: Experiment to confirm physical properties by flame retardant]

The PVB resin coating agent was prepared by changing the type of flame retardant in the preparation example, and its dispersibility, flame retardancy, applicability, and change over time were observed, and the results are shown in Table 1 below.

Kinds KJT_RF1000
(Halogen flame retardant) CNB_APP-M
(brominated flame retardant) Ecochem_LHX-999
(Phosphorus flame retardant) magnesium hydroxide
(Inorganic flame retardant) dispersibility commonly commonly Great commonly flame retardant commonly Great Great commonly applicability bad bad commonly commonly Change over time (15 days) Coagulation after 4 days Coagulation after 10 days No clotting Coagulation after 8 days

[Experimental Example 2: Experiment to confirm physical properties by dispersant]

A PVB resin coating agent was prepared by changing the type of dispersant in the above preparation example, and the dispersibility, applicability, and physical property change thereof were observed, and the results are shown in Table 2 below.

Kinds TDA 7
(polyoxyalkylene alkyl ether) NP 9
(Nonylphenol ethoxylate) TDA 5
(polyoxyalkylene alkyl ether) TDA 10
(polyoxyalkylene alkyl ether) dispersibility Great commonly commonly Great applicability commonly commonly - - change in physical properties no change decrease in film strength no change no change

[Experimental Example 3: Experiment to confirm physical properties by thickener]

In the above preparation example, a PVB resin coating agent was prepared by changing the kind of thickener, and its dispersibility and viscosity performance were observed, and the results are shown in Table 3 below.

Kinds LOTTE Fine Chemical_H-100K
(Hydroxyethyl Cellulose) BYK_Optigel-WX
(Organic Modified Clay Mineral Thickener) BYK_OPTIFLO H400
(Non-hydrophilic surfactant) dispersibility bad Great Great Viscosity performance bad Great commonly

[Experimental Example 4: Test to confirm physical properties of each antifoaming agent]

The PVB resin coating agent was prepared by changing the type of the antifoaming agent in the preparation example, and its dispersibility, antifoaming power, and introduction (reaction or not) were observed, and the results are shown in Table 4 below.

Kinds DOW_AFE-1110
(amorphous silica) EVONIK_AEROSIL
(fumed silica) DOW_AFE-0120
(amorphous silica) dispersibility Great commonly Great defoaming power commonly Great Great Reactivity no response coagulation reaction no response

Claims (6)

To a method for producing a flame-retardant peelable coating agent comprising a PVB (Polyvinyl butyral) resin,
(a) adding 1 to 10 parts by weight of a phosphorus-based flame retardant to 15 parts by weight of distilled water and stirring at 250 to 350 rpm;
(b) adding the mixture prepared in (a) to 100 parts by weight of a PVB (Polyvinyl butyral) resin, and adding a flame retardant stirring at 650 to 750 rpm for 20 to 25 minutes;
(c) adding 0.1 to 10 parts by weight of a liquid dispersant to the composition subjected to step (b) based on 100 parts by weight of PVB resin and stirring at 350 to 450 rpm for 5 to 20 minutes;
(d) 0.5 to 20 parts by weight of a powdery thickener is added to 23 parts by weight of distilled water based on 100 parts by weight of the PVB resin and mixed to prepare an aqueous thickener solution, and then put into the composition subjected to step (c) and at 100 to 400 rpm adding a thickener stirring for 35 to 45 minutes;
(e) a mixing step of adding 1 to 10 parts by weight of a surfactant to the composition subjected to step (d) based on 100 parts by weight of the PVB resin and stirring at 450 to 550 rpm for 5 to 20 minutes; and
(f) adding 0.1 to 5 parts by weight of an antifoaming agent to the composition subjected to step (e) based on 100 parts by weight of PVB resin and stirring at 250 to 350 rpm for 5 to 15 minutes;
Flame-retardant peelable PVB resin coating method comprising a. According to claim 1,
A dye adding step of adding 0.1 to 5 parts by weight of a dye to the composition that has undergone the step (f) based on 100 parts by weight of the PVB resin; Flame-retardant peelable PVB resin coating agent manufacturing method further comprising a. According to claim 1,
Step (d) is,
(d-1) dividing the total amount of the thickener aqueous solution into 5;
(d-2) adding the thickener divided into 5 in step (d-1) to the composition subjected to step (c) every 1 to 5 minutes;
(d-3) further stirring the composition subjected to step (d-2) for 10 to 40 minutes;
Flame-retardant peelable PVB resin coating method comprising a. According to claim 1,
The surfactant includes a glycol-based surfactant,
The powdery thickener includes a clay mineral-based thickener,
The dispersant comprises a wetting and dispersing agent,
The flame retardant peelable PVB resin coating agent manufacturing method, characterized in that the antifoaming agent comprises a silicone-based antifoaming agent. 5. The method of claim 4,
The surfactant comprises polyalkylene glycol,
The powdery thickener comprises an organically modified clay mineral thickener,
The dispersant comprises at least one selected from the group consisting of polyoxyalkylene alkyl ether, sodium polyacrylate, sodium alkylnaphthalene sulfonate-formalin condensate, sodium lignin sulfonate, and polyethylene glycol phenyl ether,
The antifoaming agent is a flame-retardant peelable PVB resin coating method comprising amorphous silica. According to claim 1,
Step (e) is,
It is carried out after performing a resting step of resting for 1 to 5 minutes to remove air bubbles remaining in the composition obtained in step (d),
The step (f) is,
After stirring at room temperature for 3 to 10 minutes, the method for producing a flame retardant peelable PVB resin coating agent, characterized in that the temperature is raised to maintain a temperature of 30 to 35 ℃ and stirred for 2 to 5 minutes.

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