KR20160046361A - Low specific gravity noninflammable composite material and method producing thereof - Google Patents

Abstract

The present invention relates to a low density nonflammable composite material and a production method thereof. More specifically, the present invention relates to a low-density nonflammable composite material which has a low density and exhibits more improved nonflammable, insulation, and sound absorbing and screening performance, and to a production method thereof. To this end, a foam body is formed by mixing expandable polystyrene beads with melamine-formaldehyde condensates, and high frequency is irradiated into a dispersant produced by adding, into the melamine-formaldehyde condensates, expandable polystyrene beads, a hardening agent, and a non- halogen-based flame retardant, and then dispersing the same thereafter. After that, a continuous forming process and curing process in a mold is carried out.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a low specific gravity incombustible composite material,

The present invention relates to a process for producing a foamed product by mixing an expanded bead of expanded polystyrene (EPS) with a melamine-formaldehyde condensation product to form a foamed product. The foamed product has a low specific gravity, Non-combustible composite material and a method of manufacturing the same.

Generally, a foam prepared by using a melamine-formaldehyde condensation product is an organic foam and has excellent flame retardancy and sound-absorbing properties at the same time. Therefore, it is used in various types of building materials and interior materials for automobiles. In order to improve the properties of flame retardancy, Are actively promoted.

[0004] In the above-mentioned research and development, the patent document 1 proposes a description of a foam obtained from a melamine-formaldehyde condensation product. In the case of the melamine-formaldehyde foam, it has excellent flame retardancy due to its chemical composition. However, since the heat-resistant performance of the melamine-formaldehyde condensation product is so low that it decomposes rapidly at a temperature of 300 ° C or higher, the melamine-formaldehyde foam The performance of the foam heaters required in the construction field is somewhat inadequate.

In Patent Document 2, a melamine resin foam having improved fire resistance by penetrating a melamine-formaldehyde foam with a flame retardant phosphate, especially ammonium orthophosphate and ammonium polyphosphate in an aqueous solution concentration of 1 to 50% by weight, particularly 5 to 30% . However, the above-mentioned melamine resin foam is a melamine resin foam having a flame retardant performance by infiltrating the foamed product with a phosphate, particularly an ammonium orthophosphate and a polyphosphate aqueous solution, which is a flame retardant agent, since the adhesion between the phosphate and the melamine resin foam is low, There is a problem that a phosphate aqueous solution waste is generated.

In order to solve the above-mentioned problems, the applicant of the present invention has proposed a process for producing a melamine-aldehyde product by using a dispersion prepared by adding a condensing agent, an emulsifier, a foaming agent and a curing agent to a condensation product of melamine- Heat-resistant foam stabilized through a heat treatment at 100 to 250 ° C in a foam molded by injection of a high-frequency wave having a frequency in the range of 0.95 to 3.0 GHz per 1 g of the dispersion at a temperature of 10 to 30 ° C.

In addition, as in Patent Document 4, a non-combustible composite material is produced by using a melamine foam foamed using a dispersion in which a melamine-formaldehyde condensation product, a condensing agent, an emulsifier, a foaming agent, and a curing agent are added and dispersed, And non-combustible composite materials having sound insulation properties such as heat insulation and sound absorption / sound insulation while maintaining the non-combustibility.

On the other hand, the inventors of the present invention have found that when continuous foaming and curing in a mold are performed by irradiating a high frequency to a dispersion prepared by adding expanded polystyrene beads and a curing agent to a melamine-formaldehyde condensation product, , Adiabatic and absorption / sound-absorbing characteristics, and thus the present invention has been completed.

Patent Document 1: U.S. Patent No. 4,511,678 entitled " Resilient foam based on a melamine-formaldehyde condensate " Patent Document 2: Korean Patent Laid-Open Publication No. 10-2001-0098612 entitled "Melamine Resin Foam" Patent Document 3: Korean Patent Registration No. 10-0855656 "Melamine-aldehyde condensation product, heat-resistant foam using the same, and production method thereof" Patent Document 4: Korean Patent Registration No. 10-0931647 "Non-combustible honeycomb composite material filled with melamine foam and method for manufacturing the same"

The present invention relates to a method for producing a melamine-formaldehyde condensation product by mixing expanded polystyrene beads with melted-formaldehyde condensation product to form a foam, adding a foamed polystyrene bead, a hardener and a halogen-based flame retardant to a melamine-formaldehyde condensation product, And a curing process in a mold, thereby achieving a further improved non-burning, heat insulation, and absorption / sound insulation characteristics while having a low specific gravity.

The present invention relates to a low specific gravity incombustible composite material which is foamed using a dispersion in which expanded polystyrene beads, a curing agent and a non-halogen flame retardant are added to a melamine-formaldehyde condensation product and dispersed therein .

Specifically, the low specific gravity nonflammable composite material is prepared by adding 20 to 50 parts by weight of expanded polystyrene beads, 0.2 to 1.0 parts by weight of a curing agent, and 10 to 20 parts by weight of a non-halogen flame retardant to 100 parts by weight of a melamine- It is preferable to foam it by using the dispersion liquid.

The melamine-formaldehyde condensation product is preferably a polycondensation reaction of melamine and formaldehyde at a molar ratio of 1: 2.0 to 1: 3.4.

The curing agent is preferably selected from sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, benzenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid or xylylenesulfonic acid.

The non-halogen flame retardant is preferably used alone or in combination with a nitrogen-based flame retardant, a metal hydroxide or a phosphorus flame retardant.

The present invention also provides a method for producing a low specific gravity incombustible composite material,

A step (S100) of producing a melamine-formaldehyde condensation product;

(S200) adding and dispersing expanded polystyrene beads, a curing agent and a non-halogen flame retardant to the melamine-formaldehyde condensation product prepared in the step S100;

(S300) of irradiating the dispersed dispersion liquid through the step S200 by firstly foaming the dispersion liquid; And

And a step (S400) of curing the first foamed foam through the step S300. The method for producing a low specific gravity incombustible composite material according to claim 1,

Specifically, in the step S100, it is preferable to mix the mixture so that the molar ratio of melamine and formaldehyde is 1: 2.0 to 1: 3.4 under a sodium hydroxide catalyst, and then the mixture is stirred at 110 to 130 ° C for 60 to 80 minutes to prepare a condensation product Do.

In step S200, 20 to 50 parts by weight of expanded polystyrene beads, 0.2 to 1.0 part by weight of a curing agent, and 10 to 20 parts by weight of a non-halogen flame retardant are added to 100 parts by weight of the melamine- formaldehyde condensation product, It is preferable to add and disperse a part.

In step S300, it is preferable that the high frequency wave having a frequency in the range of 0.95 to 3.0 GHz is irradiated at an output of 3 to 20 W for 60 to 90 seconds per g of the dispersed dispersion through step S200.

In addition, in step S400, it is preferable that the first foamed foam is cured in a hot air oven at 70 to 90 DEG C through step S300.

The present invention relates to a method for producing a melamine-formaldehyde condensation product by mixing expanded polystyrene beads with melted-formaldehyde condensation product to form a foam, adding a foamed polystyrene bead, a hardener and a halogen-based flame retardant to a melamine-formaldehyde condensation product, By performing the foaming and the hardening process in the mold, it is possible to have improved fire retardancy, heat insulation and absorption / sound insulation characteristics while having a low specific gravity.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow diagram illustrating a method of making a low specific gravity, incombustible composite material in accordance with the present invention.

In order to accomplish the above-mentioned effects, the present invention relates to a low specific gravity incombustible composite material and a method of manufacturing the same, wherein only parts necessary for understanding the technical structure of the present invention are explained, It will be omitted.

Hereinafter, a low specific gravity incombustible composite material and a method for producing the same will be described in detail.

The low specific gravity nonflammable composite material according to the present invention comprises 20 to 50 parts by weight of expanded polystyrene beads, 0.2 to 1.0 parts by weight of a curing agent, and 10 to 20 parts by weight of a non-halogen flame retardant, based on 100 parts by weight of a melamine-formaldehyde condensation product And dispersing the resulting mixture in a dispersion liquid.

The melamine-formaldehyde condensation product used in the present invention is obtained by a polycondensation reaction of melamine and formaldehyde in a molar ratio of 1: 2.0 to 1: 3.4. When the molar ratio of melamine to formaldehyde is less than 1: 2.0, the formed melamine- If the molar ratio exceeds 1: 3.4, the stiffness of the melamine foam increases and the compressive strength of the foam rapidly decreases.

Here, the polycondensation reaction is carried out in a conventional manner (for example, see Houben-Weyl, vol. 14/2, p. 357, European Patent Publication 355,760, Hubenweil). The polycondensation reaction is carried out under a polycondensation reaction at a reaction temperature of 80 to 200 ° C, a reaction pressure of 100 to 500 kPa and a pH of 6 to 10 to obtain a melamine-aldehyde condensation product according to the present invention .

On the other hand, it is preferable to use formaldehyde in the form of an aqueous solution having a concentration of, for example, 20 to 50% by weight, preferably 30 to 45% by weight, and the concentration of formaldehyde is not necessarily limited to the above- If necessary, the concentration can be adjusted appropriately. Further, the formaldehyde may be selected from one or more kinds of solid oligomeric or polymeric formaldehyde such as formalin, paraformaldehyde, 1,3,5-trioxane or 1,3,5,7-tetroxoxane .

The foamed polystyrene beads used in the present invention are used for foaming a non-combustible composite material according to the present invention and at the same time having a low specific gravity and having improved smoke-proofing, heat insulation and absorption / sound insulation properties. The melamine-formaldehyde condensation product 100 20 to 50 parts by weight are used in relation to parts by weight. If the amount of the expanded polystyrene beads is less than 20 parts by weight, the above-mentioned effects may be insufficiently exhibited. If the amount of the expanded polystyrene beads is more than 50 parts by weight, the bead content may be high relative to the added amount of melamine.

The curing agent used in the present invention may be selected from a small amount of acid such as sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, benzenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid and xylylenesulfonic acid. The addition amount of the curing agent is preferably 0.2 to 1.0 part by weight based on 100 parts by weight of the melamine-formaldehyde condensation product. If the addition amount of the curing agent is less than 0.2 part by weight, foaming is difficult to form. If the amount is more than 1.0 part by weight, the thickness of the foamed cell increases and the mechanical properties such as elasticity may decrease.

Examples of the non-halogen flame retardant used in the present invention include nitrogen-based flame retardants such as ammonium phosphate, ammonium carbonate, triazine compounds, melamine cyanurate, and guanidine compounds, metal hydroxides such as magnesium hydroxide, aluminum hydroxide or melamine polyphosphate, Based flame retardant such as di-ammonium phosphate, monoammonium phosphate, polyphosphoric acid amide, phosphoric acid amide, melamine phosphate or red phosphate may be used alone or in combination to further improve the flame retardant performance. In this case, If the amount of the flame retardant is less than 10 parts by weight, the effect of improving the flame retardancy may be insufficient. If the amount is more than 20 parts by weight, dispersion is difficult and the physical properties may be deteriorated.

Next, as shown in FIG. 1, the method for producing a low specific gravity incombustible composite material according to the present invention comprises the steps of: preparing a melamine-formaldehyde condensation product (S100); and adding melamine-formaldehyde A step S200 of adding foamed polystyrene beads and a curing agent to the condensation product and dispersing the foamed polystyrene beads and a curing agent to the condensation product, a step (S300) of irradiating the dispersion liquid dispersed through the step S200 with high frequency to perform primary foaming (S300) And curing the foamed product (S400).

In step S100, the melamine-formaldehyde condensation product is prepared by mixing the melamine-formaldehyde condensate in a molar ratio of melamine to formaldehyde in the range of 1: 2.0 to 1: 3.4 under a sodium hydroxide catalyst. The mixture is then heated at 110 to 130 ° C for 60 to 80 minutes Followed by stirring to produce a condensation product. If the stirring condition is out of the above range, the condensation product may not be produced properly.

The step S200 may include adding expanded polystyrene beads and a curing agent to the melamine-formaldehyde condensation product prepared through the step S100 and dispersing the expanded polystyrene beads and the curing agent in 100 parts by weight of the melamine-formaldehyde condensation product prepared in the step S100 20 to 50 parts by weight of expanded polystyrene beads, 0.2 to 1.0 parts by weight of a curing agent and 10 to 20 parts by weight of a non-halogen flame retardant.

The step S300 may include a step of irradiating the dispersed dispersion liquid through the step S200 with a high frequency to perform primary foaming. The high frequency wave having a frequency in the range of 0.95 to 3.0 GHz per g of the dispersed dispersion through the step S200 is irradiated at a high frequency of 3 to 20 W It is irradiated for 60 ~ 90 seconds at the output, and primary foaming is carried out. If the foaming condition is less than the above range, there is a fear that the foaming is not sufficiently performed. If the foaming condition exceeds the above range, excessive foaming occurs at the beginning of the foaming process to increase the cell size and the cell thickness, There is a possibility that it will appear.

The step S400 is a step of curing the primary foamed foam through the step S300, and the primary foamed foam is cured in a hot air oven at 70 to 90 DEG C through the step S300. At this time, if the curing condition is out of the above range, the molding may not be performed properly.

The low specific gravity nonflammable composite material of the present invention may be foamed and filled in a core material of a paper honeycomb material coated with aluminum hydroxide and used as a non-combustible honeycomb composite material.

Hereinafter, the present invention will be described in detail with reference to the following examples. However, the present invention is not limited to the following examples.

1. Manufacture of nonflammable composites

(Example 1)

The resulting mixture was stirred at 110 ° C for 80 minutes to prepare a condensation product (S100). With respect to 100 parts by weight of the resultant melamine-formaldehyde condensation product, a mixture of melamine and formaldehyde , 20 parts by weight of expanded polystyrene beads, 0.2 parts by weight of toluene sulfonic acid as a curing agent and 10 parts by weight of ammonium phosphate as a non-halogen flame retardant were added and dispersed (S200). Then, high frequency waves having a frequency in the range of 0.95 GHz per 1 g of the dispersed dispersion And the mixture was irradiated with an output of 20 W for 60 seconds for primary foaming, and the primary foamed material was cured in a hot air oven at 90 캜 to produce a nonflammable composite material.

(Example 2)

The resulting mixture was stirred at 130 캜 for 60 minutes to prepare a condensation product (S100). To 100 parts by weight of the resultant melamine-formaldehyde condensation product, a mixture of melamine and formaldehyde , 50 parts by weight of expanded polystyrene beads, 1.0 part by weight of phenolsulfonic acid as a curing agent, and 20 parts by weight of magnesium hydroxide as a non-halogen flame retardant were added and dispersed (S200). Then, high frequency waves having a frequency in the range of 3.0 GHz per 1 g of the dispersed dispersion And the mixture was irradiated with an output of 3 W for 90 seconds for primary foaming, and the primary foamed foams were cured in a hot air oven at 70 캜 to produce a nonflammable composite material.

(Comparative Example 1)

The mixture was mixed with sodium hydroxide catalyst so that the molar ratio of melamine and formaldehyde was 1: 2.0, and the mixture was stirred at 110 DEG C for 80 minutes to prepare a condensation product. With respect to 100 parts by weight of the resultant melamine-formaldehyde condensation product, 0.2 parts by weight of toluene sulfonic acid and 20 parts by weight of ammonium phosphate as a non-halogen flame retardant were added and dispersed. Then, a high-frequency wave having a frequency in the range of 0.95 GHz per g of the dispersed dispersion was irradiated with an output of 20 W for 90 seconds, The primary foamed foam was cured in a hot air oven at 90 캜 to prepare a nonflammable composite material.

2. Test method

1) Specific gravity

The specific gravity of the sample was measured by using a specific gravity meter and expressed as an average value after 5 measurements.

2) Compression and shear bond strength

For the compressive strength according to KS F3517, test specimens having a length of 50 mm, a width of 50 mm and a thickness of 25 mm and a shear bond strength of 50 mm in length, 50 mm in width and 25 mm in thickness were prepared and tested using an Instron universal testing machine.

3) Flammability

According to the flame resistance test method of KS F 2819 for thin construction materials, test pieces were fabricated to have a size of 30 mm × 20 mm × 4.5 mm and the burning speeds were measured for heating times of 10, 20, 30, 60, 120 and 180 seconds .

4) Thermal conductivity

The thermal conductivity was measured according to JIS A 1412-2.

5) Sound absorption

According to the sound absorption rate measurement method of KS F 2805, the sound absorption coefficient was measured by measuring the vertical incidence sound absorption rate with respect to the center frequency of 2000 Hz for a test piece of 10 mm and an area of 4.5 m ² (1500 mm × 3000 mm).

3. Test results

The properties of the non-combustible composite material prepared in Examples 1 and 2 and Comparative Example 1 were tested in the same manner as described above, and the results are shown in Table 1 below.

Test Items Example 1 Example 2 Comparative Example 1 Weight (g) 0.25 0.12 36.1 Compressive strength (kgf / cm ³ ) 4.0 4.2 3.2 Shear bond strength (kgf / cm ² ) 3.4 3.1 1.4 Flammability V-0 V-0 V-0 Thermal conductivity (W / mk) 0.020 0.015 0.052 Sound absorption coefficient (a ₀ ) 0.95 0.98 0.6

As shown in Table 1, Examples 1 and 2 according to the present invention exhibited much lower specific gravity than Comparative Example 1 and exhibited a higher compressive strength and shear bond strength than Comparative Example 1. It can be seen that Examples 1 and 2 exhibit the same flame retardancy as the Comparative Example 1 and at the same time increase the adiabatic properties and the sound absorption properties. Accordingly, the present invention provides an improved flame retardant, insulation and sound / .

As described above, the present invention proves the superiority of the physical properties through the above-mentioned embodiments. However, the present invention is not limited to the above-mentioned constitution, and various substitutions , Variations and modifications are possible.

S100: Step of producing a melamine-formaldehyde condensation product
S200: adding polystyrene beads and a curing agent to melamine-formaldehyde condensation product to disperse
S300: Step of primary foaming by irradiating high frequency to dispersion liquid
S400: Curing the primary foamed foam

Claims (10)

In a low specific gravity incombustible composite material,
A low specific gravity incombustible composite material characterized in that it is foamed using a dispersion in which expanded polystyrene beads, a curing agent and a non-halogen flame retardant are added to a melamine-formaldehyde condensation product.
The method according to claim 1,
The low specific gravity,
Characterized in that foaming is carried out using a dispersion in which 20 to 50 parts by weight of expanded polystyrene beads, 0.2 to 1.0 parts by weight of a curing agent and 10 to 20 parts by weight of a non-halogen flame retardant are added to and dispersed in 100 parts by weight of melamine-formaldehyde condensation product Low specific gravity incombustible composites.
The method according to claim 1,
The melamine-formaldehyde condensation product is a melamine-
Wherein the molar ratio of melamine to formaldehyde is 1: 2.0 to 1: 3.4.
The method according to claim 1,
The curing agent,
Characterized in that at least one of sulfuric acid, phosphoric acid, hydrochloric acid, formic acid, benzenesulfonic acid, toluenesulfonic acid, phenolsulfonic acid or xylylenesulfonic acid is selected and used.
The method according to claim 1,
The non-halogen-based flame retardant includes,
Based flame retardant, a metal hydroxide or a phosphorus flame retardant, either alone or in combination.
A method for producing a low specific gravity incombustible composite material,
A step (S100) of producing a melamine-formaldehyde condensation product;
(S200) adding and dispersing expanded polystyrene beads, a curing agent and a non-halogen flame retardant to the melamine-formaldehyde condensation product prepared in the step S100;
(S300) of irradiating the dispersed dispersion liquid through the step S200 by firstly foaming the dispersion liquid; And
(S400) of curing the first foamed foam through the step S300. ≪ Desc / Clms Page number 20 >
The method according to claim 6,
In operation S100,
Wherein the molar ratio of melamine to formaldehyde is from 1: 2.0 to 1: 3.4 in the presence of sodium hydroxide catalyst, and then the mixture is stirred at 110 to 130 DEG C for 60 to 80 minutes to produce a condensation product. ≪ / RTI >
The method according to claim 6,
In operation S200,
20 to 50 parts by weight of expanded polystyrene beads, 0.2 to 1.0 parts by weight of a curing agent and 10 to 20 parts by weight of a non-halogen flame retardant are added to and dispersed in 100 parts by weight of the melamine-formaldehyde condensation product prepared in the step S100 By weight based on the total weight of the low-specific-gravity incombustible composite material.
The method according to claim 6,
In operation S300,
And irradiating the high-frequency wave having a frequency in the range of 0.95 to 3.0 GHz per g of the dispersed dispersion through the step S200 at an output of 3 to 20 W for 60 to 90 seconds.
The method according to claim 6,
In operation S400,
Wherein the first foamed foam is cured in a hot air oven at 70 to 90 DEG C through step S300.

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