KR20000030340A - Phenolic foam and architectural panel using the same - Google Patents

Abstract

PURPOSE: A phenolic foam as raw material of heat insulating material for construction which is excellent in heat resistance, fire retardancy, chemical resistance and sound proof property, and a panel for construction using the same are provided. CONSTITUTION: The phenolic foam is obtained from a method characterized in that 100 unit of phenolic resin is used which is produced by synthesis of formalin and at least one selected from the group consisting of a combination of methylol phenol, dimethylol phenol, trimethylol phenol, etc. produced by synthesis of phenol and formalin, cresol for conditioning, and bispheonls; 5 - 40 unit of a phosphoric plasticizer is combined for giving plasticity to the foam at the time of foam forming; 0.5 - 5 unit of a cell regulator is combined, consisting of siloxanes (H<SB POS="POST">2</SB>SiO- (H<SB POS="POST">2</SB>SiO)<SB POS="POST">n</SB> -SiH<SB POS="POST">3</SB>) for controlling cell distribution and size of the foam; and 3 - 20 unit of a blowing agent such as CFCs, HFCs or HCFCs is combined, which has foaming effect.

Description

Phenolic foam and building panel using the same {PHENOLIC FOAM AND ARCHITECTURAL PANEL USING THE SAME}

The present invention relates to a phenol foam and a building panel using the same. More specifically, it is a thermosetting plastic foam (Foam) foamed with phenolic resin having thermal and chemically stable properties, and has excellent flame resistance, heat resistance, and low smoke resistance. It provides phenolic foam and its phenolic foam as intermediate insulation material, and it is related with building panels that increase the hardness of foam and solve corrosiveness by spraying liquid adhesive on the upper and lower surfaces.

As is well known, the first phenolic resin (Phenolic Resin) was produced in 1910 by L. H. BAEKELAND, USA, based on phenol and formaldehyde.

Hereinafter, the manufacturing method of the phenol foam using the resol type liquid resin is briefly described.

The method of curing the resol type is largely divided into a method of curing by heating and a method of curing by acid, and in the case of phenol foam, the latter method is generally used.

In other words, when a large amount of strong acid is added to the phenol resin (Phenolic resol) and stirred, heat is generated and a rapid curing reaction occurs, resulting in an insoluble insoluble curing resin.

The phenolic foam is prepared from the resol type using the above-mentioned principle. As a foaming agent of the liquid resin, a low boiling point solvent, a plasticizer for imparting flexibility, a surfactant for stabilizing bubbles, and the like are added.

Phenolic foam is prepared by adding and mixing a certain amount of strong acid hardener to the resin in which the raw materials are mixed, and vaporizing the solvent by heat generated by the exothermic reaction generated at this time, and the gaseous blowing agent is present in the cell by the curing reaction. do.

Examples of general formulation of the phenolic foam (Phenolic foam) is as follows.

Phenolic resin: 100

Freon-113: 15

Emulsifier: 6

PTSA (60% aqueous solution): 6

When the compound is mixed and injected into a desired mold, foam is cured in a short time by exothermic action to obtain a foam. While the resol foam prepared by the above method is easy to foam, the strong acid is used as a hardening agent, so that acid remains in the cell, thereby causing corrosion of the metal attached to or adjacent to the phenol foam. have.

In particular, when the phenolic foam (Phenolic Foam) is used as the intermediate insulation of the building panel is corroded to the outer plate of the panel by the acid (Acid) remaining in the phenolic foam is very difficult to use as an intermediate insulation. .

In addition, in the case of a general phenol foam (Phenolic Foam) having a plurality of cells (Cell) therein, there is a problem that the adhesion of the surface is very low, the hardness is low, so that the adhesive strength is lowered for use as a building insulation.

SUMMARY OF THE INVENTION The present invention has been made in view of the above-described state of the art, by injecting a liquid adhesive onto both inner walls of a steel sheet, and mixing and stirring a fixed ratio of a phenol resin, a foam stabilizer, a plasticizer, a foaming agent, and a curing agent therein. It is an object of the present invention to provide a building panel foamed with phenolic foam having excellent heat resistance, flame retardancy, chemical resistance, and sound insulation.

Figure 1a is a graph showing the carbon monoxide generation amount for phenol foam and other foam according to an embodiment of the present invention.

Figure 1b is a graph showing the amount of cyanide generated for phenolic foam and other foams according to an embodiment of the present invention.

Figure 1c is a graph showing the change over time of the amount of smoke for phenolic foam and other foams according to an embodiment of the present invention.

2 is a thermal conductivity comparison graph for phenol foams and other foams according to an embodiment of the present invention.

3 is a graph comparing the dimensional stability of phenol foams and other foams.

4 is a perspective view showing a building panel using a phenol foam according to an embodiment of the present invention.

* Description of the symbols for the main parts of the drawings *

PTSA; para-toluenesulfonic acid XSA; xylenesulfamic acid

PSA; Phenolic sulfamic acid PUR; Polyurethane foam

PIR; Polyisocyanate Foam PS; Polystyrene Foam

2: phenolic foam 4: top plate

6: bottom plate

In order to achieve the above object, according to a preferred embodiment of the present invention, methol phenol (Methyol Phenol), dimethyol phenol (Dimethyol Phenol), trimethy produced by the synthesis of phenol (Phenol) and formalin (Formalin) 100 units of a phenol resin produced by synthesizing formalin with at least one of a resin consisting of a combination of Trimethyol Phenol, or Cresol or Bisphenol for denaturation; 5 to 40 units of plasticizer for imparting flexibility to the foam when foam is generated in 100 units of the phenol resin; 5 to 40 units of a curing agent composed of sulfuric acid (H ₂ SO ₄ ) -based acid compounds are mixed to react with the phenol resin to cure the phenol foam; In order to control the cell distribution and the size of the foam, a foaming agent made of a siloxane (Siloxane; H ₂ SiO- (H ₂ SiO) n-SiH ₃ ) system is blended in 0.5 to 5 units; There is provided a phenol foam characterized by blending 3 to 20 units of a blowing agent having a predetermined foaming effect.

Further, according to another preferred embodiment of the present invention, methol phenol (Methyol Phenol), dimethyol phenol (Dimethyol Phenol), trimetholol (Trimethyol) produced by the synthesis of phenol (Phenol) and formalin (Formalin) Phenol), a mixture of phenols, bisphenols and formalin, and a plasticizer, a curing agent, a foaming agent, and a foaming agent. In the upper and lower parts of the phenolic foam panel is provided, the urethane adhesive is sprayed on the upper and lower adhesive surface of the steel sheet to adhere the phenolic foam and the steel sheet and at the same time the phenolic foam is in direct contact with the steel sheet There is provided a building panel using a phenol foam, characterized in that to prevent.

Preferably, 5 to 40 units of a curing agent made of sulfuric acid (H ₂ SO ₄ ) -based acid compound is further included to react with the phenol resin to cure the phenol foam.

Example

Hereinafter, the components of the phenol foam (Phenolic Foam) and the blending ratio of the present invention will be described in detail.

MIXING RATIO

1.Phenolic Resin: 100

Hereinafter for phenol resin 100

2. Foaming agent (silicon): 0.5 to 5

3. Plasticizer: 1 ~ 40

4. Blowing Agent: 3 ~ 20

5. Curing agent: 5 ~ 40

Hereinafter, the component with respect to the compounding ratio of the said phenol foam is demonstrated in detail.

First, the phenol resin is modified with methol phenol (Methyol Phenol), dimetholol phenol (Dimethyol Phenol), trimethyol phenol (Trimethyol Phenol) resin produced by the synthesis of phenol (Phenol) and formalin (Formalin) It is a synthetic product of at least one of cresol, bisphenols, and formalin.

On the other hand, the plasticizer is a plasticizer of the phosphorus (P) series such as TCPP, TDCPP, TCEP is used as an additive to give flexibility to the foam during foam generation, the ratio is 1 when the phenol resin is 100 units A plasticizer of -40 units is blended.

In addition, the silicon foam stabilizer is to control the cell distribution and the size of the cell (Cell) of the foam, such as L-6900, L-5421, B-8408, B-8462 (Siloxane; H ₂ A SiO- (H ₂ SiO) n-SiH ₃ ) system is used, and the proportion of the foaming agent is 0.5 to 5 units when the phenol resin is 100 units.

In addition, the foaming agent is a CFC-11 CFC-11 or HCFC-141b of HCFC-based or as an environmental problem due to ozone depletion and global warming, HFC or Pentane-based alternative blowing agent having a corresponding foaming effect is used do. When the compounding ratio is 100 units of the phenol resin, 3 to 20 units of blowing agent are blended.

The curing agent reacts with the phenol resin to cure the phenolic foam. Para-toluene sulfamic acid (P-TSA; Para-Toluene Sulfamic Acid), xylene sulfamic acid (XSA; Xylene Sulfamic Acid), phenol sulfamic acid (PSA; Phenol Sulfuric acid-based compounds such as sulfuric acid) are mainly used, and are compounded to affect the physical properties of the phenolic foam.

In addition, the mixing | blending ratio of the said hardening | curing agent mix | blends 5-40 units of hardening | curing agents when the said phenol resin is 100 units according to a use of foam.

The present invention is not limited to the configuration of the raw materials described above, and includes modifications to various embodiments according to the degree of addition and modification of various additives, such as other components, without departing from the technical scope of the present invention. .

Hereinafter, the characteristic of the phenol foam manufactured by the said structure is compared with various pseudo insulating materials.

The phenolic foam exhibits superior properties in flame retardancy, low smokeability, and the like than conventional organic insulation such as polyurethane foam (PUR). Conventional phenolic foam that has been applied until now has a weak hardness, and the corrosion of the metal in close contact with the phenolic foam, the adhesion is difficult to use for construction, but the phenolic foam has solved the problem.

Hereinafter, the reason why the said phenol foam is suitable as a heat insulating material of a building panel is demonstrated.

In general, toxic gases mainly generated during combustion of plastic foam are carbon monoxide (CO) and cyan gas (CYAN GAS).

Figure 1a is a graph showing the amount of carbon monoxide generated according to an embodiment of the present invention, Figure 1b is a graph showing the amount of cyanide gas generated according to an embodiment of the present invention, Figure 1c is a graph showing the change over time of the amount of smoke. .

As shown in Figure 1a, Figure 1b, Figure 1c, the phenolic foam according to the present invention is excellent in flame retardancy and heat resistance.

Referring to this, the X axis of Figure 1a represents the experimental elapsed time, the Y axis represents the generation amount of carbon monoxide in concentration (ppm), the test sample is a polyurethane foam and phenol foam.

The polyurethane foam has a carbon monoxide concentration of 600 ppm or more when about 6 hours have elapsed after the start of combustion. On the other hand, in the case of the phenol foam, the concentration of carbon monoxide is 200 ppm or less even when 10 hours have been taken after the start of combustion. It can be seen that it is suitable for construction.

On the other hand, the X axis of Figure 1b represents the experimental elapsed time, the Y axis represents the concentration of cyan gas (ppm), the samples are polyurethane foam and phenol foam.

When about 7 hours have elapsed after the start of combustion, the polyurethane foam generates more than 600 ppm of cyan gas, which is fatal to the human body. On the other hand, in the case of the phenol foam, the cyan gas is hardly detected even after 10 hours of combustion. Therefore, it can be seen that it is suitable for construction.

On the other hand, the X axis of Figure 1c represents the experimental elapsed time, the Y axis represents the amount of smoke.

Referring to this, in the case of styrene foam and polyurethane foam (PUR), a smoke of 80 to 100 units (volume; changes depending on the amount of sample) occurs less than 1 minute after the start of combustion, and in the case of the polyisocyanate In about 1 minute after the start of combustion, about 40 units of smoke are produced, and in the case of the phenol foam, even after 5 minutes or more after the start of combustion, a very minute smoke state is shown.

Therefore, the phenolic foam is hardly smoked as compared to the hard urethane (PUR), poly foam foam, and polyisocyanurate, and thus has high stability against combustion.

Combustion heat comparison table with plastic foam Type of form Phenolic Foam Polyurethane Foam (PUR) Polyisocyanurate Foam (PIR) Heat of combustion (Kcal / Kg) 1389 2658 1628

Table 1 shows the heat of combustion for the various foams, the heat of combustion generated by the foam during combustion is 2658Kcal per 1kg in the case of the polyurethane foam (PUR), the isocyanurate foam (PIR) is 1628Kcal per 1kg As compared with the high combustion heat generated per 1 Kg, the phenol foam has a very small amount of combustion heat per weight (Kg) compared to other foams at 1389 Kcal per 1 Kg.

Therefore, it can be seen that the phenolic foam (Phenolic Foam) is a high quality that is very suitable for use as a building panel.

Heat resistance comparison table with plastic foam Type of form Phenolic Foam Polyurethane Foam (PUR) Polystyrene Foam (PS) Operating temperature (normal) ℃ 150 ℃ 100 ~ 200 ℃ 70 ℃ Limit State 210 degrees Celsius (color change) 140 degrees Celsius (cure) 70 degrees Celsius (shrink)

Table 2 is a table comparing the heat resistance of various plastic foams.

According to the table, polystyrene foam (PS) is the maximum usable temperature is 70 ℃, the foam shrinkage occurs from 70 ℃, polyurethane foam (PUR) the maximum usable temperature is 200 ℃ but curing the foam from 140 ℃ In this case, the phenol foam has a maximum usable temperature of 150 ° C., which is superior in heat resistance to other plastic foams (polyurethane foam and polystyrene foam). .

Hereinafter, other plastic foams and phenol foams are compared with respect to heat insulation.

The thermal insulation is evaluated by the thermal conductivity (K-factor), and the lower the thermal conductivity, the better the thermal insulation.

See Table 3 and FIG. 2 for adiabatic comparison. Figure 2 is a graph comparing the thermal conductivity of various plastic foams and phenolic foam according to the present invention.

Comparison table of various insulation materials insulator Phenolic Foam Polyurethane (PUR) PS foam (Poly stylene) Isopink Rock Wool Glass Wool Thermal conductivity (Kcal / mh ℃) 0.021-0.026 0.015 to 0.020 0.032 0.023 0.023 0.038

According to Table 3, the phenolic foam shows a similar or lower thermal conductivity than that of PS (Poly stylene) foam, iso pink, rock wool, and glass wool, and in the case of hard urethane, it shows lower thermal conductivity than the phenol foam. As shown in FIG. 2, the polyurethane has a graph of unstable thermal conductivity, while the phenolic foam has a stable thermal conductivity slope.

In addition, the phenolic foam has excellent thermal insulation performance in a wide range of temperature range from cryogenic (-196 ℃) to high temperature (210 ℃).

On the other hand, it is necessary to consider the coefficient of linear expansion in order to use the phenolic foam as a heat insulating material for building panels. The coefficient of linear expansion is expressed as the ratio of the length of expansion to the rise of the unit temperature.

When the coefficient of linear expansion of the foam as the heat insulating material becomes high, the foam contracts / expands sensitively to temperature change, so when the foam is attached to the outer metal plate of the building panel, the foam is easily detached from the outer metal plate according to the temperature change. It is not supported to cause deformation of the metal plate, the thermal insulation and the strength of the panel is rapidly dropped.

Figure 3 is a graph of the dimensional stability of phenolic foam according to an embodiment of the present invention.

Referring to this, the phenolic foam according to the present invention has a low elasticity against temperature change and excellent dimensional stability because the coefficient of linear expansion is smaller than that of other organic insulating materials.

As shown in FIG. 3, the polystyrene foam shows a dimensional change rate of about 40% when the dimension for the unit length Cm is gradually changed from 50 ° C. to about 100 ° C. FIG. In other words, when the polystyrene foam is used as a building panel, when the ambient temperature rises to 100 ° C., the length is changed by about 40% from the dimension when it is first attached to the inner side of the panel.

In addition, as shown in Figure 3, the polyurethane foam exhibits the highest dimensional change rate (20%) when used continuously in a state where the ambient temperature rises to approximately 125 ℃, it can be seen that it is unsuitable at high temperatures.

On the other hand, in the case of phenol foams, the coefficient of linear expansion (30-40) × 10 ^-6 (Cm / Cm · ° C) was increased by 1 ° C. (30-40) × 10 ^-6 (Cm / Cm 占 폚) expansion occurs.

For example, even when the ambient temperature rises to 200 ° C., only a few water sides occur, and almost no deformation occurs, and thus, it can be seen that it is suitable as an intermediate material used as a heat insulating material in the interior of a building panel.

Chemical Resistance Comparison Table About product name Chemical resistance About product name Chemical resistance 20% hydrochloric acid An Jung Acetic acid ester An Jung 10% acetic acid 〃 Mineral oil 〃 10% legacy 〃 Sodium hydroxide solution 〃 Farm products Swelling Calcium hydroxide solution Swelling ammonia An Jung Ammonium chloride solution (saturated) An Jung Ben Jen 〃 Potassium hydroxide solution Swelling Calcium Aqueous Solution 〃 Carbon tetrachloride An Jung Sea water 〃 Acetic anhydride 〃 Alcohol 〃

Table 4 is an experimental table for the chemical resistance of the phenolic foam according to an embodiment of the present invention.

Phenolic foam has a slight swelling in the presence of concentrated acids, sodium hydroxide and potassium hydroxide solution, but shows a very stable reaction to various other chemicals. This is because phenolic resin having a strong chemical resistance of 50% or more is mixed in the raw material of the phenolic foam, and the phenolic foam is used for a factory with high risk of fire, or a chemical plant and a plant adjacent to seawater. It is suitable to be used as middle insulation of panel.

LIMITED OXYGEN INDEX; LOI LOI (%) Polystyrene FOAM 19.5% Polyurethane Foam (PUR) 25% Polyisocyanurate Foam (PIR) 29% Phenolic Foam 40%

Table 5 shows a comparison table for the limiting oxygen demand according to an embodiment of the present invention, which is represented by the minimum oxygen ratio required to burn the foam, for example, the higher the limiting oxygen demand (LOI), the better the flame retardancy.

According to the above table, polystyrene foam, polyurethane foam, and polyisocyanurate foam are easily burned due to the small amount of oxygen required for combustion as compared to phenol foam having a LOI of 30% or less and 40%. Compared to plastic foam (polystyrene foam, polyurethane foam, etc.), the amount of oxygen required for combustion is very difficult to oxidize.

Thus, it can be seen that phenolic foam is suitable for use as an intermediate material for building panels.

Hereinafter, the building panel in which the said phenol foam is used as an intermediate | middle insulation material of a panel is demonstrated in detail.

Figure 4 is a perspective view showing a building panel using a phenol foam according to another embodiment of the present invention.

Referring to this, panel steel sheets 2 and 4 are provided on the upper and lower portions of the phenolic foam 2 prepared according to the above embodiment, and phenolic foams are provided on the upper and lower adhesive surfaces of the steel sheets 2 and 4. When the urethane adhesive is sprayed and the phenol foam 2 is adhered to enhance the adhesion between the phenolic foam 2 and the phenolic foam 2, the phenolic foam 2 is firmly adhered to the upper and lower adhesive parts of the steel sheets 2 and 4.

In this case, the phenolic foam that is in close contact with the steel sheet is adhered by spraying the urethane adhesive between the steel sheet and the adhesive force is enhanced and the phenolic foam is not directly in contact with the steel sheet by the urethane adhesive due to its acidity It is possible to effectively prevent the steel sheet from corroding.

On the other hand, phenolic foam according to an embodiment of the present invention is not limited to this embodiment, it can be carried out variously modified within the scope of the present invention.

As described above, according to the phenol foam according to the present invention by stirring a predetermined amount of phenol resin, foam stabilizer, plasticizer, foaming agent, a phenol foam excellent in flame retardancy, heat resistance and heat insulation, chemical resistance, processability is produced, For example, the phenolic foam may be suitably used as an intermediate material for building panels of high-risk fires, chemical plants or prefabricated buildings adjacent to the coast.

In addition, since the phenolic foam and the external steel sheet is bonded by the urethane adhesive during panel manufacturing, the phenolic foam does not directly contact the steel sheet, thereby effectively preventing corrosion of the steel sheet.

Claims (2)

Resin consisting of a combination of methol phenol (Methyol Phenol), dimethyol Phenol, Trimethyol Phenol produced by the synthesis of phenol and formalin, or for modification At least one of cresol or bisphenol and formalin, and 100 units of phenol resin produced by synthesizing formalin; 5 to 40 units of plasticizer for imparting flexibility to the foam when foam is generated in 100 units of the phenol resin; 5 to 40 units of a curing agent composed of sulfuric acid (H ₂ SO ₄ ) -based acid compounds are mixed to react with the phenol resin to cure the phenol foam; In order to control the cell distribution and the size of the foam, a foaming agent made of a siloxane (Siloxane; H ₂ SiO- (H ₂ SiO) n-SiH ₃ ) system is blended in 0.5 to 5 units; A phenol foam characterized by comprising 3 to 20 units of a blowing agent having a predetermined foaming effect. Methyol Phenol, Dimethyol Phenol, Trimethyol Phenol produced by the synthesis of Phenol and Formalin, Cresol for denaturation, In using phenolic foam in which at least one of bisphenols and a phenol resin produced by the synthesis of formalin, a plasticizer, a curing agent, a foaming agent and a blowing agent are mixed and stirred, Panel steel sheets (2,4) are provided on the upper and lower portions of the phenolic foam (2), and urethane adhesive is sprayed on the upper and lower adhesive surfaces of the steel sheets (2,4) to bond the phenolic foam and the steel sheet. At the same time, the building panel using a phenol foam, characterized in that to prevent the phenol foam is in direct contact with the steel sheet.