WO2013005994A2

WO2013005994A2 - Nonflammable aluminum composite panel using a phenol resin hardened foamed body and method for manufacturing same

Info

Publication number: WO2013005994A2
Application number: PCT/KR2012/005327
Authority: WO
Inventors: 김명희; 이응기; 이민희; 김정근; 김지문
Original assignee: (주)엘지하우시스
Priority date: 2011-07-07
Filing date: 2012-07-05
Publication date: 2013-01-10
Also published as: KR101382045B1; WO2013005994A3; KR20130005747A

Abstract

The present invention relates to a highly thermally insulating nonflammable aluminum composite panel made of a phenol resin hardening foamed body, and to a method for manufacturing the panel. The aluminum composite panel of the present invention comprises a core layer formed between a front plate and a rear plate each comprising an aluminum layer, wherein a phenol resin hardened foamed body is formed in the core layer. Thus, the aluminum composite panel may have high heat insulation performance with a thermal conductivity of 0.020 W/mK or lower and nonflammability at flame retardant level 2. The panel of the present invention can be utilized as a finishing material for an outer wall for high-efficiency construction, wherein the wall may exhibit superior constructibility and prevent dew condensation.

Description

Non-combustible aluminum composite panel using phenol resin cured foam and its manufacturing method

The present invention relates to an aluminum composite panel manufacturing technology, and more particularly, by forming a core layer between the front and rear aluminum plates with a phenol resin cured foam, high thermal insulation performance of 0.020 W / mK or less level The present invention relates to a technology for providing an aluminum composite panel having a non-flammability similar to that of a second flame retardant.

Composite panels are commonly used for building exterior wall finishing. The composite panel is composed of a steel plate such as aluminum, magnesium, iron and the front panel.

In addition, the core layer (core) between the front plate and the back plate is formed of a material showing an insulating effect such as glass wool, polyethylene (PE), talc (Talc).

Here, when the core layer is formed of polyethylene (PE), the polyethylene is likely to catch fire, which is very vulnerable to the risk of fire.

As an example, Korean Patent Registration No. 10-0828630 (2008.05.02) includes 15 to 25% by weight of polyethylene (PE), 5 to 15% by weight of ethylene vinyl acetate (EVA) and 60 to 80 weight of a flame retardant filler. Disclosed is a flame retardant aluminum composite panel comprising a flame retardant synthetic resin mixed with%.

Therefore, the core layer is filled with a flame retardant or an excess of talc. In this case, the specific gravity is large so that the workability is difficult and the construction cost is high.

In addition, when the glass wool or rock wool is filled in the core layer, the panel has an advantage of being nonflammable, but there is a problem that thermal insulation performance is deteriorated due to high thermal conductivity. In addition, glass wool or rock wool has a problem that acts as a harmful element to the human body.

The present invention is an aluminum composite panel that can solve the risk of fire, a gas generation problem and construction cost problems that are a problem in the aluminum composite panel using polyethylene (PE) or talc (talc) as a core layer and It aims at providing the manufacturing method.

In addition, the present invention is to provide an aluminum composite panel having a high thermal insulation performance of the level of 0.020 W / mK or less and non-combustible according to the flame retardant class 2 and a manufacturing method thereof.

Non-combustible aluminum composite panel manufacturing method according to the present invention for achieving the above object comprises the steps of (a) providing a front plate and a back plate comprising an aluminum layer; (b) injecting a phenol resin composition comprising a blowing agent between the front plate and the back plate, and then foaming and curing to form a composite panel including a phenol resin cured foam; And (c) curing and aging the phenolic resin cured foam contained in the composite panel.

In addition, the non-combustible aluminum composite panel according to the present invention for achieving the above object is a core layer formed of a phenol resin cured foam; And a front plate and a rear plate formed on the front and rear surfaces of the core layer, each having an aluminum layer.

In the aluminum composite panel according to the present invention, the core layer is formed of a phenol resin cured foam, thereby ensuring heat insulation and flame retardancy. Therefore, the application of the composite panel according to the present invention to the building insulation provides a flame retardant level of flame retardancy because it provides an effect that can improve the safety in fire.

In addition, the heat insulation composite panel according to the present invention exhibits a high thermal insulation property of less than 0.020 W / mK thermal conductivity, there is an effect that can reduce the heating cost.

In addition, the present invention does not use a freon gas in the core material, using an environmentally friendly blowing agent such as hydrocarbon (hydrocarbon), not HCFC (hydro-chloro-fluoro-carbon) blowing agent, there is no risk factor for global warming and long-term high It provides the effect of maintaining insulation performance and condensation prevention.

1 is a flow chart showing a method for producing an aluminum composite panel comprising a phenolic resin cured foam according to the invention.

Figure 2 is a cross-sectional view showing an aluminum composite panel comprising a phenolic resin cured foam according to the present invention.

Advantages and features of the present invention and methods for achieving them will be apparent with reference to the embodiments described below in detail with the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various forms, and only the present embodiments are intended to complete the disclosure of the present invention, and the general knowledge in the art to which the present invention pertains. It is provided to fully convey the scope of the invention to those skilled in the art, and the present invention is defined only by the scope of the claims. Like reference numerals refer to like elements throughout.

Hereinafter, a high thermal insulation non-combustible aluminum composite panel using a phenol resin cured foam according to a preferred embodiment of the present invention and a method of manufacturing the same will be described in detail with reference to the accompanying drawings.

In order to manufacture the composite panel according to the present invention, the steps of forming the first and second aluminum layers to be the front plate and the back plate, respectively, and adding a phenol resin mixed solution between the first and second aluminum layers and foam hardening And preparing a panel formed by high-temperature compression and cutting it to a required size, and curing and aging to lower thermal conductivity and improve flame retardant properties.

Referring to FIG. 1, the illustrated aluminum composite panel manufacturing method includes a front plate / back plate preparing step (S100), a phenol resin cured foam forming step (S110), a high temperature compression step (S120), and a curing / aging step (S130). Include.

First, in the front plate / back plate preparing step (S100) to prepare a front plate and a back plate corresponding to the outer shell of the aluminum composite panel (S100).

The front plate and the back plate each comprise an aluminum layer. The aluminum layer may be formed of one sheet or two or more aluminum plates. It is preferable that the thickness of an aluminum layer is 0.5-2 mm. At this time, when the thickness of the aluminum layer is less than 0.5 mm it is difficult to secure the strength of the panel structurally. On the contrary, when the thickness exceeds 2 mm, the weight may be increased, thereby reducing the construction efficiency.

In addition, a protective layer, a chromate layer, or the like may be further formed on the outer surface of the aluminum layer on the front plate or the back plate. In addition, the front plate may also be added to the coating layer for improving the appearance as the exterior wall finishing material. Only one layer of these protective layers, chromate layers, paint layers, etc. may be formed on the outer surface of the aluminum layer, and a plurality of layers having the same shape as the aluminum layer / chromate layer / paint layer / protective layer It can be formed on the surface.

Next, in the step of forming a phenol resin cured foam (S110) by inserting and foaming the phenol resin composition between the front plate and the back plate, to form a core cured foam between the front plate and the back plate.

In this case, the phenol resin composition may include a foam stabilizer, a foaming agent, a curing agent, and an additive.

More specifically, the phenol resin composition may include 1 to 10% by weight foam stabilizer, 5 to 25% by weight foaming agent, 5 to 25% by weight curing agent and 0.1 to 10% by weight additive.

Foam stabilizers act as surfactants. The phenolic resin and the curing agent are hydrophilic and hydrocarbon-based blowing agents have hydrophobic characteristics. Foaming agents are used to help the hydrophilization of the blowing agent for mixing with the blowing agent and other compositions. Such foam stabilizers may be silicone-based or polysiloxane-based.

When the foam stabilizer is 1 to 10% by weight of the total weight of the phenol resin composition and the content of the foam stabilizer is less than 1% by weight, the foaming agent does not have a hydrophilic function, and thus it is difficult to mix the foaming agent with the phenol resin and the curing agent. On the contrary, when the content of the foam stabilizer exceeds 10% by weight, the hydrophilization property may be excessive, resulting in a problem that the phenol resin cannot be combined with the front plate or the back plate.

The blowing agent is a physical blowing agent, which forms a phenol resin composition into bubbles due to the heat of reaction, and is characterized by low thermal conductivity and low boiling point.

In the present invention, the blowing agent uses an aliphatic hydrocarbon having 1 to 8 carbon atoms. Conventionally, there is a problem of global warming due to ozone layer destruction using freon gas or HCFC (hydro-chloro-fluoro-carbon) as a blowing agent. However, in the present invention, by using a hydrocarbon as a blowing agent, it is possible to solve the burden on the risk of environmental threats as compared to the conventional.

Here, the hydrocarbons that can be used as the blowing agent include cyclopentane, isopentane, isobutane, and the like, and are preferably selected in consideration of thermal conductivity and boiling point of the blowing agent.

The blowing agent preferably includes at least one member selected from the group consisting of at least one of isopentane, isobutane and cyclopentane. The blowing agent is preferably included in 5 to 25% by weight of the total weight of the phenol resin composition. The content of the blowing agent is an important factor in controlling the density of the entire phenolic resin composition, and in order to prepare a phenolic resin cured foam having a density in the range of 30 to 40 kg / m ^3, it is preferable to add the above content. That is, when the content of the blowing agent is less than 5% by weight, the density of the phenol resin cured foam may exceed 40 kg / m ³ , and when the content of the blowing agent exceeds 25% by weight, the density of the phenol resin cured foam is 30 kg. It may be less than / m ³ .

The curing agent acts as a catalyst to lower the foaming temperature and to foam at a relatively low temperature. A curing agent may use benzene sulfonic acid, paratoluene sulfonic acid, xylene sulfonic acid, phenol sulfonic acid and the like.

It is preferable that a hardening | curing agent is contained in 5 to 25 weight% of the total weight of a phenol resin composition. If the content of the curing agent is less than 5% by weight, the catalytic function may not be performed. If the content of the curing agent exceeds 25%, a large amount of unreacted curing agent is generated, resulting in acidity, thereby increasing corrosion of the metal.

The additive is an organic amino group-containing compound for reducing outgassing by removing unreacted monomers.

The additive is preferably included in 0.1 to 10% by weight of the total weight of the phenol resin composition. If the weight of the additive is less than 0.1% by weight, it is difficult to remove the unreacted monomer, and outgassing may occur. If the weight of the additive is more than 10% by weight, the additive acts as an impurity to improve the quality of the entire phenolic resin foam. Can be degraded.

The additive may comprise a neutralizing agent. The neutralizing agent serves to increase the pH of the phenolic resin cured foam to about 3 to 9 bar bar, which can be used to compensate for corrosion problems on the metal adhesion surface due to the acidic curing agent.

The neutralizing agent may be a hydroxide of a metal such as aluminum hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, aluminum oxide or zinc oxide, or a metal powder such as oxide or zinc, a metal carbonate such as calcium carbonate, magnesium carbonate, barium carbonate or zinc carbonate. It may include. The said neutralizing agent can be used individually by 1 type, or can be used in combination of 2 or more type.

The neutralizing agent is preferably included in 0.1 to 10% by weight of the total weight of the phenolic resin composition, when the content of the neutralizing agent is less than 0.1% by weight of the cured phenolic resin foam formed will be acidic, in the case of more than 10% by weight Problems may occur in which the physical properties of the formed phenol resin cured foam are changed.

In addition to the above additives may include a plasticizer. The plasticizer gives flexibility to the bubble wall and prevents the wall from being broken or deteriorated so that the foaming gas in the bubble escapes and is replaced with air, thereby enhancing long-term durability. Specific examples of the plasticizer may include triphenyl phosphate, dimethyl terephthalate, dimethyl isophthalate, polyethylene glycol, polyol, and the like.

It is preferable that the said plasticizer is contained in 1 to 15 weight% of the total weight of the phenol resin composition for phenol resin cured foam formation. When the content of the plasticizer is less than 1% by weight, the phenolic resin cured foam does not affect long-term durability, and when it exceeds 15% by weight, the performance of the phenolic resin cured foam may be impaired.

On the other hand, depending on the components or foaming conditions of the phenol resin composition, the independent foaming rate of the cured phenol resin formed can be determined. In the present invention, it is preferable that the closed cell content of the phenol resin cured foam is 80% or more.

The independent bubble ratio defines the fraction of closed bubbles among the bubbles formed in the unit area. In the present invention, when the independent bubble ratio is less than 80%, the remaining gas remains inside the phenol resin-cured foam, which results in outgassing. It may cause, and the structural strength is remarkably lowered, which may result in deterioration of the characteristics of the exterior panel.

In the prior art, an aluminum composite panel is manufactured by a T-die using an extruder, and an air layer is generated and condensation occurs due to a technology of injecting a filler such as an inorganic material into the core layer between the aluminum composite panels. There was a disadvantage that the insulation performance is lowered or the durability is lowered.

However, the aluminum composite panel manufacturing method of the present invention is to prepare a front plate / back plate corresponding to the outer shell material of the aluminum composite panel (S100), while injecting the phenolic resin composition there between foaming and curing (S110) Containing, by putting a phenolic resin composition between the front plate / back plate can be immediately foamed and hardened to prevent condensation.

Next, in the high temperature compression step (S120), the aluminum composite panel is formed by compressing the phenol resin composition introduced between the front plate and the back plate through the pressing process through the front plate and the back plate. At this time, when the size of the aluminum composite panel is determined, it can be cut to a predetermined size.

The pressing step is characterized in that to press the phenol resin composition at a predetermined temperature. Specifically, it is possible to use a conveyor belt capable of pressing, the conveyor belt and the lower conveyor belt is rotated at a predetermined interval, the front plate, the phenol resin composition and the back plate may be introduced therebetween. At this time, the operating temperature and the operating pressure of the conveyor belt are important because they act as an influence factor that the foam can have uniform and independent bubbles.

The pressing process may be carried out at a temperature of 65 ~ 100 ℃, preferably 70 ~ 90 ℃. If the running temperature in the pressing process is less than 65 ℃, for example, when using the conveyor belt foam curing of the phenolic resin composition may not sufficiently occur within a limited time passing through the conveyor belt, the curing rate if the temperature exceeds 100 ℃ The evaporation or foaming rate of the blowing agent is more rapid, the cell (cell) becomes larger and burst, the heat insulation performance may be lowered.

In addition, the pressing process may be performed by applying a pressure of 0.3 ~ 2.0kgf / cm ² , preferably 0.5 ~ 1.5kgf / cm ² . When the pressure applied in the pressing process is less than 0.3kgf / cm ² , the desired aluminum panel shape cannot be maintained because the foaming pressure does not have sufficient foaming pressure to form a sufficient phenolic resin foaming agent, and a pressure exceeding 2.0kgf / cm ² is applied. In this case, a cell in which the foaming gas is trapped may be broken.

Next, in the curing / aging step, curing and aging of the phenol resin cured foam contained in the composite panel to complete a high insulation non-combustible aluminum composite panel.

At this time, curing is made for the purpose of post-curing and includes a aging step to remove VOC (volatile organic compounds). It is preferable to put in a convection oven for 10 to 200 minutes per cm ² of the core layer at less than 75 ℃. If the curing time is less than 10 minutes, the curing and aging is not sufficiently made, the thermal conductivity may increase and the thermal insulation properties may be reduced.

In addition, when the curing time exceeds 200 minutes, the improvement of the characteristics compared to the time and cost put into the curing may result in a waste of only cost.

By the above panel manufacturing method, the composite panel which has the core layer formed from the phenol resin cured foam, and the front plate / back plate provided with an aluminum layer can be manufactured.

2 is a cross-sectional view showing an aluminum composite panel using a phenol resin cured foam according to the present invention.

Referring to FIG. 2, the illustrated aluminum composite panel includes a core layer 100, a front plate 110, and a back plate 120.

The core layer 100 is formed of a phenol resin cured foam.

The front plate 110 is formed on one surface of the core layer 100 (upper core layer in FIG. 2), and the back plate 120 is formed on the other surface of the core layer 100.

These front plates 110 and back plates 120 are provided with

aluminum layers

110d and 120b.

The composite panel according to the present invention can be completed only by the basic structure of the front plate 110 and the back plate 120 having the core layer 100 and the aluminum layers 110d and 120b formed of such a phenol resin cured foam. have.

However, as shown in FIG. 2, the aluminum composite panel according to the present invention may have a separate chromate layer formed on the outer surface of the aluminum layer provided on the front plate 110 or the rear plate 120 so as to be used as an external finishing material. 110c), the paint layer 110b, the

protective layers

110a and 120a may be further formed.

At this time, the front plate 110 is defined after the construction, the name is defined based on the portion exposed to the outside, the rear plate 120 has been described as showing the opposite side, but is not limited thereto.

The present invention provides a high insulation non-combustible aluminum composite panel made of a phenol resin cured foam, and may exhibit non-combustibility according to thermal conductivity and flame retardant secondary level of 0.020 W / mK or less.

As such, a detailed embodiment of the excellent thermal insulation and non-combustible performance will be described.

[Manufacture of Composite Panel]

Example 1

First, a mixture containing 4% by weight of a polysiloxane foam stabilizer (polysiloxane), 3% by weight of a neutralizer (calcium carbonate), 3% by weight of a plasticizer (polyol), 10% by weight of a blowing agent (cyclopentane), and a curing agent (paratoluene). Sulphonic acid) 15 wt% of the phenolic resin composition by injecting and mixing in three phases was mixed between aluminum plates of 2 mm thickness using a conveyor belt carried out at an operating temperature of 80 ° C. and an operating pressure of 1.0 kgf / cm ² . And phenol resin mixtures were foamed and cured immediately on a conveyor belt for 10 minutes to form phenol resin cured foams having an independent foam ratio of 90%. After curing and aging for 60 minutes per 1 cm ² at 75 ℃ to produce an aluminum composite panel.

Example 2

An aluminum composite panel was manufactured under the same conditions as in Example 1, but the independent bubble ratio was 80%.

Comparative Example 1

An aluminum composite panel was manufactured under the same conditions as in Example 1, but the independent bubble ratio was 60%.

Comparative Example 2

An aluminum composite panel was manufactured under the same conditions as in Example 1 except that polyethylene was used as the core layer instead of the phenol resin cured foam.

Comparative Example 3

An aluminum composite panel was manufactured under the same conditions as in Example 1, except that talc was used as the core layer instead of the phenol resin cured foam.

[Performance Test and Evaluation]

The composite panels prepared according to the above Examples 1 to 2 and Comparative Examples 1 to 3 were placed in a constant temperature chamber at 85 ° C., respectively, and maintained for 3 months while comparing the thermal conductivity with those for which no full heating was performed. At this time, HC-074-200 (manufactured by EKO) thermal conductivity meter was used for the measurement of thermal conductivity. Next, by applying an acceleration factor to predict the thermal conductivity up to 0 ~ 10 years, the results are shown in Table 1 in terms of adiabatic value (W / mK).

Table 1

	Insulation value (W / mK)
	Early	1 year	2 years	3 years	4 years	5 years	6 years	7 years	8 years	9 years	10 years
Example 1	0.019	0.019	0.019	0.019	0.019	0.019	0.019	0.0191	0.0192	0.0192	0.0193
Example 2	0.020	0.020	0.020	0.020	0.020	0.020	0.020	0.0201	0.0202	0.0204	0.0205
Comparative Example 1	0.024	0.024	0.024	0.024	0.0241	0.0242	0.0242	0.0243	0.0245	0.0246	0.0247
Comparative Example 2	0.042	0.043	0.044	0.045	0.046	0.048	0.050	0.053	0.055	0.057	0.059
Comparative Example 3	0.045	0.046	0.047	0.048	0.049	0.050	0.051	0.054	0.057	0.060	0.063

In Examples 1 and 2, the initial thermal conductivity is not only lower than the comparative examples, it can be seen that the increase with time is also lower than the comparative examples.

Therefore, it can be seen that the composite panel made of a phenol resin cured foam according to the present invention has excellent initial heat insulating performance and long term durability performance. Due to this high energy load reduction rate can be seen that can be used as a high-efficiency building finishing material.

In addition, the phenolic foam of the core layer has a semi-combustibility corresponding to the flame retardant secondary. For semi-combustible grade testing methods, there are heat release rate tests (KS F ISO 5660-1) and gas hazard tests (KS F 2271). The heat release rate test shall use a cone calorimeter method and the total heat release rate shall not exceed ⁸ MJ / m ² and the maximum heat release rate shall not exceed 200 kW / m ² when 50 kW / m ² radiant heat is applied for 10 minutes. The gas hazard test may be quasi-non-combustible if the average time of inactivity is greater than 9 minutes when observing 8 rats due to the combustion gases of the test specimen. In the case of phenol foam, it can be seen that the use of non-freon gas is environmentally friendly, no harmful gas is generated, and the flame retardancy is excellent, so that the risk of fire is low.

Although the embodiments of the present invention have been described above with reference to the accompanying drawings, the present invention is not limited to the above embodiments and can be manufactured in various forms, and having ordinary skill in the art to which the present invention pertains. It will be understood by those skilled in the art that the present invention may be embodied in other specific forms without changing the technical spirit or essential features of the present invention. Therefore, it should be understood that the embodiments described above are exemplary in all respects and not restrictive.

Claims

(a) providing a front plate and a back plate comprising an aluminum layer;

(b) injecting a phenol resin composition comprising a blowing agent between the front plate and the back plate, and then foaming and curing to form a composite panel including a phenol resin cured foam; And

(c) curing and aging the phenolic resin cured foam contained in the composite panel; non-combustible aluminum composite panel manufacturing method comprising a.
The method of claim 1,

After the pressing step of pressing the phenol resin composition at a predetermined temperature,

A method of producing a non-combustible aluminum composite panel, comprising performing foaming and curing to form a composite panel comprising a phenol resin cured foam.
The method of claim 2,

The pressing process

Non-combustible aluminum composite panel manufacturing method characterized in that carried out at a temperature of 65 ~ 100 ℃.
The method of claim 2,

The pressing process

Non-combustible aluminum composite panel manufacturing method characterized in that carried out by applying a pressure of 0.3 ~ 2.0kgf / cm 2 .
The method of claim 1,

The phenolic resin composition

A method for producing a non-combustible aluminum composite panel, comprising 1 to 10 wt% of foam stabilizers, 5 to 25 wt% of blowing agents, 5 to 25 wt% of curing agents, and 0.1 to 10 wt% of additives.
The method of claim 1,

The phenolic resin composition

Non-flammable aluminum composite panel manufacturing method characterized in that it further comprises 1 to 15% by weight of a plasticizer.
The method of claim 1,

The blowing agent is a non-combustible aluminum composite panel manufacturing method characterized in that it comprises at least one selected from the group consisting of one or more (hydrocarbon) of isopentan (Isopentane), isobutane (isobutane) and cyclopentane (Cyclopentane).
The method of claim 1,

The first and second aluminum layers are each

Method for producing a non-combustible aluminum composite panel, characterized in that formed to a thickness of 0.5 ~ 2mm.
The method of claim 1,

The foam curing is

Method for producing a non-combustible aluminum composite panel, characterized in that the independent foam ratio of the phenol resin cured foam is 80% or more.
The method of claim 1,

The curing and aging

Method for producing a non-combustible aluminum composite panel, characterized in that performed for 10 to 200 minutes per 1 cm 2 of the phenol resin cured foam.
The method of claim 1,

After step (b),

Non-combustible aluminum composite panel manufacturing method further comprising the step of cutting the composite panel to a predetermined size.
A core layer formed of a phenol resin cured foam; And

Non-combustible aluminum composite panel, characterized in that it is formed on the front and rear of the core layer, each having a front plate and a back plate having an aluminum layer.
The method of claim 12,

The phenol resin cured foam

Non-combustible aluminum composite panel, characterized in that the independent bubble ratio is more than 80%.
The method of claim 12,

The aluminum layer

Non-combustible aluminum composite panel, characterized in that having a thickness of 0.5 ~ 2mm.
The method of claim 12,

In the front panel or the back panel,

Non-combustible aluminum composite panel, characterized in that at least one of a chromate layer, a protective layer and a coating layer is further formed on the outer surface of the aluminum layer.
The method of claim 12,

The composite panel is

Non-combustible aluminum composite panel, characterized in that the thermal conductivity is 0.02 W / mK or less.