KR20210068982A - Phenol foam and method of producing the same - Google Patents

Abstract

Provided is a phenolic foam, a foamed cured product of a composition comprising a phenolic resin, a foaming agent, a surfactant and a curing agent, of which the density is 30 to 33 kg/m^3, the compressive strength according to KS M ISO 845 is 90 to 170 kPa, the thermal conductivity measured at an average temperature of 20°C according to KS L 9016 is 0.018 to 0.020 W/mK, the average foam diameter in a cross section bisecting a thickness direction of a foam is 120 to 170 μm, and a standard deviation of the foam diameter in a cross section is 30% or less. It is an object of the present invention to provide the phenolic foam that exhibits excellent compressive strength, uniform cell diameter of a certain size and excellent thermal insulation while reducing weight with a low density.

Description

Phenolic foam and its manufacturing method {PHENOL FOAM AND METHOD OF PRODUCING THE SAME}

The present invention relates to a phenolic foam and a method for preparing the same.

Insulation is an essential material used to prevent energy loss in buildings. As the importance of green growth continues to be emphasized worldwide due to global warming, insulation is becoming more important to minimize energy loss.

And, it is common to handle boards of about 2M or more at the time of construction of the insulation material, for example, the construction of the insulation resistance material. In addition, if several sheets are lifted at once during construction, the weight is considerable. Accordingly, there is a need for a technology for reducing the density of the insulating material in order to reduce the handling and mass production cost during construction.

On the other hand, in the case of reducing the weight of the foam by increasing the foaming ratio, the cell diameter may increase and the cells may coalesce, and as a result, the cell diameter may become non-uniform. In addition, there may be a problem in that physical properties such as thermal insulation and strength of the foam are deteriorated.

It is an object of the present invention to provide a phenolic foam that exhibits excellent compressive strength, uniform cell diameter of a certain size, and excellent thermal insulation while being lightweight at a low density.

It is also an object of the present invention to provide a method for producing the phenolic foam.

The objects of the present invention are not limited to the objects mentioned above, and other objects and advantages of the present invention not mentioned can be understood by the following description, and will be more clearly understood by the examples of the present invention. Moreover, it will be readily apparent that the objects and advantages of the present invention may be realized by the means and combinations thereof indicated in the claims.

It is a foamed cured product of a composition comprising a phenolic resin, a foaming agent, a surfactant and a curing agent according to the present invention, the density is 30 kg/m3 to 33 kg/m3, and the compressive strength according to KS M ISO 845 is 90 kPa to 170 kPa and the thermal conductivity measured at an average temperature of 20 ° C according to KS L 9016 is 0.018 W / mK to 0.020 W / mK, and the average cell diameter in the section bisecting the thickness direction of the foam is 120 μm to 170 μm, and the cross section It is possible to provide a phenolic foam having a standard deviation of cell diameters of 30% or less.

In addition, preparing a composition comprising a phenolic resin, a foaming agent, a surfactant and a curing agent according to the present invention, and stirring the composition; And discharging the stirred composition, foaming and curing; includes, the density is 30 kg / m3 to 33 kg / m3, the compressive strength according to KS M ISO 845 is 90 kPa to 170 kPa, KS L 9016 The thermal conductivity measured at an average temperature of 20 ° C. is 0.018 W / mK to 0.020 W / mK, and the average cell diameter in the section bisecting the thickness direction of the foam is 130 μm to 150 μm, and the cell diameter in the cross section is It is possible to provide a method for producing a phenolic foam having a standard deviation of 30% or less.

The phenolic foam according to the present invention can be lightweight with a low density to increase handling properties during construction and reduce costs, and can simultaneously exhibit physical properties such as uniform cell diameters of a certain size, excellent thermal insulation properties, and excellent compressive strength.

In addition, the method for producing a phenol foam in the present invention can produce the phenol foam.

In addition to the above-described effects, the specific effects of the present invention will be described together while describing specific details for carrying out the invention below.

The above-described objects, features and advantages will be described in detail below, and accordingly, those skilled in the art to which the present invention pertains will be able to easily implement the technical idea of the present invention. In describing the present invention, if it is determined that a detailed description of a known technology related to the present invention may unnecessarily obscure the gist of the present invention, the detailed description will be omitted. Hereinafter, preferred embodiments according to the present invention will be described in detail.

Hereinafter, the phenolic foam will be described in some embodiments of the present invention.

One embodiment of the present invention is a foamed cured product of a composition including a phenol-based resin, a foaming agent, a surfactant and a curing agent, the density is 30 kg/m3 to 33 kg/m3, and the compressive strength according to KS M ISO 845 is 90 kPa to 170 kPa, and the thermal conductivity measured at an average temperature of 20 ° C according to KS L 9016 is 0.018 W / mK to 0.020 W / mK, and the average cell diameter in the section bisecting the thickness direction of the foam is 120 μm to 170 μm, and , wherein the standard deviation of the cell diameter in the cross section is about 30% or less.

In general, the foam has a density of about 40 kg/m3 and it is common to handle boards of about 2M or more when constructing an insulation material, for example, an insulation resistance material. In addition, if several sheets are lifted at once during construction, the weight is considerable. Accordingly, there is a demand for a technology for reducing the density of the insulating material in order to reduce the handling and mass production cost during construction. Accordingly, it is possible to reduce the weight of the foam by increasing the foaming ratio, but in this case, there may be a problem in that the diameter of the cells is increased and the cells may be combined, and as a result, the diameter of the cells becomes non-uniform. In addition, there may be a problem in that physical properties such as thermal insulation and strength of the foam are deteriorated.

The phenol foam is a foamed cured product of a composition including a phenol-based resin, a foaming agent, a surfactant and a curing agent, and by reducing the discharge amount of the composition, it is lightweight to a density of about 30 kg/m3 to about 33 kg/m3 can increase and reduce costs. And the phenolic foam has an average cell diameter of about 120 μm to about 170 μm in a cross section bisecting the thickness direction of the foam, and a standard deviation of the cell diameter in the cross section is about 30% or less of a uniform cell diameter of a certain size. can have In addition, the phenolic foam has a compressive strength of about 90 kPa to 170 kPa according to KS M ISO 845, and a thermal conductivity measured at an average temperature of 20° C. according to KS L 9016 is about 0.018 W/mK to about 0.020 W/mK, which is excellent It can exhibit improved physical properties such as thermal insulation and excellent compressive strength at the same time.

The phenol foam is a foamed cured product of a composition including a phenol-based resin, a foaming agent, a surfactant, and a curing agent.

Specifically, the phenolic foam includes a phenolic resin. The phenol-based resin may be obtained by reacting phenol and formaldehyde, and may include, for example, a resol-based phenol resin (hereinafter, 'resol resin'). The phenolic resin may be included in the phenolic foam in an amount of about 30% to about 90% by weight, or about 50% to about 90% by weight, or about 55% to about 90% by weight.

The phenolic foam includes a blowing agent. Specifically, the blowing agent may include an aliphatic hydrocarbon having 1 to 8 carbon atoms. In general, the phenol foam may exhibit excellent thermal insulation properties, including a hydrofluoroolefin (HFO)-based compound having excellent thermal conductivity. On the other hand, the hydrofluoroolefin-based compound has a low boiling point, so it is difficult to handle during the manufacture of the foam, and it is not included in the bubble during the manufacturing process and volatilizes, so there may be a problem in that the physical properties are lowered compared to the input amount. The phenol foam may include an aliphatic hydrocarbon having 1 to 8 carbon atoms to improve physical properties such as compressive strength and brittleness along with excellent thermal insulation properties.

For example, the phenolic foam may include one aliphatic hydrocarbon selected from the group consisting of chlorinated, unchlorinated aliphatic hydrocarbons and combinations thereof. Specifically, the hydrocarbon-based compound is dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n- pentane, isopentane, cyclopentane, hexane , heptane, cyclopentane, and may include at least one selected from the group consisting of combinations thereof.

The blowing agent may be included in an amount of about 10 parts by weight to about 13 parts by weight, based on 100 parts by weight of the phenol foam. For example, it may be included in an amount of about 10 parts by weight to about 12 parts by weight. The foaming agent is included in an appropriate amount in the composition, and may be included in the content of the above range in the phenol foam.

The phenol foam can implement weight reduction by improving the foaming ratio by reducing the discharge amount of the foam composition compared to the conventional one, while the content of the foaming agent is within the above range. For example, if the content of the foaming agent is less than the above range, there may be a problem in that a foam of a desired thickness cannot be produced because sufficient foaming is not achieved, and the deviation of the cell diameter of the foam is too large and the physical properties are deteriorated. In addition, when the content of the foaming agent exceeds the above range, there may be a problem in that the cell wall becomes too thin to decrease physical properties such as compressive strength and brittleness, and the average cell diameter of the foam becomes too large. The blowing agent may be included in an amount of about 13 parts by weight to about 14 parts by weight based on 100 parts by weight of the phenol-based resin in the composition.

And, the phenolic foam includes one surfactant selected from the group consisting of amphoteric, cationic, anionic, nonionic surfactants and combinations thereof. For example, nonionic surfactants, such as polysiloxane type, polyoxyethylene sorbitan fatty acid ester, and the ethylene oxide adduct of castor oil, etc. can be used.

The composition may include the blowing agent: the surfactant in a weight ratio of about 1: 0.3 to about 1: 0.35. In the phenol foam, the amount of the surfactant relative to the foaming agent is adjusted to the above range relative to 100 parts by weight of the phenol-based resin, thereby preventing an increase in the size of the bubbles and non-uniformity of the bubble size from occurring. Specifically, by adjusting the content of the foaming agent to the surfactant within the above range, the surface tension of the foaming agent in the phenol-based resin can be lowered, so that the foaming agent can be stably dispersed, and bubbles can be uniformly formed during the foaming process. Accordingly, in spite of including the composition of a small discharge amount and the expanded foaming agent in the above range, it may have an average cell diameter and a low standard deviation equivalent to the existing ones.

The surfactant may be included in the composition in an amount of about 3.5 parts by weight to about 5.5 parts by weight based on 100 parts by weight of the phenol-based resin, which is higher than that of the conventional one. Specifically, when the content of the surfactant is less than the above range, the foaming agent is not uniformly dispersed on the phenolic resin, it is difficult to form bubbles, and the bubbles are formed non-uniformly, so that the cells are merged or the bubble cells are opened and the independent cell ratio is can be lowered And the low compressive strength can break the cell. When it exceeds the above range, the viscosity of the composition may be lowered to promote vaporization of the foaming agent, and accordingly, the content of the foaming agent contained in the foam is reduced compared to the amount of the injected foaming agent, so that there may be a problem in that thermal insulation properties and the like are lowered.

The phenolic foam includes a curing agent. The curing agent may include one acid curing agent selected from the group consisting of toluene sulfonic acid, xylene sulfonic acid, benzenesulfonic acid, phenol sulfonic acid, ethylbenzene sulfonic acid, styrene sulfonic acid, naphthalene sulfonic acid, and combinations thereof. The phenol foam may exhibit appropriate crosslinking, curing and foaming properties by including the curing agent.

The composition may include the foaming agent: the curing agent in a weight ratio of about 1: 1.5 to about 1: 1.8. The phenolic foam can optimize the foaming curing rate in relation to the foaming agent by adjusting the content of the curing agent with respect to the foaming agent in the above range relative to 100 parts by weight of the phenolic resin, and efficiently trap the foaming agent in the foam. can And, by including the curing agent in the above range in relation to the foaming agent, it is possible to increase the heat of reaction in the manufacturing process, thereby further increasing the foaming ratio.

Specifically, when the content of the curing agent is less than the above range, the size of the bubbles grows by the content of the foaming agent, but post-foaming occurs due to insufficient heat of curing. Accordingly, there is a problem in that it is difficult to control the thickness because the foam of the desired thickness cannot be manufactured. can In addition, there may be a problem in that the closed cell ratio is lowered and the compressive strength is lowered as the cells are broken. In addition, when the ratio of the curing agent exceeds the above range, the curing rate is increased, so that the mold or curing furnace is cured without 100% filling of the foam, there may be a problem in that a proper foam cannot be formed. In addition, there may be a problem in that there is a lot of heat of curing, so heat is accumulated in the foam, and thus cracks are generated therein. The composition may include the curing agent in an amount of 19 to 26 parts by weight based on 100 parts by weight of the phenolic resin. Alternatively, the composition may include the curing agent in an amount of 19.5 parts by weight to 25.5 parts by weight based on 100 parts by weight of the phenol-based resin.

The composition may further include one additive selected from the group consisting of a nucleating agent, polyethylene glycol, and combinations thereof.

Specifically, the nucleating agent may include carbon nanotube (CNT). Although the composition contains a larger amount of foaming agent than before, including carbon nanotubes, it is possible to more easily improve physical properties such as strength by adjusting the size of the cells to an appropriate level and thickening the cell walls and skeleton. The composition can be finely dispersed in the composition, including carbon nanotubes, can generate bubbles at a low temperature, and can help to form fine bubbles. Accordingly, the cell diameter and standard deviation in the above range can be more easily adjusted, and physical properties such as thermal insulation and compressive strength can be more easily improved.

The nucleating agent may be included in an amount of about 0.1 parts by weight to about 2 parts by weight based on 100 parts by weight of the phenolic resin.

And, the composition may include polyethylene glycol. Polyethylene glycol contained in the composition may give crosslinking properties while reacting with the OH group in the terminal group and the OH group of the phenolic resin and additionally provide a flexible polymer chain structure to the foam. Accordingly, it is possible to improve the compressive strength and exhibit excellent brittleness by exhibiting durability to crushing and/or friction.

The polyethylene glycol may have a weight average molecular weight (Mw) of about 400 g/mol to about 1,000 g/mol. When the weight average molecular weight of polyethylene glycol is less than the above range, the effect may hardly be exhibited despite the inclusion of polyethylene glycol. And, when it has a weight average molecular weight exceeding the above range, since it is in a solid state at room temperature, it is difficult to inject it in a liquid state in the foaming and blending step, so there is a problem in that handling is reduced, and when the temperature is increased to inject in a liquid state, the composition Since the viscosity is lowered, there may be a problem of accelerating the vaporization of the foaming agent.

The polyethylene glycol may be included in the composition in an amount of about 2 parts by weight to about 7 parts by weight based on 100 parts by weight of the phenolic resin. For example, if the content of polyethylene glycol is less than the above range, it has no effect, and if it exceeds the above range, the crosslinking density of the phenolic resin is lowered to open the cells of the foam and there may be a problem that the closed cell ratio is lowered. have.

The phenolic foam may have a thickness of about 20 mm to about 300 mm.

The phenolic foam may have an average cell diameter of about 120 μm to about 170 μm in a cross-section bisecting the thickness direction of the foam with a density in the above range. For example, it may have an average cell diameter of about 130 μm to about 160 μm. The average cell diameter means an average value of cell diameters in a cross section bisecting the thickness direction perpendicular to the surface to which the face material is attached so as to include the most central portion of the phenolic foam. When the average cell diameter of the phenolic foam is less than the above range, it is difficult to have the above density, and when having the above density and at the same time having the cell diameter below the above range, the number of cells is too large and, accordingly, the cell wall thickness is thin to maintain low thermal conductivity for a long period of time and brittleness and other physical properties may deteriorate. And, when it exceeds the above range, there may be a problem in that the compressive strength is lowered and the conduction property through the cell wall is increased, so that the thermal insulation performance is deteriorated.

And, the phenolic foam having an average cell diameter in the above range may have a standard deviation of the cell diameter in the cross section bisecting the thickness direction of about 30% or less. For example, the standard deviation of the cell diameter may be about 10% to about 20%. In addition, since the average cell diameter of the portion close to the center of the phenol resin foam is larger than the average cell diameter of the surface of the foam, the standard deviation of the cell diameter may increase as it is closer to the center than the surface.

The phenolic foam can exhibit excellent properties such as compressive strength and brittleness by having a standard deviation of the above range in the bisected cross section in the thickness direction of the foam located at the center. Specifically, when the standard deviation of the phenolic foam exceeds the above range, there may be a problem in that the compressive strength is lowered due to non-uniform air bubbles and changes in external dimensions such as warpage occur.

The phenolic foam may have a compressive strength of about 90 kPa to about 170 kPa according to KS M ISO 845. For example, it may be about 110 kPa to about 150 kPa. Specifically, when the compressive strength is less than the above range, there may be a problem in that handling is deteriorated because it is easy to break in use. And, if it exceeds the above range, it is difficult to simultaneously satisfy the density of the above range, and if it is satisfied at the same time by adding an additive such as a strength reinforcing agent, the cost increases, and there is a problem of lowering physical properties such as thermal conductivity due to an additive mixing problem. can

In addition, the phenolic foam may have a thermal conductivity of about 0.018 W/mK to about 0.020 W/mK measured at an average temperature of 20° C. according to KS L 9016. In general, by increasing the content of the foaming agent, it is possible to increase the foaming ratio and thereby lighten the foam. On the other hand, when the foaming ratio is increased in this way, the diameter of the cells may be increased and the cells may be merged together, and there may be a problem in that the thermal conductivity is increased as the deviation of the cell diameter is increased.

The phenolic foam has a low density within the above range, has an average cell diameter and standard deviation within the above range, and at the same time exhibits excellent thermal conductivity within the above range, thereby exhibiting a function as a thermal insulation material required by the market.

The phenolic foam may have a closed cell ratio of about 75% to about 98%. In general, in the case of increasing the foaming ratio by increasing the content of the foaming agent and thus reducing the weight of the foam, there may be a problem in that the cell diameter is increased and the closed cell ratio is lowered as the cell diameter is increased. The phenolic foam may exhibit physical properties such as excellent thermal insulation, compressive strength and brittleness by maintaining the closed cell ratio within the above range. Specifically, when the closed cell ratio is less than the above range, there may be problems in that thermal conductivity is increased, compressive strength is decreased, and brittleness is increased.

The phenolic foam may exhibit a brittleness of about 25% or less according to ASTM C421-08. For example, the brittleness of the phenolic foam may be from about 15% to about 20%. Specifically, when the brittleness exceeds the above range, workability is reduced during construction, and the product is easily damaged during handling, such as transport, thereby generating dust.

Another embodiment of the present invention comprises the steps of preparing a composition comprising a phenolic resin, a foaming agent, a surfactant and a curing agent, and stirring the composition; And discharging the stirred composition, foaming and curing; includes, the density is 30 kg / m3 to 33 kg / m3, the compressive strength according to KS M ISO 845 is 90 kPa to 170 kPa, KS L 9016 The thermal conductivity measured at an average temperature of 20 ° C. is 0.018 W / mK to 0.020 W / mK, and the average cell diameter in the section bisecting the thickness direction of the foam is 130 μm to 150 μm, and the cell diameter in the cross section is A method for producing a phenolic foam having a standard deviation of 30% or less is provided.

As described above by the manufacturing method, it is possible to increase the handleability during construction by reducing the weight with a low density and reduce the cost, and having a uniform cell diameter of a certain size, excellent thermal insulation, and physical properties such as excellent compressive strength at the same time. Phenolic foams can be prepared. The phenol-based resin, foaming agent, surfactant and curing agent are the same as those described above, except for those specifically described below.

First, the method for producing the phenol foam includes preparing a composition including a phenol-based resin, a foaming agent, a surfactant and a curing agent, and stirring the composition. In this case, the stirring speed may be about 2,500 rpm to about 3,000 rpm.

In the manufacturing method, the amount of heat generated by mixing shear stress may be increased by stirring the composition at a speed within the above range, and thus the expansion ratio may be improved. Specifically, when the stirring speed is less than the above range, it is difficult to fill 100% of the foam in the mold and curing furnace, and the foaming pressure rises in the latter part, so that the size of the bubble becomes too large, and physical properties such as thermal insulation performance, compressive strength and dimensional stability There may be problems with degradation. When the stirring speed exceeds the above range, the shear stress caused by the stirring speed is excessively applied, and the temperature of the composition increases, so that foaming occurs rapidly and the foaming agent volatilizes quickly, so that there may be a problem of poor insulation performance.

And, the manufacturing method includes; discharging the stirred composition, foaming and curing. For example, the composition may be discharged on the face material, and specifically, the discharge amount of the stirred composition may be about 28 g/min to about 32 g/min. By reducing the discharge amount of the composition to the above range, it is possible to lower the density of the foam and achieve weight reduction.

In addition, the phenol foam can be foamed and cured at a temperature of about 60° C. to about 75° C. to increase the heat of reaction of the composition to improve the expansion ratio. In addition, foaming and curing at a temperature in the above range allows the foam to be well filled in the mold and curing furnace, and it is easier to prevent the foaming pressure from increasing in the latter half to increase the size of the bubbles and to lower the foam properties.

(Example)

Example 1

Resol resin having a viscosity in the range of 20,000 to 40,000 cps at 20°C, toluenesulfonic acid as a curing agent, cyclopentane as a foaming agent, an adduct obtained by reacting ethylene oxide with castor oil as a surfactant (ethylene oxide adduct of castor oil) and polyethylene glycol (Mw :600 g/mol) A composition comprising

In the composition, 19.5 parts by weight of a curing agent is mixed with respect to 100 parts by weight of the resol resin, and 3.9 parts by weight of a surfactant is mixed so that the foaming agent: curing agent weight ratio is 1: 1.5, the foaming agent: the weight ratio of the surfactant is 1: 0.3 made to be this. And, the polyethylene glycol was mixed with 100 parts by weight of the resol resin, 4 parts by weight. Then, the mixed composition was stirred at a high speed at 3,000 rpm.

Then, the stirred composition was put into a caterpillar having a width of 1200mm, a thickness of 80mm, and a caterpillar having an atmospheric temperature of 70°C at a discharge rate of about 30kg/min, and foamed and cured to prepare a phenolic foam having a thickness of 80mm. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Example 2

The composition is prepared by mixing 21.45 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 3.9 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.65, and the weight ratio of the foaming agent: surfactant is 1: 0.3 A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Example 3

The composition is prepared by mixing 21.45 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin and mixing 4.55 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.65, and the foaming agent: the weight ratio of the surfactant is 1: 0.35. A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Example 4

The composition is prepared by mixing 23.4 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 4.55 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.8, and the foaming agent: surfactant is 1: 0.35 by weight. A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Example 5

The composition is prepared by mixing 21 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 4.2 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.5, and the weight ratio of the foaming agent: surfactant is 1: 0.3. A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 12 parts by weight, based on 100 parts by weight of the phenol foam.

Example 6

The composition is prepared by mixing 23.1 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 4.2 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.65, and the weight ratio of the foaming agent: surfactant is 1: 0.3 A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 12 parts by weight, based on 100 parts by weight of the phenol foam.

Example 7

The composition is prepared by mixing 23.1 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 4.9 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.65, and the weight ratio of the foaming agent: surfactant is 1: 0.35. A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 12 parts by weight, based on 100 parts by weight of the phenol foam.

Example 8

The composition is prepared by mixing 25.2 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 4.9 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.8, and the weight ratio of the foaming agent: surfactant is 1: 0.35. A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 12 parts by weight, based on 100 parts by weight of the phenol foam.

Comparative Example 1

The composition is prepared by mixing 15 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin and mixing 0.3 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.5, and the foaming agent: the weight ratio of the surfactant is 1: 0.3 A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 9 parts by weight, based on 100 parts by weight of the phenol foam.

Comparative Example 2

The composition is prepared by mixing 19.5 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin, and 3.25 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.5, and the weight ratio of the foaming agent: surfactant is 1: 0.25 A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Comparative Example 3

The composition is prepared by mixing 11.7 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin and mixing 3.9 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 0.9, and the foaming agent: the weight ratio of the surfactant is 1: 0.3. A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Comparative Example 4

The composition is prepared by mixing 25.5 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin and mixing 5.1 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.5, and the foaming agent: the weight ratio of the surfactant is 1: 0.3 A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 14 parts by weight, based on 100 parts by weight of the phenol foam.

Comparative Example 5

The composition is prepared by mixing 19.5 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin and mixing 6.5 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 1.5, and the weight ratio of the foaming agent: surfactant is 1: 0.5 A phenolic foam was prepared in the same manner as in Example 1, except for one. In this case, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

Comparative Example 6

The composition is prepared by mixing 26 parts by weight of a curing agent with respect to 100 parts by weight of the resol resin and mixing 3.9 parts by weight of a surfactant so that the weight ratio of the foaming agent: curing agent is 1: 2, and the foaming agent: the weight ratio of the surfactant is 1: 0.3. A phenolic foam was prepared in the same manner as in Example 1, except for one. At this time, the foaming agent is included in an amount of about 11 parts by weight, based on 100 parts by weight of the phenol foam.

evaluation

Experimental Example 1: Density

The foams of Examples and Comparative Examples were prepared as specimens of a size of 100 mm × 100 mm and a corresponding thickness, respectively, and mass and volume were measured for each of the specimens, and the density was measured by the method of KS M ISO 845 standard. And, the results are shown in Table 1 below.

Experimental Example 2: Average cell diameter

Examples and Comparative Examples In order to include the central portion of the phenolic foam in the center, it was prepared as a 10mm (L) × 10mm (W) × 30mm (T) size specimen including a section in which the thickness direction of the foam was bisected. Then, a cut was made in the center of the thickness direction of the specimen, frozen with liquid nitrogen, and cut in half in the thickness direction. Then, after taking a picture of the cut surface by SEM, the size of each of 100 bubbles was measured using an image analysis tool. And the average was calculated and the results are shown in Table 1 below.

Experimental Example 3: Deviation of bubble diameter

Examples and Comparative Examples In order to include the central portion of the phenolic foam in the center, it was prepared as a 10mm (L) × 10mm (W) × 30mm (T) size specimen including a section in which the thickness direction of the foam was bisected. Then, a cut was made in the center of the thickness direction of the specimen, frozen with liquid nitrogen, and cut in half in the thickness direction. Then, after obtaining a picture of the cut surface by SEM, the size of each of 100 bubbles was measured using an image analysis tool. And the average and standard deviation were calculated and the results are shown in Table 1 below.

Experimental Example 4: Compressive strength (kPa)

The phenolic foams of Examples and Comparative Examples were prepared as specimens with a size of 50 mm (L) × 50 mm (W) × 50 mm (T), and the specimen was placed between the wide plates of Lloyd Instrument's LF Plus Universal Testing Machine (Universal Testing Machine). In the UTM equipment, the speed was set at 10%/min of the thickness of the specimen, and the compressive strength test was started, and the maximum load reached while the thickness was reduced was recorded. Compressive strength was measured by the method of KS M ISO 844 standard, and the results are shown in Table 1 below.

Experimental Example 5: Brittleness (%)

Prepare 12 phenolic foams of Examples and Comparative Examples as specimens of 25.4 mm (L) × 25.4 mm (W) × 25.4 mm (T) size, and wood 19 mm (L) × 19 mm (W) × 19 mm (T) Prepare in size Then, the specimen and the wooden cube were simultaneously put in a wooden box of 197 mm (L) × 197 mm (W) × 190 mm (T), rotated at 60 rpm for 10 minutes, and then the weight change was measured. Brittleness was measured by the ASTM C421-08 method, and the results are shown in Table 1 below.

Experimental Example 6: Thermal conductivity ( W/m·K )

The foams of Examples and Comparative Examples were cut to a thickness of 50 mm and a size of 300 mm × 300 mm to prepare a specimen, and the specimen was dried at 70° C. for 12 hours and pre-treated. And, according to the measurement conditions of KS L 9016 (Method for measuring plate heat flow metering method) for the specimen, the thermal conductivity was measured using a HC-074-300 (EKO company) thermal conductivity instrument at an average temperature of 20° C., and the results are shown in the table below. 1 is described.

Experimental Example 7: Closed cell rate (%)

Each of the foams of Examples and Comparative Examples was cut to 2.5 cm (L) X 2.5 cm (W) X 2.5 cm (T) to prepare a specimen. And, it was measured using a closed cell rate measuring device (Quantachrome, ULTRAPYC 1200e) as a KS M ISO 4590 measuring method, and the results are shown in Table 1 below.

density bubble diameter bubble diameter deviation compressive strength brittle thermal conductivity closed cell rate Example 1 32.3 150 29 140 18.0 0.0195 91 Example 2 32.1 153 25 153 18.4 0.0192 92 Example 3 32.3 141 17 142 19.0 0.0192 93 Example 4 32.2 138 21 167 17.1 0.0185 93 Example 5 32.0 157 29 128 19.7 0.0198 90 Example 6 32.0 153 30 151 19.6 0.0193 91 Example 7 31.3 133 25 158 19.2 0.0187 92 Example 8 32.3 135 19 143 20.0 0.0194 93 Comparative Example 1 35.5 173 52 150 17.0 0.0210 79 Comparative Example 2 32.3 183 63 71 24 0.0214 70 Comparative Example 3 31.1 190 50 84 32 0.0219 62 Comparative Example 4 26.7 266 83 58 44 0.0223 58 Comparative Example 5 30.7 218 67 69 26 0.0231 65 Comparative Example 6 34.9 192 53 118 19 0.0208 72

As can be seen from Table 1, the phenolic foam of Examples realizes weight reduction at a low density and, at the same time, uniform cell diameter of a certain size, excellent thermal insulation, and excellent compressive strength compared to the phenolic foam of Comparative Examples You can see both at the same time.

Although the present invention has been described as described above, the present invention is not limited by the embodiments disclosed herein, and it is apparent that various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. In addition, although the effects of the configuration of the present invention are not explicitly described and described while describing the embodiments of the present invention, it is natural that the effects predictable by the configuration should also be recognized.

Claims (12)

It is a foamed cured product of a composition comprising a phenol-based resin, a foaming agent, a surfactant and a curing agent,
The density is between 30 kg/m3 and 33 kg/m3,
Compressive strength according to KS M ISO 845 is 90 kPa to 170 kPa,
The thermal conductivity measured at an average temperature of 20 °C according to KS L 9016 is 0.018W/mK to 0.020W/mK,
The average cell diameter in the cross section bisecting the thickness direction of the foam is 120㎛ to 170㎛,
The standard deviation of the cell diameter in the cross section is 30% or less
phenolic foam.
According to claim 1,
Closed cell ratio of 75% to 98%
phenolic foam.
According to claim 1,
25% or less brittleness according to ASTM C421-08
phenolic foam.
According to claim 1,
The blowing agent comprises an aliphatic hydrocarbon having 1 to 8 carbon atoms.
phenolic foam.
According to claim 1,
The blowing agent is included in an amount of 10 to 13 parts by weight, based on 100 parts by weight of the phenol foam.
phenolic foam.
According to claim 1,
The composition comprises 100 parts by weight of the phenolic resin, the blowing agent: the surfactant in a weight ratio of 1: 0.3 to 1: 0.35
phenolic foam.
According to claim 1,
The composition comprises 100 parts by weight of the phenolic resin, the foaming agent: the curing agent in a weight ratio of 1: 1.5 to 1: 1.8
phenolic foam.
According to claim 1,
The composition further comprises one additive selected from the group consisting of a nucleating agent, polyethylene glycol, and combinations thereof.
phenolic foam.
9. The method of claim 8,
The nucleating agent includes a carbon nanotube (CNT)
phenolic foam.
Preparing a composition comprising a phenolic resin, a foaming agent, a surfactant and a curing agent, and stirring the composition; and
Including; discharging the stirred composition, foaming and curing;
The density is 30 kg/m3 to 33 kg/m3,
Compressive strength according to KS M ISO 845 is 90 kPa to 170 kPa,
The thermal conductivity measured at an average temperature of 20 °C according to KS L 9016 is 0.018W/mK to 0.020W/mK,
The average cell diameter in the cross section bisecting the thickness direction of the foam is 130㎛ to 150㎛,
The standard deviation of the cell diameter in the cross section is 30% or less
Method for producing phenolic foam.
11. The method of claim 10,
The stirring speed is 2,500 rpm to 3,000 rpm
Method for producing phenolic foam.
11. The method of claim 10,
The discharge amount of the stirred composition is 28 g / min to 32 g / min
Method for producing phenolic foam.