KR102580146B1 - Thermosetting foam, method of producing the same, and insulating material - Google Patents

Abstract

It includes a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, and the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate, trimethylamine A thermosetting foam containing at least one selected from the group consisting of alkyl phosphates and combinations thereof, or containing at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, and a pentaerythritol-based compound. provided.

Description

Thermosetting foam, manufacturing method thereof, and insulation material containing the same {THERMOSETTING FOAM, METHOD OF PRODUCING THE SAME, AND INSULATING MATERIAL}

The present invention relates to thermosetting foam, a method of manufacturing the same, and a heat insulating material containing 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.

Insulation materials include thermosetting foam insulation, EPS (expanded polystyrene foam) insulation, XPS (extruded polystyrene foam) insulation, and vacuum insulation. Among them, thermosetting foam insulation is widely used as it has the best insulation properties among existing materials except vacuum insulation. However, due to the fundamental limitations of organic materials, fire stability is inevitably weaker than that of inorganic insulation materials.

In addition, since thermosetting foam is manufactured including a surface material during the manufacturing process, flame retardancy can be improved by applying a surface material made of aluminum. However, in extreme situations such as actual fires, the flame resistance of the surface material is greatly reduced, which fundamentally reduces the flame retardancy of the foam. It is very important to always do this.

Accordingly, flame retardants such as phosphate are generally included in foamable compositions to improve flame retardancy. However, since flame retardancy and heat insulation have a trade-off, there is a problem of deterioration of heat insulation.

The purpose of the present invention is to provide a thermosetting foam that simultaneously satisfies high insulation and high flame resistance and has improved physical properties.

Another object of the present invention is to provide a method for producing the thermosetting foam.

Another object of the present invention is to provide a heat insulating material containing the thermosetting foam.

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

It includes a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant according to the present invention, wherein the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine. Contains at least one selected from the group consisting of anurate, trialkyl phosphate, and combinations thereof, or includes at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, and a pentaerythritol-based compound. A thermosetting foam can be provided.

Also according to the present invention, preparing a flame retardant composition comprising a thermosetting resin-containing base material, a curing agent, a foaming agent, and a composite flame retardant; Preparing a foam composition by stirring the base material, curing agent, foaming agent, and flame retardant composition; and foam-curing the foam composition, wherein the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate, A thermosetting foam containing at least one selected from the group consisting of trialkyl phosphates and combinations thereof, or containing at least one selected from the group consisting of melamine cyanurate, trialkyl phosphates, and combinations thereof, and a pentaerythritol-based compound. A manufacturing method can be provided.

Additionally, it is possible to provide an insulating material containing the thermosetting foam according to the present invention.

The thermosetting foam according to the present invention has improved flame retardancy and excellent thermal insulation properties, and can exhibit physical properties such as excellent compressive strength and dimensional stability.

Additionally, the method for producing a thermosetting foam according to the present invention can provide a method for producing the thermosetting foam.

In addition, the insulation material according to the present invention, including the thermosetting foam, has improved flame retardancy and excellent insulation properties at the same time, and can exhibit physical properties such as excellent compressive strength and dimensional stability.

In addition to the above-described effects, specific effects of the present invention are described below while explaining specific details for carrying out the invention.

Figure 1 is a schematic diagram briefly showing a method for measuring the dimensional stability of a thermosetting foam of the present invention.

The above-described objects, features, and advantages will be described in detail later, so that those skilled in the art 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 known technologies 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 with reference to the attached drawings. In the drawings, identical reference numerals are used to indicate identical or similar components.

Hereinafter, thermosetting foam according to some embodiments of the present invention will be described.

One embodiment of the present invention includes a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, wherein the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant. It includes at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, and a pentaerythritol-based compound. It provides a thermosetting foam comprising a.

Due to various fire accidents that have occurred recently, not only excellent insulation properties but also improved flame retardancy are required for insulation materials essential for buildings. However, the fire stability of thermosetting foam is inevitably weaker than that of inorganic insulation due to the fundamental limitations of organic materials. Accordingly, it is common to impart flame retardancy to foam through surface treatment such as aluminum face material, but there is a risk that the face material may fall off in an actual fire, and if the face material falls off, the possibility of the fire spreading increases.

Accordingly, flame retardancy is generally given to thermosetting foams by using phosphorus-based flame retardants such as phosphate. However, when using phosphorus-based flame retardants such as phosphate, flame retardancy is improved, but the problem is that foam cells are destroyed during the foaming process and insulation properties are deteriorated. there is. Additionally, when aluminum hydroxide (ATH) is used as a flame retardant in a thermosetting foam, the aluminum hydroxide is a basic substance that neutralizes the acid curing agent, which may reduce the curing reactivity of the phenolic resin. Accordingly, there is a problem that the thermal insulation properties of the foam manufactured therefrom are reduced. In addition, among thermosetting foams, phenol foam has rigid characteristics compared to other thermosetting foams and the viscosity of the resin is also high, so it is difficult to manufacture a foam suitable for insulation using other additives such as flame retardants.

The thermosetting foam includes a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, and the composite flame retardant includes a specific first flame retardant and a second flame retardant, which can improve flame retardancy and heat insulation in a trade-off relationship. there is. In addition, the thermosetting foam can also exhibit physical properties such as excellent compressive strength and dimensional stability.

Specifically, the thermosetting foam includes a thermosetting resin. The thermosetting resin may include one selected from the group consisting of epoxy resin, polyurethane resin, polyisocyanate resin, polyisocyanurate resin, polyester resin, polyamide resin, phenolic resin, and combinations thereof. You can.

For example, the thermosetting foam may include a phenolic resin that can be obtained by reacting phenol and formaldehyde with a thermosetting resin, for example, a resol-based phenol resin (hereinafter referred to as 'resol resin'). In addition, the composite flame retardant containing the first flame retardant and the second flame retardant can be well mixed with the phenolic resin containing a benzene ring and uniformly dispersed and foamed. Accordingly, the thermosetting foam, while containing a composite flame retardant, can stably form foam cells of uniform and small size and exhibit improved insulation properties not only in initial insulation properties but also in long-term insulation properties.

The thermosetting resin may be included in the thermosetting foam in an amount of about 30% by weight to about 90% by weight, or about 50% by weight to about 90% by weight, or about 55% by weight to about 90% by weight. The thermosetting foam can stably form foam cells and achieve excellent thermal conductivity by including the thermosetting resin in an amount within the above range.

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

The thermosetting foam includes a blowing agent. For example, the foaming agent may include one selected from the group consisting of hydrofluoroolefin (HFO)-based compounds, hydrocarbon-based compounds, and combinations thereof. Specifically, the hydrofluoroolefin-based compounds include, for example, monochlorotrifluoropropene, trifluoropropene, tetrafluoropropene, pentafluoropropene, hexafluorobutene, and combinations thereof. It may include at least one selected from the group consisting of And, the hydrocarbon-based compound may include hydrocarbons having 1 to 8 carbon atoms. For example, the hydrocarbon-based compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n-pentane, isopentane, cyclopentane, It may include at least one selected from the group consisting of hexane, heptane, cyclopentane, and combinations thereof. Alternatively, the hydrocarbon-based compound is a hydrocarbon having 1 to 5 carbon atoms, such as dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n-pentane, It may exhibit excellent thermal insulation properties along with environmental friendliness by containing at least one selected from the group consisting of isopentane, cyclopentane, and combinations thereof.

The thermosetting foam may include one surfactant selected from the group consisting of amphoteric, cationic, anionic, nonionic surfactants, and combinations thereof. For example, the thermosetting foam may include an ethoxylated castor oil surfactant, that is, a nonionic surfactant.

The thermosetting foam, especially the phenol resin foam, can easily disperse the composite flame retardant components including the surfactant, and stably form an appropriate foam structure in the thermosetting foam, thereby realizing excellent thermal conductivity and excellent physical strength. You can.

In addition, the thermosetting foam includes a composite flame retardant, the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate, trialkyl It contains at least one selected from the group consisting of phosphate and combinations thereof, or it contains at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, and a pentaerythritol-based compound. The second flame retardant has excellent compatibility with phosphorus, which is the first flame retardant, and can be well mixed. It suppresses the agglomeration of small-sized phosphorus particles, allows the composite flame retardant to be evenly dispersed, and foams uniformly to improve It can provide excellent insulation properties along with flame retardancy. Additionally, it can provide excellent physical properties such as compressive strength and dimensional stability.

The thermosetting foam contains phosphorus as the first flame retardant of the composite flame retardant and can form a char film through excellent carbonization during combustion. In particular, phenol resin foam can better form a carbonized film (char) by including phosphorus in the phenolic resin containing a benzene ring. In addition, the phosphorus can quickly block the spread of fire by capturing hydrogen radicals and hydroxy radicals generated during combustion, thereby preventing a chain reaction of combustion reactions.

The phosphorus can be classified into white, red, black, phosphorus, etc. depending on the structural state and color of the phosphorus. Specifically, the thermosetting foam may include enemies. The thermosetting foam can be easy to handle when forming the thermosetting foam because it contains an appropriate structure. In addition, by controlling the rate of carbonation film (Char) formation during combustion of the thermosetting foam, improved flame retardancy and insulation properties can be achieved at the same time. For example, the thermosetting foam may contain 80% or more or 100% of phosphorus.

The composite flame retardant includes a second flame retardant, and the second flame retardant includes at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, or melamine cyanurate, trialkyl phosphate, and these. It includes at least one selected from the group consisting of a combination of and a pentaerythritol-based compound. The second flame retardant has excellent compatibility with phosphorus, which is the first flame retardant, and can be well mixed. It suppresses the agglomeration of small-sized phosphorus particles, allowing the composite flame retardant to be evenly dispersed, and foams uniformly to provide improved flame retardancy. It can exhibit excellent insulation properties.

Specifically, the pentaerythritol-based compound binds between phosphorus and phosphorus during combustion to better form a carbonization film (Char) and prevent the spread of fire. The pentaerythritol-based compound may include one selected from the group consisting of monopentaerythritol, dipentaerythritol, tripentaerythritol, and combinations thereof.

In addition, when the melamine cyanurate is burned, the hydrogen bonds within the melamine cyanurate structure are endothermically decomposed, and ignition can be delayed by lowering the heat of combustion due to endotherm absorption by sublimation and decomposition of the melamine itself. Additionally, melamine cyanurate may dilute oxygen by producing nitrogen and/or ammonia gas upon combustion. In addition, the melamine cyanurate can form a carbonized film containing a multi-ring structure such as melem and melon by condensing the melamine itself generated by combustion decomposition. At this time, the melamine cyanurate can act together during the formation of the phosphorus carbonization film to improve the phosphorus carbonization film formation reaction and form a stable carbonization film. Additionally, the melamine cyanurate can form cells of uniform and small size in thermosetting foam. In addition, the melamine cyanurate can act as a nucleating agent in the foam, and can further improve thermal insulation by forming a more stable cell structure.

The average particle diameter of the melamine cyanurate may be about 1㎛ to about 20㎛ or about 1㎛ to 10㎛. The particle size can be measured by a laser particle size analyzer (model name: BT-2000). If the average particle size of melamine cyanurate is less than the above range, the viscosity of the composition containing it may increase and there may be a problem of poor dispersion. And, if it exceeds the above range, there may be a problem of reduced flame retardancy.

In addition, the trialkyl phosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (1-chloro 2-propyl) phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, and triza. Ilenyl phosphate (trixylenyl phosphate), tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di It may include one compound selected from the group consisting of (isopropylphenyl)phenyl phosphate, monoisodecyl phosphate) and combinations thereof. The trialkyl phosphate improves the uniform dispersion of the phosphorus, suppresses the agglomeration of small-sized phosphorus particles, allows the composite flame retardant to be evenly dispersed, and foams uniformly to exhibit improved flame retardancy and excellent insulation properties. . Specifically, the trialkyl phosphate may be triethyl phosphate, and can be mixed well with phosphorus with excellent compatibility to further improve flame retardancy and heat insulation.

The composite flame retardant may be included in an amount of 1 to 20 parts by weight based on 100 parts by weight of the thermosetting foam. For example, the composite flame retardant may be included in an amount of 1.5 parts by weight to 15 parts by weight or about 2 parts by weight to about 10 parts by weight. The thermosetting foam can contain the composite flame retardant within the above range to control the combustion rate of the foam in the event of a fire and stably form a carbonized film, thereby providing improved flame retardancy and excellent physical properties such as excellent thermal insulation and compressive strength.

Specifically, if the content of the composite flame retardant is less than the above range, a carbonized film may not be formed stably and a sufficient flame retardant effect may not be achieved. In addition, if it exceeds the above range, it is uneconomical as it requires a lot of cost compared to the increased flame retardant effect, and the viscosity of the foam composition increases significantly, which may cause problems during foaming. For example, if the viscosity of the foam composition increases due to the content of the composite flame retardant, the temperature of the foam composition rises significantly because a lot of torque is applied to the mixer during stirring. Additionally, the amount of volatilization of the foaming agent increases, and thus the thermal insulation properties may decrease. In addition, due to the high viscosity of the foam composition, phosphorus, foaming agent, and curing agent may not be dispersed evenly, which may cause problems in which the physical properties of the foam are not uniformly formed.

The first flame retardant may be included in an amount of 0.9 parts by weight to 15 parts by weight based on 100 parts by weight of the thermosetting foam. For example, the first flame retardant is contained in an amount of about 1 part by weight to about 10 parts by weight, or about 2 parts by weight to about 8 parts by weight, so that it is uniformly dispersed in the thermosetting resin and maintains excellent thermal insulation properties while maintaining improved flame retardancy and compressive strength, etc. Can provide excellent physical properties.

Specifically, if the phosphorus content is less than the above range, sufficient flame retardant effect may not be achieved, fire spread may not be prevented in the event of a fire, and dimensional stability may be reduced. Additionally, if it exceeds the above range, the viscosity of the foam composition may increase significantly, which may cause problems during foaming. For example, if the viscosity of the foam composition increases, the mixer's torque may increase during stirring, so the temperature of the foam composition may rise significantly. In addition, the volatilization amount of the foaming agent increases, and accordingly, the insulation properties may decrease. In addition, due to the high viscosity of the foam composition, phosphorus, foaming agent, and hardener are not evenly dispersed, which may lead to problems in which physical properties are not formed uniformly, such as lower compressive strength.

In addition, the second flame retardant may be included in an amount of 0.1 to 7 parts by weight based on 100 parts by weight of the thermosetting foam. For example, the second flame retardant may be in an amount of about 0.1 parts by weight to about 4 parts by weight. The composite flame retardant contains the second flame retardant in the above range along with the first flame retardant to control the combustion rate of the foam in the event of fire and form a stable carbonized film, thereby providing excellent flame retardancy, excellent thermal insulation, compressive strength, and dimensional stability. It can have excellent physical properties such as: If the content of the second flame retardant is less than the above range, it may not react properly with the phosphorus to form an appropriate carbonized film, and the formation rate of the carbonized film may not be sufficient, so the flame retardancy improvement effect may be reduced. In addition, if the above range is exceeded, the remaining second flame retardant compound itself may combust without reacting with phosphorus during a fire, thereby reducing flame retardancy.

Additionally, the weight ratio of the first flame retardant to the second flame retardant may be about 1:0.05 to about 1:1.2. For example, the weight ratio of the first flame retardant to the second flame retardant is from about 1:0.07 to about 1:0.6, or from about 1:0.1 to about 1:0.4. It can be. The thermosetting foam includes the first flame retardant and the second flame retardant in a weight ratio within the above range, and can simultaneously exhibit improved flame retardancy and excellent thermal insulation properties, as well as excellent physical properties. Specifically, when the second flame retardant is mixed in an amount less than the above range, the synergy effect with phosphorus is minimal, resulting in an uneconomical problem, and when the second flame retardant is mixed in an amount exceeding the above range, the flame retardancy is lowered and the high independence It may be difficult to secure the void ratio and secure sufficient compressive strength.

Specifically, the composite flame retardant may include the phosphorus and the pentaerythritol-based compound, and the weight ratio of the phosphorus to the pentaerythritol-based compound may be about 1:0.05 to about 1:0.6. For example, the weight ratio of the phosphorus to the pentaerythritol-based compound may be about 1:0.07 to about 1:0.4.

The composite flame retardant may include the phosphorus and the melamine cyanurate compound, and the weight ratio of the phosphorus to the melamine cyanurate compound may be about 1:0.05 to about 1:0.8. For example, the weight ratio of the phosphorus to the melamine cyanurate compound may be about 1:0.07 to about 1:0.6.

The composite flame retardant may include the phosphorus and the trialkyl phosphate, and the weight ratio of the phosphorus to the trialkyl phosphate may be about 1:0.05 to about 1:0.8. For example, the weight ratio of the phosphorus to the trialkyl phosphate may be about 1:0.07 to about 1:0.6.

In the relationship with the phosphorus, which is the first flame retardant, if the content of each of the second flame retardants exceeds the above range, the second flame retardant that remains without reacting with the phosphorus, which is the first flame retardant, may burn during a fire and actually reduce flame retardancy. there is. In addition, when the content of the second flame retardant is less than the above range, the dispersibility of phosphorus in the thermosetting foam may decrease, resulting in reduced insulation properties. Additionally, the synergy effect of flame retardancy resulting from the combination of the second flame retardant and the phosphorus may not appear.

In addition, the composite flame retardant may include the phosphorus, the pentaerythritol-based compound, and the melamine cyanurate, and the pentaerythritol-based compound is contained in an amount of about 1 part by weight to about 50 parts by weight relative to 100 parts by weight of the phosphorus. It may contain about 1 part by weight to about 80 parts by weight of the melamine cyanurate. For example, based on 100 parts by weight of phosphorus, the pentaerythritol-based compound may be included in an amount of about 5 parts by weight to about 30 parts by weight, and the melamine cyanurate may be included in an amount of about 5 parts by weight to about 40 parts by weight.

If the content of the pentaerythritol-based compound compared to the melamine cyanurate is less than the above range, the carbonization film formed through synergy with phosphorus and melamine cyanurate may be insufficient, and if it exceeds the above range, the excess pentaerythritol-based compound remaining without reacting may be insufficient. As the erythritol-based compound burns, there may be a problem that the flame retardancy decreases.

The composite flame retardant may include the phosphorus, the melamine cyanurate, and the trialkyl phosphate, and may include about 1 part by weight to about 80 parts by weight of the melamine cyanurate relative to 100 parts by weight of the phosphorus, and the tri It may contain about 1 part by weight to about 80 parts by weight of alkyl phosphate. For example, based on 100 parts by weight of phosphorus, the melamine cyanurate may be included in an amount of about 5 parts by weight to about 40 parts by weight, and the trialkyl phosphate may be included in an amount of about 5 parts by weight to about 40 parts by weight.

If the content of the melamine cyanurate compared to the trialkyl phosphate is less than the above range, there is a problem of insufficient formation of a carbonized film formed through a synergistic effect with phosphorus and trialkyl phosphate, and if it exceeds the above range, the excessive amount of melamine cyanurate is There may be a problem of interfering with the cell formation of the phenol foam and lowering the thermal conductivity.

The composite flame retardant may include the phosphorus, the pentaerythritol-based compound, and the trialkyl phosphate, and includes about 1 part by weight to about 50 parts by weight of the pentaerythritol-based compound based on 100 parts by weight of the phosphorus, It may contain about 1 part by weight to about 80 parts by weight of the trialkyl phosphate. For example, based on 100 parts by weight of phosphorus, the pentaerythritol-based compound may be included in an amount of about 5 parts by weight to about 30 parts by weight, and the trialkyl phosphate may be included in an amount of about 5 parts by weight to about 40 parts by weight.

If the content of the pentaerythritol-based compound compared to the trialkyl phosphate is less than the above range, the formation of a carbonized film formed through a synergistic effect with phosphorus and trialkyl phosphate may be insufficient, and if it exceeds the above range, the excess pentaerythritol-based compound remaining without reacting may be insufficient. As erythritol-based compounds burn, there may be a problem of reduced flame retardancy.

The composite flame retardant may include the phosphorus, the pentaerythritol-based compound, the melamine cyanurate, and the trialkyl phosphate, and the pentaerythritol-based compound is contained in an amount of about 1 part by weight to about 100 parts by weight of the phosphorus. It may contain 30 parts by weight, about 1 part by weight to about 50 parts by weight of the melamine cyanurate, and about 1 part by weight to about 60 parts by weight of the trialkyl phosphate. For example, based on 100 parts by weight of phosphorus, the pentaerythritol-based compound is included in an amount of about 3 parts by weight to about 20 parts by weight, the melamine cyanurate is included in an amount of about 5 parts by weight to about 30 parts by weight, and the tri It may contain about 5 parts by weight to about 40 parts by weight of alkyl phosphate.

If the weight ratio of the melamine cyanurate and the trialkyl phosphate compared to the pentaerythritol-based compound is less than the above range, there is a problem in that the synergy effect of improving flame retardancy cannot be sufficiently exerted by acting with phosphorus, the first flame retardant, and the melamine If the weight ratio of anurate and the trialkyl phosphate exceeds the above range, the formation of a cell structure of the phenol foam may be hindered by an excessive amount of flame retardant, resulting in structural instability and deterioration of thermal insulation properties.

It includes a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, and the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate, The thermosetting composition comprising at least one selected from the group consisting of trialkyl phosphates and combinations thereof, or containing at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, and a pentaerythritol-based compound. The foam has a thermal conductivity of about 0.016 W/m·K to about 0.029 W/m·K, measured at an average temperature of 20°C according to KS L 9016. For example, the thermosetting foam has a thermal conductivity measured at an average temperature of 20°C according to KS L 9016 of about 0.016 W/m·K to about 0.025 W/m·K, about 0.016 W/m·K to about 0.023 W/ m·K, may be greater than or equal to about 0.016 W/m·K, less than about 0.020 W/m·K, or greater than or equal to about 0.016 W/m·K, and less than about 0.0195 W/m·K. The thermal conductivity indicates the initial insulating properties of the foam, and the thermosetting foam can improve not only flame retardancy but also insulating properties by including the composite flame retardant.

에서 7일 동안 건조시킨 뒤에 110

에서 14일 동안 건조시킨 후, 평균 온도 20℃에서 측정한 열전도율이 약 0.017 W/m·K 내지 약 0.029 W/m·K 일 수 있다. 예를 들어, 약 0.017 W/m·K 내지 약 0.025 W/m·K 또는 약 0.017 W/m·K 이상, 약 0.023 W/m·K 미만 일 수 있다. 상기 열전도율은 발포체의 장기 단열성을 나타내는 것으로서, 상기 열경화성 발포체는 상기 복합 난연제를 포함하여 초기 단열성과 동일, 유사 범위의 장기 단열성을 나타낼 수 있다.And, the thermosetting foam according to EN13823, 70

After drying for 7 days at 110

After drying for 14 days, the thermal conductivity measured at an average temperature of 20°C may be about 0.017 W/m·K to about 0.029 W/m·K. For example, it may be about 0.017 W/m·K to about 0.025 W/m·K or greater than about 0.017 W/m·K and less than about 0.023 W/m·K. The thermal conductivity indicates the long-term insulation of the foam, and the thermosetting foam, including the composite flame retardant, may exhibit long-term insulation in the same or similar range as the initial insulation.

At the same time, the thermosetting foam may have a total heat release rate (THR600s) of about 2.0 MJ/m2 to about 15 MJ/m2 for 10 minutes by a cone calorimeter according to KS F ISO 5660-1. For example, it may be from about 2.0 MJ/m2 to about 10.0 MJ/m2 or from 2.0 MJ/m2 to less than about 8.0 MJ/m2. In other words, the thermosetting foam can have excellent flame retardancy close to semi-incombustibility even without a separate face material.

In addition, the thermosetting foam has a total heat released for 5 minutes (THR300s) measured by a cone calorimeter according to KS F ISO 5660-1 of about 1.0 MJ/㎡ to about 12 MJ/㎡, for example, about 1.0 MJ/㎡. It can exhibit excellent flame retardancy from about 7.5 MJ/m2, about 1.0 MJ/m2 to about 5 MJ/m2, or about 1.0 MJ/m2 or more and less than about 4 MJ/m2.

Additionally, the closed cell ratio of the thermosetting foam may be about 75% to about 98%. For example, the closed cell ratio of the thermosetting foam may be about 80% to about 95%.

In general, when a phosphorus-based flame retardant such as phosphate is used in a thermosetting foam to improve flame retardancy, the flame retardancy can be improved, but there is a problem in that the foam cells are destroyed during the foaming process, lowering the closed cell ratio and deteriorating insulation properties. On the other hand, the thermosetting foam can maintain a high closed cell ratio in the above range by including the composite flame retardant. In addition, it can exhibit excellent thermal insulation properties along with excellent flame retardancy or semi-incombustibility in the above-mentioned range.

In the case of phosphorus-based flame retardants such as phosphate, which are commonly used as flame retardants, they have poor compatibility with thermosetting resins and may destroy the foam cell structure, resulting in a decrease in physical properties such as compressive strength and bending failure load. Meanwhile, the thermosetting foam includes the composite flame retardant and is uniformly mixed with the thermosetting resin, the foam cell structure is not easily destroyed, and can have uniform physical properties due to uniform foaming. In addition, the phosphorus, which is the first flame retardant, acts as a filler in the thermosetting foam and provides structural stability to the thermosetting foam together with the second flame retardant, and can also provide excellent compressive strength and bending failure load in the above range.

Specifically, the thermosetting foam may have a compressive strength of about 80 kPa to about 300 kPa according to KS M ISO 844. For example, from about 150 kPa to about 230 kPa It can be.

According to KS M ISO 4898, the thermosetting foam is applied to a specimen measuring 250 mm (L) Χ 100 mm (W) Χ 20 mm (T) at a support spacing of 200 mm and a load concentration speed of 50 mm/min. The maximum load until the specimen breaks ( The bending failure load (N) may be about 15 N to about 50 N. For example, it may be about 20 N to about 50 N.

In addition, the thermosetting foam may have an average dimensional change rate of 0% to 1.0% according to Equation 1 below. For example, the thermoset foam can have an average dimensional change of about 0% to about 0.8% or about 0% to about 0.6%.

[Equation 1]

Dimensional change rate (%) = (initial length (a) - later length (a')) / initial length (a)

In Equation 1, the initial length (a) is the length of each line at n equal points in the length (L) and width (W) directions of the thermosetting foam, and the later length (a') is the length of the thermosetting foam. It means the final length (a') of each line at each point above after being left in an oven at 70°C for 48 hours. At this time, n may be 2 to 5. n may be 3.

The thermosetting foam includes the composite flame retardant as a flame retardant and has a dimensional change rate within the above range, so it can be seen that it has excellent dimensional stability. Accordingly, the thermosetting foam exhibits excellent thermal conductivity, so long-term insulation can be more effectively improved, and processability and workability can be further improved when applied to a given product.

In addition, the thermosetting foam can exhibit excellent flame retardancy with an oxygen index of about 32% or more according to KS M ISO 4589-2. Specifically, the oxygen index of the thermosetting foam may be about 32% to about 60%, about 36% to about 60%, or about 43% to about 60%. Since the thermosetting foam has an oxygen index in the above range, it may not easily burn in the event of a fire, and thus it may be easy to secure evacuation time.

Another embodiment of the present invention includes preparing a flame retardant composition including a base material containing a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant; Preparing a foam composition by stirring the base material, curing agent, foaming agent, and flame retardant composition; and foam-curing the foam composition, wherein the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate, A thermosetting foam containing at least one selected from the group consisting of trialkyl phosphates and combinations thereof, or containing at least one selected from the group consisting of melamine cyanurate, trialkyl phosphates, and combinations thereof, and a pentaerythritol-based compound. Provides a manufacturing method.

As described above, by the above manufacturing method, the thermosetting foam can be manufactured having improved flame retardancy, excellent thermal insulation properties, and physical properties such as excellent compressive strength and dimensional stability. Details regarding the thermosetting resin, curing agent, foaming agent, and composite flame retardant are the same as described above, except as specifically described below.

First, it includes preparing a flame retardant composition including a base material containing a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant. The base material may include about 1 part by weight to about 5 parts by weight of a surfactant and about 3 parts by weight to about 10 parts by weight of urea, based on 100 parts by weight of the thermosetting resin.

The composite flame retardant may include one solid material selected from the group consisting of phosphorus, pentaerythritol-based compounds, melamine cyanurate, and combinations thereof, wherein the composite flame retardant is in the form of a flame retardant composition mixed in an organic solvent. It is included in the foam composition, has appropriate flowability, is easily introduced into the production process, and can be uniformly mixed with the thermosetting resin. For example, the composite flame retardant: organic solvent may be mixed at a weight ratio of about 2:1 to about 1:2 and included in the flame retardant composition, and mixed at a content ratio within the above range may not reduce the flame retardancy improvement effect of the composite flame retardant. there is.

The organic solvent may be a low-viscosity organic solvent selected from the group consisting of polyol, surfactant, polyethylene glycol, ethylene glycol, phosphate-based compounds, and combinations thereof. The phosphate-based compounds include, for example, tris (1-chloro-2-propyl) phosphate (TCPP), tris- (2-chloroethyl) phosphate (Tris- ( It may be 2-chloroethyl)phosphate (TCEP), triethyl phosphate (TEP), etc.

The organic solvent may be added in an amount ranging from about 1 part by weight to about 15 parts by weight based on 100 parts by weight of the thermosetting resin. If the content of the organic solvent exceeds the above range, a problem of deterioration of thermal insulation may occur.

For example, the organic solvent may be one first organic solvent selected from the group consisting of TCPP, TCEP, TEP, and combinations thereof, and one selected from the group consisting of polyol, surfactant, polyethylene glycol, ethylene glycol, and combinations thereof. It may be a mixed organic solvent of the second organic solvent.

At this time, at 20°C, the viscosity difference (△V=|V1 - V2|) between the viscosity (V1) of the thermosetting resin and the viscosity (V2) of the flame retardant composition may be about 30,000 cps or less or about 20,000 cps or less. It may be about 0 or more and about 10,000 cps or less. By adjusting the viscosity difference (△V) between the viscosity (V1) of the thermosetting resin and the viscosity (V2) of the flame retardant composition within the above range, the composite flame retardant containing a solid material does not precipitate during the foam manufacturing process, and the thermosetting composition It is evenly mixed with the resin and can exhibit excellent insulation properties along with improved flame retardancy.

Specifically, if the viscosity difference (ΔV) exceeds the above range, uniform mixing and foaming of the composite flame retardant and the thermosetting resin may become difficult, and thus the physical properties of the thermosetting foam may deteriorate. In addition, as the overall viscosity of the foam composition including the thermosetting resin and the flame retardant composition increases, the torque of the stirring mixer increases, and the temperature of the foam composition rapidly increases, which may increase the volatilization amount of the foaming agent before the foam is cured. And, as a result, the insulation may be reduced.

And, the viscosity (V1) of the thermosetting resin may be about 10,000 cps to about 80,000 cps, about 10,000 cps to about 50,000 cps, or about 20,000 cps to about 50,000 cps at 20°C. By adjusting the viscosity difference (ΔV) and the viscosity (V1) of the thermosetting resin within the above range, the curing reaction rate of the thermosetting resin in which the composite flame retardant is dispersed can be appropriately adjusted. Accordingly, it is possible to form a thermosetting foam that is structurally stable and has an appropriate cross-linked structure, so that the thermosetting foam maintains excellent insulation at a certain level along with improved flame retardancy, and can exhibit excellent physical properties such as excellent compressive strength. .

The foaming agent may be included in an amount of about 5 parts by weight to about 15 parts by weight based on about 100 parts by weight of the thermosetting resin. By including the foaming agent in the content within the above range, the foam composition containing the composite flame retardant dispersed in the thermosetting resin is foamed uniformly at an appropriate foaming pressure during the foaming process, thereby improving physical properties such as flame retardancy, heat insulation, and compressive strength. It is possible to form a thermosetting foam having. For example, if the content of the foaming agent exceeds the above range, the foam cells may be destroyed, the insulation may be reduced, the dimensional change rate of the foam may increase, and the compressive strength may be reduced.

Additionally, the curing agent may be included in an amount of about 15 to about 25 parts by weight based on 100 parts by weight of the thermosetting resin. The curing agent refers to a mixture of substances such as toluenesulfonic acid mixed with a solvent. By including the curing agent in the above range, the balance between foaming and curing can be appropriately adjusted in a composition containing a composite flame retardant, and thus physical properties such as heat insulation and excellent compressive strength can be imparted along with excellent flame retardancy.

In addition, the method for producing the thermosetting foam includes the step of preparing a foam composition by stirring the base material, curing agent, foaming agent, and flame retardant composition. In the method of producing the thermosetting foam, the flame retardant composition containing the composite flame retardant can be mixed and stirred separately from the main substance containing the thermosetting resin. Accordingly, it is possible to prevent the viscosity of the base material containing the thermosetting resin from increasing rapidly, and a thermosetting foam having the above-mentioned physical properties can be easily manufactured.

In addition, the method for producing the thermosetting foam includes the step of foaming and curing the foam composition. For example, the thermosetting foam can be foamed and cured under temperature conditions of about 50°C to about 90°C. In addition, the foaming and curing may be performed for a time of about 2 minutes to about 20 minutes, but is not limited thereto and may vary appropriately depending on the purpose and use of the invention.

Another embodiment of the present invention provides an insulating material including the thermosetting foam.

The thermosetting foam can be applied, for example, as a construction insulation material, and thus can simultaneously satisfy the excellent insulation properties required as a construction insulation material as well as significantly improved flame retardancy. Additionally, it can have excellent compressive strength, bending failure load (N), dimensional stability, and high oxygen index.

For example, the building insulation material may further include a face material on one or both sides of the thermosetting foam, and the face material may include aluminum to further improve flame retardancy.

(Example)

Example 1:

A mixture of 100 parts by weight of resol resin with a viscosity in the range of 30,000 cps at 20°C, 1 part by weight of ethoxylated castor oil surfactant, and 3.5 parts by weight of powdered urea was prepared, with toluenesulfonic acid as a curing agent and cyclopentane as a foaming agent. . Then, a flame retardant composition was prepared by mixing a composite flame retardant of red and melamine cyanurate with an organic solvent in which castor oil surfactant and ethylene glycol were mixed at a weight ratio of 2:1.

And, based on 100 parts by weight of the resol resin, the flame retardant composition was added to the pipe along with 18 parts by weight of a mixture of 80% by weight of toluenesulfonic acid mixed with 15% by weight of ethylene glycol and 5% by weight of water and 8 parts by weight of cyclopentane. It was supplied to a stirrer and stirred to prepare a foam composition.

Then, the stirred foam composition was put into a Caterpillar operating at a speed of 5 m/min to finally produce a phenolic resin foam having a density of 40 kg/m3. At this time, the temperature of the caterpillar was 70°C and the thickness was 50mm.

At this time, by adjusting the content of melamine cyanurate and the organic solvent contained in the flame retardant composition, the viscosity difference between the viscosity (V1) of the resol resin and the viscosity (V2) of the flame retardant composition at 20 ° C. △V=|V1 - V2|) was ensured to be within 10,000 cps. The viscosity was measured using a Brookfield viscometer (Brookfield, DV3T Rheometer, #63 spindle).

And, finally, the phenol resin foam was made to contain 6 parts by weight of melamine cyanurate and 2 parts by weight of melamine cyanurate, based on 100 parts by weight of the phenol resin foam.

Example 2:

A phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red and triethyl phosphate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, based on 100 parts by weight of the phenol resin foam, 6 parts by weight of phosphorus and 2 parts by weight of triethyl phosphate were included.

Example 3:

A phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, monopentaerythritol, and melamine cyanurate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, based on 100 parts by weight of the phenol resin foam, it contained 6 parts by weight of polyethylene, 1 part by weight of monopentaerythritol, and 1 part by weight of melamine cyanurate.

Example 4:

A phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, melamine cyanurate, and triethyl phosphate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, based on 100 parts by weight of the phenol resin foam, it contained 6 parts by weight of red, 1 part by weight of melamine cyanurate, and 1 part by weight of triethyl phosphate.

Example 5:

A phenolic foam was prepared in the same manner as in Example 1, except that instead of the composite flame retardant of red and melamine cyanurate, a composite flame retardant of red, monopentaerythritol, and triethyl phosphate was used. And, finally, based on 100 parts by weight of the phenol resin foam, it contained 6 parts by weight of red, 1 part by weight of monopentaerythritol, and 1 part by weight of triethyl phosphate.

Example 6:

A phenol foam was prepared in the same manner as in Example 1, except that instead of the composite flame retardant of red and melamine cyanurate, a composite flame retardant of red, monopentaerythritol, melamine cyanurate, and triethyl phosphate was used. And, finally, based on 100 parts by weight of the phenol resin foam, it contained 6 parts by weight of red, 0.3 parts by weight of monopentaerythritol, 0.7 parts by weight of melamine cyanurate, and 1 part by weight of triethyl phosphate.

Comparative Example 1:

A phenolic foam was prepared in the same manner as in Example 1, except that only melamine cyanurate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, 8 parts by weight of melamine cyanurate was included based on 100 parts by weight of the phenol resin foam.

Comparative Example 2:

A phenol foam was prepared in the same manner as in Example 1, except that only pentaerythritol was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, 8 parts by weight of pentaerythritol was included based on 100 parts by weight of the phenol resin foam.

Comparative Example 3:

A phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of ammonium polyphosphate and melamine cyanurate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, based on 100 parts by weight of the phenol resin foam, 6 parts by weight of ammonium polyphosphate and 2 parts by weight of melamine cyanurate were included.

Comparative Example 4:

A phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of ammonium polyphosphate and monopentaerythritol was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, based on 100 parts by weight of the phenol resin foam, 6 parts by weight of ammonium polyphosphate and 2 parts by weight of monopentaerythritol were included.

Comparative Example 5:

A phenol foam was prepared in the same manner as in Example 1, except that only triethyl phosphate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, 8 parts by weight of triethyl phosphate was included based on 100 parts by weight of the phenol resin foam.

evaluation

Experimental Example 1: Initial thermal conductivity ( W/m·K )

The phenolic resin foams of Examples and Comparative Examples were cut to a thickness of 50 mm and a size of 300 mm x 300 mm to prepare specimens, and the specimens were pretreated by drying at 70°C for 12 hours. Then, the thermal conductivity of the specimen was measured using a HC-074-300 (EKO) thermal conductivity device at an average temperature of 20°C according to the measurement conditions of KS L 9016 (flat plate heat flow measurement method), and the results are shown in the table below. It is described in 1.

Experimental Example 2: Long-term thermal conductivity ( W/m·K )

Samples were prepared by cutting the phenolic resin foams of Examples and Comparative Examples to a thickness of 50 mm and a size of 300 mm After drying, the thermal conductivity was measured using a HC-074-300 (EKO) thermal conductivity instrument at an average temperature of 20°C, and the results are listed in Table 1 below.

Experimental Example 3: THR 300s ( MJ/㎡ )

The phenol resin foams of the above examples and comparative examples were manufactured into specimens measuring 100 mm (L) Χ 100 mm (W) Χ 50 mm (T) using a Grizzly band saw.

And, the measurement conditions of KS F ISO 5660-1 were set as follows. The temperature of the cone heater was set to 700°C with 50kW/m ² radiant heat, the speed of the blower was 24L/min, and the oxygen concentration was started at 20.950%. Then, using a cone calorimeter measuring device (Festek International), 50 kW/m ² radiant heat was applied to the specimen for 5 minutes and the total heat released (THR300) was measured. And the results are listed in Table 1 below.

Experimental Example 4: THR 600s ( MJ/㎡ )

Using a cone calorimeter measuring device (Festek International), 50 kW/m ² radiant heat was applied to the specimen for 10 minutes and the total heat released (THR600) was measured in the same manner as in Experimental Example 3. And the results are listed in Table 1 below.

Experimental Example 5: Closed cell rate (%)

Examples and Comparative Examples Each phenol resin foam was cut into 2.5 cm (L) × 2.5 cm (W) × 2.5 cm (T) to prepare specimens. In addition, the KS M ISO 4590 measurement method was used to measure the closed cell ratio (Quantachrome, ULTRAPYC 1200e), and the results are listed in Table 1 below.

Experimental Example 6: Compressive Strength (kPa)

The phenolic resin foams of Examples and Comparative Examples were prepared into specimens measuring 50 mm (L) Χ 50 mm (W) Χ 50 mm (T), and the specimens were placed between the wide plates of the Lloyd Instruments LF Plus Universal Testing Machine. , the UTM equipment was set at a speed of 10% mm/min of the specimen thickness, the compressive strength experiment was started, and the strength at the first compressive yield point that appeared while the thickness was decreasing was recorded. Compressive strength was measured using the method of the KS M ISO 844 standard, and the results are listed in Table 1 below.

Experimental Example 7: Dimensional stability (%)

Figure 1 is a schematic diagram briefly showing a method for measuring the dimensional stability of a thermosetting foam of the present invention.

The phenol resin foams of Examples and Comparative Examples were prepared as specimens with sizes of 100 mm (L) Χ 100 mm (W) Χ 50 mm (T). As shown in Figure 1, lines are drawn at n (n=3) equal points in the length (L) and width (W) directions of the specimen, and the initial length (a) of each line is measured at 25°C. did.

Then, the final length (a') of each point was measured after the specimen was left in an oven at 70°C for 48 hours, and the dimensional change rate (%) changed from the initial dimension was measured using Equation 1 below, and the average value was calculated as It is listed in Table 1. Dimensional stability was measured using the method of the KS M ISO 2796 standard.

[Equation 1]

Dimensional change rate (%) = (initial length (a) - later length (a')) / initial length (a)

Experimental Example 8: Oxygen Index (LOI)

The minimum concentration of oxygen required to sustain combustion of the foams of Examples and Comparative Examples was measured under the test conditions specified in the KS M ISO 4589-2 standard, and the results are listed in Table 1 below. Test results are given as volume percent of oxygen in the oxygen and nitrogen mixture injected at a temperature of 23 ± 2°C.

Experimental Example 9: Flexural failure load (N)

The phenolic resin foams of Examples and Comparative Examples were prepared as specimens of 250 mm (L) Χ 100 mm (W) Χ 20 mm (T) in size, and the specimens were subjected to a support spacing of 200 mm and a load concentration of 50 mm/min according to KS M ISO 4898. The maximum load (N) until fracture of the specimen at the speed was measured and the results are listed in Table 1 below.

Initial thermal conductivity (W/m·K) Long-term thermal conductivity (W/m·K) THR 300s
(MJ/㎡) THR 600s
(MJ/㎡) Closed cell rate (%) Compressive strength (kPa) size
stability(%) Oxygen Index (LOI) Flexural failure load (N) Example 1 0.01989 0.02234 3.6 6.6 85.6 184.2 0.54 46.8 26.8 Example 2 0.01953 0.02172 4.5 7.5 86.7 174.2 0.42 44.1 25.4 Example 3 0.01957 0.02037 3.8 5.8 88.9 210.5 0.46 48.2 32.3 Example 4 0.01942 0.02146 3.4 5.6 89.4 178.6 0.43 49.5 29.1 Example 5 0.01916 0.02088 4.2 6.2 90.4 196.5 0.38 47.7 30.5 Example 6 0.01924 0.01986 3.0 4.3 90.1 201.5 0.34 51.7 33.5 Comparative Example 1 0.02362 0.02847 12.4 19.8 78.2 138.5 0.88 35.6 14.1 Comparative example 2 0.01945 0.02111 14.8 24.6 89.4 187.2 0.61 31.0 19.6 Comparative Example 3 0.03154 0.03324 3.9 7.7 8.5 112.2 1.22 41.5 12.1 Comparative example 4 0.02994 0.03245 5.2 9.5 10.4 124.5 1.07 39.8 13.9 Comparative Example 5 0.02314 0.03003 14.6 22.7 64.8 105.2 1.18 29.8 12.5

As shown in Table 1, the thermosetting foam of the example exhibits excellent flame retardancy with a low total heat release and a high oxygen index, and also has an excellent initial heat conductivity and a long-term heat conductivity in a similar range, maintaining a constant low heat conductivity over time. You can check that it is maintained at the same level. In addition, it can be confirmed that the thermosetting foam of the example simultaneously satisfies a high closed cell ratio, improved compressive strength, flexural failure load, and dimensional change rate.

As described above, the present invention has been described with reference to the illustrative drawings, but the present invention is not limited to the embodiments and drawings disclosed herein, and various modifications may be made by those skilled in the art within the scope of the technical idea of the present invention. It is obvious that transformation can occur. In addition, although the operational effects according to the configuration of the present invention were not explicitly described and explained while explaining the embodiments of the present invention above, it is natural that the predictable effects due to the configuration should also be recognized.

Claims (21)

Contains phenolic resin, curing agent, foaming agent and composite flame retardant,
The composite flame retardant includes a first flame retardant and a second flame retardant,
The first flame retardant is phosphorus,
The second flame retardant includes at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, and penta Contains an erythritol-based compound,
The composite flame retardant is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the phenolic foam,
The thermal conductivity measured at an average temperature of 20°C according to KS L 9016 is 0.016 W/m·K to 0.023 W/m·K,
The total heat released for 10 minutes (THR600s) by a cone calorimeter according to KS F ISO 5660-1 is less than 2.0 MJ/㎡ to 8 MJ/㎡.
Phenolic foam.
delete According to paragraph 1,
The first flame retardant is contained in an amount of 0.9 parts by weight to 15 parts by weight based on 100 parts by weight of the phenolic foam.
Phenolic foam.
According to paragraph 1,
The trialkyl phosphates include trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (1-chloro 2-propyl) phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, and trixylenyl. Phosphate (trixylenyl phosphate), tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (iso) Containing one compound selected from the group consisting of propylphenyl) phenyl phosphate, monoisodecyl phosphate) and combinations thereof
Phenolic foam.
According to paragraph 1,
The second flame retardant is contained in an amount of 0.1 to 7 parts by weight based on 100 parts by weight of the phenolic foam.
Phenolic foam.
According to paragraph 1,
The weight ratio of the first flame retardant to the second flame retardant is 1:0.05 to 1:1.2.
Phenolic foam.
According to paragraph 1,
The composite flame retardant includes phosphorus and melamine cyanurate compounds,
The weight ratio of the phosphorus to the melamine cyanurate compound is 1:0.05 to 1:0.8.
Phenolic foam.
According to paragraph 1,
The composite flame retardant includes phosphorus and trialkyl phosphate,
The weight ratio of the phosphorus to the trialkyl phosphate is 1:0.05 to 1:0.8.
Phenolic foam.
According to paragraph 1,
The composite flame retardant includes phosphorus, a pentaerythritol-based compound, and melamine cyanurate,
Comprising 1 to 50 parts by weight of the pentaerythritol-based compound and 1 to 80 parts by weight of the melamine cyanurate, based on 100 parts by weight of phosphorus.
Phenolic foam.
According to paragraph 1,
The composite flame retardant includes phosphorus, melamine cyanurate, and trialkyl phosphate,
Comprising 1 to 80 parts by weight of the melamine cyanurate and 1 to 80 parts by weight of the trialkyl phosphate, relative to 100 parts by weight of the phosphorus.
Phenolic foam.
According to paragraph 1,
The composite flame retardant includes phosphorus, a pentaerythritol-based compound, and a trialkyl phosphate,
Comprising 1 to 50 parts by weight of the pentaerythritol-based compound and 1 to 80 parts by weight of the trialkyl phosphate, relative to 100 parts by weight of phosphorus.
Phenolic foam.
According to paragraph 1,
The composite flame retardant includes phosphorus, a pentaerythritol-based compound, melamine cyanurate, and trialkyl phosphate,
Comprising 1 to 30 parts by weight of the pentaerythritol-based compound, 1 to 50 parts by weight of the melamine cyanurate, and 1 to 60 parts by weight of the trialkyl phosphate, based on 100 parts by weight of phosphorus.
Phenolic foam.
delete According to paragraph 1,
According to EN13823, after drying at 70°C for 7 days and then at 110°C for 14 days, the thermal conductivity measured at an average temperature of 20°C is 0.017 W/m·K to 0.029 W/m·K.
Phenolic foam.
According to paragraph 1,
Compressive strength of 80kPa to 300kPa according to KS M ISO 844
Phenolic foam.
delete According to paragraph 1,
According to KS M ISO 4898, bending is the maximum load (N) until fracture of the specimen at 200mm support spacing and load concentration speed of 50mm/min on a specimen of size 250mm(L)Χ100mm(W)Χ20mm(T) Breaking load (N) is 15 N to 50 N
Phenolic foam.
According to paragraph 1,
The average value of the dimensional change rate according to Equation 1 below is 0% to 1.0%.
Phenolic foam:

[Equation 1]
Dimensional change rate (%) = (initial length (a) - later length (a')) / initial length (a)

In Equation 1, the initial length (a) is the length of each line at n equal points in the length (L) and width (W) directions of the phenol foam, and the later length (a') is the length of the phenolic foam. It means the final length (a') of each line at each point above after being left in an oven at 70°C for 48 hours. (n is 2 to 5)
Preparing a flame retardant composition including a base material containing a phenolic resin, a curing agent, a foaming agent, and a composite flame retardant;
Preparing a foam composition by stirring the base material, curing agent, foaming agent, and flame retardant composition; and
Comprising: foaming and curing the foam composition,
The composite flame retardant includes a first flame retardant and a second flame retardant,
The first flame retardant is phosphorus, and the second flame retardant includes at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, or melamine cyanurate, trialkyl phosphate, and these. It includes at least one selected from the group consisting of a combination of and a pentaerythritol-based compound,
The composite flame retardant is contained in an amount of 1 to 20 parts by weight based on 100 parts by weight of the phenolic foam,
The thermal conductivity measured at an average temperature of 20°C according to KS L 9016 is 0.016 W/m·K to 0.023 W/m·K,
The total heat released for 10 minutes (THR600s) by a cone calorimeter according to KS F ISO 5660-1 is less than 2.0 MJ/㎡ to 8 MJ/㎡.
Method for producing phenolic foam.
According to clause 19,
At 20°C, the viscosity difference (△V=|V1 - V2|) between the viscosity (V1) of the phenolic resin and the viscosity (V2) of the flame retardant composition is 30,000 cps or less.
Method for producing phenolic foam.
A heat insulating material comprising the phenol foam according to any one of claims 1, 3 to 12, 14, 15, 17 and 18.

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