JP7355824B2 - Thermosetting foam, manufacturing method thereof, and heat insulating material containing the same - Google Patents

Description

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

Insulation is a material that is always used to prevent energy loss in buildings. As global warming emphasizes the importance of green growth throughout the world, insulation is becoming even more important to minimize energy loss.

Examples of the heat insulating material include thermosetting foam heat insulating material, EPS (expanded polystyrene foam) heat insulating material, XPS (extruded polystyrene foam) heat insulating material, and vacuum heat insulating material. Among these, thermosetting foam insulation materials are widely used because they have the best insulation properties among existing materials other than vacuum insulation materials. However, due to the fundamental limitations of organic materials, they are less fire safe than inorganic insulation materials.

In addition, thermosetting foams include a surface material in the manufacturing process, so although it is possible to improve flame retardancy by applying an aluminum surface material, in reality, in extreme situations such as a fire, However, since the flame resistance of the surface material is greatly reduced, it is extremely important to fundamentally improve the flame retardancy of the foam.

In this regard, although flame retardants such as phosphate are usually included in foamable compositions to improve flame retardancy, flame retardancy and heat insulation properties have a trade-off relationship; There is a problem that the value decreases.

An object of the present invention is to provide a thermosetting foam that simultaneously satisfies high heat insulation properties and high flame retardance and has improved physical properties.

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

Moreover, the objective of this invention is to provide the heat insulating material containing the said thermosetting foam.

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

The present invention includes a thermosetting resin, a curing agent, a blowing agent, and a composite flame retardant, the composite flame retardant includes a first flame retardant and a second flame retardant, and 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 combinations thereof. It is possible to provide a thermosetting foam containing both at least one selected from the group consisting of a pentaerythritol compound and a pentaerythritol compound.

Further, a step of preparing a flame retardant composition including a base resin including a thermosetting resin, a curing agent, a blowing agent, and a composite flame retardant according to the present invention; stirring the base resin, curing agent, blowing agent, and flame retardant composition; and foam-curing the foam composition; the composite flame retardant includes a first flame retardant and a second flame retardant, and 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; It is possible to provide a method for producing a thermosetting foam containing both a pentaerythritol compound and at least one selected from the group consisting of phosphates and combinations thereof.

Furthermore, a heat insulating material including the thermosetting foam according to the present invention can be provided.

Thermosetting foams according to the present invention have improved flame retardancy as well as excellent thermal insulation properties and can exhibit physical properties such as excellent compressive strength and dimensional stability.

Moreover, the method for manufacturing a thermosetting foam according to the present invention can provide a method for manufacturing the thermosetting foam.

Further, the heat insulating material according to the present invention includes the thermosetting foam, has improved flame retardance, has excellent heat insulation properties, and can exhibit physical properties such as excellent compressive strength and dimensional stability.

The above-mentioned effects and specific effects of the present invention will be described together with the following specific matters for carrying out the invention.

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

The above-mentioned objects, features and advantages will be described in detail later, so that those with ordinary knowledge in the technical field to which the present invention pertains can easily implement the technical idea of the present invention. In the description of the present invention, if it is determined that detailed description of known techniques related to the present invention would obscure the gist of the present invention, detailed description will be omitted. In the following, preferred embodiments of the invention will be explained in detail with reference to the accompanying drawings. The same reference numbers in the drawings are used to indicate the same or similar elements.

Thermosetting foams according to some embodiments of the present invention are described below.

An embodiment of the present invention includes a thermosetting resin, a curing agent, a blowing agent, and a composite flame retardant, the composite flame retardant includes a first flame retardant and a second flame retardant, and the first flame retardant comprises: 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 a combination thereof, and a pentaerythritol compound.

Due to various fire accidents that have occurred recently, there is a demand for not only excellent heat insulating properties but also improved flame retardancy in heat insulating materials that are always used in buildings. However, thermoset foams are less fire safe than inorganic insulation materials due to the fundamental limitations of organic matter. In this regard, although it is common to impart flame retardancy to foam through surface treatments such as aluminum facings, there is a risk that the facings will fall off in an actual fire. is more likely to spread.

In this regard, flame retardancy is usually imparted to thermosetting foams by using phosphorus-based flame retardants such as phosphate, but when using phosphorus-based flame retardants such as phosphate, flame retardance improves, but on the other hand, There is a problem that the foam cells are destroyed during the foaming process, resulting in a decrease in insulation properties. 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 and reduces the curing reactivity of the phenolic resin. etc. may fall. As a result, there is a problem in that the heat insulation properties of the foam produced therefrom are reduced. Among thermosetting foams, phenolic foams have more rigid characteristics than other thermosetting foams, and the viscosity of the resin is high, so other additives such as flame retardants are not required. However, it is difficult to produce foam suitable for insulation.

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

Specifically, the thermosetting foam contains a thermosetting resin. The thermosetting resin is one selected from the group consisting of epoxy resins, polyurethane resins, polyisocyanate resins, polyisocyanurate resins, polyester resins, polyamide resins, phenolic resins, and combinations thereof. It may contain one.

For example, the thermosetting foam may include, as the thermosetting resin, a phenolic resin obtained by reacting phenol and formaldehyde, such as a resol-based phenolic resin (hereinafter referred to as "resol resin"). The composite flame retardant including the first flame retardant and the second flame retardant mixes well with the phenolic resin including a benzene ring, and can be uniformly dispersed and foamed. As a result, the thermosetting foam can stably form uniform and small-sized foam cells even though it contains a composite flame retardant, and has improved not only initial insulation properties but also long-term insulation properties. can be shown.

The thermosetting resin is included in the thermosetting foam in a content of about 30% to about 90%, or about 50% to about 90%, or about 55% to about 90% by weight. You can leave it there. By containing the thermosetting resin in an amount within the above range, the thermosetting foam can stably form foam cells and exhibit excellent thermal conductivity.

The thermosetting foam includes a curing agent. The curing agent is one acid curing agent selected from the group consisting of toluenesulfonic acid, xylenesulfonic acid, benzenesulfonic acid, phenolsulfonic acid, ethylbenzenesulfonic acid, styrenesulfonic acid, naphthalenesulfonic acid, and combinations thereof. May contain. The thermosetting foam contains the curing agent and can exhibit appropriate crosslinking, curing, and foaming properties.

The thermosetting foam contains a blowing agent. For example, the blowing agent may include one selected from the group consisting of a hydrofluoroolefin (HFO) compound, a hydrocarbon compound, and a combination thereof. Specifically, the hydrofluoroolefin compound is, for example, at least one selected from the group consisting of monochlorotrifluoropropene, trifluoropropene, tetrafluoropropene, pentafluoropropene, hexafluorobutene, and combinations thereof. May contain. The hydrocarbon compound may contain a hydrocarbon having 1 to 8 carbon atoms. For example, the hydrocarbon compounds include dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n-pentane, isopentane, cyclopentane, hexane, heptane, cyclo It may contain at least one selected from the group consisting of pentane and a combination thereof. Alternatively, the hydrocarbon 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, It contains at least one selected from the group consisting of n-pentane, isopentane, cyclopentane, and combinations thereof, and is environmentally friendly and can exhibit excellent heat insulation properties.

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

The thermosetting foam, especially the phenolic resin foam, contains the surfactant and can easily disperse the composite flame retardant component, etc., and can stably form an appropriate foam structure in the thermosetting foam. It can be formed to have excellent thermal conductivity and excellent physical strength.

Further, 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 first flame retardant includes a first flame retardant and a second flame retardant. The second flame retardant comprises at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof, or selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof. and a pentaerythritol compound. The second flame retardant has excellent compatibility with the phosphorus, which is the first flame retardant, and can be mixed well, suppressing the agglomeration phenomenon of small-sized phosphorus particles and uniformly distributing the composite flame retardant. It can be dispersed in the foam and foamed uniformly to provide improved flame retardancy and excellent heat insulation properties. In addition, excellent physical properties such as compressive strength and dimensional stability can be imparted.

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, the phenolic resin foam contains phosphorus in the phenolic resin containing a benzene ring, and can form a carbonized film (char) better. In addition, the phosphorus can capture hydrogen groups and hydroxyl groups generated during combustion, thereby preventing a chain reaction of combustion reactions and quickly blocking the spread of fire.

The phosphorus can be classified into white phosphorus, red phosphorus, black phosphorus, purple phosphorus, etc. depending on its structural state and color. Specifically, the thermosetting foam may contain red phosphorus. The thermosetting foam may include red phosphorus with a proper structure and may be easy to handle when forming the thermosetting foam. In addition, by controlling the formation rate of a char film during combustion of the thermosetting foam, it is possible to have improved flame retardancy and heat insulation properties at the same time. For example, the thermosetting foam may contain 80% or more or 100% of red phosphorus as the 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 a combination thereof; It contains at least one selected from the group consisting of nurate, trialkyl phosphate, and a combination thereof, and a pentaerythritol compound. The second flame retardant has excellent compatibility with phosphorus, which is the first flame retardant, and can be mixed well, suppressing the agglomeration phenomenon of small-sized phosphorus particles and uniformly distributing the composite flame retardant. It can be dispersed and foamed uniformly to exhibit excellent heat insulation properties along with improved flame retardancy.

Specifically, the pentaerythritol-based compound can bond between the phosphorus and phosphorus during combustion to better form a carbonized film (Char), thereby preventing the spread of fire. The pentaerythritol 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 the heat of combustion is lowered by the endotherm due to sublimation and decomposition of the melamine itself, thereby delaying ignition. Additionally, melamine cyanurate can generate nitrogen and/or ammonia gas upon combustion to dilute oxygen. In the melamine cyanurate, melamine itself generated by combustion decomposition condenses to form a carbonized film including a multi-ring structure such as melem and melon. At this time, the melamine cyanurate acts together during the formation of the carbonized film of phosphorus, improves the reaction of forming the carbonized film of phosphorus, and can form a stable carbonized film. Furthermore, the melamine cyanurate can form uniform and small-sized cells in the thermosetting foam. The melamine cyanurate can act as a nucleating agent in the foam, forming a more stable cell structure and further improving the heat insulation properties.

The average particle size of the melamine cyanurate may be from about 1 μm to about 20 μm, or from about 1 μm to 10 μm. The particle size can be measured by a laser particle size analyzer (model: BT-2000). When the average particle size of melamine cyanurate is less than the above range, the viscosity of the composition containing it increases, and there may be a problem that dispersion is not performed well. If the content exceeds the above range, there may be a problem that flame retardancy decreases.

Further, 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 tricylenyl phosphate. (trixylenyl phosphate), tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaptyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (isopropylphenyl) phenyl phosphate, It may also include one compound selected from the group consisting of monoisodecyl phosphate, and combinations thereof. The trialkyl phosphate improves the uniform dispersion of the phosphorus, suppresses the agglomeration phenomenon of small-sized phosphorus particles, and allows the composite flame retardant to be uniformly dispersed, foamed uniformly, and improved. It can exhibit excellent heat insulation properties as well as flame retardancy. Specifically, the trialkyl phosphate may be triethyl phosphate, and due to its excellent compatibility with the phosphorus, it can be mixed well and the flame retardance and heat insulation properties can be further improved.

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 contains the composite flame retardant in the above range, and in the event of a fire, the combustion rate of the foam is adjusted to stably form a carbonized film, resulting in improved flame retardancy and excellent heat insulation. It can provide excellent physical properties such as hardness and compressive strength.

Specifically, when the content of the composite flame retardant is less than the above range, a carbonized film cannot be stably formed, and a sufficient flame retardant effect may not be exhibited. If it exceeds the above range, it will be more expensive and uneconomical than the increased flame retardant effect, and the viscosity of the foam composition will increase 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, a large amount of torque is applied to the mixer during stirring, resulting in a high temperature rise of the foam composition. Then, the amount of volatilization of the blowing agent increases, which may reduce the heat insulation properties. Further, due to the high viscosity of the foam composition, phosphorus, a blowing agent, a hardening agent, etc. may not be uniformly dispersed, and the physical properties of the foam may not be uniform.

The first flame retardant may be included in an amount of 0.9 to 15 parts by weight based on 100 parts by weight of the thermosetting foam. For example, the first flame retardant may be included 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 the first flame retardant is uniformly dispersed within the thermosetting resin and provides excellent heat insulation properties. It is possible to impart excellent physical properties such as improved flame retardance and compressive strength while maintaining the same properties.

Specifically, if the phosphorus content is less than the above range, sufficient flame retardant effect may not be exhibited, the spread of fire may not be prevented in the event of a fire, and dimensional stability may deteriorate. . If it exceeds the above range, the viscosity of the foam composition will increase significantly and problems may occur during foaming. For example, if the viscosity of the foam composition increases, the mixer will apply more torque during stirring, which may cause the temperature of the foam composition to increase. Then, the amount of volatilization of the blowing agent increases, which may reduce the heat insulation properties. In addition, due to the high viscosity of the foam composition, phosphorus, blowing agent, curing agent, etc. are not uniformly dispersed, which may cause problems such as decreased compressive strength and non-uniform physical properties.

Further, 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 about 0.1 parts by weight to about 4 parts by weight. The composite flame retardant includes the first flame retardant and the second flame retardant in the above-mentioned range, and in the event of a fire, the composite flame retardant controls the combustion rate of the foam to form a stable carbonized film and has excellent flame retardancy. In addition to its properties, it can also have excellent physical properties such as excellent heat insulation properties, compressive strength, and dimensional stability. If the content of the second flame retardant is less than the above range, it cannot react favorably with the phosphorus, so a proper carbonized film cannot be formed, and the rate of formation of the carbonized film is insufficient. The effect of improving flame retardancy may be reduced. If the above range is exceeded, the second flame retardant compound itself that remains without reacting with phosphorus may be burned out in the event of a fire, resulting in a decrease in flame retardancy.

Also, 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 may be from about 1:0.07 to about 1:0.6, or from about 1:0.1 to about 1:0.4. good. The thermosetting foam may include the first flame retardant and the second flame retardant in a weight ratio within the above range, exhibit improved flame retardancy and excellent heat insulation properties, and exhibit excellent physical properties. can. Specifically, if the second flame retardant is mixed in a content less than the above range, there is a problem that the synergistic effect with phosphorus is small and it is uneconomical. If they are mixed, the flame retardance may be reduced, and it may be difficult to ensure a high closed cell ratio and sufficient compressive strength.

Specifically, the composite flame retardant may include the phosphorus and the pentaerythritol compound, and the weight ratio of the phosphorus to the pentaerythritol compound is about 1:0.05 to about 1:0. It may be .6. For example, the weight ratio of the phosphorus to the pentaerythritol 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 is about 1:0.05 to about 1:0.8. Good too. For example, the weight ratio of the phosphorus to the melamine cyanurate compound may be from 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 from about 1:0.05 to about 1:0.8. . For example, the weight ratio of the phosphorus to the trialkyl phosphate may be from about 1:0.07 to about 1:0.6.

In relation to the phosphorus, which is the first flame retardant, if the content of each of the second flame retardants exceeds the above range, the remaining second flame retardant without reacting with the phosphorus, which is the first flame retardant, may cause a fire. While sometimes flammable, it can actually reduce flame retardancy. If 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 a decrease in heat insulation. Further, the synergistic effect of flame retardancy resulting from the combination of the second flame retardant and the phosphorus may not appear.

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

If the content of the pentaerythritol compound relative to the melamine cyanurate is less than the above range, there is a possibility that the carbonized film formed by the synergistic action with phosphorus and melamine cyanurate will be insufficient, and if it exceeds the above range, the reaction will not occur. There may be a problem that while the excessive amount of pentaerythritol compound left behind is burned out, the flame retardance may be reduced.

The composite flame retardant may include the phosphorus, the melamine cyanurate, and the trialkyl phosphate, and contains the melamine cyanurate in an amount of about 1 part by weight to about 80 parts by weight based on 100 parts by weight of the phosphorus; The trialkyl phosphate may be included in an amount of about 1 part by weight to about 80 parts by weight. For example, 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, based on 100 parts by weight of the phosphorus.

If the content of the melamine cyanurate relative to the trialkyl phosphate is less than the above range, there is a problem that the formation of a carbonized film formed by synergy with phosphorus and trialkyl phosphate is insufficient, and if it exceeds the above range, an excessive amount of melamine Cyanurate can be a problem, counteracting cell formation in the phenolic foam and reducing thermal conductivity.

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

If the content of the pentaerythritol compound relative to the trialkyl phosphate is less than the above range, the formation of a carbonized film formed by synergy with phosphorus and trialkyl phosphate may be insufficient, and if it exceeds the above range, no reaction occurs. There may be a problem that while the excessive amount of pentaerythritol compounds left behind burns out, the flame retardance deteriorates.

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

If the weight ratio of the melamine cyanurate and the trialkyl phosphate to the pentaerythritol compound is less than the above range, it will act with phosphorus, which is the first flame retardant, to fully exert the synergistic effect of improving flame retardancy. If the weight ratio of the melamine cyanurate and the trialkyl phosphate exceeds the above range, an excessive amount of flame retardant may prevent the formation of a cell structure in the phenol foam, resulting in structural failure. There may be problems with stability and poor insulation.

The method includes the thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, the composite flame retardant includes a first flame retardant and a second flame retardant, and 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 the second flame retardant comprises at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate, and combinations thereof. The thermosetting foam containing both at least one selected from the following and a pentaerythritol-based compound has a thermal conductivity of about 0.016 W/m·K to about 0.05 W/m·K as measured at an average temperature of 20° C. according to KSL 9016. 029W/m·K. For example, the thermosetting foam may have a thermal conductivity of about 0.016 W/m·K to about 0.025 W/m·K, about 0.016 W/m·K, measured at an average temperature of 20° C. according to KS L 9016. K ~ about 0.023W/m・K, about 0.016W/m・K or more, less than about 0.020W/m・K, or about 0.016W/m・K or more, less than about 0.0195W/m・K It may be. The thermal conductivity indicates the initial heat insulating property of the foam, and the thermosetting foam contains the composite flame retardant and can improve not only the flame retardance but also the heat insulating property.

Further, the thermosetting foam has a thermal conductivity of about 0.017 W/m measured at an average temperature of 20°C after drying at 70°C for 7 days and at 110°C for 14 days according to EN13823. - 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 about 0.017 W/m·K or more and less than about 0.023 W/m·K. The thermal conductivity indicates long-term heat insulation properties of the foam, and the thermosetting foam contains the composite flame retardant and exhibits long-term heat insulation properties in the same or similar range as the initial heat insulation properties. I can do it.

At the same time, the thermosetting foam has a total heat release rate of about 2.0 MJ/m ² to about 15 MJ/m ² in 10 minutes (THR 600 s) by a cone calorimeter according to KS F ISO 5660-1. good. For example, it may be from about 2.0 MJ/m ² to about 10.0 MJ/m ² , or from 2.0 MJ/m ² to less than about 8.0 MJ/m ² . That is, the thermosetting foam can have excellent flame retardancy close to quasi-nonflammability even without a separate face material.

Further, the thermosetting foam has a total heat release amount (THR300s) of about 1.0 MJ/m ² to about 12 MJ/m 2 in 5 minutes measured by a cone calorimeter according to KS F ISO 5660-1, for example, about 1.0 MJ/m ² to about 12 MJ/m 2 . Excellent flame retardancy: 0 MJ/m ² to about 7.5 MJ/m ² , about 1.0 MJ/m ² to about 5 MJ/m ² , or about 1.0 MJ/m ² or more and less than about 4 MJ/m ² can be shown.

Further, the thermosetting foam may have a closed cell ratio of about 75% to about 98%. For example, the thermoset foam may have a closed cell content of about 80% to about 95%.

Normally, when a phosphorus-based flame retardant such as phosphate is used in a thermosetting foam to improve flame retardancy, the flame retardance can be improved, but the foam cells are destroyed during the foaming process, resulting in a low closed cell ratio. Therefore, there is a problem that the insulation properties deteriorate. On the other hand, the thermosetting foam contains the composite flame retardant and can maintain a high closed cell ratio within the above range. In addition, it can exhibit excellent flame retardancy or quasi-nonflammability within the above-mentioned range, as well as excellent heat insulation properties.

In the case of phosphorus-based flame retardants such as phosphates, which are commonly used as flame retardants, compatibility with thermosetting resins decreases, which can destroy the foam cell structure and reduce physical properties such as compressive strength and flexural failure load. Meanwhile, the thermosetting foam includes the composite flame retardant, is uniformly mixed with the thermosetting resin, has a foam cell structure that is not easily destroyed, and has uniform physical properties due to uniform foaming. Further, the phosphorus, which is the first flame retardant, acts as a filler in the thermosetting foam, and together with the second flame retardant, provides structural stability to the thermosetting foam, and falls within the above range. It can provide excellent compressive strength and bending failure load.

Specifically, the thermoset foam may have a compressive strength according to KSM ISO 844 of about 80 kPa to about 300 kPa. For example, it may be about 150 kPa to about 230 kPa.

The thermosetting foam was prepared according to KS M ISO 4898 in specimens with dimensions of 250 mm (L) x 100 mm (W) x 20 mm (T) with a support spacing of 200 mm and a load concentration rate of 50 mm/min. The bending breaking load (N), which is the maximum load (N) until the piece breaks, may be about 15N to about 50N. For example, it may be about 20N to about 50N.

Further, the thermosetting foam may have an average dimensional change rate of 0% to 1.0% according to the following formula 1. 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%.

[Formula 1]
Dimensional change rate (%) = (initial length (a) - subsequent length (a')) / initial length (a) x 100

In the above formula 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; The length (a') means the length (a') of each line at each point after the thermosetting foam was left in an oven at 70°C for 48 hours. At this time, n may be 2 to 5. n may be 3.

It can be seen that the thermosetting foam has excellent dimensional stability when it contains the composite flame retardant as a flame retardant and has a dimensional change rate within the above range. Accordingly, the thermosetting foam exhibits excellent thermal conductivity, effectively improves long-term heat insulation properties, and has excellent processability and workability when applied to a given product.

Further, the thermosetting foam can exhibit excellent flame retardancy, with an oxygen index of about 32% or more according to KSM ISO 589-2. Specifically, the thermoset foam may have an oxygen index of about 32% to about 60%, about 36% to about 60%, or about 43% to about 60%. Since the thermosetting foam has an oxygen index within the above range, it may not be easily extinguished in the event of a fire, which may make it easier to secure evacuation time.

Another embodiment of the present invention provides a step of preparing a flame retardant composition including a base resin including a thermosetting resin, a curing agent, a blowing agent, and a composite flame retardant; and foaming and curing the foam composition; the composite flame retardant includes a first flame retardant and a second flame retardant; The 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, Provided is a method for producing a thermosetting foam containing both a pentaerythritol compound and at least one selected from the group consisting of trialkyl phosphate and combinations thereof.

As described above, the manufacturing method makes it possible to produce the thermosetting foam having physical properties such as improved flame retardancy, excellent heat insulation properties, and excellent compressive strength and dimensional stability. Matters regarding the thermosetting resin, curing agent, foaming agent, and composite flame retardant are as described above, except as specifically stated below.

First, the method includes the step of preparing a flame retardant composition including a base agent including a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant. The base resin may contain 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 phase material selected from the group consisting of phosphorus, a pentaerythritol compound, melamine cyanurate, and a combination thereof; It is included in the foam composition in the form of a flame retardant composition mixed in a solvent, has proper flowability, can be 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 in a weight ratio of about 2:1 to about 1:2 and included in the flame retardant composition, and may be mixed in a content ratio in the above range, Does not reduce the flame retardant improvement effect of the composite flame retardant.

The organic solvent may be a low viscosity organic solvent selected from the group consisting of polyols, surfactants, polyethylene glycol, ethylene glycol, phosphate compounds, and combinations thereof. Examples of the phosphate compounds include Tris-(1-chloro-2-propyl) phosphate (TCPP) and Tris-(2-chloroethyl) phosphate (Tris-(2-chloroethyl)). It may also be chloroethyl phosphate (TCEP), triethyl phosphate (TEP), or the like.

The organic solvent may be added in an amount of 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 may arise in which heat insulation properties are deteriorated.

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

At this time, at 20° C., the viscosity difference (ΔV=|V1−V2|) between the viscosity (V1) of the thermosetting resin and the viscosity (V2) of the flame retardant composition is 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 to the above range, the composite flame retardant containing the solid phase substance becomes a foam. It does not precipitate during the manufacturing process and is uniformly and well mixed with the thermosetting resin, thereby exhibiting improved flame retardancy and excellent heat insulation properties.

Specifically, when the viscosity difference (△V) exceeds the above range, uniform mixing and foaming of the composite flame retardant and thermosetting resin may become difficult, which may impair the physical properties of the thermosetting foam. may decrease. Then, as the viscosity of the foam composition containing the thermosetting resin and the flame retardant composition increases as a whole, a large amount of torque is applied to the stirring mixer, and the temperature of the foam composition rises rapidly. As a result, the amount of blowing agent volatilization may increase before the foam is cured, which may reduce insulation properties.

Further, the viscosity (V1) of the thermosetting resin is 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. It's okay. By adjusting the viscosity difference (ΔV) and the viscosity (V1) of the thermosetting resin within the above ranges, the curing reaction rate of the thermosetting resin in which the composite flame retardant is dispersed can be adjusted as appropriate. As a result, it is possible to form a thermosetting foam that is structurally stable and has an appropriate crosslinked structure, and the thermosetting foam has improved flame retardancy and excellent heat insulation properties at a certain level. can be maintained and exhibit excellent physical properties such as excellent compressive strength.

The blowing 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 foams uniformly at an appropriate foaming pressure during the foaming process, resulting in improved performance. Thermoset foams can be formed that have physical properties such as flame retardancy, thermal insulation, and compressive strength. For example, if the content of the blowing agent exceeds the above range, the foam cells may be destroyed, the insulation properties may be reduced, the dimensional change rate of the foam may be increased, and the compressive strength may be reduced.

Further, 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 a solvent and a substance such as toluenesulfonic acid. In a composition containing a curing agent in an amount within the above range and a composite flame retardant, the balance between foaming and curing can be adjusted as appropriate, thereby providing excellent flame retardancy, heat insulation properties, excellent compressive strength, etc. It is possible to impart the following physical properties.

Moreover, the method for producing a thermosetting foam includes the step of stirring the base agent, curing agent, foaming agent, and flame retardant composition to produce a foam composition. In the method for producing the thermosetting foam, the flame retardant composition containing the composite flame retardant may be separately separated from the base material containing the thermosetting resin, and then mixed and stirred. Thereby, it is possible to prevent the viscosity of the main ingredient containing the thermosetting resin from increasing rapidly, and it is possible to easily produce a thermosetting foam having the above-mentioned physical properties.

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

Yet another embodiment of the present invention provides a heat insulating material including the thermosetting foam.

The thermosetting foam can be applied, for example, to architectural insulation applications, whereby it simultaneously satisfies the excellent thermal insulation properties required of architectural insulation materials, as well as significantly improved flame retardancy. obtain. In addition, it can have excellent compressive strength, flexural failure load (N), dimensional stability, high oxygen index, etc.

The building insulation material may further include a facing material on one or both surfaces of the thermosetting foam, and the facing material may include aluminum to further improve flame retardance.

(Example)
Example 1:
100 parts by weight of a resol resin with a viscosity of 30,000 cps at 20°C, 1 part by weight of an ethoxylated castor oil surfactant, and 3.5 parts by weight of powdered urea as a base agent, and toluenesulfonic acid as a curing agent. , cyclopentane was prepared as a blowing agent. A flame retardant composition was prepared by mixing a composite flame retardant of red phosphorus and melamine cyanurate with an organic solvent containing a mixture of castor oil surfactant and ethylene glycol at a weight ratio of 2:1.

Further, with respect to 100 parts by weight of the resol resin, 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, the flame-retardant composition The material was supplied to a stirrer via piping and stirred to produce a foam composition.

In addition, the stirred foam composition was fed into a Caterpillar operating at a speed of 5 m/min to produce a phenolic resin foam having a final density of 40 kg/m ³ . At this time, the temperature of the caterpillar was 70° C., and the thickness was 50 mm.

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

Finally, the phenolic resin foam contained 6 parts by weight of red phosphorus and 2 parts by weight of melamine cyanurate based on 100 parts by weight of the phenolic resin foam.

Example 2:
A phenol foam was produced in the same manner as in Example 1, except that a composite flame retardant of red phosphorus and triethyl phosphate was used instead of the composite flame retardant of red phosphorus and melamine cyanurate. Finally, 6 parts by weight of red phosphorus and 2 parts by weight of triethyl phosphate were added to 100 parts by weight of the phenolic resin foam.

Example 3:
A phenol foam was produced in the same manner as in Example 1, except that a composite flame retardant of red phosphorus, monopentaerythritol, and melamine cyanurate was used instead of the composite flame retardant of red phosphorus and melamine cyanurate. was manufactured. Finally, 6 parts by weight of red phosphorus, 1 part by weight of monopentaerythritol, and 1 part by weight of melamine cyanurate were contained per 100 parts by weight of the phenolic resin foam.

Example 4:
A phenol foam was produced in the same manner as in Example 1, except that a composite flame retardant of red phosphorus, melamine cyanurate, and triethyl phosphate was used instead of the composite flame retardant of red phosphorus and melamine cyanurate. Manufactured. Finally, 6 parts by weight of red phosphorus, 1 part by weight of melamine cyanurate, and 1 part by weight of triethyl phosphate were contained per 100 parts by weight of the phenolic resin foam.

Example 5:
A phenol foam was produced in the same manner as in Example 1, except that a composite flame retardant of red phosphorus, monopentaerythritol, and triethyl phosphate was used instead of the composite flame retardant of red phosphorus and melamine cyanurate. Manufactured. Finally, 6 parts by weight of red phosphorus, 1 part by weight of monopentaerythritol, and 1 part by weight of triethyl phosphate were contained per 100 parts by weight of the phenolic resin foam.

Example 6:
In the same manner as in Example 1, except that a composite flame retardant of red phosphorus, monopentaerythritol, melamine cyanurate, and triethyl phosphate was used instead of the composite flame retardant of red phosphorus and melamine cyanurate. A phenol foam was produced. Finally, 100 parts by weight of the phenolic resin foam contained 6 parts by weight of red phosphorus, 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 phenol foam was produced in the same manner as in Example 1, except that only melamine cyanurate was used instead of the composite flame retardant of red phosphorus and melamine cyanurate. Finally, 8 parts by weight of melamine cyanurate was added to 100 parts by weight of the phenolic resin foam.

Comparative example 2:
A phenol foam was produced in the same manner as in Example 1, except that only pentaerythritol was used instead of the red phosphorus and melamine cyanurate composite flame retardant. Finally, 8 parts by weight of pentaerythritol was added to 100 parts by weight of the phenolic resin foam.

Comparative example 3:
A phenol foam was produced 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 phosphorus and melamine cyanurate. Finally, 6 parts by weight of ammonium polyphosphate and 2 parts by weight of melamine cyanurate were contained per 100 parts by weight of the phenolic resin foam.

Comparative example 4:
A phenol foam was produced 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 phosphorus and melamine cyanurate. Finally, 6 parts by weight of ammonium polyphosphate and 2 parts by weight of monopentaerythritol were added to 100 parts by weight of the phenolic resin foam.

Comparative example 5:
A phenol foam was produced in the same manner as in Example 1, except that only triethyl phosphate was used instead of the red phosphorus and melamine cyanurate composite flame retardant. Finally, 8 parts by weight of triethyl phosphate was added to 100 parts by weight of the phenolic resin foam.

Evaluation Experimental example 1: Initial 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 x 300 mm, and the samples 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 instrument at an average temperature of 20°C according to the measurement conditions of KS L 9016 (flat plate heat flow meter measurement method). The results are shown in Table 1 below.

Experimental example 2: Long-term thermal conductivity (W/m・K)
Test specimens 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 x 300 mm, and the test specimens were dried at 70°C for 7 days according to EN13823, and then After drying at .degree. C. for 14 days, the thermal conductivity was measured using a HC-074-300 (EKO) thermal conductivity instrument at an average temperature of 20.degree. C., and the results are listed in Table 1 below.

Experimental example 3: THR300s (MJ/m ² )
The phenolic resin foams of the Examples and Comparative Examples were manufactured into specimens measuring 100 mm (L) x 100 mm (W) x 50 mm (T) using a grizzly band saw.

In addition, the measurement conditions of KS F ISO 5660-1 were adjusted as follows. Including radiant heat of 50 kW/m ² , the temperature of the cone heater was 700° C., the blower speed was 24 L/min, and the oxygen concentration was 20.950%. Then, radiant heat of 50 kW/m ² was applied to the specimen for 5 minutes using a cone calorimeter measuring device (Pestec International) to measure the total amount of released heat (THR 300). The results were then listed in Table 1 below.

Experimental example 4: THR600s (MJ/m ² )
Experimental Example 3 except that the total released heat amount (THR600) was measured by applying 50 kW/ ^m2 radiant heat to the above specimen for 10 minutes using a cone calorimeter measuring device (Pestec International). Measured using the same method as above. The results are listed in Table 1 below.

Experimental example 5: Closed cell ratio (%)
Each of the phenolic resin foams of Examples and Comparative Examples was cut into pieces of 2.5 cm (L) x 2.5 cm (W) x 2.5 cm (T) to produce test pieces. Then, it was measured using a closed cell ratio measuring device (Quantachrome, ULTRAPYC 1200e) according to the KSM ISO 4590 measuring method, 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 test pieces with a size of 50 mm (L) x 50 mm (W) x 50 mm (T), and the test pieces were tested using a Lloyd instrument LF Plus universal material testing machine (Universal). Place the specimen between the wide plates of the Testing Machine, set the speed at 10% mm/min of the specimen thickness in the UTM equipment, start the compressive strength experiment, and measure the strength at the initial compressive yield point as the thickness decreases. was recorded. The compressive strength was measured according to the KSM ISO 844 standard method, and the results are shown in Table 1 below.

Experimental example 7: Dimensional stability (%)
FIG. 1 is a schematic diagram illustrating a method for measuring the dimensional stability of a thermosetting foam according to the present invention.

The phenolic resin foams of Examples and Comparative Examples were prepared into specimens measuring 100 mm (L) x 100 mm (W) x 50 mm (T). Then, 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 values of each line are set at 25°C. The length (a) was measured.

In addition, after the specimen was left in an oven at 70°C for 48 hours, the length (a') of each point was measured, and the dimensional change rate (%) from the initial dimension was calculated using the following formula 1. The average value is shown in Table 1. Dimensional stability was measured according to the KSM ISO 2796 standard method.

[Formula 1]
Dimensional change rate (%) = (initial length (a) - subsequent length (a')) / initial length (a) x 100

Experimental example 8: Oxygen index (LOI)
Under the test conditions specified in the KSM ISO 4589-2 standard, the minimum concentration of oxygen required to sustain the combustion of the foams of Examples and Comparative Examples was measured, and the results are listed in Table 1 below. did. The test result values are expressed as volume % of oxygen in the oxygen and nitrogen mixture injected at a temperature of 23±2°C.

Experimental example 9: Bending failure load (N)
The phenolic resin foams of Examples and Comparative Examples were prepared into test pieces with a size of 250 mm (L) x 100 mm (W) x 20 mm (T), and the test pieces were prepared according to KSM ISO 4898 with a support interval of 200 mm, The maximum load (N) until the specimen broke at a load concentration rate of 50 mm/min was measured, and the results are listed in Table 1 below.

As shown in Table 1 above, the thermosetting foams of the Examples exhibit low total heat release, high oxygen index, and excellent flame retardancy, as well as excellent initial thermal conductivity and a similar range. It can be confirmed that the material has a long-term thermal conductivity of , and maintains a low thermal conductivity at a constant level over time. Moreover, it can be confirmed that the thermosetting foam of the example satisfies a high closed cell ratio, improved compressive strength, bending failure load, and dimensional change rate at the same time.

As mentioned above, the present invention has been described with reference to the drawings illustrating the invention, but the present invention is not limited to the embodiments and drawings disclosed in this specification, and is not limited to the examples and drawings disclosed in this specification. It is obvious that various modifications may be made by different engineers. Furthermore, although the embodiments of the present invention have been described above, even if the effects of the configuration of the present invention are not explicitly described and explained, it is natural that effects that can be predicted by the configuration should also be acknowledged. .

Claims (18)

A phenolic foam,
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 is
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(1-chloro-2-propyl) phosphate, tri(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tris(isopropyl) phenyl) phosphate, tris(phenylphenyl) phosphate, trinaptyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di(isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, and these one phosphate compound selected from the group consisting of combinations, melamine cyanurate, and at least one selected from the group consisting of combinations thereof, or
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(1-chloro-2-propyl) phosphate, tri(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tris(isopropyl) phenyl) phosphate, tris(phenylphenyl) phosphate, trinaptyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di(isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, and these one phosphate compound selected from the group consisting of a combination, melamine cyanurate, and at least one selected from the group consisting of a combination thereof, and a pentaerythritol compound,
The weight ratio of the first flame retardant to the second flame retardant is 1:0.1 to 1:0.4,
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.
Phenolic foam. The first flame retardant is included in an amount of 0.9 to 15 parts by weight based on 100 parts by weight of the phenol foam.
The phenolic foam according to claim 1. The second flame retardant is included in an amount of 0.1 to 7 parts by weight based on 100 parts by weight of the phenol foam.
The phenolic foam according to claim 1. The composite flame retardant includes phosphorus and a melamine cyanurate compound,
the weight ratio of the phosphorus to the melamine cyanurate compound is from 1:0.05 to 1:0.8;
The phenolic foam according to claim 1. The composite flame retardant includes phosphorus and the selected one phosphate compound,
the weight ratio of the phosphorus to the selected one phosphate compound is from 1:0.05 to 1:0.8;
The phenolic foam according to claim 1. The composite flame retardant includes phosphorus, a pentaerythritol compound, and melamine cyanurate,
The pentaerythritol compound is contained in an amount of 1 to 50 parts by weight per 100 parts by weight of the phosphorus, and the melamine cyanurate is contained in an amount of 1 to 80 parts by weight.
The phenolic foam according to claim 1. The composite flame retardant includes phosphorus, melamine cyanurate, and the selected one phosphate compound,
The melamine cyanurate is contained in an amount of 1 to 80 parts by weight per 100 parts by weight of the phosphorus, and the selected one phosphate compound is contained in an amount of 1 to 80 parts by weight.
The phenolic foam according to claim 1. The composite flame retardant includes phosphorus, a pentaerythritol compound, and the selected one phosphate compound,
The pentaerythritol compound is contained in an amount of 1 to 50 parts by weight per 100 parts by weight of the phosphorus, and the selected one phosphate compound is contained in an amount of 1 to 80 parts by weight.
The phenolic foam according to claim 1. The composite flame retardant includes phosphorus, a pentaerythritol compound, melamine cyanurate, and the selected one phosphate compound,
The pentaerythritol compound is contained in an amount of 1 to 30 parts by weight per 100 parts by weight of the phosphorus, the melamine cyanurate is contained in an amount of 1 to 50 parts by weight, and the selected one phosphate compound is contained in an amount of 1 to 60 parts by weight. including,
The phenolic foam according to claim 1. Thermal conductivity measured at an average temperature of 20° C. according to KS L 9016 is between 0.016 W/m·K and 0.029 W/m·K,
The phenolic foam according to claim 1. According to EN13823, after drying at 70 °C for 7 days, after drying at 110 °C for 14 days, the thermal conductivity measured at an average temperature of 20 °C is between 0.017 W/m K and 0.029 W/m K. be,
The phenolic foam according to claim 1. The compressive strength according to KSM ISO 844 is 80 kPa to 300 kPa,
The phenolic foam according to claim 1. The total heat released for 10 minutes (THR600s) by a cone calorimeter according to KS F ISO 5660-1 is 2.0 MJ/m ² to 15 MJ/m ² ,
The phenolic foam according to claim 1. According to KS M ISO 4898, the maximum value until the specimen breaks when the specimen is 250 mm (L) x 100 mm (W) x 20 mm (T) in size with a support interval of 200 mm and a load concentration speed of 50 mm/min. The bending breaking load (N) which is the load (N) is 15N to 50N,
The phenolic foam according to claim 1. The average value of the dimensional change rate according to the following formula 1 is 0% to 1.0%,
Phenolic foam according to claim 1:
[Formula 1]
Dimensional change rate (%) = (initial length (a) - subsequent length (a')) / initial length (a) x 100
In Equation 1 above, 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 subsequent length (a) a') means the length (a') of each line at each point after the phenol foam was left in an oven at 70° C. for 48 hours (n is 2 to 5). A method for producing a phenolic foam, the method comprising:
preparing a flame retardant composition including a base agent including a phenolic resin, a curing agent, a blowing agent, and a composite flame retardant;
stirring the base agent, the curing agent, the foaming agent, and the flame retardant composition to produce a foam composition; and
foam-curing the foam composition;
The composite flame retardant includes a first flame retardant and a second flame retardant,
The first flame retardant is phosphorus,
The second flame retardant is
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(1-chloro-2-propyl) phosphate, tri(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tris(isopropyl) phenyl) phosphate, tris(phenylphenyl) phosphate, trinaptyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di(isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, and these one phosphate compound selected from the group consisting of combinations, melamine cyanurate, and at least one selected from the group consisting of combinations thereof, or
Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris(1-chloro-2-propyl) phosphate, tri(2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, tricylenyl phosphate, tris(isopropyl) phenyl) phosphate, tris(phenylphenyl) phosphate, trinaptyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di(isopropylphenyl) phenyl phosphate, monoisodecyl phosphate, and these one phosphate compound selected from the group consisting of a combination, melamine cyanurate, and at least one selected from the group consisting of a combination thereof, and a pentaerythritol compound,
The weight ratio of the first flame retardant to the second flame retardant is 1:0.1 to 1:0.4,
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.
Method for producing phenolic foam. At 20° C., the viscosity difference (ΔV=|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;
The method for producing a phenol foam according to claim 16 . A heat insulating material comprising a phenolic foam according to any one of claims 1 to 15 .

Images