WO2021162528A1

WO2021162528A1 - Thermosetting foam and method for preparing same

Info

Publication number: WO2021162528A1
Application number: PCT/KR2021/001922
Authority: WO
Inventors: 박건표; 박인성; 김명희; 배성재; 김도훈; 강길호; 하혜민; 김채훈; 김한수
Original assignee: (주)엘지하우시스
Priority date: 2020-02-11
Filing date: 2021-02-15
Publication date: 2021-08-19
Also published as: KR20210102115A; KR102478779B9; KR102478779B1

Abstract

Provided is a thermosetting foam comprising a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, wherein the composite flame retardant comprises a first flame retardant and a second flame retardant. The first flame retardant is phosphorus, and the second flame retardant comprises at least one selected from the group consisting of a melamine-based flame retardant, trialkyl phosphate, and a combination thereof, or comprises, together with a pentaerythritol-based compound, at least one selected from the group consisting of a melamine-based flame retardant, trialkyl phosphate, and a combination thereof.

Description

Thermosetting foam and manufacturing method thereof

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

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

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

In addition, since the thermosetting foam is manufactured including the surface material in the manufacturing process, the flame retardancy can be improved by applying the aluminum surface material, but in extreme situations such as an actual fire, the flame resistance of the surface material is greatly reduced, so the flame resistance of the foam is fundamentally It is very important to always let

Accordingly, in general, flame retardancy is improved by including a flame retardant such as phosphate in the foamable composition, but flame retardancy and thermal insulation properties have a trade-off, so there is a problem in that thermal insulation properties are reduced.

It is an object of the present invention to provide a thermosetting foam having improved physical properties while simultaneously satisfying high heat insulation and high flame retardancy.

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

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

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 a melamine-based flame retardant. Thermosetting comprising at least one selected from the group consisting of flame retardants, trialkyl phosphates, and combinations thereof, or at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and a pentaerythritol compound together A foam may be provided.

In addition, at least one region of 1.2 mm (length, L) X 0.9 mm (width, W) included in the cross section perpendicular to the thickness direction of the foam according to the present invention contains 10 or more phosphorus, and the diameter of the phosphorus is A thermosetting foam of 1 μm to 80 μm can be provided.

In addition, according to the present invention, the method comprising: preparing a flame retardant composition comprising a main agent including a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant; preparing a foam composition by stirring the base, curing agent, foaming agent and flame retardant composition; and foaming and 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 a melamine-based flame retardant, tree At least one selected from the group consisting of alkyl phosphates and combinations thereof, or at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and a pentaerythritol-based compound. method can be provided.

Although the thermosetting foam according to the present invention contains a flame retardant, foaming and curing are appropriately controlled, so that the foam cell is not destroyed and well formed, and it may have a structure in which the flame retardant is uniformly distributed. Accordingly, it can exhibit improved flame retardancy, have excellent thermal insulation properties, and exhibit physical properties such as excellent compressive strength and dimensional stability.

In addition, the method for producing a thermosetting foam according to the present invention may provide a method for producing the thermosetting foam.

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

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

Figure 2 is a picture taken using a digital microscope (Digital Microscope) of the area of 1.2 mm (length, L) X 0.9 mm (width, W) included in the cross section perpendicular to the thickness direction of the thermosetting foam of the present invention it has been shown

3 shows a photograph in which the region of the thermosetting foam of the present invention is equally divided into 4 (length, L) X 3 (width, W).

Figure 4 is a schematic view showing the side of the foam when 50kW / m2 radiant heat is applied to a phenolic foam having a size of 100mm (length) Χ100mm (width) Χ50mm (thickness) according to KS F ISO 5660-1 for 10 minutes, Fig. 4a is a case of a conventional phenolic foam, and Figure 4b is a schematic diagram when applied to a phenolic foam according to an embodiment of the present invention.

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

Hereinafter, the 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, 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 contains at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof, or at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and a pentaerythritol-based compound together It provides a thermosetting foam comprising.

Due to various fire accidents that have occurred recently, not only excellent thermal insulation properties but also improved flame retardancy are required for insulation materials essential for buildings. However, the thermosetting foam is inevitably weaker in fire stability than inorganic insulating materials due to the fundamental limitations of organic materials. Therefore, it is common to impart flame retardancy to the 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 when the face material falls off, the possibility of fire spreading increases.

Accordingly, in general, flame retardancy is provided by using a phosphorus-based flame retardant such as phosphate to a thermosetting foam, but when a phosphorus-based flame retardant such as phosphate is used, the flame retardancy is improved, whereas the foam cell is destroyed in the foaming process and the thermal insulation property is lowered. have. And, when aluminum hydroxide (ATH) is used as a flame retardant in the thermosetting foam, the aluminum hydroxide is a basic material and neutralizes the acid curing agent, so that the curing reactivity of the phenol-based resin may be deteriorated. Accordingly, there is a problem in that the thermal insulation properties of the foam produced therefrom is lowered. And, among thermosetting foams, phenolic foams have rigid (RIGID) characteristics compared to other thermosetting foams, and the viscosity of the resin is also high. It is difficult to manufacture.

The thermosetting foam comprises a thermosetting resin, a curing agent, a foaming agent and a composite flame retardant, and comprises a specific first flame retardant and a second flame retardant as the composite flame retardant, so that foaming and curing are appropriately controlled, for example, even in a phenolic foam, It may have a structure in which the foam cell is not destroyed and the flame retardant is uniformly distributed. Thus, it is possible to improve flame retardancy and heat insulation, which are trade-offs. In addition, the thermosetting foam may 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 an epoxy-based resin, a polyurethane-based resin, a polyisocyanate-based resin, a polyisocyanurate-based resin, a polyester-based resin, a polyamide-based resin, a phenol-based resin, and combinations thereof. can

For example, the thermosetting foam may include a phenol-based resin obtained by reacting phenol and formaldehyde with a thermosetting resin, for example, a resol-based phenol resin (hereinafter, 'resol resin'). In addition, the composite flame retardant including the first flame retardant and the second flame retardant may be well mixed with the phenolic resin including a benzene ring and uniformly dispersed and foamed. Accordingly, the thermosetting foam, for example, the phenolic foam, while including the composite flame retardant, while stably forming a uniform and small-sized foam cell, as well as the initial thermal insulation properties as well as long-term thermal insulation can exhibit improved thermal insulation properties.

The thermosetting resin may be included in the thermosetting foam in an amount of about 30 wt% to about 90 wt%, or about 50 wt% to about 90 wt%, or about 55 wt% to about 90 wt%. The thermosetting foam may stably form a foamed cell and implement excellent thermal conductivity by including the thermosetting resin in an amount within the range.

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

The thermosetting foam includes a blowing agent. For example, the blowing agent may include one selected from the group consisting of a hydrofluoroolefin (HFO)-based compound, a hydrocarbon-based compound, and combinations thereof. Specifically, the hydrofluoroolefin-based compound is, 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 a hydrocarbon having 1 to 8 carbon atoms. For example, the hydrocarbon-based compound is dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n- pentane, isopentane, cyclopentane, It may include at least one selected from the group consisting of hexane, heptane, cyclopentane, and combinations thereof. or the hydrocarbon-based compound is a hydrocarbon having 1 to 5 carbon atoms, dichloroethane, propyl chloride, isopropyl chloride, butyl chloride, isobutyl chloride, pentyl chloride, isopentyl chloride, n-butane, isobutane, n-pentane, By including at least one selected from the group consisting of isopentane, cyclopentane, and combinations thereof, it may exhibit excellent thermal insulation properties and eco-friendliness.

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, particularly the phenolic resin foam, can more easily disperse the composite flame retardant components including the surfactant, and stably form an appropriate foaming structure in the thermosetting foam to realize excellent thermal conductivity and excellent physical strength, etc. can

And, 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 (Phosphorus), and the second flame retardant is a melamine-based flame retardant, trialkyl phosphate And at least one selected from the group consisting of combinations thereof, or at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and a pentaerythritol-based compound together. The second flame retardant has excellent compatibility with the phosphorus of the solid phase, which is the first flame retardant, and thus can be mixed well, and suppresses the aggregation of small-sized phosphorus particles so that the flame retardant can be evenly dispersed, and uniformly It can be foamed to provide excellent thermal insulation with improved flame retardancy. 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 with excellent carbonization action during combustion. In particular, the phenolic resin foam can better form a carbonized film (char) by including phosphorus in the phenolic resin including a benzene ring. In addition, the phosphorus traps hydrogen radicals and hydroxy radicals generated during combustion to prevent the combustion reaction from occurring in a chain, thereby quickly blocking fire propagation.

The phosphorus may be classified into white, red, black, and phosphorus according to the structural state and color of phosphorus. Specifically, the thermosetting foam may include red. The thermosetting foam may be easily handled when the thermosetting foam is formed, including red with an appropriate structure. In addition, it is possible to have improved flame retardancy and heat insulation at the same time by controlling the rate of formation of a carbonized film (Char) during combustion of the thermosetting foam. For example, the thermosetting foam may include about 80% or more or about 100% of the phosphorus red.

The phosphor may have an average particle diameter of about 1 to about 50 μm. Here, the average particle diameter means an average value of the diameters that one particle can have. The thermosetting foam may include phosphorus having an average particle diameter in the above range, and may include phosphorus in a large surface area relative to the same weight part. Accordingly, excellent flame retardancy can be exhibited, and excellent thermal insulation properties can be exhibited at the same time by not interfering with the formation of foam cells. The average particle diameter of the phosphorus may be measured using a laser particle size analyzer.

The foam includes red as a first flame retardant, and phosphorus can be observed in the form of red dots when photographing with a digital microscope, as shown in FIG. 2 . Through this, it is possible to check the content level and dispersion degree of red in the foam.

In general, the foam may consist of cell walls and struts of foam cells. At this time, as shown in FIG. 2 or FIG. 3 , it can be seen that the foam contains a red dot, that is, a red dot on the strut. By including the phosphorus or red phosphorus in the strut portion of the foam, it may help to implement the flame retardant performance without significant deterioration in thermal insulation properties. It is important to ensure that the person or enemy is formed in the strut section. If phosphorus or enemy is located on the cell wall, the voids or non-uniform foaming may occur due to the breakage of air bubbles. Accordingly, it may be difficult to achieve the desired effect. Various conditions described below may be helpful in including the phosphorus or enemy in the strut portion. The particle size of phosphorus or phosphorus, combination with the second flame retardant and uniform dispersion before and after foaming through it may help to include phosphorus or phosphorus in the strut.

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-based flame retardants, trialkyl phosphates, and combinations thereof, or melamine-based flame retardants, trialkyl phosphates, and combinations thereof It contains at least one selected from the group consisting of and a pentaerythritol-based compound. The second flame retardant has excellent compatibility with the phosphorus, which is the first flame retardant, so that it can be mixed well, and the aggregation phenomenon of small-sized phosphorus particles is appropriately suppressed so that phosphorus of an appropriate size can be evenly dispersed in the composite flame retardant, By uniformly foaming, it can exhibit excellent thermal insulation with improved flame retardancy. A second flame retardant comprising a melamine-based flame retardant, a trialkyl phosphate and pentaerythritol together, or a second flame retardant comprising a melamine-based flame retardant and a trialkyl phosphate combination, or a melamine-based flame retardant and a pentaerythritol Alternatively, it may be more helpful to include trialkylphosphate and pentaerythritol.

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

The melamine-based flame retardant may include at least one selected from the group consisting of melamine, melamine phosphate, melamine polyphosphate, melamine cyanurate, and combinations thereof. For example, the melamine-based flame retardant may be melamine cyanurate, and may exhibit excellent compatibility in relation to a phenol-based resin. By using the melamine-based flame retardant having excellent compatibility with the phenol-based resin, it helps to achieve flame retardant performance without significant deterioration in thermal insulation performance.

The melamine-based flame retardant may work together to form a carbonized film of phosphorus to improve a reaction for forming a carbonized film of phosphorus and form a stable carbonized film. The melamine-based flame retardant may condense melamine itself generated by combustion decomposition to form a carbonized film including a multi-ring structure such as melem and melon. In addition, the melamine-based flame retardant may delay ignition by lowering the combustion heat due to endothermic heat due to sublimation and decomposition of melamine itself in the melamine-based flame retardant structure during combustion. In addition, the melamine-based flame retardant may dilute oxygen by generating nitrogen and/or ammonia gas during combustion. In addition, the melamine-based flame retardant may form uniform and small-sized cells in the thermosetting foam. In addition, the melamine-based flame retardant may act as a nucleating agent in the foam, and more stably form a cell structure to further improve thermal insulation properties.

The average particle diameter of the melamine-based flame retardant may be about 1㎛ to about 20㎛. Here, the average particle diameter means an average value of the diameters that one particle can have. For example, if the particle is geometrically spherical, it means the average of the diameter, and in the case of other shapes, it means the average length of the major axis when divided into a major axis and a minor axis. The particle size can be measured by a laser particle size analyzer (Laser Particle Size Analyzer, model name: BT-2000). If the average particle diameter of the melamine-based flame retardant is less than the above range, there may be a problem in that the viscosity of the composition comprising the same increases and the dispersion is not good. And, when it exceeds the above range, there may be a problem that the flame retardancy is lowered.

And, the trialkyl phosphate is trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (1-chloro 2-propyl) phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, triza Ilenyl phosphate (trixylenyl phosphate), tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, diphenyl (2-ethylhexyl) phosphate (isopropylphenyl)phenylphosphate, monoisodecylphosphate) and combinations thereof. The trialkyl phosphate improves the uniform dispersion of the phosphorus, suppresses the aggregation of small-sized phosphorus particles, so that the composite flame retardant can be evenly dispersed, and uniformly foams to exhibit excellent thermal insulation properties with improved flame retardancy. . Specifically, the trialkyl phosphate may be triethyl phosphate (TEP) or tris (1-chloro 2-propyl) phosphate (TCPP), and a trialkyl phosphate, that is, triethyl phosphate or tris (1-chloro 2-propyl) Phosphate (TCPP) is well mixed with the phosphorus with excellent compatibility, can help control the viscosity of the composite flame retardant with little adverse effect on foam curing, and does not interfere with the foaming and curing of phenolic foam, thereby providing flame retardancy and heat insulation properties can be further improved. The trialkyl phosphate may be advantageous in uniform distribution of the first flame retardant when mixed in advance rather than separately added from the first flame retardant.

The composite flame retardant may be included in an amount of about 1 part by weight to about 12 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 about 1 part by weight to about 10 parts by weight or about 1 part by weight to about 8 parts by weight. The thermosetting foam contains the composite flame retardant in the above range, particularly in a small amount, while controlling the combustion rate of the foam in case of fire and stably forming a carbonized film to provide excellent properties such as improved flame retardancy and excellent thermal insulation and compressive strength. can

Specifically, when the content of the composite flame retardant is less than the above range, the carbonization film may not be stably formed and a sufficient flame retardant effect may not be exhibited. And, although it is not limited to exceeding the above range, when it exceeds the above range, it is uneconomical to bar a high cost compared to the rising flame retardant effect, and the viscosity of the foam composition is greatly increased, which may cause problems during foaming. For example, when the viscosity of the foam composition increases due to the content of the composite flame retardant, the temperature of the foam composition is increased because a large amount of torque of the mixer is taken during stirring. And, the amount of volatilization of the foaming agent is increased, and thus thermal insulation properties may be deteriorated. In addition, due to the high viscosity of the foam composition, phosphorus, a foaming agent, a curing agent, etc. may not be evenly dispersed, which may cause a problem in that the physical properties of the foam are not uniformly formed.

The composite flame retardant may include phosphorus (Phosphorus) as the first flame retardant, or phosphorus (Phosphorus) and trialkyl phosphate, and inductively coupled plasma optical emission spectrometer: 　ICP-OES, Agilent Company, model name 5110 ), it is possible to measure the content of the element P (phosphorus) contained in the composite flame retardant.

Specifically, the thermosetting foam may be in the shape of a board having a length, width and thickness. At this time, in order to exclude the influence of contaminants, a sample including portions spaced apart from each other by about 1 cm or more from the entire outer surface of the foam is prepared. At this time, the sample or the part with an abnormality such as a very large void or contamination in the sample is excluded. In addition, a sample may be collected and measured from at least one region of at least one cross-section perpendicular to the thickness direction of the foam (parallel to the surface to which the surface material is attached). For example, a sample in which about 1 cm is cut off from the entire outer surface of the foam is prepared. After that, samples are taken at arbitrary m points of the cross section perpendicular to the 1/2 point in the thickness direction of the foam. (The above m = an integer of 2 to 10) At this time, each of the m points is uniform in the cross section. It may be a very spaced point. About 200 (±20) mg of the sample collected at each of the above points is put into a microwave container together with 5 ml of nitric acid, respectively, and wait for about 10 minutes for the reaction to occur sufficiently. After assembling the microwave container, put it in a microwave device (Preekem, model name: TOPEX) and enter the program so that the temperature rises gradually up to 200°C to perform microwave decomposition. Then, confirm that the sample is completely dissolved (no precipitate), and add deionized water so that the volume of the decomposition solution becomes 50 mL in total. And, compared to the control group without the sample, the content of P(phosphorus) element (P1, P2,.., Pm) in each solution after the pretreatment was analyzed using ICP-OES (Agilent, model name 5110) do. And, the average value (=(P1+ P2+,.., Pm)/m)) is taken as the content of P(phosphorus) element included in the foam. For example, the content (P1, P2, P3) of element P (P1, P2, P3) measured at three arbitrary points (m = 3) included in the cross section was measured using ICP-OES (Agilent, model name 5110). It can be analyzed and its average value (=(P1+P2+P3)/3)) can be determined. The thermosetting foam may include the composite flame retardant in a certain amount, and may include P(phosphorus) element in an average content of about 9,000 mg/kg to about 100,000 mg/kg according to ICP-OES. for example, from about 10,000 mg/kg to about 80,000 mg/kg or from about 10,000 mg/kg to about 60,000 mg/kg of element P(phosphorus) in an average content.

The first flame retardant may be included in an amount of about 0.9 parts by weight to about 10 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 8 parts by weight, or about 1 part by weight to about 6 parts by weight to be uniformly dispersed in the thermosetting resin, and improved flame retardancy and compressive strength while maintaining excellent thermal insulation properties, etc. excellent physical properties of

Specifically, when the phosphorus content is less than the above range, a sufficient flame retardant effect may not be exhibited, fire propagation may not be prevented, and dimensional stability may be deteriorated. And, when it exceeds the above range, the viscosity of the foam composition is greatly increased, and a problem may occur during foaming. For example, when the viscosity of the foam composition increases, the temperature of the foam composition may be increased because a large amount of torque of the mixer is applied during stirring. And, the amount of volatilization of the foaming agent is increased, and accordingly, thermal insulation properties may be deteriorated. In addition, due to the high viscosity of the foam composition, phosphorus, a foaming agent, a curing agent, etc. may not be evenly dispersed, which may cause a problem in that physical properties are not formed uniformly, such as a decrease in compressive strength.

In addition, the second flame retardant may be included in an amount of about 0.001 parts by weight to about 6 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 0.01 parts by weight to about 6 parts by weight or about 0.05 parts by weight to about 4 parts by weight. The composite flame retardant, together with the first flame retardant, includes the second flame retardant in an amount within the above range, so that foaming and curing are easily controlled and the foam cell is not destroyed, and the flame retardant is uniformly distributed. And, by controlling the combustion rate of the foam in case of fire and forming a stable carbonized film, it can have excellent properties such as excellent flame retardancy and excellent thermal insulation, compressive strength, and dimensional stability at the same time. If the content of the second flame retardant is less than the above range, the phosphorus and the phosphorus may not react properly to form an appropriate carbonized film, and the flame retardant improvement effect may be lowered because the formation rate of the carbonized film is not sufficient. In addition, when the above range is exceeded, the second flame retardant compound itself that remains without reacting with phosphorus in a fire is combusted, thereby reducing the flame retardancy.

And, the weight ratio of the first flame retardant to the second flame retardant may be about 1: 0.001 to about 1: 0.8. For example, the weight ratio of the first flame retardant to the second flame retardant is from about 1: 0.01 to about 1: 0.8, from about 1: 0.02 to about 1: 0.8, or from about 1: 0.05 to about 1: 0.6 can be The thermosetting foam may include the first flame retardant and the second flame retardant in a weight ratio within the above range, and simultaneously exhibit improved flame retardancy and excellent thermal insulation, and exhibit excellent physical properties. Specifically, when the second flame retardant is mixed in an amount less than the above range, there is an uneconomical problem due to insignificant synergistic effect with phosphorus, and when the second flame retardant is mixed in excess of the above range, the flame retardancy is rather reduced, and high independence It may be difficult to secure the cell ratio, and it may be difficult to 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-based flame retardant, and the weight ratio of the phosphorus to the melamine-based flame retardant may be from about 1: 0.001 to about 1: 0.8. For example, the weight ratio of the phosphorus to the melamine-based flame retardant may be from about 1: 0.01 to about 1: 0.8 or from about 1: 0.07 to about 1: 0.6.

The thermosetting foam containing the melamine-based flame retardant in the above range may exhibit a detection peak of melamine by pyrolysis gas chromatography/mass spectrometry (py-GC/MS) (600° C.). Specifically, in order to exclude the influence of contaminants, a sample including portions spaced apart by about 1 cm or more from the entire outer surface of the foam are prepared, and perpendicular to the thickness direction of the foam (parallel to the surface to which the surface material is attached) A melamine peak peak may be detected at at least one point of the at least one cross-section. . At this time, the sample or the part with an abnormality such as a very large void or contamination in the sample is excluded. For example, prepare a sample comprising portions spaced about 1 cm each from the entire outer surface of the foam. After that, samples are taken at arbitrary j points of the cross section perpendicular to about 1/2 point in the thickness direction of the foam (the above j = an integer of 2 to 10). In this case, each of the j points may be points uniformly spaced apart from each other in the cross section. About 0.2 to 0.3 mg of each sample collected at each of the j points is placed in a sample cup. Then, put the sample cup into a pyrolysis gas chromatography/mass spectrometer (py-GC/MS, manufacturer: Agilent, model name: 7890A/5975C), and measure the gas produced by thermally decomposing the sample at 600° C. under inert gas conditions. The characteristic peak of melamine can be confirmed. A peak of melamine may appear at at least one of the j points. For example, a peak of melamine may appear at one or more points among any three points (j=3) of the cross section. When the thermosetting foam contains the melamine-based flame retardant in less than the above range, the melamine peak may not appear according to the GC/MS (600° C.). The thermosetting foam shows a detection peak of melamine by the GC/MS (600° C.), and it can be seen that the melamine-based flame retardant is included in the content within the above range.

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: 0.001 to about 1: 0.8. For example, the weight ratio of the phosphorus to the trialkyl phosphate may be from about 1: 0.01 to about 1: 0.8 or from about 1: 0.07 to about 1: 0.6.

When the content of each of the second flame retardants exceeds the above range in the relationship with the causality of the first flame retardant, the second flame retardant remaining without reacting with the phosphorus, which is the first flame retardant, burns in a fire and can rather reduce the flame retardancy. have. And, when the content of the second flame retardant is less than the above range, the dispersibility of phosphorus in the thermosetting foam may decrease, thereby reducing the thermal insulation properties. And, the synergistic effect of flame retardancy according to the combination of the second flame retardant and the phosphorus may not appear.

The trialkylphosphate may be triethylphosphate (TEP) or tris(1-chloro 2-propyl)phosphate (TCPP), in the above range triethylphosphate (TEP) or tris(1-chloro 2-propyl)phosphate ( TCPP) was obtained by pyrolysis gas chromatography/mass spectrometry (py-GC/MS) (200° C.) of triethylphosphate (TEP) or tris(1-chloro 2-propyl)phosphate (TCPP). A detection peak may be indicated. Specifically, in order to exclude the influence of contaminants, a sample including portions spaced apart by about 1 cm or more from the entire outer surface of the foam are prepared, and perpendicular to the thickness direction of the foam (parallel to the surface to which the surface material is attached) A peak of triethylphosphate (TEP) or tris(1-chloro 2-propyl)phosphate (TCPP) may be detected at at least one point of at least one cross-section. Put the sample cup into a pyrolysis gas chromatography/mass spectrometer (py-GC/MS, manufacturer: Agilent, model name: 7890A/5975C), and measure the gas produced by pyrolyzing the sample at 200°C under inert gas conditions to measure triethyl phosphate The GC/MS measurement method is the same as described above, except that characteristic peaks of (TEP) or tris(1-chloro 2-propyl)phosphate (TCPP) were identified. For example, a peak of triethylphosphate (TEP) or tris(1-chloro 2-propyl)phosphate (TCPP) may appear at one or more of any three points (k=3) of the cross section. . When the thermosetting foam contains triethyl phosphate (TEP) or tris (1-chloro 2-propyl) phosphate (TCPP) in an amount less than the above range, according to the GC/MS (200° C.), triethyl The peaks of phosphate (TEP) or tris(1-chloro 2-propyl)phosphate (TCPP) may not appear. The thermosetting foam shows a detection peak of triethyl phosphate (TEP) or tris (1-chloro 2-propyl) phosphate (TCPP) by the GC/MS (200° C.), through which triethyl phosphate (TEP) or tris It can be seen that (1-chloro 2-propyl) phosphate (TCPP) is included in an amount within the above range.

In addition, the composite flame retardant may include the phosphorus, the pentaerythritol-based compound, and the melamine-based flame retardant, and contains about 0.1 parts by weight to about 50 parts by weight of the pentaerythritol-based compound relative to 100 parts by weight of the phosphorus. and about 0.1 parts by weight to about 80 parts by weight of the melamine-based flame retardant. For example, based on 100 parts by weight of the phosphorus, about 1 part by weight to about 50 parts by weight of the pentaerythritol-based compound, about 1 part by weight to about 80 parts by weight of the melamine-based flame retardant, or 100 parts by weight of the phosphorus , It may contain about 5 parts by weight to about 30 parts by weight of the pentaerythritol-based compound, and about 5 parts by weight to about 50 parts by weight of the melamine-based flame retardant.

When the content of the pentaerythritol-based compound compared to the melamine-based flame retardant is less than the above range, the carbonized film formed by a synergistic action with phosphorus and the melamine-based flame retardant may be insufficient. There may be a problem in that the flame retardancy is rather reduced while the system compound is burned.

The composite flame retardant may include the phosphorus, the melamine-based flame retardant, and the trialkyl phosphate, and contains about 0.1 parts by weight to about 80 parts by weight of the melamine-based flame retardant, relative to 100 parts by weight of the phosphorus, and the trialkyl phosphate It may contain from about 0.1 parts by weight to about 80 parts by weight. For example, based on 100 parts by weight of the phosphorus, about 1 part by weight to about 80 parts by weight of the melamine-based flame retardant, about 1 part by weight to about 80 parts by weight of the trialkyl phosphate, or 100 parts by weight of the phosphorus, It may include about 5 parts by weight to about 50 parts by weight of the melamine-based flame retardant, and about 5 parts by weight to about 50 parts by weight of the trialkyl phosphate.

When the content of the melamine-based flame retardant compared to the trialkyl phosphate is less than the above range, there is a problem in that the carbonization film formed in a synergistic action with phosphorus and trialkyl phosphate is insufficient, and when it exceeds the above range, the excess melamine-based flame retardant is a phenolic foam There may be a problem of lowering thermal conductivity by rather inhibiting cell formation of

The composite flame retardant may include the phosphorus, the pentaerythritol-based compound, and the trialkyl phosphate, and contains about 0.1 parts by weight to about 50 parts by weight of the pentaerythritol-based compound relative to 100 parts by weight of the phosphorus, It may contain about 0.1 parts by weight to about 80 parts by weight of the trialkyl phosphate. For example, based on 100 parts by weight of the phosphorus, about 1 part by weight to about 50 parts by weight of the pentaerythritol-based compound, about 1 part by weight to about 80 parts by weight of the trialkyl phosphate, or 100 parts by weight of the phosphorus In contrast, about 5 parts by weight to about 50 parts by weight of the pentaerythritol-based compound, and about 5 parts by weight to about 50 parts by weight of the trialkyl phosphate may be included.

When 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 by a synergistic action with phosphorus and trialkyl phosphate may be insufficient. As the erythritol-based compound burns, there may be a problem in that the flame retardancy is lowered.

The composite flame retardant may include the phosphorus, the pentaerythritol-based compound, the melamine-based flame retardant, and the trialkyl phosphate, and the pentaerythritol-based compound is contained in an amount of about 0.1 parts by weight to about 30 parts by weight relative to 100 parts by weight of the phosphorus. Including parts by weight, including about 0.1 parts by weight to about 50 parts by weight of the melamine-based flame retardant, and may include about 0.1 parts by weight to about 60 parts by weight of the trialkyl phosphate. For example, based on 100 parts by weight of the phosphorus, about 1 part by weight to about 30 parts by weight of the pentaerythritol-based compound, about 1 part by weight to about 50 parts by weight of the melamine-based flame retardant, about 1 part by weight to the trialkyl phosphate About 60 parts by weight, or 100 parts by weight of the phosphorus, about 3 parts by weight to about 20 parts by weight of the pentaerythritol-based compound, and about 5 parts by weight to about 30 parts by weight of the melamine-based flame retardant, It may include about 5 parts by weight to about 40 parts by weight of the trialkyl phosphate.

Compared to the pentaerythritol-based compound, when the weight ratio of the melamine-based flame retardant and the trialkyl phosphate is less than the above range, the first flame retardant, phosphorus, does not sufficiently exert a synergistic effect of flame retardancy improvement, and the melamine-based flame retardant And when the weight ratio of the trialkyl phosphate exceeds the above range, there may be a problem in that the cell structure formation of the phenol foam due to an excess of the flame retardant is prevented, resulting in structural instability and deterioration of thermal insulation properties.

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, the first flame retardant is phosphorus (Phosphorus), the second flame retardant is a melamine-based flame retardant, tree The thermosetting foam comprising at least one selected from the group consisting of alkyl phosphates and combinations thereof, or including at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and a pentaerythritol-based compound together The thermal conductivity measured at an average temperature of 20°C according to KS L 9016 is about 0.016 W/m·K to about 0.029 W/m·K. 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, at least about 0.016 W/m·K, less than about 0.020 W/m·K, or at least about 0.016 W/m·K, and less than about 0.0195 W/m·K. The thermal conductivity represents the initial thermal insulation of the foam, and the thermosetting foam may include the composite flame retardant to improve not only flame retardancy but also thermal insulation.

And, according to EN13823, the thermosetting foam has a thermal conductivity measured at an average temperature of 20° C. of about 0.017 W/m·K to about 0.029 W/ It may be m·K. For example, it may be from about 0.017 W/m·K to about 0.025 W/m·K or greater than or equal to about 0.017 W/m·K and less than about 0.023 W/m·K. The thermal conductivity represents the long-term thermal insulation properties of the foam, and the thermosetting foam includes the composite flame retardant and may exhibit the same initial thermal insulation properties and long-term thermal insulation properties in a similar range.

At the same time, the thermosetting foam may have a total amount of heat released for 10 minutes (THR600s) by a cone calorimeter according to KS F ISO 5660-1 of about 2.0 MJ/m2 to about 17 MJ/m2. For example, from about 2.0 MJ/m to about 12.0 MJ/m or from 2.0 MJ/m to less than about 9.0 MJ/m, or from 2.0 MJ/m to about 8.0 MJ/m, or from 2.0 MJ/m to about 7.0 MJ/m It may be less than m2. That is, the thermosetting foam may have excellent flame retardancy close to semi-incombustibility without a separate face material.

And, the thermosetting foam has a total amount of heat released for 5 minutes (THR300s) by a cone calorimeter according to KS F ISO 5660-1 of about 1.0 MJ/m2 to about 12 MJ/m2, for example, about 1.0 MJ/m2 to about 7.5 MJ/m 2 may exhibit excellent flame retardancy.

In addition, 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 may be improved, but the foam cell is destroyed in the foaming process, so that the closed cell ratio is lowered and the thermal insulation property is lowered. On the other hand, the thermosetting foam can maintain a high closed cell ratio in the above range by including the composite flame retardant. And, together with the excellent flame retardancy or semi-incombustibility in the above-described range, it can exhibit excellent thermal insulation.

In the case of a phosphorus-based flame retardant such as phosphate, which is generally used as a flame retardant, compatibility with the thermosetting resin is poor, and physical properties such as compressive strength and flexural fracture load may be reduced by destroying the foam cell structure. On the other hand, the thermosetting foam is uniformly mixed with the thermosetting resin including the composite flame retardant, the foam cell structure is not easily destroyed, and may have uniform physical properties through uniform foaming. In addition, the phosphorus, which is the first flame retardant, acts as a filler in the thermosetting foam to impart structural stability to the thermosetting foam together with the second flame retardant, and to impart excellent compressive strength and flexural fracture load in the following range.

Specifically, the thermosetting foam may have a compressive strength of about 60 kPa to about 300 kPa according to KS M ISO 844. For example, from about 80 kPa to about 300 kPa can be

The thermosetting foam is, according to KS M ISO 4898, the maximum load ( The flexural breaking load (N) of 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 value of dimensional change according to Equation 1 below about 0% to about 1.0%. For example, the thermoset foam can have an average dimensional change of from about 0% to about 0.8% or from about 0% to about 0.6%.

[Equation 1]

Dimensional change rate (%)={|Initial length (a) - Later length (a')| /initial length(a)} X 100

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

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

And, the thermosetting foam may exhibit excellent flame retardancy with an oxygen index of about 39% or more according to KS M ISO 4589-2. For example, the oxygen index of the thermosetting foam may be about 40% or more or about 42% or more. The upper limit is not limited thereto, but may be about 60%. Since the thermosetting foam has an oxygen index in the above range, it may not burn easily in case of fire, and thus it may be easy to secure an evacuation time.

In another embodiment of the present invention, at least one region of 1.2 mm (length, L) X 0.9 mm (width, W) included in the cross section perpendicular to the thickness direction of the foam contains 10 or more phosphorus, and the phosphorus ( Phosphorus) provides a thermosetting foam having a diameter of about 1 μm to about 80 μm. This indicates the content and the degree of distribution of the phosphorus contained in the foam. The thermosetting foam includes the above-described composite flame retardant, and is manufactured by a manufacturing method to be described later, and may include the phosphorus in the structure and distribution as described above. The thermosetting foam may exhibit physical properties such as excellent thermal insulation as well as excellent flame retardancy by having the above structure.

A normal thermosetting foam is provided with flame retardance using flame retardants, such as phosphate. However, when a flame retardant such as phosphate is included, the foam cell is destroyed during the foaming process, so that an appropriate foam cell may not be formed well. Accordingly, the degree of dispersion of the flame retardant may be reduced, and thermal insulation may be deteriorated. In addition, flame retardants such as phosphate are easily agglomerated and are not well dispersed, and there is a problem in that the flame retardant effect is not sufficient compared to the content of the flame retardant. Accordingly, when a flame retardant such as phosphate is included, the foam cannot have the above structure.

The thermosetting foam may include the above-described composite flame retardant and the like, and may appropriately control the foaming and curing reaction, and may prevent aggregation of the flame retardants and the like, thereby improving the dispersibility of the flame retardant. Accordingly, it is possible to simultaneously exhibit physical properties such as excellent heat insulation and excellent flame retardancy by including the phosphorus particles in the above range in the region. For example, the thermoset foam may include from about 10 to about 300 phosphorus in the region. When the number of phosphorus is less than the above range, the phosphorus content is insufficient, or the phosphorus is non-uniformly dispersed, so that sufficient flame retardancy at a desired level cannot be ensured, and thermal insulation properties may be lowered. And, when the number of phosphorus exceeds the above range, the flame retardancy may be better, but due to the high phosphorus content, the balance between foaming and curing is broken, and there may be a problem in that the thermal insulation properties are deteriorated.

The number of phosphorus means the number of particles having a diameter of 1 μm to 80 μm. The thermosetting foam may include phosphorus having an average particle diameter of about 1 to about 50 μm, and in this case, the phosphorus may be partially aggregated during foaming and curing. The phosphorus included in the cross section may be formed by gathering one phosphorus or a part of phosphorus. In this case, the number of phosphorus means particles having a size of 1 μm to 80 μm. The diameter of phosphorus can be measured simultaneously when taking a cross-section using a digital microscope, and the diameter means the longest diameter of the phosphorus particle (eg, the red dot in FIG. 2 ). When the diameter of the phosphorus particles exceeds the above range, it means that the dispersing power of phosphorus is lowered and aggregation occurs a lot, and it is not included in the calculation of the number of phosphorus. And, when two or more phosphorus particles have independent interfaces, the number of phosphorus particles is calculated as separate particles even when the particles are located adjacent to each other.

Specifically, at least one cross-section perpendicular to the thickness direction of the foam, for example, at least one 1.2 mm (length , L) X 0.9 mm (width, W) area may include at least 10 or more Phosphorus particles. The phosphorus particles are obtained by using a digital microscope (Digital Microscope, manufacturer: Leica Microsystems, model name: DVM6), specifically, by setting the magnification of the objective lens having a field of view (FOV) of 12.55 to 8.0x, It was enlarged to observe an arbitrary 1.2 mm (length) X 0.9 mm (width) area of the cross section. Then, a three-dimensional image was taken at intervals of 10 um in the thickness direction within a range of 400 um from the upper portion of the cut surface to obtain a planar two-dimensional image of the cut surface, and the number and diameter of red dots visible in the two-dimensional image were measured.

In general, when the balance of foaming and curing of the foam is not controlled and the foam cells are often destroyed, solid particles such as phosphorus tend to be drawn to the surface. On the other hand, in the thermosetting foam, the distribution of phosphorus particles uniformly dispersed to the same degree as described above can be confirmed even at 1/2 of the thickness including the composite flame retardant.

wherein the thermosetting foam has about 60% to about 100% of an area comprising at least 10 phosphorus out of i areas comprising an area of 1.2 mm (length, L) X 0.9 mm (width, W) in the cross section (integer of i=2 to 15) For example, among the ten regions (i=10), the region including at least 10 phosphorus is from about 60% to about 100% or from about 80% to about It can be 100%. The thermosetting foam may have a structure in which phosphorus in the same content as described above is uniformly distributed. Accordingly, it is possible to exhibit uniformly improved flame retardancy throughout the foam, have excellent thermal insulation properties, and exhibit physical properties such as excellent compressive strength and dimensional stability.

The cross-section perpendicular to the thickness direction of the foam may include a region including 10 or more phosphorus particles per unit area (1 mm2), from about 60% to about 100% or from about 80% to about 100% of the cross-section. can The foam contains the phosphorus particles dispersed in the structure as described above, including the composite flame retardant, and thus, can exhibit excellent thermal insulation and flame retardancy at the same time. When the area containing the phosphorus in the cross section is less than the above range, the dispersibility of phosphorus is poor, and there may be a problem in that the flame retardancy does not appear depending on the location where the fire occurs, so that sufficient flame retardancy cannot be exhibited. And, as the distribution of phosphorus is inclined to one side, foaming and curing may also occur non-uniformly, thereby reducing thermal insulation properties.

The thermosetting foam may include 7 or more or 8 or more zones including at least one phosphorus among 12 zones in which the zone is equally divided by a size of 4 (length, L) × 3 (width, W). The thermosetting foam may include the phosphorus in an appropriate dispersed distribution as described above, including the composite flame retardant. Accordingly, it is possible to simultaneously exhibit excellent thermal insulation properties as well as improved flame retardancy.

In addition, in the thermosetting foam, the area containing at least one phosphorus among the areas in which the area is equally divided by the size of 4 (length) X X 3 (width) may be about 60% or more. The thermosetting foam may be uniformly well formed without destroying the foam cells by proper foaming and curing, including the composite flame retardant. And, it is uniformly dispersed and distributed on the struts of the foam cells.

Figure 2 shows a picture taken using a digital microscope (Digital Microscope) of one area of the thermosetting foam according to an embodiment of the present invention. As shown in FIG. 2, it can be seen that the thermosetting foam hardly shows any breakage of the foam cells. And, the thermosetting foam contains red as the first flame retardant, and as shown in FIG. 2 , it can be seen that red dots (red, phosphorus particles) are uniformly distributed on the struts of the foam.

Figure 3 shows a photograph in which the area of the thermosetting foam of the present invention is divided equally in the size of 4 (length) X 3 (width). In the thermosetting foam, it can be seen that among the 12 zones, 8 or more zones containing at least one phosphorus were uniformly dispersed in an appropriate content in the foam in an amount of about 60% or more. If the content of phosphorus contained in one area is less than the above range, the desired level of flame retardancy cannot be secured, and if the area containing the phosphorus in the area is less than the above range, the dispersibility of phosphorus decreases and a fire occurs. Accordingly, there may be a problem in that the flame retardancy does not appear and sufficient flame retardancy cannot be exhibited. In addition, the foam may have at least 60% of the area including at least one phosphorus among the areas in which the unit area (1 mm 2 ) is equally divided by the size of 4 (length) X 3 (width).

The thermosetting foam contains 10 or more phosphorus in at least one area of 1.2 mm (length, L) X 0.9 mm (width, W) included in the cross section perpendicular to the thickness direction of the foam, as described above, It is possible to exhibit excellent flame retardancy while exhibiting thermal insulation properties of a certain level or higher. Specifically, the thermosetting foam may have a structure that maintains a _{cross-sectional area (S f} ) of at least a certain level after a flame retardant test. And, it may include cracks having a size less than or equal to a certain size. Further, after combustion, cracks, holes, etc. are not formed below a certain thickness of the foam, so that the collapse of the foam and the like can be prevented.

Specifically, the thermosetting foam is a foam having a thickness of 100mm (Li, length) Х100mm (Wi, width) Х50mm (Ti) according to KS F ISO 5660-1. When 50kW/m2 radiant heat is applied for 10 minutes, the _{The area (S f} ) of the cross section of the 1/2 point (T _1/2 ) of the initial thickness of the foam (T _i ) may satisfy Equation 2 below.

[Equation 2]

Si X 50% ≤ Sf ≤ Si X 100%

Here, Si means the cross-sectional area (Si) of the 1/2 point (T1/2) of the initial thickness (Ti) of the foam before applying the radiant heat, and Sf is the initial thickness (Ti) of the foam after applying the radiant heat ) means the cross-sectional area (Sf) of the 1/2 point (T1/2).

The thermosetting foam has a surface area (Sf) in the above range under the above conditions, thereby exhibiting excellent resistance to flame propagation or diffusion, and may exhibit structural stability during combustion. Accordingly, even when an impact or vibration occurs during a fire, the foam can easily fall off and the fire can be prevented from spreading. For example, under the above conditions, when the surface area (Sf) of the thermosetting foam is less than the above range, the content of the foam lost by combustion is too large, so it is structurally unstable. can do it The thermosetting foam may be Si X 75% ≤ Sf ≤ Si X 100%. The thermosetting foam according to an embodiment of the present invention may have a surface area (Sf) within the above range.

A cross section at a point (T1/2) of the initial thickness of the foam after application of the radiant heat may include cracks. Here, the crack means that the foam is formed by cracking the surface while shrinking by heat and combustion. It appears conspicuously when a char is formed, and the amount of foam that is burned and destroyed increases, meaning a shape different from that of a pit. The crack may have a structure similar to a needle having a relatively long longitudinal direction and a relatively short width direction, that is, a width direction perpendicular to the longitudinal direction, in cross section. The length means a value measured in the cross section.

The foam may include a crack in the cross-section, and the maximum length in the width direction perpendicular to the longitudinal direction of the crack may be about 15 mm or less. That is, the maximum length of the width of the crack may be about 15 mm or less. For example, it can be from about 1 mm to about 15 mm or from about 1 mm to about 11 mm. Specifically, when the width of the crack exceeds the above range, the foam may be easily broken by vibration or external impact, and thus there may be a problem in that the flame spreads and spreads. The cross-section may include a plurality of cracks, and each of the plurality of cracks may have a length within the above range. The thermosetting foam according to an embodiment of the present invention may include cracks as described above.

And, the thermosetting foam is a foam having a size of 100mm (length) ХΧ100mm (width) ХΧ50mm (thickness) according to KS F ISO 5660-1 When 50kW/m2 radiant heat is applied for 10 minutes, 5 from the bottom of the foam A thickness of mm to 23 mm may be free of cracks, grooves or holes. For example, no cracks, grooves, or holes may be formed in a thickness of about 13 mm to about 23 mm. Specifically, when cracks, grooves, or holes are formed to a thickness less than the above range, there may be a problem in that the foam is easily removed by vibration or external impact, thereby accelerating the propagation and diffusion of the flame. The thermosetting foam according to an embodiment of the present invention may have no cracks, grooves or holes within the thickness of the range from the bottom surface.

Another embodiment of the present invention comprises the steps of: preparing a flame retardant composition comprising a main agent comprising a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant; preparing a foam composition by stirring the base, curing agent, foaming agent and flame retardant composition; and foaming and 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 a melamine-based flame retardant, tree At least one selected from the group consisting of alkyl phosphates and combinations thereof, or at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and a pentaerythritol-based compound. provide a way

As described above by the manufacturing method, while including the flame retardant, foaming and curing are appropriately controlled so that the foam cell is not destroyed, and the flame retardant is uniformly distributed. Accordingly, as described above, it is possible to prepare the thermosetting foam having physical properties such as improved flame retardancy, excellent thermal insulation, and excellent compressive strength and dimensional stability. The thermosetting resin, the curing agent, the foaming agent and the composite flame retardant are the same as those described above, except for those specifically described below.

First, it includes the step of 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 subject 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 be pre-mixed with the first flame retardant and the second flame retardant or mixed with a thermosetting resin such as a phenol resin, respectively. It may be advantageous in terms of uniform mixing and viscosity control to prepare a flame retardant composition by mixing the first flame retardant and the second flame retardant in advance and then mix them with a phenolic resin. In addition, when the phenolic resin is mixed with the foaming agent and the curing agent, the premixed composite flame retardant may be mixed or the phenolic resin may be mixed with the phenolic resin before the blowing agent or the curing agent is mixed. This can be adjusted according to the type of mixer and process conditions.

It may be advantageous to prepare the flame retardant composition including the first flame retardant and the second flame retardant to an appropriate viscosity before mixing with the phenolic resin. This can help uniform mixing with the phenolic resin. For example, if the viscosity is too high due to a solid flame retardant such as phosphorus or red phosphorus, uniform mixing may not occur, resulting in non-uniform foam hardening, which may deteriorate strength and thermal insulation properties or may deteriorate long-term physical properties. In addition, in adjusting the viscosity, it is preferable to adjust the viscosity in consideration of not only the viscosity of the composite flame retardant before input, but also the compatibility between the composite flame retardant and the material serving to control the viscosity, and side effects during foam curing later. It may be advantageous to adjust the viscosity of the flame retardant composition including the composite flame retardant before the phenol resin is added through the second flame retardant. In this case, the flame retardant composition may mean a mixture of the first flame retardant and the second flame retardant that does not include a separate organic solvent. It may also be advantageous to further include polyols and/or surfactants and/or ethylene glycol and/or polyethylene glycol in the flame retardant composition. For example, the viscosity may be adjusted by mixing the composite flame retardant in advance with water, a foaming agent, a curing agent, etc., but in terms of process convenience and compatibility, a liquid second flame retardant, polyol, surfactant, ethylene glycol, polyethylene glycol, etc. It is advantageous to control the viscosity of the flame retardant composition comprising the composite flame retardant. Regardless of whether or not a flame retardant is included when manufacturing a foam, a surfactant is sometimes added separately. In the case of including a surfactant at the time of manufacturing the foam as described above, it is preferable to adjust the viscosity of the flame retardant composition by adding a portion of the surfactant in advance to the flame retardant mixture, that is, the flame retardant composition, and determine whether to add the surfactant.

When the flame retardant composition includes an organic solvent of low viscosity selected from the group consisting of the polyol, surfactant, polyethylene glycol, ethylene glycol, and combinations thereof, the composite flame retardant: organic solvent is about 2:1 to about 1:2 It may be mixed in a weight ratio of the flame retardant composition. Mixed in the content ratio in the above range may not reduce the flame retardant improving effect of the composite flame retardant. 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. When the content of the organic solvent exceeds the above range, there may be a problem in that the thermal insulation is deteriorated.

And, at 20 ℃, the viscosity difference (ΔV=|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 (ΔV) between the viscosity (V1) of the thermosetting resin and the viscosity (V2) of the flame-retardant composition in the above range, the composite flame retardant containing a solid material does not precipitate in the foam manufacturing process, and the thermosetting It can be uniformly mixed with the resin and exhibit excellent thermal insulation properties with improved flame retardancy.

Specifically, when the viscosity difference (ΔV) exceeds the above range, uniform mixing and foaming of the composite flame retardant and the thermosetting resin may be difficult, and thus the physical properties of the thermosetting foam may be reduced. And, as the viscosity of the foam composition including the thermosetting resin and the flame-retardant composition increases as a whole, a lot of torque of the stirring mixer is taken, and the temperature of the foam composition is rapidly increased to increase the volatilization amount of the foaming agent before the foam is cured. and, accordingly, thermal insulation properties may be deteriorated.

In addition, the viscosity (V1) of the thermosetting resin may be from about 10,000 cps to about 80,000 cps, from about 10,000 cps to about 50,000 cps, or from 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 may be appropriately adjusted. Accordingly, it is possible to form a thermosetting foam that is structurally stable and has an appropriate cross-linked structure, and the thermosetting foam maintains excellent thermal insulation at a certain level with improved flame retardancy, and exhibits 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 in the above range, the foam composition including the composite flame retardant dispersed in the thermosetting resin is uniformly foamed at an appropriate foaming pressure in the process of foaming, thereby improving properties such as flame retardancy, heat insulation and compressive strength. It is possible to form a thermosetting foam having For example, when the content of the foaming agent exceeds the above range, the foaming cells are destroyed and thermal insulation properties are lowered, the dimensional change rate of the foam is increased, and the compressive strength may be reduced.

In addition, 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 in which a solvent such as toluenesulfonic acid is mixed. By including the curing agent in the content in the above range, the balance of foaming and curing can be appropriately adjusted in the composition including the composite flame retardant, and thus physical properties such as heat insulation and excellent compressive strength can be imparted with excellent flame retardancy.

And, the method for producing the thermosetting foam includes the step of preparing a foam composition by stirring the main agent, a curing agent, a foaming agent and a flame retardant composition. In the method for producing the thermosetting foam, the flame-retardant composition including the composite flame retardant may be separated from the main agent including the thermosetting resin, mixed and stirred. Accordingly, it is possible to prevent the viscosity of the main material containing the thermosetting resin from rapidly increasing, and it is possible to easily manufacture the thermosetting foam having the above-described physical properties.

And, 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 a temperature condition of, for example, 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 appropriately vary depending on the purpose and use of the invention.

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

The thermosetting foam can be applied, for example, for use as a building insulation material, and thus can simultaneously satisfy a remarkably improved flame retardancy with excellent thermal insulation properties required as a building insulation material. And, it may have excellent compressive strength, flexural fracture load (N), dimensional stability, high oxygen index, and the like.

The building insulation may further include a face material on one or both sides of the thermosetting foam, for example, and may further improve flame retardancy by including aluminum as the face material.

(실시예) (Example)

Example 1:

100 parts by weight of a resol resin having a viscosity in the range of 20,000 cps at 20° C., 1.5 parts by weight of an ethoxylated castor oil surfactant, 3 parts by weight of powdery urea, toluenesulfonic acid as a curing agent, and cyclopentane as a foaming agent were prepared. . And, the viscosity of the flame-retardant composition was adjusted by mixing a flame retardant complex of red and melamine cyanurate in an organic solvent in which a castor oil surfactant: ethylene glycol was mixed in a weight ratio of 2:1.

And, with respect to 100 parts by weight of the resol resin, 15 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, 6 parts by weight of cyclopentane, along with 6 parts by weight of cyclopentane, the flame retardant composition is piped It was supplied to a stirrer through the and stirred to prepare a foam composition.

Then, the stirred foam composition was put into a caterpillar operated at a speed of 10 m/min to finally prepare a phenolic resin foam having a density of 43 kg/m 3 . At this time, the temperature of the caterpillar was 65 ℃, the thickness was set to 50mm.

At this time, by adjusting the content of red, melamine cyanurate and the content of 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 made to be within 10,000 cps. The viscosity was measured using a Brookfield viscometer (Brookfield, DV3T Rheometer, #63 spindle).

And, finally, the phenolic resin foam was made to include 6 parts by weight of red and 2 parts by weight of melamine cyanurate relative to 100 parts by weight of the phenolic 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, compared to 100 parts by weight of the phenolic resin foam, it was made to contain 6 parts by weight of red and 2 parts by weight of triethyl phosphate.

Example 3:

A phenol 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 phenolic resin foam, 6 parts by weight of red, 1 part by weight of monopentaerythritol, and 1 part by weight of melamine cyanurate were included.

Example 4:

A phenol 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 phenolic resin foam, 6 parts by weight of red, 1 part by weight of melamine cyanurate, and 1 part by weight of triethyl phosphate were included.

Example 5:

A phenol foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, monopentaerythritol, 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 phenolic resin foam, 6 parts by weight of red, 1 part by weight of monopentaerythritol, and 1 part by weight of triethyl phosphate were included.

Example 6:

A phenol foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, monopentaerythritol, 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 phenolic resin foam, 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 were included.

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 red and melamine cyanurate composite flame retardants. And, finally, compared to 100 parts by weight of the phenolic resin foam, 8 parts by weight of melamine cyanurate was included.

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 red and melamine cyanurate complex flame retardant. And, finally, compared to 100 parts by weight of the phenolic resin foam, 8 parts by weight of pentaerythritol was included.

Comparative Example 3:

A phenol 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 phenolic 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 red and melamine cyanurate complex flame retardant. And, finally, compared to 100 parts by weight of the phenol resin foam, 8 parts by weight of triethyl phosphate was included.

평가evaluation

Experimental Example 1: Diameter (㎛) and dispersion (%) of the first flame retardant (phosphorus)

20mm (L) X 20mm (W) X 20mm (T) samples were prepared at portions spaced apart from each other by about 1 cm or more from the entire outer surface of the phenolic resin foams of Examples and Comparative Examples. Then, after freeze-drying the sample with liquid nitrogen for 1 minute, with a sharp thin razor blade, the 1/2 point in the thickness direction is 10 mm perpendicular to the thickness direction (parallel to the surface to which the surface material is attached) to include the middle part. Cut flat to thickness. The cut section was photographed with a Digital Microscope (manufacturer: Leica Microsystems, model name: DVM6). Specifically, with an objective lens having a field of view (FOV) of 12.55 and a diffuser adapter mounted, the magnification of the objective lens is set to 8.0x, and any 1.2mm (length) X 0.9mm ( width) was enlarged to observe the size of the area. Then, a three-dimensional image is taken at intervals of 10 um in the thickness direction within a range of 400 um from the top of the cut surface to obtain a planar two-dimensional image of the cut surface. The intensity of the light source is set to 60% of the intensity of ring light illumination (RL Light), 60% of coaxial illumination (CXI Light), and 80% of transmitted light illumination (BLI Light), and the exposure time is 24.5 milliseconds (ms). The pixels of the image are 2 mega (1600 x 1200 pixels).

2 is a picture taken using a digital microscope (Digital Microscope) of the region of the thermosetting foam according to Example 6. After confirming the red dots (Phosphorus particles) observed in the region, the number of red dots (red dots) having a diameter of 1 μm to 80 μm was counted and described in Table 1. In this case, the diameter of the red dot was measured using the program of the Digital Microscope device as the longest axis length among the diameters of the red dot. The diameter of the smallest particle (minimum) and the largest particle diameter (maximum) among the diameters of the target particles were checked, and the results are shown in Table 1 below. And, FIG. 3 shows a photograph in which the area is equally divided into a size of 4 (length) X 3 (width). It can be seen that the strut of the phenolic foam contains red dots and redness. As shown in FIG. 3, the area is equally divided into 12 areas with a size of 4 (length) X X 3 (width), counting the number of areas containing at least one phosphorus among the areas, and calculating this as a percentage Table 1 shows the results. The published material of Comparative Example did not include phosphorus, which is the first flame retardant, and was not observed.

	인의 개수number of people	인의 직경(㎛)Phosphorus diameter (μm)	인의 분산도(구역수)Phosphorus dispersion (number of districts)	인의 분산도 (%)Phosphorus dispersion (%)
실시예1Example 1	8787	최소: 16, 최대: 68Min: 16, Max: 68	88	6767
실시예2Example 2	9494	최소: 13, 최대: 57Min: 13, Max: 57	99	7575
실시예3Example 3	9797	최소: 12, 최대: 53Min: 12, Max: 53	1010	8383
실시예4Example 4	121121	최소: 8, 최대: 41Min: 8, Max: 41	1212	100100
실시예5Example 5	108108	최소: 10, 최대: 45Min: 10, Max: 45	1111	9292
실시예6Example 6	134134	최소: 5, 최대: 38Min: 5, Max: 38	1212	100100
비교예1∼5Comparative Examples 1 to 5	XX	XX	XX	XX

Experimental Example 2: 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 × 300 mm to prepare a specimen, and the specimen was dried at 70° C. for 12 hours and pre-treated. And, according to the measurement conditions of KS L 9016 (Method for measuring plate heat flow metering method) for the specimen, the thermal conductivity was measured using a HC-074-300 (EKO company) thermal conductivity instrument at an average temperature of 20° C., and the results are shown in the table below. 2 was described.

Experimental Example 3: Long-term thermal conductivity (W/m·K)

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 × 300 mm, and the specimens were dried at 70° C. for 7 days according to EN13823, and then at 110° C. for 14 days. 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 shown in Table 2 below.

Experimental Example 4: THR 300s (MJ/m2)

The phenolic resin foams of Examples and Comparative Examples were prepared as specimens having a size of 100 mm (L) ХΧ100 mm (W) ХΧ 50 mm (T) using a grizzly band saw.

And, the measurement conditions of KS F ISO 5660-1 were adjusted as follows. The temperature of the heater to match the cone 50kW / m ² radiation was 700 ℃ road, the speed of the Blower is 24L / min, oxygen 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 amount of heat released (THR300) was measured. And, the results are shown in Table 2 below.

Experimental Example 5: THR 600s (MJ/m2)

Using a cone calorimeter measuring instrument (Festek International), 50 kW/m ² radiant heat was applied to the specimen for 10 minutes, and the total amount of heat released (THR600) was measured in the same manner as in Experimental Example 4. And, the results are shown in Table 2 below.

Experimental Example 6: Closed cell rate (%)

Specimens were prepared by cutting each of the phenolic resin foams of Examples and Comparative Examples to 2.5 cm (L) X 2.5 cm (W) X 2.5 cm (T). And, it was measured using a closed cell rate measuring device (Quantachrome, ULTRAPYC 1200e) as a KS M ISO 4590 measuring method, and the results are shown in Table 2 below.

Experimental Example 7: Compressive strength (kPa)

The phenolic resin foams of Examples and Comparative Examples were prepared as specimens with a size of 50 mm (L) ХΧ 50 mm (W) Х Χ 50 mm (T), and the specimen was placed between the wide plates of Lloyd Instrument's LF Plus Universal Testing Machine. , the UTM equipment was set at a rate of 10% mm/min of the thickness of the specimen, and the compressive strength test was started, and the strength at the first compressive yield point that appeared while the thickness was decreased was recorded. Compressive strength was measured by the method of KS M ISO 844 standard, and the results are shown in Table 2 below.

Experimental Example 8: Dimensional Stability (%)

The phenolic resin foams of Examples and Comparative Examples were prepared as specimens having a size of 100 mm (L) ХΧ 100 mm (W) Х Χ 50 mm (T). And, as shown in Figure 1, a line is drawn at n (n = 3) equal points in the length (L) and width (W) directions of the specimen, and the initial length ( a) was measured.

Then, the later length (a') of each point is measured after the specimen is left in an oven at 70° C. for 48 hours, and the dimensional change rate (%) changed from the initial dimension is measured by Equation 1 below, and the average value is Table 2 shows. Dimensional stability was measured by the method of KS M ISO 2796 standard.

[Equation 1]

Experimental Example 9: Oxygen Index (LOI)

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

Experimental Example 10: Flexural fracture load (N)

The phenolic resin foams of Examples and Comparative Examples were prepared as specimens with a size of 250 mm (L) ХΧ 100 mm (W) ХΧ 20 mm (T), and the specimen was prepared according to KS M ISO 4898, 200 mm support interval, load concentration of 50 mm/min The maximum load (N) until the specimen breaks at the speed was measured, and the results are shown in Table 2 below.

Experimental Example 11: Area (Sf) of the cross section at the 1/2 point (T1/2) of the initial thickness (Ti)

The foams of the Examples and Comparative Examples were prepared as specimens with a size of 100 mm (L) Χ 100 mm (W) Χ 50 mm (T) using a grizzly band saw, and 1/2 of the initial thickness (Ti) of the specimen (T1/2). ) of the cross-sectional area (Si) was first measured.

And, the remaining 5 sides except for the heating side of the specimen having a size of 100mm(L)Χ100mm(W)Χ50mm(T) are wrapped with aluminum foil, and according to KS F ISO 5660-1, The temperature was set to 700°C, the blower speed was 24L/min, and the oxygen concentration was 20.950%, and the test was started for a total of 10 minutes.

A 25 mm point (ie, a 1/2 point (T1/2) of the initial thickness Ti) was cut from the bottom surface of the specimen on which the test was completed, and the area (Sf) of the cross-section was measured.

Specifically, a photograph was taken with the cut surface facing the front, and then a photographic image was formed using “ImageJ” software. Then, after obtaining the total area of the sample by drawing a rectangle, the area (Sf) of the cut surface was measured by excluding the area of cracks/holes by drawing freely (Freehand selections). In addition, it was confirmed how much ratio (=Sf/Si X 100) the Sf occupies in the relationship with the Si, and the results are shown in Table 3 below.

Experimental Example 12: Maximum length in the width direction of cracks formed in the cross section of Experimental Example 11

The foams of Examples and Comparative Examples were prepared as specimens having a size of 100 mm (L) Χ 100 mm (W) Χ 50 mm (T) using a grizzly band saw.

And, the remaining 5 sides except the heating side of the specimen were wrapped with aluminum foil, and the temperature of the cone heater was set to 700°C by matching 50kW/m2 radiant heat according to KS F ISO 5660-1, and the speed of the blower was 24L/min. , the oxygen concentration was 20.950%, starting the test, and proceeded for a total of 10 minutes.

Cut a 25mm point from the bottom of the test specimen (that is, 1/2 of the initial thickness (Ti) (T1/2)), and measure the maximum width (width) of cracks occurring on the surface (heating side) did.

Specifically, when a crack occurs in a downward direction perpendicular to the heating surface as shown in FIG. 4B, when the surface of the sample where the crack occurs is observed with the naked eye, the surface of the crack part, which is determined to be the widest part, is measured using a steel ruler. do. All parts that are visible at a similar distance to the naked eye shall be measured. At this time, the values measured in the widest length are shown in Table 3 below.

If, after the test, the sample does not have cracks from the surface as shown in FIG. 4A and the sample is widely dissipated, it is indicated as “50 mm or more”.

Experimental Example 13: Thickness from the bottom of the foam with cracks, grooves or holes

So, on the side of the test-completed specimen, the presence or absence of cracks, grooves or holes was visually judged while marking the specimen at 4 heights of 10 mm, 20 mm, 30 mm, and 40 mm from the bottom in the horizontal direction, and cutting at intervals of 2 mm from the bottom. Then, the thickness at which the crack occurred from the bottom surface was confirmed through the distance from the point where the crack, groove or hole was confirmed and the point marked on the side surface, and the results are shown in Table 3 below.

	초기열전도율(W/m·K)Initial thermal conductivity (W/m·K)	장기열전도율(W/m·K)Long-term thermal conductivity (W/m·K)	THR 300s(MJ/㎡)THR 300s (MJ/㎡)	THR 600s(MJ/㎡)THR 600s (MJ/㎡)	독립기포율(%)Closed cell rate (%)	압축 강도(kPa)Compressive strength (kPa)	치수안정성(%)Dimensional stability (%)	산소 지수 (LOI)Oxygen Index (LOI)	굴곡파괴하중(N)Flexural fracture load (N)
실시예1Example 1	0.019450.01945	0.022240.02224	4.54.5	7.57.5	86.686.6	128.4128.4	0.620.62	45.145.1	23.123.1
실시예2Example 2	0.019360.01936	0.021960.02196	4.84.8	7.97.9	87.487.4	115.2115.2	0.550.55	43.543.5	22.822.8
실시예3Example 3	0.019310.01931	0.021580.02158	4.14.1	7.07.0	88.188.1	136.7136.7	0.510.51	46.246.2	27.427.4
실시예4Example 4	0.019150.01915	0.020900.02090	3.83.8	6.66.6	89.689.6	144.6144.6	0.410.41	49.649.6	30.430.4
실시예5Example 5	0.019240.01924	0.021240.02124	4.04.0	7.17.1	88.488.4	131.7131.7	0.490.49	46.346.3	26.526.5
실시예6Example 6	0.019100.01910	0.020640.02064	3.53.5	6.16.1	90.590.5	152.9152.9	0.390.39	50.350.3	31.031.0
비교예1Comparative Example 1	0.022760.02276	0.027450.02745	13.213.2	18.718.7	75.375.3	104.5104.5	0.880.88	35.635.6	18.218.2
비교예2Comparative Example 2	0.020130.012013	0.022540.02254	14.914.9	26.426.4	85.485.4	110.5110.5	0.750.75	31.031.0	19.619.6
비교예3Comparative Example 3	0.030980.03098	0.032200.03220	5.65.6	9.89.8	6.36.3	77.877.8	1.361.36	41.541.5	11.411.4
비교예4Comparative Example 4	0.029480.02948	0.031570.03157	6.36.3	10.410.4	7.87.8	83.683.6	1.101.10	39.839.8	12.812.8
비교예5Comparative Example 5	0.024110.02411	0.026820.02682	14.314.3	23.523.5	61.261.2	78.978.9	1.281.28	29.829.8	14.514.5

	(S _f/S _i) X 100(%)(S _f /S _i ) X 100(%)	크랙의 너비 방향 길이(폭)(㎜)Length (width) in the width direction of the crack (mm)	크랙, 홈 또는 홀 생성 두께(㎜)Thickness of crack, groove or hole creation (mm)
실시예1Example 1	78.178.1	99	1212
실시예2Example 2	82.482.4	88	1414
실시예3Example 3	80.580.5	77	1212
실시예4Example 4	81.981.9	77	1616
실시예5Example 5	85.485.4	66	1818
실시예6Example 6	91.691.6	55	2020
비교예1Comparative Example 1	33.333.3	3030	44
비교예2Comparative Example 2	15.115.1	50 이상50 or more	00
비교예3Comparative Example 3	65.665.6	1717	88
비교예4Comparative Example 4	70.570.5	1616	88
비교예5Comparative Example 5	19.919.9	3535	44

As shown in Table 1, in the thermosetting foam of Examples, the phenomenon of easily aggregating phosphorus was suppressed, and phosphorus having a diameter of more than about 80 μm was not observed because it was uniformly dispersed, and about 1 μm to about 80 μm. It can be seen that there are 10 or more phosphorus within the diameter range, and the phosphorus is present in 8 or more zones, occupying more than 60% of the area. It can be confirmed that, while exhibiting excellent flame retardancy due to heat quantity and high oxygen index, it has excellent initial thermal conductivity and long-term thermal conductivity in a similar range, maintaining low thermal conductivity at a certain level even over time. In addition, it can be confirmed that the thermosetting foam of the embodiment simultaneously satisfies a high closed cell ratio, improved compressive strength, flexural fracture load and dimensional change rate.

In addition, as shown in Table 3, it can be seen that, unlike the comparative example, the Example satisfies Equation 2 along with the excellent thermal insulation properties to simultaneously exhibit excellent flame retardancy.

As described above, the present invention has been described with reference to the illustrated drawings, but the present invention is not limited by the embodiments and drawings disclosed in the present specification. It is obvious that variations can be made. In addition, although the effects of the configuration of the present invention are not explicitly described and described while describing the embodiments of the present invention, it is natural that the effects predictable by the configuration should also be recognized.

Claims

a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant;

The composite flame retardant comprises a first flame retardant and a second flame retardant,

The first flame retardant is phosphorus (Phosphorus),

The second flame retardant includes at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof, or at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof and pentaerythritol containing the compound

thermosetting foam.
According to claim 1,

The composite flame retardant is included in an amount of 1 to 12 parts by weight based on 100 parts by weight of the thermosetting foam.

thermosetting foam.
According to claim 1,

The first flame retardant comprises in an amount of 0.9 to 10 parts by weight based on 100 parts by weight of the thermosetting foam

thermosetting foam.
According to claim 1,

The trialkyl phosphate is trimethyl phosphate, triethyl phosphate, tributyl phosphate, tris (1-chloro 2-propyl) phosphate, tri (2-ethylhexyl) phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl Phosphate (trixylenyl phosphate), tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate, di (iso Propylphenyl) comprising one compound selected from the group consisting of phenyl phosphate, monoisodecyl phosphate) and combinations thereof

thermosetting foam.
According to claim 1,

The second flame retardant is included in an amount of 0.001 parts by weight to 6 parts by weight based on 100 parts by weight of the thermosetting foam.

thermosetting foam.
According to claim 1,

The weight ratio of the first flame retardant to the second flame retardant is 1: 0.001 to 1: 0.8

thermosetting foam.
According to claim 1,

The composite flame retardant includes phosphorus and a melamine-based flame retardant,

The weight ratio of the phosphorus to the melamine-based flame retardant is 1: 0.001 to 1: 0.8

thermosetting foam.
According to claim 1,

The composite flame retardant comprises phosphorus and trialkylphosphate,

wherein the weight ratio of the phosphorus to the trialkyl phosphate is 1: 0.001 to 1: 0.8

Thermosetting foam.
According to claim 1,

The composite flame retardant includes phosphorus, a pentaerythritol-based compound, and a melamine-based flame retardant,

Based on 100 parts by weight of the phosphorus, 0.1 to 50 parts by weight of the pentaerythritol-based compound, and 0.1 to 80 parts by weight of the melamine-based flame retardant

thermosetting foam.
According to claim 1,

The composite flame retardant includes phosphorus, a melamine-based flame retardant and a trialkyl phosphate,

Based on 100 parts by weight of the phosphorus, 0.1 to 80 parts by weight of the melamine-based flame retardant, and 0.1 to 80 parts by weight of the trialkyl phosphate

thermosetting foam.
According to claim 1,

The composite flame retardant includes phosphorus, a pentaerythritol-based compound, and a trialkyl phosphate,

Based on 100 parts by weight of the phosphorus, 0.1 to 50 parts by weight of the pentaerythritol-based compound, and 0.1 to 80 parts by weight of the trialkyl phosphate

thermosetting foam.
According to claim 1,

The composite flame retardant includes phosphorus, a pentaerythritol-based compound, a melamine-based flame retardant and a trialkyl phosphate,

Based on 100 parts by weight of the phosphorus, 0.1 to 30 parts by weight of the pentaerythritol-based compound, 0.1 to 50 parts by weight of the melamine-based flame retardant, and 0.1 to 60 parts by weight of the trialkyl phosphate

thermosetting foam.
According to claim 1,

In accordance with KS L 9016, the thermal conductivity measured at an average temperature of 20°C is 0.016 W/m·K to 0.029 W/m·K

thermosetting foam.
According to claim 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

thermosetting foam.
According to claim 1,

Compressive strength of 60 kPa to 300 kPa according to KS M ISO 844

thermosetting foam.
According to claim 1,

Total heat released for 10 minutes (THR600s) by cone calorimeter according to KS F ISO 5660-1 is 2.0 MJ/m2 to 17 MJ/m2

Thermosetting foam.
According to claim 1,

According to KS M ISO 4898, the maximum load (N) until the specimen breaks at a 200mm support interval and a load concentration rate of 50mm/min on a specimen of 250mm(L)ХΧ100mm(W)ХΧ20mm(T) size. When the breaking load (N) is 15 N to 50 N

thermosetting foam.
According to claim 1,

The average value of the dimensional change rate by the following formula 1 is 0% to 1.0%

Thermosetting foam:

[Equation 1]

Dimensional change rate (%)={|Initial length (a) - Later length (a')| /initial length(a)} X 100

In Equation 1, the initial length (a) is the length of each line of n equal points in the length (L) and width (W) directions of the thermosetting foam, and the later length (a') is the thermosetting foam It means the later length (a') of each line at each point after standing in an oven at 70° C. for 48 hours. (n is 2 to 5)
According to claim 1,

The detection peak of melamine shows by pyrolysis gas chromatography/mass spectrometry (py-GC/MS) (600°C)

thermosetting foam.
At least one area of 1.2 mm (length, L) X 0.9 mm (width, W) included in the cross section perpendicular to the thickness direction of the foam contains 10 or more phosphors,

The diameter of the phosphorus is 1㎛ to 80㎛

thermosetting foam.
21. The method of claim 20,

Among the areas in which the area is equally divided into 4 (length) × 3 (width), 60% or more of the area containing at least one phosphorus

thermosetting foam.
21. The method of claim 20,

The thermosetting foam has an oxygen index (LOI) of 39% or more

thermosetting foam.
Preparing a flame-retardant composition comprising a base material comprising a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant;

preparing a foam composition by stirring the base, curing agent, foaming agent and flame retardant composition; and

Including; foam curing the foam composition;

The composite flame retardant comprises a first flame retardant and a second flame retardant,

The first flame retardant is phosphorus (Phosphorus), and the second flame retardant includes at least one selected from the group consisting of melamine-based flame retardants, trialkyl phosphates, and combinations thereof, or melamine-based flame retardants, trialkyl phosphates, and combinations thereof. At least one selected from the group consisting of and a pentaerythritol-based compound

A method for producing a thermosetting foam.
24. The method of claim 23,

At 20 ℃, the viscosity difference (ΔV=|V1 - V2|) of the viscosity (V1) of the thermosetting resin and the viscosity (V2) of the flame-retardant composition is 30,000 cps or less

A method for producing a thermosetting foam.