WO2020117029A1 - Mousse thermodurcissable, procédé de fabrication associé et isolateur la comportant - Google Patents

Mousse thermodurcissable, procédé de fabrication associé et isolateur la comportant Download PDF

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Publication number
WO2020117029A1
WO2020117029A1 PCT/KR2019/017321 KR2019017321W WO2020117029A1 WO 2020117029 A1 WO2020117029 A1 WO 2020117029A1 KR 2019017321 W KR2019017321 W KR 2019017321W WO 2020117029 A1 WO2020117029 A1 WO 2020117029A1
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Prior art keywords
flame retardant
weight
parts
foam
phosphate
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PCT/KR2019/017321
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English (en)
Korean (ko)
Inventor
박건표
배성재
민경서
김채훈
강길호
김명희
박인성
하혜민
김도훈
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(주)엘지하우시스
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Priority claimed from KR1020190082172A external-priority patent/KR20200070077A/ko
Application filed by (주)엘지하우시스 filed Critical (주)엘지하우시스
Priority to CN201980080556.7A priority Critical patent/CN113490705B/zh
Priority to JP2021531829A priority patent/JP7355824B2/ja
Publication of WO2020117029A1 publication Critical patent/WO2020117029A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/016—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/05—Alcohols; Metal alcoholates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
    • C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
    • C08L61/22—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds
    • C08L61/24—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen of aldehydes with acyclic or carbocyclic compounds with urea or thiourea

Definitions

  • the present invention relates to a thermosetting foam, a method for manufacturing the same, and a heat insulating material including the same.
  • Insulation is an essential material to prevent energy loss in buildings. As global warming continues to emphasize the importance of green growth worldwide, insulation is becoming more important to minimize energy loss.
  • Thermal insulation materials include thermosetting foam insulation, EPS (expanded polystyrene foam) insulation, XPS (extruded polystyrene foam) insulation, and vacuum insulation materials.
  • thermosetting foam insulation materials are widely used because they have the best insulation properties, excluding vacuum insulation materials among existing materials.
  • fire stability is inevitably weaker than inorganic insulating materials.
  • thermosetting foam is manufactured by including the surface material in the manufacturing process, it is possible to improve the flame retardancy by applying the surface material of aluminum material, but in the extreme situation such as a real fire, the flame resistance of the surface material is greatly reduced, so the flame retardancy of the foam is basically It is very important to always.
  • a flame retardant is improved by including a flame retardant such as phosphate in the foamable composition, but the flame retardancy and heat insulation have a trade-off, and there is a problem that the heat insulation is deteriorated.
  • An object of the present invention is to provide a thermosetting foam that satisfies both high thermal insulation and high flame retardancy and has improved physical properties.
  • thermosetting foam It is also an object of the present invention to provide a method for producing the thermosetting foam.
  • thermosetting foam It is also an object of the present invention to provide a heat insulating material comprising the thermosetting foam.
  • thermosetting resin according to the present invention 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 melamine
  • preparing a flame retardant composition comprising a subject, a curing agent, a blowing agent and a composite flame retardant comprising a thermosetting resin; Preparing a foam composition by stirring the subject, a curing agent, a foaming agent, and a flame retardant composition; And foam-curing the foam composition; wherein the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate,
  • a thermosetting foam comprising at least one selected from the group consisting of trialkylphosphates and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkylphosphates and combinations thereof, and a pentaerythritol-based compound. It can provide a manufacturing method.
  • thermosetting foam according to the present invention.
  • thermosetting foam according to the present invention has improved flame retardancy and excellent heat insulation properties, and can exhibit physical properties such as excellent compressive strength and dimensional stability.
  • thermosetting foam according to the present invention can provide a method for manufacturing the thermosetting foam.
  • the heat insulating material according to the present invention includes the thermosetting foam, has improved flame retardancy and excellent heat insulation properties, and can exhibit excellent compressive strength, dimensional stability, and other physical properties.
  • thermosetting foam of the present invention is a schematic view schematically showing a method for measuring dimensional stability of a thermosetting foam of the present invention.
  • thermosetting foam according to some embodiments of the present invention will be described.
  • thermosetting resin a curing agent, a blowing 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 Is at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkyl phosphate and combinations thereof and a pentaerythritol-based compound It provides a thermosetting foam comprising a.
  • thermosetting foams are inevitably weaker in fire stability than inorganic insulating materials.
  • it is common to impart flame retardancy to the foam through surface treatment such as aluminum face material but there is a fear that the face material may fall off from the actual fire, and if the face material falls off, the probability of fire spreading increases.
  • thermosetting foam is imparted with a flame retardant by using a phosphorus-based flame retardant such as phosphate, but when using a phosphorus-based flame retardant such as phosphate, the flame retardancy is improved, while the foam cell is destroyed during the foaming process and the problem of deterioration in thermal insulation is caused.
  • a phosphorus-based flame retardant such as phosphate
  • the flame retardancy is improved, while the foam cell is destroyed during the foaming process and the problem of deterioration in thermal insulation is caused.
  • the aluminum hydroxide is a basic material, which neutralizes an acid curing agent, so that the curing reactivity of the phenolic resin may deteriorate. Accordingly, there is a problem that the heat insulating properties of the foam produced therefrom are lowered.
  • thermosetting foams in the case of the phenolic foam, it has a rigid (RIGID) property compared to other thermosetting foams, and the viscosity of the resin is also high, so it is difficult to produce a foam suitable for a heat insulating material using other additives such as flame retardants.
  • thermosetting foam includes a thermosetting resin, a curing agent, a foaming agent, and a composite flame retardant, and includes a specific first flame retardant and a second flame retardant as the composite flame retardant, thereby improving flame retardancy and thermal insulation in trade-off.
  • thermosetting foam can exhibit excellent physical properties such as compressive strength and dimensional stability.
  • thermosetting foam includes a thermosetting resin.
  • the thermosetting resin may include one selected from the group consisting of epoxy resin, polyurethane resin, polyisocyanate resin, polyisocyanurate resin, polyester resin, polyamide resin, phenol resin and combinations thereof. Can be.
  • the thermosetting foam may include a phenol-based resin that can be obtained by reacting phenol and formaldehyde as a thermosetting resin, for example, a resol-based phenol resin (hereinafter referred to as'resol resin').
  • the composite flame retardant comprising the first flame retardant and the second flame retardant can be well mixed with the phenolic resin containing a benzene ring and uniformly dispersed and foamed.
  • the thermosetting foam may include a composite flame retardant, while stably forming a uniform and small-sized foam cell, and exhibit improved thermal insulation properties as well as initial thermal insulation properties as well as long-term thermal insulation properties.
  • 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 can stably form a foam cell by including the thermosetting resin in an amount within the above range, and realize excellent thermal conductivity.
  • the thermosetting foam contains a curing agent.
  • the curing agent may include one acid curing agent selected from the group consisting of toluene sulfonic acid, xylene sulfonic acid, benzene sulfonic acid, phenol sulfonic acid, ethylbenzene sulfonic acid, styrene sulfonic acid, naphthalene sulfonic acid, and combinations thereof.
  • the thermosetting foam may exhibit appropriate crosslinking, curing and foaming properties including the curing agent.
  • the thermosetting foam contains a blowing agent.
  • the blowing agent may include one selected from the group consisting of hydrofluoroolefin (HFO)-based compounds, hydrocarbon-based compounds, and combinations thereof.
  • 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.
  • the hydrocarbon-based compound may include 1 to 8 carbon atoms.
  • 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.
  • 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, Including at least one selected from the group consisting of isopentane, cyclopentane, and combinations thereof, it may exhibit excellent thermal insulation properties along with eco-friendliness.
  • thermosetting foam may include a surfactant selected from the group consisting of amphoteric, cationic, anionic, and nonionic surfactants and combinations thereof.
  • the thermosetting foam may include castor oil surfactant that is ethoxylated, that is, a nonionic surfactant.
  • thermosetting foam particularly the phenolic resin foam
  • the thermosetting foam can easily disperse the complex flame retardant components including the surfactant, and stably form an appropriate foam structure on the thermosetting foam, thereby realizing excellent thermal conductivity and excellent physical strength. Can be.
  • 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
  • the second flame retardant is melamine cyanurate, trialkyl At least one selected from the group consisting of phosphates and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkylphosphates and combinations thereof, and a pentaerythritol-based compound.
  • the second flame retardant is excellent in compatibility with the first flame retardant, the phosphorus, so that it can be mixed well, and suppresses agglomeration of small-sized phosphorus particles so that the composite flame retardant is evenly dispersed and improved by uniform foaming.
  • excellent heat insulation properties can be imparted.
  • excellent physical properties such as compressive strength and dimensional stability can be imparted.
  • the thermosetting foam can be well formed as a first flame retardant of the composite flame retardant, including phosphorus, with excellent carbonization during combustion.
  • the phenolic resin foam may contain phosphorus in the phenolic resin containing a benzene ring to better form a char.
  • the phosphorus can capture the hydrogen radicals and hydroxy radicals generated during combustion, thereby preventing the combustion reaction from occurring in a chain, thereby rapidly blocking the propagation of fire.
  • the phosphorus can be divided into white, red, black, and white, depending on the structural state and color of the phosphorus.
  • the thermosetting foam may include red.
  • the thermosetting foam may be easily handled when forming a thermosetting foam, including an enemy having an appropriate structure.
  • the thermosetting foam may include 80% or more or 100% of the phosphorous enemy.
  • the composite flame retardant comprises a second flame retardant, the second flame retardant comprises at least one selected from the group consisting of melamine cyanurate, trialkylphosphates and combinations thereof, or melamine cyanurate, trialkylphosphates and these And at least one selected from the group consisting of pentaerythritol-based compounds.
  • the second flame retardant is excellent in compatibility with the first flame retardant phosphorus and can be mixed well, and suppresses the agglomeration of small-sized phosphorus particles so that the composite flame retardant is evenly dispersed and uniformly foamed to improve flame retardancy Together with it can exhibit excellent thermal insulation.
  • the pentaerythritol-based compound may form a carbonized film (Char) by bonding between the phosphorus and phosphorus during combustion, and prevent fire propagation.
  • the pentaerythritol-based compound may include one selected from the group consisting of monopentaerythritol, dipentaerythritol, tripentaerythritol, and combinations thereof.
  • melamine cyanurate hydrogen bonds in the melamine cyanurate structure are endothermally decomposed upon combustion, and combustion heat may be lowered by delaying ignition by absorbing heat by sublimation and decomposition of melamine itself.
  • melamine cyanurate can dilute oxygen by generating nitrogen and/or ammonia gas upon combustion.
  • the melamine cyanurate may condense the melamine itself generated by combustion decomposition to form a carbonized film including multiple ring structures such as melem and melon. At this time, the melamine cyanurate acts together when forming the carbonized film of the phosphorus, thereby improving the reaction of forming the carbonized film and forming a stable carbonized film.
  • the melamine cyanurate can form a uniform and small cell in a thermosetting foam.
  • the melamine cyanurate may act as a nucleating agent in the foam, and the structure of the cell may be more stably formed to further improve heat insulation.
  • the melamine cyanurate may have an average particle diameter of about 1 ⁇ m to about 20 ⁇ m or about 1 ⁇ m to 10 ⁇ m.
  • the particle diameter can be measured by a laser particle size analyzer (Laser Particle Size Analyner, model name: BT-2000). If the average particle diameter of melamine cyanurate is less than the above range, there may be a problem that the viscosity of the composition containing it is increased and dispersion is not good. And, if it exceeds the above range, there may be a problem that the flame retardancy is lowered.
  • 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 Trienylenyl phosphate, tris(isopropylphenyl)phosphate, tris(phenylphenyl)phosphate, trinaphthylphosphate, cresyldiphenylphosphate, xylenyldiphenylphosphate, diphenyl(2-ethylhexyl)phosphate, di (Isopropylphenyl)phenylphosphate, monoisodecylphosphate) and combinations thereof.
  • the trialkyl phosphate improves the uniform dispersion of the phosphorus, suppresses the agglomeration of small-sized phosphorus particles so that the composite flame retardant can be evenly dispersed, and uniformly foams to exhibit excellent heat insulation with improved flame retardancy.
  • the trialkyl phosphate may be triethyl phosphate, and it is well mixed with the phosphorus to improve the flame retardancy and heat insulation.
  • the composite flame retardant may be included in an amount of 1 to 20 parts by weight compared to 100 parts by weight of the thermosetting foam.
  • the composite flame retardant may be included in an amount of 1.5 parts by weight to 15 parts by weight or about 2 parts by weight to about 10 parts by weight.
  • the thermosetting foam may include the composite flame retardant in the above range to control the combustion speed of the foam during a fire and stably form a carbonized film, and at the same time, provide excellent physical properties such as improved flame retardancy and excellent heat insulation and compressive strength.
  • the content of the composite flame retardant when the content of the composite flame retardant is less than the above range, it may not stably form a carbonized film and may not exhibit a sufficient flame retardant effect. And, if it exceeds the above range, it is uneconomical because it takes a lot of 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, if the viscosity of the foam composition is increased due to the content of the composite flame retardant, the temperature of the foam composition is increased because the torque of the mixer is high during stirring. In addition, the amount of volatilization of the blowing agent is increased, and accordingly, thermal insulation may be deteriorated. In addition, due to the high viscosity of the foam composition, phosphors, foaming agents, curing agents, and the like are not evenly dispersed, which may cause a problem that the physical properties of the foam are not uniformly formed.
  • the first flame retardant may be included in an amount of 0.9 to 15 parts by weight compared to 100 parts by weight of the thermosetting foam.
  • the first flame retardant is contained in about 1 part by weight to about 10 parts by weight, or about 2 parts by weight to about 8 parts by weight, uniformly dispersed in the thermosetting resin, and improved flame retardancy and compressive strength while maintaining excellent thermal insulation It can give excellent physical properties.
  • the viscosity of the foam composition is greatly increased, which may cause problems during foaming. For example, if the viscosity of the foam composition is increased, the temperature of the foam composition may be increased because the torque of the mixer is high during stirring. In addition, the amount of volatilization of the blowing agent is increased, and accordingly, thermal insulation may be deteriorated. In addition, due to the high viscosity of the foam composition, phosphors, foaming agents, curing agents, and the like are not evenly distributed, and a problem that physical properties such as poor compressive strength may not be formed may occur.
  • the second flame retardant may be included in an amount of 0.1 to 7 parts by weight compared to 100 parts by weight of the thermosetting foam.
  • the second flame retardant may be about 0.1 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 to control the combustion rate of the foam during a fire and to form a stable carbonized film, thereby providing excellent flame retardancy, excellent thermal insulation, compressive strength, and dimensional stability. It can have excellent physical properties such as.
  • the content of the second flame retardant When the content of the second flame retardant is less than the above range, it may not properly react with the phosphorus to form an appropriate carbonized film, and the rate of formation of the carbonized film may not be sufficient, thereby improving the flame retardant improving effect. In addition, when the amount exceeds the above range, the second flame retardant compound itself, which does not react with phosphorus in the fire, may burn and deteriorate flame retardancy.
  • the weight ratio of the first flame retardant to the second flame retardant may be about 1: 0.05 to about 1: 1.2.
  • the weight ratio of the first flame retardant to the second flame retardant is about 1: 0.07 to about 1: 0.6, or about 1: 0.1 to about 1: 0.4
  • the thermosetting foam includes the first flame retardant and the second flame retardant in a weight ratio in the above range, and simultaneously exhibits improved flame retardancy and excellent heat insulation, and can also exhibit excellent physical properties.
  • the second flame retardant is mixed in an amount less than the above range, the synergistic effect of phosphorus is insignificant and there is an uneconomical problem.
  • the second flame retardant is mixed above the above range, the flame retardance is lowered, and the high independent Bubble rate is difficult to secure, it may be difficult to secure a sufficient compressive strength.
  • 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.
  • the weight ratio of the phosphorus to the pentaerythritol-based compound may be about 1: 0.07 to about 1: 0.4.
  • the composite flame retardant may include the phosphorus and the melamine cyanurate compound, and the weight ratio of the phosphorus to the melamine cyanurate compound may be about 1: 0.05 to about 1: 0.8.
  • the weight ratio of the phosphorus to the melamine cyanurate compound may be about 1: 0.07 to about 1: 0.6.
  • the composite flame retardant may include the phosphorus and the trialkyl phosphate, and the weight ratio of the phosphorus to the trialkyl phosphate may be about 1: 0.05 to about 1: 0.8.
  • the weight ratio of the phosphorus to the trialkylphosphate may be about 1: 0.07 to about 1: 0.6.
  • the second flame retardant that remains without reacting with the phosphorus that is the first flame retardant may be burned during a fire and deteriorate flame retardancy. have.
  • the content of the second flame retardant is less than the above range, the dispersibility of phosphorus in the thermosetting foam is poor and the heat insulating property may be deteriorated.
  • a synergistic effect of flame retardancy according to the combination of the second flame retardant and the phosphorus may not be exhibited.
  • the composite flame retardant may include the phosphorus, the pentaerythritol-based compound, and the melamine cyanurate, compared to 100 parts by weight of the phosphorus, the pentaerythritol-based compound from about 1 part by weight to about 50 parts by weight And about 1 part by weight to about 80 parts by weight of the melamine cyanurate.
  • the pentaerythritol-based compound may include about 5 parts by weight to about 30 parts by weight
  • the melamine cyanurate may include about 5 parts by weight to about 40 parts by weight.
  • the composite flame retardant may include the phosphorus, the melamine cyanurate, and the trialkyl phosphate, and the phosphorus, compared to 100 parts by weight of the melamine cyanurate, including about 1 part by weight to about 80 parts by weight of the tree,
  • the alkyl phosphate may include about 1 part by weight to about 80 parts by weight.
  • the melamine cyanurate may include about 5 parts by weight to about 40 parts by weight
  • the trialkyl phosphate may include about 5 parts by weight to about 40 parts by weight.
  • the content of the melamine cyanurate compared to the trialkyl phosphate is less than the above range, there is a problem of insufficient formation of a carbonized film formed by synergy with phosphorus and trialkyl phosphate, and when it exceeds the above range, the excess melamine cyanurate There may be a problem of lowering the thermal conductivity by rather hindering the cell formation of the phenolic foam.
  • the composite flame retardant may include the phosphorus, the pentaerythritol-based compound, and the trialkyl phosphate, and the pentaerythritol-based compound to about 1 part by weight to about 50 parts by weight, compared to 100 parts by weight of the phosphorus,
  • the trialkyl phosphate may include about 1 part by weight to about 80 parts by weight.
  • the pentaerythritol-based compound may include about 5 parts by weight to about 30 parts by weight
  • the trialkyl phosphate may include about 5 parts by weight to about 40 parts by weight.
  • 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 synergy with phosphorus and trialkyl phosphate may be insufficient, and when it exceeds the above range, the excess penta remaining without reacting As the erythritol-based compound is burned, there may be a problem of deteriorating flame retardancy.
  • the composite flame retardant may include the phosphorus, the pentaerythritol-based compound, the melamine cyanurate, and the trialkyl phosphate, compared to 100 parts by weight of the phosphorus, the pentaerythritol-based compound from about 1 part by weight to about 30 parts by weight, the melamine cyanurate may include about 1 part by weight to about 50 parts by weight, and the trialkyl phosphate may include about 1 part by weight to about 60 parts by weight.
  • the pentaerythritol-based compound includes about 3 parts by weight to about 20 parts by weight
  • the melamine cyanurate contains about 5 parts by weight to about 30 parts by weight
  • the tree The alkyl phosphate may include about 5 parts by weight to about 40 parts by weight.
  • thermosetting resin a curing agent, a blowing agent and a composite flame retardant
  • the composite flame retardant includes a first flame retardant and a second flame retardant
  • the first flame retardant is Phosphorus (Phosphorus)
  • the second flame retardant is melamine cyanurate
  • the thermosetting comprising at least one selected from the group consisting of trialkyl phosphates and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkyl phosphates and combinations thereof, and a pentaerythritol-based compound.
  • the foam has a thermal conductivity of about 0.016 W/m ⁇ K to about 0.029 W/m ⁇ K measured at an average temperature of 20° C. according to KS L 9016.
  • the thermosetting foam has a thermal conductivity 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/ measured at an average temperature of 20° C. according to KS L 9016. m ⁇ K, about 0.016 W/m ⁇ K or more, about 0.020 W/m ⁇ K or less, or about 0.016 W/m ⁇ K or more, and less than about 0.0195 W/m ⁇ K.
  • the thermal conductivity indicates the initial thermal insulation of the foam, and the thermally curable foam includes the composite flame retardant, and may improve thermal insulation as well as flame retardancy.
  • thermosetting foam according to EN13823 dried for 7 days at 70°C and then dried for 14 days at 110°C
  • the thermal conductivity measured at an average temperature of 20°C is about 0.017 W/mK to about 0.029 W/ It can be m ⁇ K.
  • it may be about 0.017 W/m ⁇ K to about 0.025 W/m ⁇ K or about 0.017 W/m ⁇ K or more and less than about 0.023 W/m ⁇ K.
  • the thermal conductivity indicates long-term thermal insulation of the foam, and the thermal-curable foam may exhibit long-term thermal insulation of the same or similar range as the initial thermal insulation by including the composite flame retardant.
  • the thermosetting foam may have a total heat emission rate (THR600s) of 10 minutes by a cone calorimeter according to KS F ISO 5660-1 from about 2.0 MJ/m 2 to about 15 MJ/m 2.
  • TRR600s total heat emission rate
  • KS F ISO 5660-1 total heat emission rate
  • the thermosetting foam may have excellent flame retardancy close to semi-incombustibility even without a separate face material.
  • thermosetting foam has a total heat emission rate (THR300s) of about 1.0 MJ/m 2 to about 12 MJ/m 2, for example, about 1.0 MJ/m 2 by concalimeter according to KS F ISO 5660-1. To about 7.5 MJ/m 2, about 1.0 MJ/m 2 to about 5 MJ/m 2 or about 1.0 MJ/m 2 or more, and less than about 4 MJ/m 2, it may exhibit excellent flame retardancy.
  • the independent bubble rate of the thermosetting foam may be from about 75% to about 98%.
  • the independent bubble rate of the thermosetting foam may be from about 80% to about 95%.
  • thermosetting foam when a phosphorus-based flame retardant such as phosphate is used in the thermosetting foam to improve the flame retardancy, the flame retardancy may be improved, but the foam cell is destroyed during the foaming process, resulting in a decrease in the independent bubble rate and a decrease in thermal insulation.
  • the thermosetting foam can maintain a high independent bubble rate in the above range including the composite flame retardant.
  • thermosetting foam is uniformly mixed with the thermosetting resin, including the composite flame retardant, the foam cell structure is not easily destroyed, it can have uniform properties by uniform foaming.
  • 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, together with it, to provide excellent compressive strength and flexural breaking load in the above range.
  • thermosetting foam may have a compressive strength of about 80 kPa to about 300 kPa according to KS M ISO 844.
  • KS M ISO 844 For example, about 150 kPa to about 230 kPa Can be
  • thermosetting foam according to KS M ISO 4898, 200 mm support spacing on a specimen of 250 mm (L) ⁇ 100 mm (W) ⁇ 20 mm (T), the maximum load until the specimen breaks at a load concentration rate of 50 mm/min ( N), the flexural breaking load (N) may be from about 15 N to about 50 N. For example, it may be about 20 N to about 50 N.
  • thermosetting foam may have an average value of a dimensional change rate according to Equation 1 below from 0% to 1.0%.
  • the thermosetting foam may have an average dimensional change rate of about 0% to about 0.8% or about 0% to about 0.6%.
  • Dimensional change rate (%) (Initial length(a)-Last length(a'))/Initial length(a) X 100
  • Equation 1 the initial length (a) is the length of each line at n points equal 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 leaving the oven at 70°C for 48 hours. At this time, n may be 2 to 5. n can be 3.
  • thermosetting foam includes the composite flame retardant as a flame retardant, and thus has a dimensional change rate within the above range, and it can be seen that it has excellent dimensional stability. Accordingly, the thermosetting foam exhibits excellent thermal conductivity, so that long-term thermal insulation can be more effectively improved, and workability and workability can be more excellent when applied as a predetermined product.
  • thermosetting foam may exhibit excellent flame retardancy with an oxygen index of about 32% or more according to KS M ISO 4589-2.
  • the oxygen index of the thermosetting foam may be about 32% to about 60%, about 36% to about 60% or about 43% to about 60%. Since the thermosetting foam has an oxygen index in the above range, it may not be easily burned in a fire, and thus it may be easy to secure an evacuation time.
  • Another embodiment of the present invention comprises the steps of preparing a flame retardant composition comprising a subject, a curing agent, a blowing agent and a composite flame retardant comprising a thermosetting resin; Preparing a foam composition by stirring the subject, a curing agent, a foaming agent, and a flame retardant composition; And foam-curing the foam composition; wherein the composite flame retardant includes a first flame retardant and a second flame retardant, the first flame retardant is phosphorus, and the second flame retardant is melamine cyanurate,
  • a thermosetting foam comprising at least one selected from the group consisting of trialkylphosphates and combinations thereof, or at least one selected from the group consisting of melamine cyanurate, trialkylphosphates and combinations thereof, and a pentaerythritol-based compound. It provides a method of manufacturing.
  • thermosetting foam having improved flame retardancy, excellent thermal insulation properties, and excellent compressive strength and dimensional stability. Matters relating to the thermosetting resin, curing agent, foaming agent and composite flame retardant are as described above, except as specifically described below.
  • a step of preparing a flame retardant composition comprising a subject, a curing agent, a blowing agent, and a composite flame retardant, comprising a thermosetting resin.
  • Subjects may include from about 1 part to about 5 parts by weight of surfactant and from about 3 parts to about 10 parts by weight of urea, relative to 100 parts by weight of thermosetting resin.
  • the composite flame retardant may include one solid material selected from the group consisting of phosphorus, pentaerythritol-based compounds, melamine cyanurate, and combinations thereof, wherein the composite flame retardant is in the form of a flame retardant composition mixed with an organic solvent. It is included in the furnace foam composition and has proper flowability and is easily introduced into the production process, and can be uniformly mixed with the thermosetting resin.
  • the composite flame retardant: the organic solvent may be mixed in a weight ratio of about 2:1 to about 1:2 to be included in the flame retardant composition, and may be mixed at a content ratio in the above range to not decrease the flame retardant enhancing effect of the composite flame retardant. have.
  • the organic solvent may be a low-viscosity organic solvent selected from the group consisting of polyols, surfactants, polyethylene glycol, ethylene glycol, phosphate-based compounds, and combinations thereof.
  • the phosphate-based compound is, for example, Tris(1-chloro-2-propyl)phosphate (TCP), Tris-(2-chloroethyl)phosphate (Tris-( 2-chloroethyl)phosphate, TCEP), and triethyl phosphate (TEP).
  • the organic solvent may be added in a range of about 1 part by weight to about 15 parts by weight relative to 100 parts by weight of the thermosetting resin. When the content of the organic solvent exceeds the above range, a problem that thermal insulation is deteriorated may occur.
  • the organic solvent is a first organic solvent selected from the group consisting of TCPP, TCEP, TEP and combinations thereof and one selected from the group consisting of polyol, surfactant, polyethylene glycol, ethylene glycol and combinations thereof. It may be a mixed organic solvent of the second organic solvent.
  • the difference in viscosity ( ⁇ V
  • ) 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 between about 0 and about 10,000 cps.
  • thermosetting foam when the viscosity difference ( ⁇ V) exceeds the above range, uniform mixing and foaming of the composite flame retardant and the thermosetting resin may be difficult, and accordingly, the physical properties of the thermosetting foam may deteriorate.
  • the viscosity of the foam composition including the thermosetting resin and the flame retardant composition increases, the torque of the stirring mixer takes a lot, and the temperature of the foam composition rises rapidly so that the volatilization amount of the foaming agent may increase before the foam is cured. And, accordingly, thermal insulation may be deteriorated.
  • the viscosity (V1) of the thermosetting resin may be about 10,000 cps to about 80,000 cps, about 10,000 cps to about 50,000 cps, or about 20,000 cps to about 50,000 cps at 20°C.
  • ⁇ V difference in viscosity
  • V1 viscosity of the thermosetting resin
  • the curing reaction rate of the thermosetting resin in which the composite flame retardant is dispersed can be appropriately adjusted. Accordingly, it is possible to form a thermosetting foam having a structurally stable and moderate cross-linking structure, and the thermosetting foam maintains excellent thermal insulation properties at a constant level with improved flame retardancy, and exhibits excellent physical properties such as excellent compressive strength. .
  • the blowing agent may be included to be about 5 parts by weight to about 15 parts by weight based on about 100 parts by weight of the thermosetting resin.
  • the foam composition comprising the composite flame retardant dispersed in the thermosetting resin uniformly foams at an appropriate blowing pressure in the process of foaming to improve physical properties such as improved 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 foam cell is destroyed and the heat insulating property is lowered, the dimensional change rate of the foam is increased, and the compressive strength may be lowered.
  • the curing agent may be included in an amount of about 15 to about 25 parts by weight compared to 100 parts by weight of the thermosetting resin.
  • the curing agent refers to a mixture of a substance such as toluene sulfonic acid in a solvent.
  • a composition containing a composite flame retardant by including a curing agent in the above range the balance of foaming and curing can be appropriately adjusted, and accordingly, physical properties such as heat insulation and excellent compressive strength can be imparted along with excellent flame retardancy.
  • the method for manufacturing the thermosetting foam includes the steps of preparing the foam composition by stirring the subject, the curing agent, the foaming agent and the flame retardant composition.
  • the flame retardant composition containing the composite flame retardant can be separately mixed and stirred by separating from the subject containing the thermosetting resin. Accordingly, it is possible to prevent the viscosity of the subject containing the thermosetting resin from rapidly increasing, and the thermosetting foam having the above-described physical properties can be easily produced.
  • the method of manufacturing the thermosetting foam comprises the step of foam-curing the foam composition.
  • the thermosetting foam can be foamed and cured, for example, under temperature conditions from about 50°C to about 90°C.
  • 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 be appropriately changed according to the purpose and use of the invention.
  • Another embodiment of the present invention provides a heat insulating material comprising the thermosetting foam.
  • thermosetting foam can be applied, for example, to the use of a building insulation material, and accordingly, can simultaneously satisfy a significantly improved flame retardancy along with excellent heat insulation required as a building insulation material. And, it can have excellent compressive strength, flexural breaking load (N), dimensional stability, and high oxygen index.
  • the building insulation material may further include, for example, a face material on one side or both sides of the thermosetting foam, and further include aluminum as the face material to further improve flame retardancy.
  • Toluenesulfonic acid as a curing agent and cyclopentane as a foaming agent were prepared by mixing 100 parts by weight of a resol resin having a viscosity of 30,000 cps at 20°C, 1 part by weight of castor oil surfactant subjected to an ethoxylation reaction, and 3.5 parts by weight of a powdery urea. . Then, a flame retardant composition was prepared by mixing a composite flame retardant 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.
  • the toluene sulfonic acid 80 parts by weight of ethylene glycol 15% by weight and 5% by weight of a mixture of 18 parts by weight of the mixture, 8 parts by weight of cyclopentane, piping the flame retardant composition It was supplied to the stirrer through and stirred to prepare a foam composition.
  • the stirred foam composition was introduced into a caterpillar operated at a speed of 5 m/min to finally prepare a phenolic resin foam having a density of 40 kg/m3.
  • the temperature of the caterpillar was 70°C, and the thickness was 50 mm.
  • the viscosity difference between the viscosity of the resol resin (V1) and the viscosity of the flame retardant composition (V2) was made to be within 10,000 cps.
  • the viscosity was measured using a Brookfield viscometer (Brookfield, DV3T Rheometer, #63 spindle).
  • the phenolic resin foam was prepared to contain 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.
  • a phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red and triethylphosphate 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 include 6 parts by weight of red and 2 parts by weight of triethyl phosphate.
  • a phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, monopentaerythritol and melamine cyanurate was used instead of the composite flame retardant of red and melamine cyanurate. And, finally, compared to 100 parts by weight of the phenolic resin foam, it was made to include 6 parts by weight of red, 1 part by weight of monopentaerythritol and 1 part by weight of melamine cyanurate.
  • a phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, melamine cyanurate and triethylphosphate 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, 6 parts by weight of red, 1 part by weight of melamine cyanurate and 1 part by weight of triethyl phosphate.
  • a phenolic foam was prepared in the same manner as in Example 1, except that a composite flame retardant of red, monopentaerythritol and triethylphosphate 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 include 6 parts by weight of red, 1 part by weight of monopentaerythritol and 1 part by weight of triethyl phosphate.
  • a phenolic foam was prepared in the same manner as in Example 1, except that the 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, compared to 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.
  • a phenolic foam was prepared in the same manner as in Example 1, except that only melamine cyanurate was used in place of the above-mentioned composite flame retardant of melamine cyanurate. And, finally, compared to 100 parts by weight of the phenolic resin foam, it was made to contain 8 parts by weight of melamine cyanurate.
  • a phenolic foam was prepared in the same manner as in Example 1, except that only pentaerythritol was used instead of the above-mentioned composite flame retardant of melamine cyanurate. And, finally, compared to 100 parts by weight of the phenolic resin foam, it was made to include 8 parts by weight of pentaerythritol.
  • a phenolic foam was prepared in the same manner as in Example 1, except that the composite flame retardant of ammonium polyphosphate and melamine cyanurate was used instead of the above-mentioned composite flame retardant of melamine cyanurate. And finally, compared to 100 parts by weight of the phenolic resin foam, it was made to include 6 parts by weight of ammonium polyphosphate and 2 parts by weight of melamine cyanurate.
  • a phenolic foam was prepared in the same manner as in Example 1, except that the composite flame retardant of ammonium polyphosphate and monopentaerythritol was used instead of the composite flame retardant of the above and melamine cyanurate. And, finally, compared to 100 parts by weight of the phenolic resin foam, it was made to include 6 parts by weight of ammonium polyphosphate and 2 parts by weight of monopentaerythritol.
  • a phenolic foam was prepared in the same manner as in Example 1, except that only the triethyl phosphate was used instead of the above-mentioned composite flame retardant of melamine cyanurate. And, finally, compared to 100 parts by weight of the phenolic resin foam, it was made to include 8 parts by weight of triethyl phosphate.
  • 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 specimens, and the specimens were dried at 70° C. for 12 hours for pretreatment. Then, according to the measurement conditions of KS L 9016 (flat plate heat flow meter method) for the specimen, the thermal conductivity was measured using an HC-074-300 (EKO) thermal conductivity device at an average temperature of 20°C, and the results are shown in the table below. It was described in 1.
  • 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 specimens, and the specimens were dried for 7 days at 70° C. according to EN13823, followed by 14 days at 110° C. After drying, the thermal conductivity was measured using an HC-074-300 (EKO) thermal conductivity device at an average temperature of 20°C, and the results are shown in Table 1 below.
  • the phenolic resin foams of the above examples and comparative examples were fabricated into specimens having a size of 100 mm(L) ⁇ 100 mm(W) ⁇ 50 mm(T) using a grizzly band saw.
  • KS F ISO 5660-1 Then, the measurement conditions of KS F ISO 5660-1 were set as follows. The heat of the heater was set to 700°C by matching 50kW/m 2 radiant heat, the blower speed was 24L/min, and the oxygen concentration started at 20.950%. Then, using a cone-calorimeter (Fasttech 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 1 below.
  • the phenol resin foam of each of the examples and comparative examples was cut into 2.5 cm (L) X 2.5 cm (W) X 2.5 cm (T) to prepare specimens. And, using the KS M ISO 4590 measurement method using an independent bubble rate measuring instrument (Quantachrome, ULTRAPYC 1200e) equipment and the results are shown in Table 1 below.
  • the phenolic resin foams of Examples and Comparative Examples were prepared as specimens having a size of 50mm(L) ⁇ 50mm(W) ⁇ 50mm(T), and the specimens were placed between wide plates of a Lloyd instrument company LF Plus Universal Testing Machine. , UTM equipment was set at a rate of 10% mm/min of the specimen thickness, and the compressive strength experiment was started to record the strength at the first compressive yield point during the thickness reduction. Compressive strength was measured by the method of KS M ISO 844 standard, and the results are shown in Table 1 below.
  • thermosetting foam of the present invention is a schematic view schematically showing a method for measuring dimensional stability of a thermosetting foam of the present invention.
  • Dimensional change rate (%) (Initial length(a)-Last length(a'))/Initial length(a) X 100
  • the phenolic resin foams of Examples and Comparative Examples were prepared as specimens having a size of 250 mm (L) ⁇ 100 mm (W) ⁇ 20 mm (T), and the specimens according to KS M ISO 4898, 200 mm support spacing, 50 mm/min load concentration
  • the maximum load (N) from the velocity until the specimen fractured was measured and the results are shown in Table 1 below.
  • thermosetting foam of the embodiment exhibits excellent flame retardancy with low total emission heat and high oxygen index, and at the same time, has excellent initial thermal conductivity and long-term thermal conductivity in a similar range, and has a constant low thermal conductivity over time. You can see that it stays at the level.
  • thermosetting foam of the Example satisfies the high independent bubble rate, the improved compressive strength, the flexural fracture load, and the dimensional change rate at the same time.

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Abstract

L'invention concerne une mousse thermodurcissable qui comprend une résine thermodurcissable, un agent de durcissement, un agent d'expansion et un ignifugeant composite, ce dernier comprenant un premier ignifugeant et un second ignifugeant. Le premier ignifugeant est le phosphore, et le second ignifugeant comporte au moins un composé choisi dans le groupe constitué par le cyanurate de mélamine, le phosphate de trialkyle et les combinaisons de ces derniers, ou comporte un composé à base de pentaérythritol et au moins un composé choisi dans le groupe consititué par le cyanurate de mélamine, le phosphate de trialkyle et les combinaisons de ces derniers.
PCT/KR2019/017321 2018-12-07 2019-12-09 Mousse thermodurcissable, procédé de fabrication associé et isolateur la comportant WO2020117029A1 (fr)

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