Flame retardant composition for polyurethane foam and flame retardant polyurethane foam containing the same

Abstract

To provide: a non-red phosphorus-type flame retardant composition for polyurethane foam, which causes no drip ignition during combustion of the polyurethane foam and forms a char layer easily; and a flame-retardant polyurethane foam having the flame retardant composition for polyurethane foam mixed therein.SOLUTION: Provided is a flame retardant composition for polyurethane foam having an excellent carbonization property, comprising a phosphorus compound represented by formula (1). (In the formula, M is Mg, Al, Ca, Ti, or Zn; and m is 2, 3, or 4.)SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a flame retardant composition for polyurethane foam that does not use red phosphorus and that easily forms a charred layer without melting or dripping during combustion, and to a flame-retardant polyurethane foam containing the flame retardant composition for polyurethane foam. The flame retardants of the present invention are applicable to either flexible or semi-rigid or rigid polyurethane foams. [Background technology]

[0002] Traditionally, polyurethane foam has been used not only as a sound-absorbing, sound-proofing, and thermal insulation material in automobiles and electrical appliances, but also as a thermal insulation measure for detached houses and condominiums, using a foam-in-place insulation method in which polyurethane foam is sprayed onto the surface of concrete members or interior wall materials. However, when used in automobiles and electrical appliances, high flame retardancy standards such as UL-94V are required. Furthermore, for architectural applications, polyurethane foam itself is flammable, which could lead to a major accident if a fire breaks out inside a building. The cone calorimeter test method addresses this issue. In this case, flame retardancy standards also require a very high level of flame retardancy that exceeds even UL-94V. Therefore, various methods have been developed to address these issues.

[0003] For example, in construction applications, a fire-resistant material made of a non-flammable inorganic coating material primarily composed of cement is sprayed onto sprayed polyurethane foam. However, this method requires two spraying stages, as the fire-resistant material is sprayed onto the polyurethane foam, and time must be secured for the hardening reaction to complete at each stage, which results in the time-consuming construction process and makes process management difficult.

[0004] In addition, methods for improving the flame retardancy of polyurethane foams used in insulation materials for automobiles and electrical appliances have been attempted, such as making the polyurethane foam itself flame retardant or giving it self-extinguishing properties in case of fire. These methods include blending a flame retardant into the polyurethane foam raw materials and introducing a flame-retardant component into the polyurethane foam by copolymerization as one of its constituent components.

[0005] The most common method for improving the flame retardancy of polyurethane foams is to add flame retardants, because it is inexpensive to produce, the type and amount of flame retardant can be freely adjusted in post-production processes, and it is suitable for small-lot, high-mix production.

[0006] Conventionally, phosphate esters have been the main flame retardants used in polyurethane foams, but because phosphate esters have a plasticizing effect, they have the problem of causing shrinkage and a deterioration in the mechanical properties of polyurethane foam. Therefore, there is a need to reduce the amount of phosphate esters used and to find alternative flame retardants that do not adversely affect physical properties.

[0007] An alternative flame retardant is red phosphorus, which has relatively excellent flame retardancy. In fact, various flame retardant methods using red phosphorus have been proposed. For example, Patent Document 1 below discloses a flame-retardant polyurethane resin composition containing expandable graphite, polyphosphate or red phosphorus, and tricresyl phosphate in a polyurethane resin. Furthermore, Patent Document 2 listed below describes a flame-retardant urethane resin composition that contains red phosphorus as an essential component and further contains other flame retardants such as phosphate esters in combination. Furthermore, hypophosphites may be used as flame retardants in thermoplastic resins. In this case, even if the flame retardancy measured by the oxygen index is somewhat excellent, it is unclear whether they can be used for urethane resins, which are used in applications requiring higher flame retardancy than thermoplastic resins. Patent Document 3 below describes a thermoplastic polyamide composition containing a dialkyl phosphinate, which is an organic aluminum phosphinate. In this composition, the dialkyl phosphinate is selected and used in consideration of the stability of the molten thermoplastic polyamide. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2005-133054 [Patent Document 2] Japanese Patent Application Publication No. 2017-075326 [Patent Document 3] Japanese Patent Application Publication No. 2018-511685 Summary of the Invention [Problem to be solved by the invention]

[0009] However, although the red phosphorus used in Patent Documents 1 and 2 has high flame retardancy, it has a unique reddish hue, which may impart undesired coloring to the product. Furthermore, in order to balance coloring inhibition and flame retardancy, a considerable amount of a color-decoloring agent must be added, which may result in problems such as a decrease in flame retardancy and poor light resistance of the color-decoloring agent. Furthermore, red phosphorus is a flammable substance, and its handling is regulated by the Fire Service Act, making its use problematic from a safety perspective. Furthermore, the thermoplastic polyamide composition described in Patent Document 3 solves the problems inherent to flame retardant-containing thermoplastic polyamide compositions by selecting a specific organic aluminum phosphinate, and is not applicable to resins other than thermoplastic polyamides.

[0010] The present invention has been made in consideration of the above-mentioned conventional situation, and aims to provide a flame retardant composition for polyurethane foam that does not use red phosphorus, that easily forms a charred layer without melting or dripping during combustion, and that can exhibit high flame retardancy without using red phosphorus, and a flame-retardant polyurethane foam containing the flame retardant composition for polyurethane foam. The greatest challenge at present is that the above-mentioned very high level of non-combustibility criteria of the cone calorimeter test cannot be met without using red phosphorus, and therefore there is a need for a flame retardant composition that has high flame retardancy as an alternative to red phosphorus. Furthermore, there is a demand for further reduction in the amount of shrinkage and weight loss rate when heated, which are characteristic of polyurethane foams. [Means for solving the problem]

[0011]

[0006] As a result of intensive research to achieve the above object, the present inventors have found that by using a flame retardant composition containing a phosphorus compound represented by the following formula (1) and, if necessary, a concomitant flame retardant, as a flame retardant composition for polyurethane foam, it is possible to obtain polyurethane foam with excellent flame retardancy, i.e., low total heat release, low maximum heat release rate, and low weight loss, and small shrinkage and weight loss in the transverse and thickness directions after testing. That is, the present inventors have found that the use of the phosphorus compound represented by the following formula (1) makes it possible to obtain a flame retardant composition for polyurethane foam that easily forms a charred layer without melting or dripping during combustion and that exhibits high flame retardancy without using red phosphorus, and a flame-retardant polyurethane foam containing the flame retardant composition for polyurethane foam, and have completed the present invention.

[0012] That is, the present invention provides: (1) A flame retardant composition for polyurethane foam, A phosphorus compound represented by the following formula (1): and one or more combined flame retardants selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine phthalate, melamine, melamine cyanurate, ammonium polyphosphate, ammonium phosphate, zinc phosphate, non-halogenated phosphate esters, halogenated phosphate esters, bromine-based compounds, barium borate, borax, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, calcium molybdate, zinc molybdate, magnesium molybdate, magnesium silicate, hydrated gypsum, kaolin clay, mica, calcium carbonate, alumite, basic magnesium carbonate, calcium hydroxide, wollastonite, and a zeolite-structured clathrate compound of zinc hydrogen phosphate and ethylenediamine, A flame retardant composition for polyurethane foams having excellent carbonization properties, comprising 0 to 600 parts by weight per 100 parts by weight of a phosphorus compound represented by formula (1). [ka] (In the formula, M is Mg, Al, Ca, Ti, or Zn, and m is 2, 3, or 4.)

[0013] (2) The phosphorus compound represented by the formula (1) is an Al salt, The flame retardant composition for polyurethane foam according to (1), wherein the combined flame retardant is one or more flame retardants selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, diammonium hydrogen phosphate, ammonium polyphosphate, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc stannate, antimony trioxide, antimony pentoxide, non-halogenated phosphate esters, halogenated phosphate esters, decabromodiphenylethane, trisdibromoneopentyl phosphate, wollastonite, and a zeolite-structured clathrate compound of zinc hydrogen phosphate and ethylenediamine;

[0014] (3) A flexible or semi-rigid flame-retardant polyurethane foam containing the flame retardant composition for polyurethane foam according to (1) or (2), which has excellent charring properties and satisfies UL-94 V-0 without melting or dripping. (4) A flexible or semi-rigid flame-retardant polyurethane foam having excellent carbonization performance according to (3), characterized in that the flame retardant composition for polyurethane foam contains a phosphorus compound represented by formula (1) and one or more combined flame retardants selected from the group consisting of melamine, melamine cyanurate, melamine polyphosphate, ammonium polyphosphate, and zinc borate, and the combined flame retardant is contained in an amount of 0 to 100 parts by weight per 100 parts by weight of the phosphorus compound represented by formula (1).

[0015] (5) A flexible or semi-rigid flame-retardant polyurethane foam having excellent carbonization performance according to (3) or (4), which is free of red phosphorus and / or organic phosphinate. (6) A rigid flame-retardant polyurethane foam containing the flame retardant composition for polyurethane foam according to (1) or (2), which has a radiant heat intensity of 50 kW / m in a cone calorimeter test according to ISO-5660. 2 When heated at 1000kJ / m, the total heat generated after 5 minutes is 10MJ / m 2 or less, and the maximum heat generation rate exceeds 10 seconds and is 200 kW / m 2 A rigid flame-retardant polyurethane foam with excellent carbonization performance, characterized by satisfying a performance not exceeding

[0016] (7) In the ISO-5660 cone calorimeter test, the radiant heat intensity was 50 kW / m 2 When heated at 20 minutes, the total heat generated is 8MJ / m 2 A rigid flame-retardant polyurethane foam having excellent carbonization performance according to (6), characterized in that: (8) The rigid flame-retardant polyurethane foam having excellent carbonization performance according to (6), characterized in that the flame retardant composition for polyurethane foam contains a phosphorus compound represented by formula (1) and a non-halogenated phosphate ester and / or a halogenated phosphate ester as a combined flame retardant, and the combined flame retardant is contained in an amount of 0 to 600 parts by weight per 100 parts by weight of the phosphorus compound represented by formula (1). (9) The rigid flame-retardant polyurethane foam having excellent carbonization performance according to (8), characterized in that the flame retardant composition for polyurethane foam further contains zinc borate as a concomitant flame retardant. (10) A rigid flame-retardant polyurethane foam having excellent carbonization performance according to any one of (6) to (9), which does not contain red phosphorus and / or organic phosphinate. (11) The rigid flame-retardant polyurethane foam according to any one of (6) to (10), characterized in that the rigid flame-retardant polyurethane foam is formed by spray foaming. The gist of this paper is as follows. [Effects of the Invention]

[0017] According to the flame retardant composition for polyurethane foam of the present invention, a flame retardant composition for polyurethane foam that easily forms a carbonized layer without melting or dripping during combustion and that can exhibit high flame retardancy without using red phosphorus, and a flame-retardant polyurethane foam containing the flame retardant composition for polyurethane foam can be provided.

[0018] In particular, the flame retardant composition for polyurethane foam of the present invention has excellent carbonization properties during combustion, does not melt or drip, and can provide flexible or semi-rigid flame-retardant polyurethane foams that meet the flame retardancy standard UL-94 V-0. Furthermore, in the ISO-5660 cone calorimeter test, the flame retardant composition has a radiant heat intensity of 50 kW / m 2 When heated at 1000kJ / m, the total heat generated after 5 minutes is 10MJ / m 2 or less, and the maximum heat generation rate exceeds 10 seconds and is 200 kW / m 2 It is possible to provide a rigid flame-retardant polyurethane foam that satisfies the performance not exceeding the above. Furthermore, when a phosphorus compound represented by formula (1) of the present invention is added to a polyurethane foam, the maximum heat release rate during heating, which is specific to polyurethane foam, can be reduced, and the total heat release amount, shrinkage amount, and weight loss rate can be reduced, compared to when an organic phosphinate such as organic aluminum phosphinate is added to the polyurethane foam. DETAILED DESCRIPTION OF THE INVENTION

[0019] Hereinafter, embodiments of the flame-retardant polyurethane foam of the present invention will be described. [Flame retardant (formula (1) below)] The flame retardant used in the present invention is a compound represented by the following formula (1). [ka] (In the formula, M is Mg, Al, Ca, Ti, or Zn, and m is 2, 3, or 4.)

[0020] As M in the above formula (1), Al is preferred. Specific examples of the flame retardant represented by the above formula (1) include zinc phosphinate, aluminum phosphinate, magnesium phosphinate, calcium phosphinate, and the like. These phosphorus compounds represented by formula (1) are usually colorless or white powders, so they can be used without interfering with the colorability of the product. Among these, aluminum salts in particular have excellent flame retardancy and carbonization properties.

[0021] The phosphorus compound represented by the above formula (1) can be obtained by heating and reacting, in an aqueous solution, either phosphinic acid or an alkali metal salt of phosphinic acid with any one of water-soluble aluminum, zinc, magnesium, or calcium nitrates, sulfates, carbonates, and hydroxides. This is a type of acid-base reaction or salt reaction in an aqueous solution, and is advantageous in that the reaction proceeds quickly and the target compound is produced in a relatively short time of 1 to 3 hours.

[0022] In addition to the phosphorus compound of formula (1), the flame retardant composition of the present invention may also contain one or more additional flame retardants to further improve flame retardancy. Specific examples of the additional flame retardants include melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine phthalate, melamine, melamine cyanurate, ammonium polyphosphate, ammonium phosphate, zinc phosphate, non-halogenated phosphate esters, halogenated phosphate esters, bromine-based compounds, barium borate, borax, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, calcium hydroxide, antimony trioxide, antimony pentoxide, calcium molybdate, zinc molybdate, magnesium molybdate, magnesium silicate, hydrated gypsum, kaolin clay, mica, calcium carbonate, alumite, basic magnesium carbonate, wollastonite, and a zeolite-structured clathrate compound of zinc hydrogen phosphate and ethylenediamine. The blending amount of these combined flame retardants is 0 to 600 parts by weight per 100 parts by weight of the phosphorus compound represented by formula (1). However, it is preferable to use only a non-halogenated phosphate ester and / or a halogenated phosphate ester as a concomitant flame retardant for a rigid polyurethane foam, or to use a combination of a non-halogenated phosphate ester and / or a halogenated phosphate ester with another concomitant flame retardant. When a combination of a non-halogenated phosphate ester and / or a halogenated phosphate ester with another concomitant flame retardant is used, the amount of the other concomitant flame retardant is preferably 3 to 100 parts by weight, more preferably 5 to 90 parts by weight, and even more preferably 15 to 75 parts by weight, per 100 parts by weight of the phosphorus compound represented by formula (1). Examples of the non-halogenated phosphate ester, halogenated phosphate ester and bromine-based compound used as the combined flame retardant are as follows: The flame retardant composition of the present invention does not contain red phosphorus and / or organic phosphinate. Here, "not containing" means that the composition does not contain an amount sufficient to exert a flame retardant effect, or does not contain any of the above.

[0023] Non-halogenated phosphate esters Trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri(2-ethylhexyl) phosphate, tributoxyethyl phosphate, triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate, tris(isopropylphenyl) phosphate, tris(phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, resorcinol bis(diphenyl) phosphate, bisphenol A bis(diphenyl) phosphate, bisphenol A bis(dicresyl) phosphate, and the like. Halogenated phosphate esters Tris(chloroethyl) phosphate, tris(β-chloropropyl) phosphate, tris(dichloropropyl) phosphate, tetrakis(2-chloroethyl)dichloroisopentyl diphosphate, polyoxyalkylene bis(dichloroalkyl) phosphate, poly[oxy[(2-chloro-1-methylethoxy)phosphinylidene]oxy-1,2-ethanediyloxy-1,2-ethanediyl], α-(2-chloro-1-methylethyl)-ω-[[bis(2-chloro-1-methylethoxy)phosphinyl]oxy], and the like. Bromine compounds Hexabromobenzene, pentabromotoluene, decabromodiphenylethane, tetrabromobisphenol A, dibromoneopentyl glycol, tribromoneopentyl alcohol, trisdibromoneopentyl phosphate, etc.

[0024] Among the combinations of the phosphorus compound of formula (1) and the concomitant flame retardant, it is preferred that the phosphorus compound is an aluminum salt and the concomitant flame retardant is one or more kinds of concomitant flame retardants selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, diammonium hydrogen phosphate, ammonium polyphosphate, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc stannate, antimony trioxide, antimony pentoxide, non-halogenated phosphate esters, halogenated phosphate esters, decabromodiphenylethane, trisdibromoneopentyl phosphate, wollastonite, and zeolite-structured clathrate compounds of zinc hydrogen phosphate and ethylenediamine. Among these combined flame retardants, it is more preferable to use one or more combined flame retardants selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, zinc borate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, non-halogenated phosphate esters, halogenated phosphate esters, decabromodiphenylethane, and zeolite-structured clathrate compounds of zinc hydrogen phosphate and ethylenediamine. The blending ratio of the phosphorus compound of formula (1) and the combined flame retardant is preferably 0 to 600 parts by weight, more preferably 0 to 400 parts by weight, in total of at least one compound of the combined flame retardant, per 100 parts by weight of the phosphorus compound of formula (1) of the present invention.

[0025] The amount of the flame retardant composition added to the polyurethane foam of the present invention is in the range of 2 to 200 parts by weight, preferably 10 to 150 parts by weight, per 100 parts by weight of polyol. If the amount added exceeds 200 parts by weight, the foaming ability of the polyurethane foam may be inhibited, and if it is less than 2 parts by weight, sufficient flame retardancy may not be obtained.

[0026] [Flame-retardant polyurethane foam] The flame-retardant polyurethane foam of the present invention is produced by foaming a polyurethane foam formulation containing polyol, isocyanate, catalyst, blowing agent, and flame retardant as essential raw materials, and optionally further containing a crosslinking agent, foam stabilizer, and other additives. Each component will be described below.

[0027] [Flame retardant composition] The flame retardant composition used in the present invention contains the phosphorus compound of formula (1) as an essential component, and may further contain a concomitant flame retardant, if necessary. When a concomitant flame retardant is added, the blending ratio of each is 0 to 600 parts by weight of the concomitant flame retardant per 100 parts by weight of the phosphorus compound of formula (1). The phosphorus compound of formula (1) may be a salt of Mg, Al, Ca, Ti, or Zn. The flame retardant used in combination may be one or more selected from the group consisting of melamine phosphate, melamine pyrophosphate, melamine polyphosphate, melamine phthalate, melamine, melamine cyanurate, ammonium polyphosphate, ammonium phosphate, zinc phosphate, non-halogenated phosphate esters, halogenated phosphate esters, bromine-based compounds, barium borate, borax, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, calcium molybdate, zinc molybdate, magnesium molybdate, magnesium silicate, hydrated gypsum, kaolin clay, mica, calcium carbonate, alumite, basic magnesium carbonate, calcium hydroxide, wollastonite, and a zeolite-structured clathrate compound of zinc hydrogen phosphate and ethylenediamine.

[0028] In the combination of the phosphorus compound of formula (1) and the concomitant flame retardant, the most preferable flame retardant performance is exhibited when an aluminum salt is used as the phosphorus compound of formula (1) and one or more flame retardants selected from the group consisting of melamine, melamine cyanurate, melamine phosphate, melamine polyphosphate, diammonium hydrogen phosphate, ammonium polyphosphate, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc stannate, antimony trioxide, antimony pentoxide, non-halogenated phosphate esters, halogenated phosphate esters, decabromodiphenylethane, trisdibromoneopentyl phosphate, wollastonite, and zeolite-structured clathrate compounds of zinc hydrogen phosphate and ethylenediamine are used as the concomitant flame retardant.

[0029] Furthermore, for flexible or semi-rigid flame-retardant urethane foams, the phosphorus compound of formula (1) alone exhibits excellent flame-retardant performance, and furthermore, when used in combination with melamine, melamine cyanurate, melamine polyphosphate, ammonium polyphosphate, or zinc borate as a concomitant flame retardant, favorable flame-retardant performance is also exhibited. For rigid flame-retardant urethane foams, favorable flame-retardant performance is exhibited when the phosphorus compound of formula (1) is used in combination with a non-halogenated phosphate ester and / or a halogenated phosphate ester as a combined flame retardant, and favorable flame-retardant performance is also exhibited when a non-halogenated phosphate ester and / or a halogenated phosphate ester is used in combination with zinc borate as another flame retardant.

[0030] [Polyol] The polyol used in the present invention is not particularly limited, and any of the polyols typically used as raw material polyols for polyurethane foams, such as polyether polyols, polyester polyols, and phenolic polyols, can be suitably used. A polyester polyol can be used alone, or a polyester polyol and a polyether polyol can be used in combination. Examples of polyester polyols include polyhydric alcohol-polycarboxylic acid condensation polyester polyols and polyester polyols of cyclic ester ring-opening polymers. Examples of polyhydric alcohols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, butanediol, hexanediol, trimethylolpropane, and methylpropanediol. Examples of carboxylic acids include succinic acid, adipic acid, sebacic acid, maleic acid, phthalic anhydride, isophthalic acid, and terephthalic acid. Examples of ring-opening systems include polyester polyols obtained by ring-opening addition polymerization of ε-caprolactone with glycol.

[0031] [Isocyanate] The isocyanate used in the present invention may be a compound having at least two isocyanate groups, including, but not limited to, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), triphenyl diisocyanate, polymethylene polyphenyl polyisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate.

[0032] [catalyst] Catalysts known for use in polyurethane foams can be used. Examples include amine catalysts such as triethylamine, triethylenediamine, diethanolamine, dimethylaminomorpholine, N-ethylmorpholine, N,N-dimethylcyclohexylamine, and tetramethylguanidine; tin catalysts such as stannous octoate and dibutyltin dilaurate; nitrogen-containing aromatic compounds such as tris(dimethylaminomethyl)phenol, 2,4-bis(dimethylaminomethyl)phenol, and 2,4,6-tris(dialkylaminoalkyl)hexahydro-S-triazine; alkali metal salts of carboxylic acids such as potassium acetate, potassium 2-ethylhexanoate, and potassium octoate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt, and triphenylammonium salt; and quaternary ammonium salts such as tetramethylammonium salt, tetraethylammonium, and tetraphenylammonium salt. These catalysts can be used alone or in combination. The amount of catalyst used is preferably 0.1 to 10 parts by weight per 100 parts by weight of polyol.

[0033] [Foaming agent] Examples of blowing agents that can be used include organic physical blowing agents such as water, low-boiling hydrocarbons such as propane and butane; chlorinated aliphatic hydrocarbon compounds such as dichloroethane and butyl chloride; fluorine compounds such as hydrofluoroolefins (HFOs) such as trichloromonofluoromethane, trichlorotrifluoroethane, and trans-1-chloro-3,3,3-trifluoropropene; hydrochlorofluorocarbon compounds such as dichloromonofluoroethane, chlorodifluoromethane, and 1-chloro-1,1-difluoroethane; hydrofluorocarbon compounds such as 1,1,1,3,3-pentafluoropropane and 1,1,1,3,3-pentafluorobutane; ether compounds such as diisopropyl ether; and inorganic physical blowing agents such as nitrogen gas, oxygen gas, argon gas, and carbon dioxide gas. These blowing agents can be used alone or in combination. The amount of these blowing agents used is preferably 1 to 40 parts by weight per 100 parts by weight of polyol.

[0034] [Other additives] The resin composition for polyurethane foam of the present invention may contain, as necessary, various components other than the polyol component, polyisocyanate component, flame retardant, concomitant flame retardant, catalyst, and blowing agent, such as a foam stabilizer, crosslinking agent, foaming aid, dehydrating agent, plasticizer, weathering agent, colorant, and filler, in amounts that do not impair the effects of the present invention. These various components may be added to the polyol component or polyisocyanate component in advance, or they may be added when the polyol component and polyisocyanate component are mixed.

[0035] Examples of the foam stabilizer include commercially available foam stabilizers used in the production of polyurethane foam. While not particularly limited, examples of the foam stabilizer include surfactants, such as organic silicone surfactants, including nonionic surfactants such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. The amount of the silicone compound foam stabilizer is preferably 0.5 parts by weight or more relative to 100 parts by weight of the polyol.

[0036] [Production of flame-retardant polyurethane foam] The method for producing the polyurethane foam containing the flame retardant composition of the present invention is not particularly limited, and it can be produced by a conventional method. Specifically, the polyurethane foam can be produced by a known foaming method in which polyurethane foam raw materials containing the polyol, isocyanate, catalyst, blowing agent, foam stabilizer, and flame retardant are stirred, mixed, and reacted.

[0037] There are two foaming methods: slab foaming and mold foaming, and either molding method can be used. Slab foaming is a method in which mixed polyurethane foam raw materials are discharged onto a belt conveyor and foamed at atmospheric pressure and room temperature (20±15°C). On the other hand, mold foaming is a method in which mixed foam raw materials are filled into a mold (forming tool) and foamed inside the mold. These foaming methods are intended for producing what are called flexible or semi-rigid polyurethane foams.

[0038] Another foaming method is the in-situ foaming method, which refers to a so-called rigid polyurethane foam produced by mechanically or manually foaming a polyurethane foam resin composition at the molding site. This method employs spray foaming, specifically, a polyurethane foam molding method in which the polyurethane foam resin composition is sprayed in a mist form by a foaming machine and sprayed directly onto the target object, thereby simultaneously foaming and adhering the polyurethane foam to the target object.

[0039] Since it is difficult to control the temperature in in-situ spray foaming, the resin composition for polyurethane foam used is preferably one that has low viscosity and is easy to handle even at room temperature (20±15°C), and this method is a production method for what is generally called rigid polyurethane foam. The density of the flame-retardant polyurethane foam of the present invention is 30 to 120 kg / m in the case of a rigid flame-retardant polyurethane foam. 3 and more preferably 40 to 90 kg / m 3 and for flexible and semi-rigid flame-retardant polyurethane foams, it is 10 to 70 kg / m 3 is preferable, and more preferably 20 to 60 kg / m 3 is.

[0040] The flame retardant composition of the present invention can be used for any of rigid, semi-rigid and flexible polyurethane foams, and the uses of the resulting flame retardant polyurethane foam are not limited to automotive sound absorbing, sound deadening and vibration insulating materials and building heat insulating materials. For example, the flame retardant composition can also be used for heat insulating materials or interior materials for vehicles, railways, aircraft and ships, such as seat cushions, floor carpets, ceiling materials, engine filters, oil filters, insulators, cushioning materials for furniture, electrical components (for filling gaps in wiring cable boxes, piping penetrations and the like), packaging materials, cushioning materials, etc. [Example]

[0041] The present invention will be explained in more detail below with reference to examples and comparative examples, but the technical scope of the present invention is not limited to the following examples. In the following examples, unless otherwise specified, "%" refers to % by weight and "parts" refers to parts by weight. Each flame-retardant polyurethane foam was evaluated by the following method.

[0042] [Evaluation of flame retardancy, etc.] (Sample preparation) Rigid and flexible polyurethane foams were produced by the following method and subjected to tests for flame retardancy and the like. Rigid polyurethane foam sample preparation method The polyol compound, foam stabilizer, amine catalyst, and polymerization catalyst were weighed into a 1000 mL polypropylene beaker and stirred at 20° C. for 30 seconds with a stirrer. The flame retardant component was added to the mixture after stirring and mixed with a stirrer. Next, water and a blowing agent such as HFO were added and mixed, and finally, organic isocyanate (Cosmonate M-200) was added and stirred vigorously for about 10 seconds until the density reached 60 kg / m 3 A foam of 1000g was prepared. Flexible polyurethane foam sample preparation method The polyol compound, water as a blowing agent, catalyst, foam stabilizer, and other additives as required were placed in a 1000 mL polypropylene beaker and stirred at 25° C. for 30 seconds with a stirrer. After stirring, the flame retardant component was added to the mixture and mixed with a mixer. Finally, organic isocyanate (Millionate MR-200) was added and stirred vigorously for about 10 seconds until the density reached 29 kg / m 3 A foam of 1000g was prepared.

[0043] (Evaluation method) Rigid polyurethane foam Cone Calorimeter Test A 10cm x 10cm x 5cm cone calorimeter test sample was cut out from the rigid polyurethane foam prepared by the above method, and the sample was measured in accordance with ISO-5660 with a radiant heat intensity of 50kW / m 2 The total heat generated when heated for 5, 10, and 20 minutes is 200 kW / m 2 Over time, the maximum heat release rate was measured. This measurement method is a test method specified by the General Building Testing Laboratory, a public institution stipulated in Article 108-2 of the Enforcement Order of the Building Standards Act, as a method that corresponds to the standards based on the cone calorimeter method.

[0044] (density measurement) The dimensions of the cone calorimeter test sample were measured using a vernier caliper, and the mass was measured using an electronic balance, and the density was calculated from the measured values.

[0045] (Evaluation of residue condition) After the ISO-5660 test, if cracks or holes penetrating to the back surface were visually observed in the sample, it was rated as "present," and if no deformation reaching the back surface was observed, it was rated as "absent."

[0046] (Measurement of shrinkage) After the ISO-5660 test, the distance the sample deformed from 10 cm in the horizontal direction and from 5 cm in thickness was measured relative to its original dimensions. Expansion was marked "+", and contraction was marked "-". This is because if there is a large amount of contraction or expansion when a fire occurs, cracks or peeling from the wall may occur, which may lead to continued combustion, so it is desirable to have as little expansion and contraction as possible.

[0047] (weight reduction) The mass of the sample before and after the ISO-5660 test was measured using an electronic balance, and the weight loss rate was calculated from the obtained measurements.

[0048] Soft polyurethane foam UL-94V test Test pieces measuring 127 mm in length, 12.7 mm in width, and 3.0 mm in thickness were prepared from the flexible polyurethane foam prepared by the above method. A vertical combustion test was carried out in accordance with the UL-94V standard. V-0 is the highest rating, with flame retardancy decreasing as the rating goes down to V-1 and V-2. However, materials that did not fall into any of the V-0 to V-2 ratings were given a NC rating.

[0049] (Evaluation results) Regarding the flame retardancy test of rigid polyurethane foam, the evaluation results of the examples and comparative examples are shown in Tables 1 and 2. Furthermore, the criteria for the evaluation results in Table 2 based on the above-mentioned cone calorimeter test are as follows: Non-flammable: Total heat generation after 20 minutes of heating is 8.0MJ / m 2 below Semi-non-flammable: Total heat generation after 10 minutes of heating is 8.0MJ / m 2 below Flame retardant: Total heat generation after 5 minutes of heating is 8.0MJ / m 2 below

[0050] [Table 1-1]

[0051] [Table 1-2]

[0052] [Table 2]

[0053] Polyester polyol: Actocol ES-258N (Mitsui Chemicals SKC Polyurethanes Co., Ltd.) Polyether polyol: Actocol T-700S (Mitsui Chemicals SKC Polyurethanes Co., Ltd.) Phthalic acid polyol: Maximol RFK-505 (Kawasaki Chemical Industries, Ltd.) Silicone foam stabilizer: NIAX L-6620 (MOMENTIVE) Amine catalyst: N,N-dimethylcyclohexylamine Polymerization catalyst (13%): Potassium octylate TMCPP; Tris(β-chloropropyl)phosphate (Daihachi Chemical Industry Co., Ltd.) Polyoxyalkylene bis(dichloroalkyl) phosphate; CR-504L (Daihachi Chemical Industry Co., Ltd.) Tris(dichloropropyl)phosphate; Tris(dichloropropyl)phosphate (Tokyo Chemical Industry Co., Ltd.) Cresyl diphenyl phosphate; CDP (Daihachi Chemical Industry Co., Ltd.) Resorcinol bis(diphenyl)phosphate; CR-733S (Daihachi Chemical Industry Co., Ltd.) Zinc borate; ZB2335 (Kinseimatec Co., Ltd.) Zinc stannate; ZHS (Kinseimatec Co., Ltd.) Magnesium hydroxide; Kisma 5A (Kyowa Chemical Industry Co., Ltd.) Aluminum hydroxide; Hijilite H-32 (Showa Denko K.K.) Zinc molybdate; Zinc molybdate (Kojundo Chemical Laboratory Co., Ltd.) Melamine phosphate; BUDIT310 (CBC Co., Ltd.) Melamine polyphosphate; BUDIT3141 (CBC Corporation) Diammonium phosphate; Diammonium hydrogen phosphate (Taihei Chemical Industry Co., Ltd.) Ammonium polyphosphate; FR CROS484 (CBC Co., Ltd.) Aluminum tris(diethylphosphinate) (organoaluminum phosphinate); EXOLIT OP930 (Clariant Chemicals) Decabromodiphenylethane; SAYTEX8010 (Albemarle Japan Co., Ltd.) Trisdibromoneopentyl phosphate; CR-900 (Daihachi Chemical Industry Co., Ltd.) Antimony trioxide; Antimony trioxide (Suzuhiro Chemical Co., Ltd.) Antimony pentoxide; BurnEx 30-107 (NYACOL Nano Technologies, Inc.) Wollastonite; SH-400 (Kinseimatec Co., Ltd.) Zinc hydrogen phosphate; Firecut ZPO-3 (Suzuhiro Chemical Co., Ltd.) A clathrate compound of zeolite-structured zinc hydrogen phosphate and ethylenediamine Red phosphorus; Nova Excel 140 (Rinkagaku Sangyo Co., Ltd.) HFO; HFO-1233zdE (Honeywell Japan, Ltd.) Polymethylene polyphenyl polyisocyanate; Cosmonate M-200 (Mitsui Chemicals SKC Polyurethanes Co., Ltd.)

[0054] The index in Tables 1-1 and 1-2 is defined as (equivalents of polyisocyanate) ÷ (equivalents of polyol + equivalents of water). Here, the equivalents of the polyol compound are expressed as [hydroxyl value of polyol compound (mg KOH / g)] × [weight of polyol compound (g)] ÷ [molecular weight of potassium hydroxide]. The equivalents of the polyisocyanate are expressed as [molecular weight of polyisocyanate group] × 100 ÷ [weight % of isocyanate group], and the equivalents of water are expressed as [weight of water (g)] × 2 ÷ [molecular weight of water].

[0055] Regarding the flame retardancy test of flexible polyurethane foams, the evaluation results of Examples and Comparative Examples are shown in Table 3.

[0056] [Table 3]

[0057] Polyether polyol: Sannix GP-3000V (Sanyo Chemical Industries, Ltd.) Triethylenediamine dipropylene glycol solution; TEDA-L33 (Tosoh Corporation) Stannous octoate; MRH-110 (Johoku Chemical Industry Co., Ltd.) Silicone foam stabilizer: L-540 (Dow Corning Toray Co., Ltd.) Melamine cyanurate; STABIACE MC-2010N (Sakai Chemical Industry Co., Ltd.) Melamine (Mitsui Chemicals, Inc.) Melamine polyphosphate; BUDIT3141 (CBC Corporation) Ammonium polyphosphate; FR CROS484 (CBC Co., Ltd.) Zinc borate; ZB2335 (Kinseimatec Co., Ltd.) TMCPP; Tris(β-chloropropyl)phosphate (Daihachi Chemical Industry Co., Ltd.) Polymeric MDI (Tosoh Corporation)

[0058] As can be seen from Tables 1-1 and 1-2, the flame-retardant polyurethane foam using the flame retardant of the present invention has the same or higher flame retardancy and a lower maximum heat release rate as the foam using the red phosphorus flame retardant, while also having a lower total heat release value at 5 minutes and maintaining good physical properties as a foam. According to the results shown in Table 2, when the flame retardant of the present invention was used for polyurethane foam, the density was lower than when organic aluminum phosphinate was used, and the total heat release amount, maximum heat release rate, and weight loss rate at 5 minutes, 10 minutes, and 20 minutes were all lower. The polyurethane foam also had small shrinkage amounts and weight loss rates in the transverse and thickness directions after the test, and was non-flammable. Furthermore, the results in Table 3 show that when the composition of the present invention is used in a flexible polyurethane foam, high flame retardancy can be achieved even at a lower density.

Claims

1. A flame retardant composition for polyurethane foams, comprising a polyol compound including a polyester-based polyol and a polymerization catalyst, A phosphorus compound represented by the following formula (1): and containing 15 to 600 parts by weight in total of one or more selected from tris(β-chloropropyl)phosphate, polyoxyalkylene bis(dichloroalkyl)phosphate, and tris(dichloropropyl)phosphate, and the following other combined flame retardants per 100 parts by weight of the phosphorus compound represented by the following formula (1), Furthermore, one or more other flame retardants selected from the group consisting of melamine phosphate, melamine cyanurate, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, and a zeolite-structured zinc hydrogen phosphate and ethylenediamine clathrate compound, The phosphorus compound represented by the following formula (1) contains 15 to 75 parts by weight per 100 parts by weight, and has a radiant heat intensity of 50 kW / m in a cone calorimeter test according to ISO-5660. ２ When heated at 1000kJ / m, the total heat generated after 5 minutes was 10 MJ / m ２ or less, and the maximum heat generation rate exceeds 10 seconds and is 200 kW / m ２ A flame retardant composition for polyurethane foams for obtaining rigid flame-retardant polyurethane foams that satisfy the performance not exceeding 1. 【Chemical 1】 (In the formula, M is Mg, Al, Ca, Ti, or Zn, and m is 2, 3, or 4.) However, this does not include cases where a composite flame retardant of aerogel powder and a phosphate ester flame retardant is contained, cases where clay is contained, and cases where expandable graphite is contained.

2. the phosphorus compound represented by formula (1) is a salt of Al, 2. The flame retardant composition for polyurethane foam according to claim 1, wherein the other concomitant flame retardant is one or more flame retardants selected from the group consisting of melamine cyanurate, melamine phosphate, magnesium hydroxide, aluminum hydroxide, zinc borate, zinc stannate, antimony trioxide, antimony pentoxide, and a zeolite-structured clathrate compound of zinc hydrogen phosphate and ethylenediamine.

3. A phosphorus compound represented by the following formula (1): 【Chemical 1】 (In the formula, M is Mg, Al, Ca, Ti, or Zn, and m is 2, 3, or 4.) and one or more selected from tris(β-chloropropyl)phosphate, polyoxyalkylene bis(dichloroalkyl)phosphate, and tris(dichloropropyl)phosphate, and the following other combined flame retardants are contained in a total amount of 15 to 600 parts by weight per 100 parts by weight of the phosphorus compound represented by the above formula (1), Furthermore, one or more other flame retardants selected from the group consisting of melamine phosphate, melamine cyanurate, zinc borate, zinc stannate, magnesium hydroxide, aluminum hydroxide, antimony trioxide, antimony pentoxide, and a zeolite-structured zinc hydrogen phosphate and ethylenediamine clathrate compound, A rigid flame-retardant polyurethane foam produced by blending a flame retardant composition for polyurethane foam containing a polyol compound including a polyester polyol, in which the polyol compound contains 15 to 75 parts by weight per 100 parts by weight of the phosphorus compound represented by formula (1), and a polymerization catalyst, A rigid flame-retardant polyurethane foam with excellent carbonization performance, characterized by satisfying the following performance characteristics: when heated at a radiant heat intensity of 50 kW / m 2 in an ISO-5660 cone calorimeter test, the total heat release amount after 5 minutes is 10 MJ / m 2 or less, and the maximum heat release rate does not exceed 200 kW / m 2 in more than 10 seconds. However, this does not include the cases where the flame retardant composition for polyurethane foam contains a composite flame retardant of the above-mentioned aerogel powder and a phosphate ester-based flame retardant, where clay is contained, or where expandable graphite is contained.

4. In the ISO-5660 cone calorimeter test, the radiant heat intensity was 50kW / m ２ When heated at 20 minutes, the total heat generated was 8 MJ / m ２ 4. The rigid flame-retardant polyurethane foam having excellent carbonization properties according to claim 3, wherein:

5. 5. The rigid flame-retardant polyurethane foam having excellent carbonization resistance according to claim 3, wherein the flame retardant composition for polyurethane foam further contains zinc borate as another concomitant flame retardant.

6. 6. The rigid flame-retardant polyurethane foam having excellent carbonization properties according to any one of claims 3 to 5, which does not contain red phosphorus and / or organic phosphinate.

7. 7. The rigid flame-retardant polyurethane foam having excellent carbonization resistance according to claim 3, wherein the rigid flame-retardant polyurethane foam is formed by spray foaming.

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