JP2015193839A - flame-retardant urethane resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a flame-retardant urethane resin composition excellent in flame resistance and handleability.SOLUTION: The flame-retardant urethane resin composition contains a polyisocyanate compound, a polyol compound, a trimerization catalyst, foaming agent, a foam stabilizer, and an additive, where the trimerization catalyst is 0.1 to 10 pts.wt. based on 100 pts.wt. of an urethane resin consisting of the polyisocyanate compound and the polyol compound, and the additive contains red phosphorus of 3.5 to 20 pts.wt. and water content discharging material of 4 to 30 pts.wt.

Description

  The present invention relates to a flame retardant urethane resin composition.

  Rigid polyurethane foam is used as a thermal insulation layer for concrete in buildings such as houses, various facilities, and commercial buildings. As one of the performance required for such rigid polyurethane foam, the spread of buildings due to fire is spread. Fire resistance is required to prevent it.

  As a polyurethane resin composition constituting a rigid polyurethane foam, a halogen-based flame retardant generates a large amount of toxic gas at the time of a fire, so a non-halogen-based flame retardant resin composition not containing a halogen-based flame retardant is used. It is becoming.

  Patent Document 1 describes a method for producing a flame-retardant polyurethane foam containing red phosphorus as a flame retardant. Patent Document 2 describes a non-halogen flame retardant resin composition containing a metal hydroxide as a flame retardant.

Special table 2012-532237 JP 2006-8940

  However, as in Patent Document 1, when red phosphorus is used as a flame retardant, flame retardance is not expressed unless a large amount of red phosphorus is added, and if the content is too large, red phosphorus itself is flammable. Therefore, there exists a problem that the flame retardance of a polyurethane resin composition is impaired.

  Further, when a metal hydroxide is used as a flame retardant, flame retardancy is not exhibited unless a large amount of metal hydroxide is added.

  An object of the present invention is to provide a flame retardant urethane resin composition excellent in flame retardancy and handleability.

  In the flame retardant urethane composition containing a polyisocyanate, a polyol, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive, red phosphorus and metal hydroxide are added as a specific ratio as an additive. It has been found that a flame retardant synergistic effect can be obtained even if the total amount of the additives is small by containing the water-releasing substance such as and the like, and the present invention has been completed.

  That is, the present invention is as follows.

  Item 1. A polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive, and the trimerization catalyst is 0.1 parts per 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. The flame retardant urethane resin composition, wherein the additive contains 3.5 to 20 parts by weight of red phosphorus and 4 to 30 parts by weight of a moisture releasing substance.

  Item 2. Item 2. The flame-retardant urethane resin composition according to Item 1, wherein the moisture-releasing material has a weight loss rate in the range of 200 to 500 ° C measured by thermogravimetric analysis of 15% or more.

  According to this invention, it is providing the flame-retardant urethane resin composition which can express a flame retardance with addition of a small amount of flame retardant, and was excellent in handling.

The graph of the thermogravimetric analysis (TG) and the differential thermal analysis (DTA) of the flame-retardant urethane resin composition of the Example of this invention.

  Hereinafter, the flame-retardant urethane composition according to the present invention will be described.

The flame retardant urethane resin composition of the present invention includes a polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer and an additive, and is based on 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. The trimerization catalyst is 0.1 to 10 parts by weight, and the additive contains 3.5 to 20 parts by weight of red phosphorus and 4 to 30 parts by weight of the moisture releasing substance.
Examples of the polyisocyanate compound that is a main component of the polyisocyanate compound urethane resin include aromatic polyisocyanate, alicyclic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include phenylene diisocyanate, tolylene diisocyanate, xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, triphenylmethane triisocyanate, naphthalene diisocyanate, polymethylene polyphenyl polyisocyanate, and the like.

  Examples of the alicyclic polyisocyanate include cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and dimethyldicyclohexylmethane diisocyanate.

  Examples of the aliphatic polyisocyanate include methylene diisocyanate, ethylene diisocyanate, propylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate.

One or two or more polyisocyanates can be used. The main component of the urethane resin is preferably diphenylmethane diisocyanate for reasons such as ease of use and availability.
Examples of the polyol compound is a polyol compound urethane resin curing agent, for example, polylactone polyols, polycarbonate polyols, aromatic polyols, alicyclic polyols, aliphatic polyols, polyester polyols, polymer polyols, polyether polyols, and the like.

  Examples of the polylactone polyol include polypropiolactone glycol, polycaprolactone glycol, and polyvalerolactone glycol.

  Examples of the polycarbonate polyol include a polyol obtained by a dealcoholization reaction of a hydroxyl group-containing compound such as ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, octanediol, and nonanediol with diethylene carbonate, dipropylene carbonate, and the like. Etc.

  Examples of the aromatic polyol include bisphenol A, bisphenol F, phenol novolac, and cresol novolak.

  Examples of the alicyclic polyol include cyclohexanediol, methylcyclohexanediol, isophoronediol, dicyclohexylmethanediol, dimethyldicyclohexylmethanediol, and the like.

  Examples of the aliphatic polyol include ethylene glycol, propylene glycol, butanediol, pentanediol, and hexanediol.

  Examples of the polyester polyol include a polymer obtained by dehydration condensation of a polybasic acid and a polyhydric alcohol, a polymer obtained by ring-opening polymerization of a lactone such as ε-caprolactone and α-methyl-ε-caprolactone, Examples thereof include condensates of hydroxycarboxylic acid and the above polyhydric alcohol.

  Specific examples of the polybasic acid include adipic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, and succinic acid. Specific examples of the polyhydric alcohol include bisphenol A, ethylene glycol, 1,2-propylene glycol, 1,4-butanediol, diethylene glycol, 1,6-hexane glycol, neopentyl glycol, and the like. .

  Specific examples of the hydroxycarboxylic acid include castor oil, a reaction product of castor oil and ethylene glycol, and the like.

  Examples of the polymer polyol include a polymer obtained by graft polymerization of an ethylenically unsaturated compound such as acrylonitrile, styrene, methyl acrylate, and methacrylate on an aromatic polyol, alicyclic polyol, aliphatic polyol, polyester polyol, or the like, polybutadiene Examples thereof include polyols, modified polyols of polyhydric alcohols, and hydrogenated products thereof.

  Examples of the modified polyol of the polyhydric alcohol include those modified by reacting the raw material polyhydric alcohol with an alkylene oxide.

  Examples of the polyhydric alcohol include trihydric alcohols such as glycerin and trimethylolpropane; pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc., sucrose, glucose, mannose, fructose, methylglucoside and Tetravalent to octavalent alcohols such as derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1,3,6,8-tetrahydroxynaphthalene Phenol polybutadiene polyols such as anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene; castor oil polyol; hydroxyalkyl (meth) acrylate Polyfunctional (e.g. functionality 2 to 100) polyol such as (co) polymers and polyvinyl alcohol rate, and condensation products of phenol and formaldehyde (novolac) is.

  The method for modifying the polyhydric alcohol is not particularly limited, but a method of adding alkylene oxide (hereinafter abbreviated as AO) is preferably used.

As AO, C2-C6 AO, for example, ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propyloxide, 1,2- Examples include butylene oxide and 1,4-butylene oxide.
Among these, from the viewpoints of properties and reactivity, PO, EO, and 1,2-butylene oxide are preferable, and PO and EO are more preferable. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  As the polyether polyol, for example, in the presence of at least one low molecular weight active hydrogen compound having two or more active hydrogens, at least one alkylene oxide such as ethylene oxide, propylene oxide or tetrahydrofuran is subjected to ring-opening polymerization. The polymer obtained by making it contain is mentioned.

  Examples of the low molecular weight active hydrogen compound having two or more active hydrogens include diols such as bisphenol A, ethylene glycol, propylene glycol, butylene glycol, and 1,6-hexanediol, and triols such as glycerol and trimethylolpropane. And amines such as ethylenediamine and butylenediamine.

  The polyol used in the present invention is preferably a polyester polyol or a polyether polyol because the effect of reducing the total calorific value upon combustion is great.

  Among them, it is more preferable to use a polyester polyol having a molecular weight of 200 to 800, and it is more preferable to use a polyester polyol having a molecular weight of 300 to 500.

  The isocyanate index is an equivalent ratio of the isocyanate group of the polyisocyanate to the hydroxyl group of the polyol as a percentage. A value exceeding 100 means that the isocyanate group is in excess of the hydroxyl group.

  The range of the isocyanate index of the urethane resin used in the present invention is preferably in the range of 120 to 1000, more preferably in the range of 200 to 800, and even more preferably in the range of 300 to 600.

Trimerization catalyst The trimerization catalyst causes the isocyanate group contained in polyisocyanate, which is the main component of the polyurethane resin, to react and trimerize to promote the formation of an isocyanurate ring.

  In order to promote the formation of an isocyanurate ring, for example, as a trimerization catalyst, tris (dimethylaminomethyl) phenol, 2,4-bis (dimethylaminomethyl) phenol, 2,4,6-tris (dialkylaminoalkyl) Nitrogen-containing aromatic compounds such as hexahydro-S-triazine; alkali metal carboxylates such as potassium acetate and potassium 2-ethylhexanoate; tertiary ammonium salts such as trimethylammonium salt, triethylammonium salt and triphenylammonium salt; tetra Quaternary ammonium salts such as methylammonium salt, tetraethylammonium salt, and tetraphenylammonium salt can be used.

  The addition amount of the trimerization catalyst used in the flame retardant urethane composition is usually in the range of 0.1 to 10 parts by weight, and 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. The range is preferably from 0.6 parts by weight to 8 parts by weight, more preferably from 0.6 parts by weight to 6 parts by weight, and from 0.6 parts by weight to Most preferably, it is in the range of 3.0 parts by weight. When the amount is 0.1 parts by weight or more, there is no problem that the trimerization of the isocyanate is inhibited. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained, and the handleability is excellent.

The foaming agent used in the foaming agent flame-retardant urethane composition promotes foaming of the urethane resin.

Specific examples of the blowing agent include, for example, water, propane, butane, pentane, hexane, heptane, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, and other low boiling hydrocarbons, dichloroethane, propyl chloride, isopropyl chloride, Hydrochloric compounds such as chlorinated aliphatic hydrocarbon compounds such as butyl chloride, isobutyl chloride, pentyl chloride and isopentyl chloride, fluorine compounds such as trichloromonofluoromethane and trichlorotrifluoroethane, and hydrous such as CHF ₃ , CH ₂ F ₂ and CH ₃ F Fluorocarbons, dichloromonofluoroethane (eg, HCFC141b (1,1-dichloro-1-fluoroethane), HCFC22 (chlorodifluoromethane), HCFC142b (1-chloro-1,1-difluoroethane)), Hydrochlorofluorocarbon compounds such as HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), and ether compounds such as diisopropyl ether Or organic physical foaming agents such as mixtures of these compounds, inorganic physical foaming agents such as nitrogen gas, oxygen gas, argon gas and carbon dioxide gas.

  The range of the foaming agent is preferably in the range of 0.1 to 30 parts by weight with respect to 100 parts by weight of the urethane resin. The foaming agent is more preferably in the range of 0.1 to 18 parts by weight, still more preferably in the range of 0.5 to 18 parts by weight with respect to 100 parts by weight of the urethane resin. Most preferably, it is in the range of 10 to 10 parts by weight.

  When the water range is 0.1 parts by weight or more, foaming is promoted and the density of the obtained molded product can be reduced. When the water range is 30 parts by weight or less, the foam does not foam and no foam is formed. Can be prevented.

The foam stabilizer foam stabilizer, for example, polyoxyalkylene foam stabilizer of polyoxyalkylene alkyl ether surface active agents, silicone foam stabilizer such as organopolysiloxane or the like, and the like.

  The amount of the foam stabilizer used for the urethane resin cured by the chemical reaction is appropriately set depending on the urethane resin cured by the chemical reaction used. For example, for 100 parts by weight of the urethane resin, A range of 0.1 to 10 parts by weight is preferable.

  One or two or more of the catalyst, the foaming agent and the foam stabilizer can be used.

The additive additive includes red phosphorus and a moisture releasing substance. The water-releasing substance refers to a water-containing inorganic substance that releases water when the substance itself burns.

  The content of red phosphorus is usually 3.5 to 20 parts by weight, preferably 3.5 to 15 parts by weight, more preferably 4 parts by weight, based on 100 parts by weight of a urethane resin composed of a polyisocyanate compound and a polyol compound. -10 parts by weight, more preferably 6-10 parts by weight. If the amount of red phosphorus is less than 3 parts by weight, the flame retardancy of the flame retardant urethane resin composition becomes insufficient. If the amount of red phosphorus exceeds 20 parts by weight, the red phosphorus itself is flammable. Flame retardancy is impaired.

  The content of the water-releasing substance is usually 4 to 30 parts by weight, preferably 4 to 25 parts by weight, more preferably 4 to 15 parts by weight, based on 100 parts by weight of the urethane resin composed of a polyisocyanate compound and a polyol compound. More preferably, it is 4-8 weight part. The moisture-releasing substance imparts flame retardancy to the flame retardant urethane resin composition and acts to prevent ignitability and deformation.

  When the total range of the additives is 7 parts by weight or more with respect to 100 parts by weight of the urethane resin, the molded product made of the flame retardant urethane resin composition is prevented from cracking the dense residue formed by the heat of the fire. In the case of 50 parts by weight or less, foaming of the flame retardant urethane resin composition is not inhibited.

  When the moisture-releasing substance is used alone as a flame retardant, the flame retardant urethane resin composition cannot exhibit sufficient flame retardancy, and when combined with red phosphorus in the above proportion, each is used alone. Even if it is a small amount, it has a sufficient flame retardant synergistic effect. The theory of this synergistic effect is not necessarily clear, and it is not intended to limit the invention, but when phosphoric acid reacts with water, red phosphorus, and oxygen in the air, polyphosphoric acid is produced, This is considered to impart flame retardancy by forming a film on the surface of the resin, and by adding a water-releasing substance to this, the water is further released during combustion, and the optimum conditions for generating the film appear This is an unexpected finding of the present inventors.

  Further, the weight ratio of red phosphorus to the moisture releasing substance in the flame retardant urethane resin composition is 1:10 to 5: 1, preferably 3: 1 to 1: 3. Within this range, the flame retardant urethane resin composition exhibits excellent flame retardancy.

  Examples of moisture releasing substances include inorganic flame retardants, for example, metal hydroxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide; metal compounds having crystal water such as hydrated aluminum silicate and hydrated magnesium silicate; Examples thereof include clay minerals such as kaolin clay and hydrotalcite, but are not limited thereto. One or two or more kinds of moisture releasing substances can be used.

  In particular, metal hydroxides are excellent in obtaining the effects of the present invention, and among them, trivalent metal hydroxides and alkaline earth metal hydroxides, particularly magnesium hydroxide, aluminum hydroxide and calcium hydroxide. Is preferred.

  The moisture releasing substance has a weight loss rate of 15% or more, more preferably 20% or more in a temperature range of 200 to 500 ° C., more preferably 200 to 400 ° C., more preferably 200 to 350 ° C. measured by thermogravimetric analysis. Yes, and this is thought to promote film formation during combustion of the flame retardant urethane resin composition.

  The additive may further contain at least one selected from a phosphate ester, a phosphate-containing flame retardant, and a bromine-containing flame retardant.

  The phosphate ester is not particularly limited, but it is preferable to use a monophosphate ester, a condensed phosphate ester, or the like. Phosphoric acid ester can use 1 type, or 2 or more types.

  The phosphate-containing flame retardant contains phosphoric acid. The phosphoric acid used for the phosphate-containing flame retardant is not particularly limited, and examples thereof include various phosphoric acids such as monophosphoric acid, pyrophosphoric acid, polyphosphoric acid, and combinations thereof.

  Examples of the phosphate-containing flame retardant include phosphorus composed of salts of various phosphoric acids and at least one metal or compound selected from metals of Group IA to IVB of the periodic table, ammonia, aliphatic amines, and aromatic amines. There may be mentioned acid salts. Examples of the metals of Groups IA to IVB of the periodic table include lithium, sodium, calcium, barium, iron (II), iron (III), and aluminum. One or two or more phosphate-containing flame retardants can be used.

  The bromine-containing flame retardant is not particularly limited as long as it is a compound containing bromine in the molecular structure, and examples thereof include aromatic brominated compounds. One or more bromine-containing flame retardants can be used.

The other component flame-retardant urethane composition may further contain a catalyst other than the above-mentioned trimerization catalyst. Examples of such a catalyst include triethylamine, N-methylmorpholine bis (2-dimethylaminoethyl) ether, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N′-trimethylaminoethyl-ethanolamine, bis (2-dimethylaminoethyl) ether, N-methyl, N′-dimethylamino Nitrogen atom-containing catalysts such as ethylpiperazine and imidazole compounds in which the secondary amine functional group in the imidazole ring is substituted with a cyanoethyl group.

  The addition amount of the catalyst is a total amount of the trimerization catalyst and the catalyst other than the trimerization catalyst, and is preferably in the range of 0.6 to 10 parts by weight with respect to 100 parts by weight of the urethane resin. More preferably, it is in the range of 6 parts by weight to 8 parts, more preferably in the range of 0.6 parts by weight to 6 parts by weight, and in the range of 0.6 parts by weight to 3.0 parts by weight. Most preferred.

  When the amount is 0.6 parts by weight or more, there is no problem that the formation of urethane bonds is hindered. When the amount is 10 parts by weight or less, an appropriate foaming rate can be maintained and the handling is easy.

  The flame retardant urethane composition may further contain an inorganic filler. The inorganic filler is not particularly limited. For example, silica, diatomaceous earth, alumina, wax, quartz, marble, Portland cement, titanium oxide, calcium oxide, magnesium oxide, zinc oxide, iron oxide, tin oxide, and oxidation. Antimony, ferrites, basic magnesium carbonate, calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dosonite, hydrotalcite, calcium sulfate, barium sulfate, gypsum fiber, potassium salts such as calcium silicate, talc, clay , Mica, montmorillonite, bentonite, kaolinite, activated carbon, carbon black, activated clay, sepiolite, imogolite, sericite, glass fiber, glass beads, silica parun, aluminum nitride, boron nitride, silicon nitride, carbon black, graphite, Carbon fiber, carbon parun, charcoal powder, various metal powders, potassium titanate, magnesium sulfate, lead zirconate titanate, aluminum porate, natural / synthetic mica, glass beads, sericite, sulfide ore, sulfide calcined ore, molybdenum sulfide, Examples thereof include silicon carbide, stainless steel fiber, various magnetic powders, slag fiber, fly ash, silica alumina fiber, alumina fiber, silica fiber, and zirconia fiber.

  One or more inorganic fillers can be used.

  The flame retardant urethane composition is a range that does not impair the object of the present invention, as required, such as phenol-based, amine-based, sulfur-based antioxidants, heat stabilizers, metal damage inhibitors, antistatic agents. , Stabilizers, crosslinking agents, lubricants, softeners, pigments, auxiliary components such as tackifier resins, and tackifiers such as polybutene and petroleum resins.

Flame Retardant Urethane Resin Composition and Flame Retardant Polyurethane Foam Since the above components are mixed and the flame retardant urethane resin composition reacts and cures, its viscosity changes over time. Therefore, before using the flame retardant urethane resin composition, the flame retardant urethane resin composition is divided into two or more to prevent the flame retardant urethane resin composition from reacting and curing. And when using a flame-retardant urethane resin composition, a flame-retardant urethane resin composition is obtained by putting together the flame-retardant urethane resin composition divided | segmented into two or more.

  In addition, when dividing the flame retardant urethane resin composition into two or more, each component of the flame retardant urethane resin composition divided into two or more does not start to cure, and each of the flame retardant urethane resin composition Each component may be divided so that the curing reaction starts after the components are mixed.

  Next, the manufacturing method of the said flame-retardant urethane resin composition is demonstrated. Although there is no limitation in particular in the manufacturing method of the said flame-retardant urethane resin composition, For example, the method of mixing each component of the said flame-retardant urethane resin composition, the said flame-retardant urethane resin composition is suspended in the organic solvent Or a method such as heating and melting to form a paint, a method of preparing a slurry by dispersing in a solvent, and the reaction curable resin component contained in the flame retardant urethane resin composition at room temperature When a component that is solid at (25 ° C.) is contained, the flame retardant urethane resin composition can be obtained by a method such as melting the flame retardant urethane resin composition under heating.

  The flame retardant urethane resin composition is obtained by kneading each component of the flame retardant urethane resin composition using a known device such as a Banbury mixer, a kneader mixer, a kneading roll, a lycaic machine, a planetary stirring machine, or the like. Can be obtained.

  Alternatively, the main component of urethane resin and the curing agent may be separately kneaded together with a filler or the like and kneaded with a static mixer, a dynamic mixer or the like immediately before injection.

  Further, the components of the flame retardant urethane resin composition excluding the catalyst and the catalyst may be kneaded in the same manner immediately before injection.

  The flame-retardant urethane resin composition can be obtained by the method described above.

  Next, a method for curing the flame retardant urethane resin composition will be described.

  When each component of the flame retardant urethane resin composition is mixed, the reaction starts, the viscosity increases with the passage of time, and the fluidity is lost. For example, a molded product made of a flame retardant urethane resin composition can be obtained as a flame retardant urethane resin foam by injecting the flame retardant urethane resin composition into a container such as a mold or a frame material and curing it. .

  When obtaining the molded object which consists of a flame-retardant urethane resin composition, heat can be added or a pressure can be applied.

  A molded body made of a flame retardant urethane resin composition is a polyisocyanurate foam, and is excellent in both fire resistance and heat insulation. Moreover, since the polyurethane foam heat insulation layer is a closed-cell type, it is excellent also in waterproofness and airtightness.

  The molded body made of the flame retardant urethane resin composition is preferably in the range of 0.03 to 0.13 in specific gravity because it is easy to handle, and preferably in the range of 0.04 to 0.1. The range is more preferably 0.04 to 0.08, and most preferably 0.05 to 0.06.

  Next, application examples of the flame retardant urethane resin composition according to the present invention will be described.

  A foam layer composed of a flame retardant urethane resin composition can be formed on the surface of a structure by spraying the flame retardant urethane resin composition onto a structure such as a building, furniture, automobile, train, or ship. it can.

  For example, the flame retardant urethane resin composition is divided into a polyisocyanate compound and other components, mixed while spraying both, and sprayed onto the surface of the structure, polyisocyanate compound, and other The method of spraying on the surface of the said mixture after mixing with said component is mentioned.

Fire resistant test A flame retardant polyurethane foam composed of a flame retardant urethane resin composition is cut into a length of 10 cm, a width of 10 cm and a thickness of 5 cm to prepare a sample for a corn calorimeter test.

Using the sample for corn calorimeter test, the total calorific value by the corn calorimeter test when heated at a radiant heat intensity of 50 kW / m ^{2 for} 20 minutes can be measured according to the test method of ISO-5660. .

Example 1-22 Production of Cured Foam of Flame Retardant Urethane Composition According to the formulation shown in Table 1, the flame retardant urethane resin composition according to Example 1-22 was (1) a polyol composition, (2 It was prepared by dividing into three components: polyisocyanate) and (3) additive. In addition, the detail of each component in a table | surface is as follows (The ratio of each component is shown by the weight part with respect to 100 weight part of polyisocyanurate resin).
(1) Polyol composition / polyol compound p-phthalic acid polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd., product name: Maximol RFK-505, hydroxyl value = 250 mgKOH / g)
・ Foam stabilizer Polyalkylene glycol foam stabilizer (manufactured by Toray Dow Corning, product name: SH-193)
Trimerization catalyst (A-1) Potassium 2-ethylhexanoate (Tokyo Chemical Industry Co., Ltd., product code: P0048)
(A-2) Trimerization catalyst (product name: TOYOCAT-TR20, manufactured by Tosoh Corporation)
・ Urethaneization catalyst Pentamethyldiethylenetriamine (manufactured by Tosoh Corporation, product name: TOYOCAT-DT) ・ Foaming agent
(B-1) Water
(B-2) HFC HFC-365mfc (1,1,1,3,3-pentafluorobutane, manufactured by Central Glass) and HFC-245fa (1,1,1,3,3-pentafluoropropane, Nippon Solvay) (Made by company), mixing ratio HFC-365mfc: HFC-245fa = 7: 3, hereinafter referred to as “HFC”)
(2) Polyisocyanate MDI (manufactured by Nippon Urethane Industry Co., Ltd., product name: Millionate MR-200) Viscosity: 167 mPa · s
(3) Additive (C-1) Red phosphorus (Rin Chemical Industry Co., Ltd., product name: Nova Excel 140)
(C-2) Aluminum hydroxide (C-3) Magnesium hydroxide (C-4) Calcium hydroxide In accordance with the formulation shown in Table 1 below, 1000 mL of (1) the component of the polyol composition and (3) the component of the additive Weighed in a polypropylene beaker and stirred by hand mixing at 25 ° C. for 1 minute. (2) Polyisocyanate component is added to the kneaded mixture of (1) polyol composition and (3) additive component after stirring, and foamed by worshiping for about 10 seconds with a hand mixer. did. The obtained flame-retardant urethane resin composition lost fluidity over time, and a flame-retardant urethane resin foam was obtained. The foam was evaluated according to the following criteria, and the results are shown in Table 1. [Measurement of calorific value]
When a sample for cone calorimeter test is cut out from the cured foam so as to be 10 cm long × 10 cm wide × 5 cm thick, and heated for 20 minutes at a radiant heat intensity of 50 kW / m ² in accordance with the test method of ISO-5660. The total calorific value was measured by a corn calorimeter test. The total amount of heat generated by heating 20 minutes and pass those 15 mJ / m ² or less, quasi incombustible standard ones (8 MJ / m ² or less in 10 minutes) ○, (20 minutes 8 MJ / m ²⁾ incombustible standard The thing was ◎.
[Measurement of expansion]
When the test of ISO-5660 was carried out, it was described in Table 1 as x when the molded body after expansion contacted the igniter, and as ◯ when it did not contact.
[Measurement of shrinkage]
When the test of ISO-5660 was carried out, “x” was observed when deformation of 1 cm or more in the lateral direction and 5 mm or more was observed in the thickness direction of the test sample, and “◯” when deformation was not observed. As listed in Table 1.
[Measurement of deformation (cracks and cracks)]
When the test of ISO-5660 was carried out, the deformation reaching the back surface of the test sample was indicated as x, and when the deformation reaching the back surface was not observed, it was indicated as ◯.
[Comprehensive evaluation]
If the measurement of calorie, measurement of expansion, measurement of deformation and measurement of shrinkage are all ◯ (the amount of heat is ◯ or ◎), it is marked as ◎, whether it is calorie measurement, expansion measurement, deformation measurement or shrinkage measurement The case where either was ◯ (the amount of heat was ◯ or と し) was evaluated as △, and the others were determined as ×.

Comparative Example 1-11 Production of Cured Foam of Flame Retardant Urethane Composition Using the same components as in the flame retardant urethane resin composition according to Example 1-22, the composition shown in Table 2 was compared. A flame-retardant urethane resin composition according to Example 1-11 was also produced, and the evaluation results are shown in Table 2.

Example 23 Measurement Evaluation of Thermogravimetric Analysis (TG) and Differential Thermal Analysis (DTA) of Moisture Release Material When Al (OH) ₃ , Mg (OH) ₂ and Ca (OH) ₂ were used as metal hydroxides Three thermogravimetric analyzes (TG) and differential thermal analysis (DTA) were measured using TG / DTA7300 (manufactured by Hitachi High-Tech Science Co., Ltd.). The results are shown in FIG.

  Although (1)-(3) in FIG. 1 are measured values of thermogravimetric analysis (TG), a weight reduction rate of 20% or more occurs in any metal hydroxide in the temperature range of 200 to 500 ° C. I understand.

Claims (2)

  A polyisocyanate compound, a polyol compound, a trimerization catalyst, a foaming agent, a foam stabilizer, and an additive, and the trimerization catalyst is 0.1 parts per 100 parts by weight of the urethane resin composed of the polyisocyanate compound and the polyol compound. The flame retardant urethane resin composition, wherein the additive contains 3.5 to 20 parts by weight of red phosphorus and 4 to 30 parts by weight of a moisture releasing substance.   2. The flame-retardant urethane resin composition according to claim 1, wherein the moisture-releasing material has a weight loss rate in a range of 200 to 500 ° C. measured by thermogravimetric analysis of 15% or more.