JP2015168794A - Rigid urethane foam and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a rigid urethane foam that causes no sedimentation of a solid component during storage of a polyol composition for producing a rigid urethane foam, has a practically suitable density and has very high flame retardancy and to provide a method for producing the flame-retardant rigid urethane foam.SOLUTION: The rigid urethane foam is produced by reacting (A) a polyol and (B) a polyisocyanate in the presence of (C) a catalyst, (D) a flame retardant and (E) a foaming agent under the condition that the isocyanate index is 300 or more. In the thus-produced rigid urethane foam, the polyol (A) contains an aromatic polyester polyol; the catalyst (C) contains a quarternary ammonium salt represented by formula (1); the frame retardant (D) comprises tris(2-chloropropyl)phosphate as a flame retardant which is liquid at room temperature; the amount of the flame retardant (D) used is 50-120 pts.wt. based on 100 pts.wt. of the polyol (A); and the foaming agent (E) contains a hydrogen atom-containing halogenated hydrocarbon.

Description

  The present invention relates to a rigid urethane foam and a method for producing the same.

  Rigid urethane foam is used for construction, civil engineering-related thermal insulation materials and structural materials, electrical equipment-related thermal insulation materials such as refrigerators, plant and marine thermal insulation materials, vehicle-related cold storage cabinets, etc. It is widely used as a heat insulating material for refrigeration vehicles. Especially for hard urethane foam used in the construction field, there are cases where hard urethane foam is caused by increased fire damage, so the flame retardant standards required for hard urethane foam for building materials are becoming stricter. There is a need for improved flame retardant technology for rigid urethane foam.

  The improvement of the flame retardancy of the rigid urethane foam is carried out, for example, by introducing an isocyanurate ring structure by using an isocyanate trimerization catalyst, or by adding a general-purpose phosphate ester flame retardant (for example, Patent Documents 1 to 4). reference). Further, when a higher degree of flame retardancy is required, it is known that a solid flame retardant such as red phosphorus or ammonium polyphosphate is used as the flame retardant (see, for example, Patent Document 5). ).

  However, the rigid urethane foam obtained by the techniques described in Patent Documents 1 to 4 has insufficient flame retardancy. In addition, the solid flame retardant (ammonium polyphosphate) used in Patent Document 5 is insoluble in polyol compositions and polyisocyanate compounds used in polyurethane foam production, and at the time of storage of these raw urethane foam production raw material compositions. Solid flame retardant settles. For this reason, it is necessary to uniformly disperse the solid flame retardant settled immediately before molding the rigid urethane foam, which causes problems such as introduction of stirring equipment.

JP 09-328530 A JP 2001-310925 A JP 2010-53267 A JP 2010-95565 A Japanese Patent Laid-Open No. 2001-200027

  The present invention has been made in view of the above-mentioned background art, and the object thereof is that there is no sedimentation of solid components during storage of the composition for producing rigid urethane foam, the density is practically suitable, and It is providing the rigid urethane foam which has high flame retardance, and the manufacturing method of the said flame-retardant rigid urethane foam.

  As a result of diligent research to solve the above problems, the present inventors have found that a high isocyanate index formulation using a specific raw material composition does not contain a solid flame retardant, has a practically suitable density, The present inventors have found that a rigid urethane foam having flame retardancy can be obtained, and have completed the present invention.

  That is, this invention relates to the flame-retardant rigid urethane foam as shown below, and its manufacturing method.

[1] In a flame retardancy test using a cone calorimeter based on ISO-5660-1, the maximum heat generation rate measured under the condition of a heating strength of 50 kW / m ² is 70 kW / m ² or less, a flame retardant Rigid urethane characterized by containing only a liquid flame retardant at room temperature, a quaternary ammonium salt represented by the following general formula (1), and a density in the range of ³⁰ to 70 kg / m ³ Form.

(In the formula, R ^{1 to} R ⁴ each independently represents an integer aliphatic hydrocarbon group having 1 to 12 carbon atoms or an integer aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents an integer in the range of 1 to 3. X ^b- represents an inorganic acid group or an integer of a carboxylic acid group in the range of 1 to 8 carbon atoms, and b represents an integer in the range of 1 to 3).
[2] The rigid urethane foam as described in [1] above, which contains tris (2-chloropropyl) phosphate as a flame retardant liquid at room temperature.

  [3] reacting the polyol (A) with the polyisocyanate (B) in the presence of the catalyst (C), the flame retardant (D), and the foaming agent (E) under a condition where the isocyanate index is 300 or more, The polyol (A) contains an aromatic polyester polyol, the catalyst (C) contains a quaternary ammonium salt represented by the following general formula (1), and the flame retardant (D) is a liquid flame retardant only at room temperature. The flame retardant (D) is used in an amount of 50 to 120 parts by weight based on 100 parts by weight of the polyol (A), and the blowing agent (E) contains a hydrogen atom-containing halogenated hydrocarbon. The method for producing a rigid urethane foam according to the above [1] or [2].

(In the formula, R ^{1 to} R ⁴ each independently represents an integer aliphatic hydrocarbon group having 1 to 12 carbon atoms or an integer aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents an integer in the range of 1 to 3. X ^b- represents an inorganic acid group or an integer of a carboxylic acid group in the range of 1 to 8 carbon atoms, and b represents an integer in the range of 1 to 3).
[4] The production method according to the above [3], comprising tris (2-chloropropyl) phosphate as the flame retardant (D).

  [5] The production method according to [3] or [4], wherein the polyol (A) is an aromatic polyester-based polyol having a phthalic acid structure.

  [6] The production method according to any one of [3] to [5], wherein the foaming agent (E) contains 1,1-dichloro-1-fluoroethane.

  [7] The production method according to any one of [3] to [6], wherein the catalyst (C) is a solution of a quaternary ammonium salt represented by the general formula (1).

  [8] The method for producing a rigid urethane foam according to any one of [3] to [7], wherein the isocyanate index is in a range of 300 to 500.

  [9] The polyol (A), the catalyst (C), the flame retardant (D), and the foaming agent (E) are contained, the polyol (A) contains an aromatic polyester polyol, and the catalyst (C) is the following. It contains a quaternary ammonium salt represented by the general formula (1), the flame retardant (D) consists only of a liquid flame retardant at room temperature, and the content of the flame retardant (D) is 100 parts by weight of the polyol (A). And a foaming agent (E) containing a hydrogen atom-containing halogenated hydrocarbon, and a polyol composition for producing a rigid urethane foam.

(In the formula, R ^{1 to} R ⁴ each independently represents an integer aliphatic hydrocarbon group having 1 to 12 carbon atoms or an integer aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents an integer in the range of 1 to 3. X ^b- represents an inorganic acid group or an integer of a carboxylic acid group in the range of 1 to 8 carbon atoms, and b represents an integer in the range of 1 to 3).
[10] The hard material according to [1] or [2], wherein the polyol composition according to [9] and the polyisocyanate (B) are reacted under a condition where the isocyanate index is 300 or more. Production method of urethane foam.

  Since the rigid urethane foam of the present invention does not use a solid flame retardant, it can be molded without causing a sedimentation problem of solid components during storage of the polyol composition before foam molding, and only a flame retardant liquid at room temperature is used. Nevertheless, since it has a highly excellent flame retardancy, it is extremely useful as a heat insulating material or a structural material that requires flame retardancy.

  Hereinafter, the present invention will be described in more detail.

The rigid urethane foam of the present invention is
(1) In a flame retardancy test using a cone calorimeter based on ISO-5660-1, the maximum heat generation rate measured under the condition where the heating intensity is 50 kW / m ² is 70 kW / m ² or less.
(2) Containing only a flame retardant that is liquid at room temperature as a flame retardant,
(3) containing a quaternary ammonium salt represented by the above general formula (1), and (4) a density in the range of ³⁰ to 70 kg / m ³ ,
Is the feature.

  In addition, the rigid urethane foam of this invention does not contain a solid component, especially a solid flame retardant.

The rigid urethane foam of the present invention is
(1) reacting the polyol (A) with the polyisocyanate (B) in the presence of the catalyst (C), the flame retardant (D), and the foaming agent (E) under a condition where the isocyanate index is 300 or more,
(2) The polyol (A) contains an aromatic polyester polyol,
(3) The catalyst (C) contains a quaternary ammonium salt represented by the general formula (1),
(4) The flame retardant (D) consists only of a liquid flame retardant at room temperature,
(5) The flame retardant (D) is used in an amount of 50 to 120 parts by weight with respect to 100 parts by weight of the polyol (A), and (6) the blowing agent (E) contains a hydrogen atom-containing halogenated hydrocarbon. To do,
Can be manufactured by.

  In the present invention, the polyol (A) contains an aromatic polyester polyol.

  The aromatic polyester polyol is not particularly limited. For example, phthalates such as orthophthalic acid, isophthalic acid, terephthalic acid, or condensed polyester polyol obtained by reacting phthalic anhydride with a polyhydric alcohol, polyethylene terephthalate and the like. Examples thereof include phthalic acid-based recovered polyester polyols obtained by decomposing acid-based polyester molded articles.

  As the polyol (A) of the present invention, polyester polyol, polyether polyol, polymer polyol and the like can be used without departing from the spirit of the present invention.

  The polyester polyol is not particularly limited. For example, a condensation product obtained by reacting a polybasic acid such as succinic acid, adipic acid, sebacic acid, maleic acid, dimer acid or trimellitic acid with a polyhydric alcohol. Examples thereof include polylactone polyols obtained by ring-opening polymerization of lactones such as polyester polyol and ε-caprolactone.

  The polyether polyol is not particularly limited. For example, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, neopentyl glycol. , Glycerin, trimethylolbropan, pentaerythritol, methyl glucoside, sorbitol, sucrose, and other polyhydric alcohols; pyrogallol, hydroquinone, and other polyhydric phenols; bisphenol A, bisphenol S, bisphenol F, low in phenol and formaldehyde Bisphenols such as condensates; propylenediamine, hexamethylenediamine, ethylenediamine, diethylenetriamine, triethylenetetramine, pentamethyle Aliphatic amines such as hexamine, ethanolamine, diethanolamine, triethanolamine, aminoethylethanolamine; aromatic amines such as aniline, phenylenediamine, xylylenediamine, methylenedianiline, diphenyletherdiamine; isophoronediamine, cyclohexylenediamine Alicyclic amines such as aminoethylpiperazine and the like; active hydrogen compounds such as polyhydric phenols and Mannich polyols (compounds obtained by reaction of the aliphatic amines and formalin), alkylene A compound to which an oxide is added; and the like. These active hydrogen compounds may be a mixture of two or more.

  Although it does not specifically limit as alkylene oxide added to an active hydrogen compound, For example, ethylene oxide, propylene oxide, butylene oxide, etc. are mentioned, You may use these 2 or more types together. Preferred as the alkylene oxide is ethylene oxide, propylene oxide, or a combination thereof.

  Although it does not specifically limit as a polymer polyol, For example, the above-mentioned polyether polyol and ethylenically unsaturated monomers (for example, butadiene, acrylonitrile, styrene etc.) were made to react in presence of a radical polymerization catalyst. A polymer polyol etc. are mentioned.

  Among these, in order to develop excellent flame retardancy, the ratio of the aromatic polyester polyol to the total amount of polyol is preferably 70% by weight or more, and more preferably 80% by weight or more.

  In the present invention, the polyisocyanate (B) is not particularly limited. For example, an aliphatic polyisocyanate, isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and the like Aromatic polyisocyanates such as isocyanate, xylylene diisocyanate, tetramethyl xylylene diisocyanate, and modified products thereof (for example, carbodiimide modification, allophanate modification, urea modification, burette modification, isocyanurate modification, oxazolidone modification), isocyanate group Examples include terminal prepolymers. In order to improve the flame retardancy of the rigid urethane foam obtained, it is preferable to use an aromatic polyisocyanate.

  Specific examples of the aromatic polyisocyanate include 2,4- or 2,6-toluene diisocyanate (TDI), crude TDI, diphenylmethane 2,4′- or 4,4′-diisocyanate (MDI), and polymethylene polyisocyanate. Examples include phenyl isocyanate (crude MDI).

  Specific examples of the aliphatic polyisocyanate include isophorone diisocyanate, 1,6-hexamethylene diisocyanate, 4,4-dicyclohexylmethane diisocyanate, and the like.

  In the present invention, it is important to contain the quaternary ammonium salt represented by the general formula (1) as the catalyst (C).

In the general formula (1), R ^{1 to} R ⁴ each independently represents an aliphatic hydrocarbon group having 1 to 12 carbon atoms or an aromatic hydrocarbon group having 6 to 14 carbon atoms, and Xb− represents an acidic group. A represents an integer in the range of 1 to 3, and b represents an integer in the range of 1 to 3. a is preferably 1 or 2, and b is preferably 1 or 2.

In the general formula (1), when R ^{1 to} R ⁴ are aliphatic hydrocarbon groups, the aliphatic hydrocarbon groups may be linear or branched, and may be either saturated or unsaturated. Examples of the aliphatic hydrocarbon group having 1 to 12 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n- Pentyl group, isopentyl group, neopentyl group, t-pentyl group, n-hexyl group, 1-methylpentyl group, 4-methyl-2-pentyl group, 3,3-dimethylbutyl group, 2-ethylbutyl group, n-heptyl Group, 1-methylhexyl group, n-octyl group, tert-octyl group, 1-methylheptyl group, 2-ethylhexyl group, 2-propylpentyl group, n-nonyl group, n-decyl group, n-undecyl group, An n-dodecyl group etc. are mentioned. In the general formula (1), when R ^{1 to} R ⁴ are aromatic hydrocarbon groups, the aromatic hydrocarbon group may be monocyclic or polycyclic. Examples of the aromatic hydrocarbon group having 6 to 14 carbon atoms include a phenyl group, (2-, 3-, 4-) biphenylyl group, (1-, 2-) naphthyl group, acenaphthylene- (1-, 3- , 4-, 5-) yl group, fluorene- (1-, 2-, 3-, 4-, 9-) yl group, phenalene- (1-, 2-) yl group, (1-, 2-, 3-, 4-, 9-) phenanthryl group and the like.

In the general formula (1), an aromatic hydrocarbon group R ¹ an aliphatic having 1 to 12 carbon atoms used as to R ⁴ hydrocarbon groups or 6-14 carbon atoms, further have a substituent May be. Examples of such a substituent include the above-described aliphatic hydrocarbon groups having 1 to 12 carbon atoms and aromatic hydrocarbon groups having 6 to 14 carbon atoms.

Furthermore, in the said General formula (1), any two of R < ¹ > -R < ⁴ > may form the alicyclic ring or the heterocyclic ring through the carbon atom, the oxygen atom, or the nitrogen atom.

In the general formula (1), R ^{1 to} R ⁴ are not particularly limited. However, the smaller the molecular weight of the quaternary ammonium salt, the greater the amount of substance per weight and the higher the activity. Therefore, R ^{1 to} R ⁴ Is preferably a methyl group.

In the general formula (1), the acidic group (X ^b− ) represents an inorganic acid group or a carboxylic acid group having 1 to 8 carbon atoms.

  Examples of inorganic acid groups include chloric acid groups such as hydrochloric acid groups, perchloric acid groups, chloric acid groups, chlorous acid groups, and hypochlorous acid groups, hydrobromic acid groups, perbromic acid groups, bromine Bromate groups such as acid groups, bromite groups, hypobromite groups, hydroiodic acid groups, periodate groups, iodate groups, iodate groups, iodate groups such as hypoiodite groups, Sulfuric acid group such as sulfuric acid group, disulfuric acid group, thiosulfuric acid group, sulfamic acid group, sulfurous acid group, disulfite group, thiosulfuric acid group, nitrogen acid such as nitric acid group, nitrite group, hyponitrite group, nitroxyl acid group Groups, orthophosphoric acid groups, phosphorous acid groups, hypophosphorous acid groups, phosphinic acid groups, phosphenic acid groups, phosphinic acid groups, diphosphoric acid groups, triphosphoric acid groups, phosphoric acid groups such as metaphosphoric acid groups, Boric acid groups such as orthoboric acid group, metaboric acid group, perboric acid group, hypoboric acid group, boronic acid group, borinic acid group, hydrogen carbonate group, carbonic acid group Etc. The.

  Examples of the carboxylic acid group having 1 to 8 carbon atoms include formic acid group, acetic acid group, propionic acid group, butanoic acid group, pentanoic acid group, hexanoic acid group, heptanoic acid group, octylic acid group, and 2-ethylhexanoic acid group. Aliphatic monocarboxylic acid groups such as aliphatic monocarboxylic acid groups such as oxalic acid groups, malonic acid groups, succinic acid groups, glutaric acid groups and adipic acid groups, benzoic acid groups, and toluic acid groups. Groups, aromatic polycarboxylic acid groups such as phthalic acid groups, isophthalic acid groups, terephthalic acid groups, and nitrophthalic acid groups.

  These acidic groups can be used as one kind or a mixture of two or more kinds.

  Among these, an acidic group having an acid dissociation constant in water of 3.0 or more is preferable because the quaternary ammonium salt is easily dissociated and activated.

  Of these, the smaller the molecular weight of the quaternary ammonium salt, the higher the amount of substance per weight and the higher the activity. Therefore, a carboxylic acid group having 1 to 4 carbon atoms is preferred.

In the present invention, specific examples of the inorganic acid group or the carboxylic acid having 1 to 8 carbon atoms constituting the acidic group (X ^b− ) include acetic acid, formic acid, 2-ethylhexanoic acid, boric acid, and carbonic acid. Acetic acid, formic acid, carbonic acid and the like are particularly preferable.

  In the present invention, the catalyst (C) is tetramethylammonium acetate, tetramethylammonium formate, tetramethylammonium 2-ethylhexanoate, tetraethylammonium acetate, trimethylmonoethylammonium acetate, trimethylmonon-octylammonium. It is preferable to contain at least one quaternary ammonium salt selected from the group consisting of acetate and trimethylmono n-dodecyl ammonium acetate. Particularly preferred is tetramethylammonium acetate, tetramethylammonium formate or trimethylmono n-dodecylammonium acetate.

  In the present invention, the amount of the catalyst (C) used is not particularly limited, but is usually in the range of 0.1 to 8 parts by weight, preferably 0.5 to 100 parts by weight of the polyol (A). The range is ˜5 parts by weight. If the amount of the catalyst (C) used is less than 0.1 parts by weight, the flame retardancy and mechanical strength of the rigid urethane foam may be insufficient. If it exceeds 8 parts by weight, the liquid flow during the production of the rigid urethane foam May decrease.

  In the present invention, the catalyst (C) is more preferably a solution of a quaternary ammonium salt represented by the general formula (1).

  Although it does not specifically limit as a solvent of the quaternary ammonium salt solution of a catalyst (C), For example, glycols, such as ethylene glycol, water, etc. are mentioned. The concentration of the quaternary ammonium salt solution is preferably 50% by weight or more.

  In the present invention, the amount of the quaternary ammonium salt represented by the general formula (1) contained in the catalyst (C) is preferably 0.05 to 7 with respect to 100 parts by weight of the polyol (A). It is the range of a weight part, More preferably, it is the range of 0.25-5 weight part. If the amount of the quaternary ammonium salt contained in the catalyst (B) is less than 0.05 parts by weight, the flame retardancy and mechanical strength of the rigid urethane foam may be insufficient, and if it exceeds 7 parts by weight There is a possibility that the liquid flow property at the time of manufacturing the rigid urethane foam is lowered.

  In the present invention, as the catalyst (C), in addition to the quaternary ammonium salt represented by the general formula (1), known catalysts such as tertiary amines and carboxylates may be used. In order to exhibit the effect, the amount used is desirably 50% by weight or less based on the quaternary ammonium salt represented by the general formula (1).

  Such tertiary amines are not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N , N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyl- (3-aminopropyl) ethylenediamine, N, N, N ′, N ″, N "-Pentamethyldipropylenetriamine, N, N, N ', N'-tetramethylguanidine, 1,3,5-tris (N, N-dimethylaminopropyl) hexahydro-S-triazine, 1,8-diazabicyclo [ 5.4.0] Undecene-7, triethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, N, N′-dimethylpiperazine, dimethyl Chlorhexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethylaminopropyl A conventionally well-known compound, such as imidazole, is mentioned.

  In addition, the carboxylate is not particularly limited, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. Here, the carboxylic acid is not particularly limited, but examples thereof include aliphatic mono- and dicarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid and adipic acid, and aromatic mono-monomers such as benzoic acid and phthalic acid. And conventionally known compounds such as dicarboxylic acids. Moreover, as a metal which should form carboxylate, alkaline earth metals, such as alkali metals, such as lithium, sodium, and potassium, and calcium, magnesium, are mentioned as a suitable example.

  In the present invention, the flame retardant (D) is a liquid flame retardant at room temperature, and preferably contains tris (2-chloropropyl) phosphate.

  The flame retardant that is liquid at room temperature other than tris (2-chloropropyl) phosphate is not particularly limited. For example, propoxylated phosphoric acid and propoxylated obtained by addition reaction of phosphoric acid and alkylene oxide. Reactive flame retardants such as phosphorus-containing polyols such as dibutyl pyrophosphate; phosphate esters such as tricresyl phosphate; halogen-containing phosphate esters such as trischloroethyl phosphate; and the like.

  The usage-amount of a flame retardant (D) is the range of 50-120 weight part with respect to 100 weight part of polyols (A), Preferably it is the range of 70-120 weight part. When the flame retardant (D) is 50 parts by weight or more, high flame retardancy can be exhibited. However, if the amount of the flame retardant (D) exceeds 120 parts by weight, the polymer physical properties of the urethane foam may be lowered.

  In the present invention, a foaming agent containing a hydrogen atom-containing halogen hydrocarbon is used as the foaming agent (E).

  Although it does not specifically limit as a hydrogen atom containing halogenated hydrocarbon foaming agent, Specifically, a thing of HCFC type (For example, "HCFC-123", "HCFC-141b", "HCFC-22", "HCFC-142b" etc.), HFC type (eg "HFC-134a", "HFC-245fa", "HFC-245ca", "HFC-365mfc", "HFC-236ea" etc.), and these A mixture of two or more kinds is exemplified. Among these, as the blowing agent (E), “HCFC-141b”, “HFC-134a”, “HFC-245fa”, “HFC-365mfc”, and a mixture of two or more thereof are preferable. Particularly preferred is HCFC-141b (1,1-dichloro-1-fluoroethane).

  In the present invention, as the blowing agent (E), other hydrogen blowing agents may be mixed with the above hydrogen atom-containing halogen hydrocarbon without departing from the spirit of the present invention. Although it does not specifically limit as another foaming agent, For example, a low boiling point hydrocarbon, water, etc. are mentioned. In the present invention, the “low boiling point hydrocarbon” means a hydrocarbon having a normal boiling point of 0 to 50 ° C., and specific examples thereof include propane, butane, pentane, cyclopentane, and mixtures thereof.

  However, from the viewpoint of flame retardancy of the obtained rigid urethane foam, the proportion of the hydrogen atom-containing halogenated hydrocarbon is preferably 80% by weight or more in all the foaming agents (E).

  Although the usage-amount of a foaming agent (E) is not specifically limited, It is the range of 20-100 weight part normally with respect to 100 weight part of polyols (A), Preferably it is the range of 30-80 weight part.

  In the present invention, other auxiliary agents other than the above (A) to (E) may be included as long as the effects of the present invention are obtained. Examples of such auxiliary agents include foam stabilizers, colorants, anti-aging agents, and other conventionally known additives. The type and amount of these additives may be within the normal usage range of the additive used.

  Examples of the foam stabilizer include conventionally known organosilicon surfactants, and are not particularly limited. Specifically, organosiloxane-polyoxyalkylene copolymers, silicone-grease copolymers. Nonionic surfactants such as these, and mixtures thereof are exemplified.

  Although the usage-amount of a foam stabilizer is not specifically limited, The range of 0.1-10 weight part is preferable with respect to 100 weight part of polyols (A), and 0.3-5 weight part is more preferable.

  In the production method of the present invention, the isocyanate index [(the number of equivalents of isocyanate groups in the isocyanate component per equivalent of active hydrogen groups of all raw materials) × 100] is 300 or more, more preferably in the range of 300 to 500. preferable.

  Although it does not specifically limit as a concrete implementation method of the manufacturing method of this invention, For example, the polyol composition which mixed uniformly all the raw materials except polyisocyanate (B) among the raw materials for rigid urethane foam manufacture beforehand The product is mixed with polyisocyanate (B), and after mixing and stirring rapidly with the above-mentioned isocyanate index, the desired flame-retardant rigid urethane foam is produced by injecting into an appropriate container or mold and foam molding. can do.

  The specific manufacturing apparatus is not particularly limited as long as these can be mixed uniformly. For example, a low pressure or high pressure for injection foaming used in manufacturing a small mixer or a general urethane foam. Spray-type foaming devices such as foaming machines, low-pressure or high-pressure foaming machines for slab foaming, low-pressure or high-pressure foaming machines for continuous lines, and the like can be used.

The rigid urethane foam of the present invention has a density in the range of ³⁰ to 70 kg / m ³ . When the density is less than 30 kg / m ³ , the strength of the rigid urethane foam is lowered, and when the density exceeds 70 kg / m ³ , the cost of the foamed material is increased, which is not preferable. A preferred density is in the range of 35-60 kg / m ³ .

The rigid urethane foam of the present invention has a maximum heat generation rate measured under the condition of a heating strength of 50 kW / m ² in a flame retardancy test using a cone calorimeter based on ISO-5660-1 which is a flame retardance index. Is 70 kW / m ² or less, and has a feature of showing high flame retardancy.

  Due to this feature, the flame-retardant rigid urethane foam of the present invention can be used in various applications. For example, heat insulation and structural materials related to construction, civil engineering, electrical equipment related, heat insulating materials such as freezer, refrigerator, freezer showcase, etc., plant and ship related, LPG, LNG tanker and pipeline heat insulating materials, vehicle related Applications such as cold storage and heat insulation for refrigerated vehicles can be mentioned.

  The following examples further illustrate the present invention, but the present invention is not limited to these examples. In addition, (pbw) in a table | surface shows the weight part of another agent when a polyol is 100 weight part.

  In the following examples, the measurement method for each measurement item is as follows.

<Reactivity measurement items>
Cream time: The rising start time of the foamed foam was measured visually.

  Gel time: The time required for the reaction to progress to a resinous substance from a liquid substance was measured.

<Core density of foam>
The center part of the foam foamed in a 5 L (liter) mold having an inner size of 25 cm × 25 cm × 8 cm was cut into a size of 20 cm × 20 cm × 4 cm, and the core density was calculated by accurately measuring the size and weight.

<Maximum heat generation rate during foam combustion>
Samples for evaluation of combustion characteristics cut to dimensions of 10 cm × 10 cm × 4 cm were cut out from the rigid urethane foams prepared in Examples and Comparative Examples, and flame retardancy using a cone calorimeter compliant with ISO-5660-1 In the test, the maximum heat generation rate was measured under the condition where the heating intensity was 50 kW / m ² .

Example 1 Production of flame retardant rigid urethane foam.
In a 500 mL polyethylene container, 30 g of aromatic polyester polyol (Invista, product name: HT-1000, OH value = 315 mgKOH / g), aromatic polyester polyol (Invista, product name: HT-1100, OH value = 260 mgKOH) / G) 30 g was added and stirring was started at room temperature. Subsequently, 2.4 g of a 75% by weight aqueous solution of tetramethylammonium acetate as a catalyst, 0.6 g of N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine (Tosoh Corporation, product name: TOYOCAT-DT), 2.0 g of a silicone surfactant (trade name: SZ1642 manufactured by Toray Dow Corning Co., Ltd.) as a foam stabilizer, and tris (2-chloropropyl) phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., trade name: TMCPP) as a flame retardant ) 66 g, and finally 60 g of 1,1-dichloro-1-fluoroethane (manufactured by Tokyo Chemical Industry Co., Ltd.) and 0.3 g of water as foaming agents were added and stirring continued, and it was difficult to adjust the temperature to 20 ° C. A polyol composition for producing a flammable rigid urethane foam was obtained.

  Polymeric MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., product name: MR-200, NCO content 31.0% by weight) 204 g was adjusted to 20 ° C. as a polyisocyanate, and 6000 rpm using a lab mixer. Stir for 5 seconds to mix uniformly. Subsequently, this was put in a mold whose temperature was adjusted to 50 ° C., and foam molding was performed. At this time, the reactivity was measured. The mold was removed after 7 minutes from the time when the mixed raw materials were put into the mold to produce a flame-retardant rigid urethane foam. The core density of the obtained flame-retardant rigid urethane foam was measured. Further, this foam was cut, and the maximum heat generation rate was measured by a flame retardancy test using a corn calorimeter. These results are also shown in Table 1.

実施例２〜５、比較例１〜４ 難燃性硬質ウレタンフォームの製造．
表１に示す組成で、実施例１と同様の方法により、硬質ウレタンフォームを製造した。また、反応性、フォームのコア密度、燃焼試験の最大発熱速度を実施例１と同様の方法により測定した。これらの結果を表１に併せて示す。

Examples 2 to 5, Comparative Examples 1 to 4 Production of flame retardant rigid urethane foam.
With the composition shown in Table 1, a rigid urethane foam was produced by the same method as in Example 1. The reactivity, foam core density, and maximum heat generation rate in the combustion test were measured in the same manner as in Example 1. These results are also shown in Table 1.

As is clear from Examples 1 to 5 in Table 1, the rigid urethane foam of the present invention exhibited excellent flame retardancy with a maximum heat generation rate of 70 kW / m ² or less.

On the other hand, in Comparative Examples 1 to 4 in Table 1, the maximum heat generation rate exceeded 70 kW / m ^2, and the heat generation rate during combustion was large, so the results were poor in flame retardancy.

  The rigid urethane foam of the present invention has excellent flame retardancy, and heat insulation and structural materials related to construction, civil engineering, freezers related to electrical equipment, refrigerators, freezer showcases, plant and ship related It is useful as a heat insulating material such as LPG, LNG tanker, etc., a cold storage for vehicles, a heat insulating material for a freezer car, and the like.

Claims (10)

In the flame retardancy test using a cone calorimeter based on ISO-5660-1, the maximum heat generation rate measured under the condition of heating strength of 50 kW / m ² is 70 kW / m ² or less, and as a flame retardant at room temperature A rigid urethane foam characterized by containing only a liquid flame retardant, containing a quaternary ammonium salt represented by the following general formula (1), and having a density in the range of ³⁰ to 70 kg / m ³ .

(In the formula, R ^{1 to} R ⁴ each independently represents an integer aliphatic hydrocarbon group having 1 to 12 carbon atoms or an integer aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents an integer in the range of 1 to 3. X ^b- represents an inorganic acid group or an integer of a carboxylic acid group in the range of 1 to 8 carbon atoms, and b represents an integer in the range of 1 to 3). 2. The rigid urethane foam according to claim 1, comprising tris (2-chloropropyl) phosphate as a liquid flame retardant at room temperature. Reacting a polyol (A) with a polyisocyanate (B) in the presence of a catalyst (C), a flame retardant (D), and a foaming agent (E) under a condition of an isocyanate index of 300 or more; a polyol (A ) Contains an aromatic polyester polyol, the catalyst (C) contains a quaternary ammonium salt represented by the following general formula (1), and the flame retardant (D) consists only of a liquid flame retardant at room temperature. The flame retardant (D) is used in an amount of 50 to 120 parts by weight based on 100 parts by weight of the polyol (A), and the foaming agent (E) contains a hydrogen atom-containing halogenated hydrocarbon. The manufacturing method of the rigid urethane foam of Claim 1 or Claim 2 to do.

(In the formula, R ^{1 to} R ⁴ each independently represents an integer aliphatic hydrocarbon group having 1 to 12 carbon atoms or an integer aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents an integer in the range of 1 to 3. X ^b- represents an inorganic acid group or an integer of a carboxylic acid group in the range of 1 to 8 carbon atoms, and b represents an integer in the range of 1 to 3). The production method according to claim 3, wherein tris (2-chloropropyl) phosphate is contained as the flame retardant (D). The production method according to claim 3 or 4, wherein the polyol (A) is an aromatic polyester-based polyol having a phthalic acid structure. The production method according to any one of claims 3 to 5, wherein the foaming agent (E) contains 1,1-dichloro-1-fluoroethane. The production method according to any one of claims 3 to 6, wherein the catalyst (C) is a solution of a quaternary ammonium salt represented by the general formula (1). The method for producing a rigid urethane foam according to any one of claims 3 to 7, wherein an isocyanate index is in a range of 300 to 500. The polyol (A), the catalyst (C), the flame retardant (D), and the foaming agent (E) are contained, the polyol (A) contains an aromatic polyester polyol, and the catalyst (C) is represented by the following general formula ( 1) containing the quaternary ammonium salt represented by 1), the flame retardant (D) is composed only of a liquid flame retardant at room temperature, and the content of the flame retardant (D) is 100 parts by weight of the polyol (A). A polyol composition for producing rigid urethane foam, wherein the polyol composition is 50 to 120 parts by weight and the foaming agent (E) contains a hydrogen atom-containing halogenated hydrocarbon.

(In the formula, R ^{1 to} R ⁴ each independently represents an integer aliphatic hydrocarbon group having 1 to 12 carbon atoms or an integer aromatic hydrocarbon group having 6 to 14 carbon atoms. Represents an integer in the range of 1 to 3. X ^b- represents an inorganic acid group or an integer of a carboxylic acid group in the range of 1 to 8 carbon atoms, and b represents an integer in the range of 1 to 3). The method for producing a rigid urethane foam according to claim 1 or 2, wherein the polyol composition according to claim 9 and the polyisocyanate (B) are reacted under a condition where the isocyanate index is 300 or more. .