JP4901225B2 - Polyol mixture for polyurethane foam production - Google Patents

Description

  The present invention relates to a polyol mixture for producing polyurethane foam. More specifically, it is used in building materials, refrigerated warehouses, heat insulating materials such as bathtubs, piping, anti-condensation materials such as detached houses, condominiums and industrial piping, and building material parts such as bay windows and sashes to maintain the product shape. The present invention relates to a method for producing a polyurethane foam that can be suitably used as a lightweight core material to be packed, a polyol mixture that can be suitably used for producing a polyurethane foam, and a heat insulating material comprising the polyurethane foam. The method for producing a polyurethane foam of the present invention can be suitably used particularly when producing a construction material such as a panel or a board in a factory line, particularly an on-site construction type heat insulating material and anti-condensation material by a spray method.

  Polyurethane foam is used as a heat insulating material for building materials, refrigerated warehouses, bathtubs, piping, and the like because it has good heat insulating properties. For example, when using polyurethane foam as a heat insulating material for houses, buildings, etc., using a spray machine or the like, a component mainly composed of polyol and a component mainly composed of isocyanate are used as a foaming agent, a catalyst, and as required. It is manufactured by a method of mixing in the presence of other auxiliaries, spraying it onto a target site such as a wall surface or ceiling at a construction site such as a house or a building, and foaming and curing.

  In recent years, a method for producing a polyurethane foam using only water as a foaming agent has been proposed (see, for example, Patent Documents 1 to 3). Since the polyurethane foam production methods described in these patent documents use a relatively large amount of water, the shrinkage (dimensional stability) of the polyurethane foam is reduced, that is, the cells are connected. Is solved by.

  In particular, in recent years, from the viewpoint of protecting the global environment, even if all of the foaming agent is substantially water, there has been a demand for lowering the density of polyurethane foam in order to further reduce weight and reduce the amount of waste. In order to produce such a polyurethane foam, it is necessary to increase the content of the foaming agent, that is, the content of water in the polyol mixture. As a result, the compatibility of the polyol mixture deteriorates, and it becomes cloudy or separated. Therefore, before the polyol mixture and the isocyanate component are reacted, it is necessary to sufficiently mix and stir the polyol mixture in advance.

  Furthermore, when producing polyurethane foam on site, the polyol mixture usually has to meet a warranty period of several months by drumming, which facilitates the separation of the polyol mixture during its storage. Therefore, if the polyol mixture is not sufficiently stirred before the polyol mixture and the isocyanate component are reacted in advance, the reaction between the polyol mixture and the isocyanate component becomes inhomogeneous. In the produced polyurethane foam, voids are generated or cells are disturbed, so that a homogeneous polyurethane foam cannot be obtained.

On the other hand, when a foaming agent other than water is used, the foaming agent is quickly vaporized by the heat of reaction between the hydroxyl group and isocyanate group of a relatively large amount of polyol, whereas a good polyurethane foam can be produced. When the foaming agent consists essentially of water, the reaction activity between water and isocyanate groups is basically low, so it takes time to generate carbon dioxide gas as the foaming agent. In such a case, problems such as liquid sag occur.
Japanese Patent Laid-Open No. 10-45862 Japanese Patent Laid-Open No. 11-336881 JP 2002-179756 A

  In the present invention, even when a large amount of water is used as a blowing agent, the polyol mixture is uniform and transparent. Polyol mixture that can not only increase production efficiency but also increase the reactivity at the time of production of polyurethane foam and can quickly produce polyurethane foam excellent in workability, and method for producing polyurethane foam using the same Another object is to provide a heat insulating material comprising the polyurethane foam.

The present invention
(1) A polyol mixture for producing a polyurethane foam containing a polyol component, 4 parts by weight or more of water with respect to 100 parts by weight of the polyol component, and a fatty acid amine salt having 10 to 24 carbon atoms,
(2) A method for producing a polyurethane foam in which the polyol mixture is reacted with an isocyanate component, and (3) a heat insulating material comprising a polyurethane foam obtained by the production method.

  According to the present invention, even when a large amount of water is used as a foaming agent, the polyol mixture is uniform and transparent, and the process of mixing and stirring the complicated polyol mixture at the time of construction on site is reduced. Not only can the production efficiency of the foam be increased, but also the polyurethane foam excellent in workability can be rapidly produced by increasing the reactivity during the production of the polyurethane foam.

  The polyol mixture for producing a polyurethane foam of the present invention contains a polyol component, water of 4 parts by weight or more, and a fatty acid amine salt having 10 to 24 carbon atoms with respect to 100 parts by weight of the polyol component.

  As a polyol component, when manufacturing a polyurethane foam, what is generally used can be illustrated. Representative examples of the polyol component include, for example, polyester polyols, ethylenediamine-based polyether polyols and polyoxy acids described in “Polyurethane resin handbook” edited by Keiji Iwata (published on September 25, 1987, published by Nikkan Kogyo Shimbun). Examples include polyether polyols such as alkylene-based polyether polyols, polymer polyols, phenol resin-based polyols, and Mannich-based polyols, and these can be used alone or in admixture of two or more.

When producing a polyurethane foam having a relatively low density of 8 to 20 kg / m ³ and a small closed cell ratio, the cell component is controlled in the polyol component to improve the dimensional stability and adhesiveness of the polyurethane foam. From the viewpoint, it is preferable that a polyoxyalkylene-based polyol and / or polymer polyol having a hydroxyl value of 25 to 120 mgKOH / g is contained. The density of the polyurethane foam means the “core density” measured by the measurement method described in “Example” described later.

  From the viewpoint of controlling the cell connection and improving the dimensional stability and adhesiveness of the polyurethane foam, the hydroxyl value of the polyoxyalkylene polyol and / or polymer polyol is preferably 30 to 110 mgKOH / g, more preferably, respectively. Is 35-100 mg KOH / g. The hydroxyl value is a value obtained based on JIS K1557.

  In consideration of the viscosity at the time of handling and the physical properties of the polyurethane foam, the number of functional groups of the polyoxyalkylene polyol and the polymer polyol is preferably 2 to 4, more preferably 2 to 3, respectively.

  Examples of polyoxyalkylene-based polyols include polyoxypropylene-based polyols and terminal ethylene oxide-added polyoxypropylene polyols having the hydroxyl value and / or the number of functional groups. These may be used alone or in combination of two or more. It can be used by mixing.

  Examples of suitable polyoxyalkylene-based polyols include glycerin-based polyoxypropylene triol, dipropylene glycol-based polyoxypropylene diol, and their terminal ethylene oxide addition compounds.

  Examples of the polymer polyol include those in which polyacrylonitrile fine particles and polystyrene fine particles are dispersed in a polyoxyalkylene-based polyol, but the present invention is not limited to such examples.

  The polyol component includes, for example, an ethylenediamine-based polyether polyol, a tolylenediamine-based polyether polyol, and a glycerin-based one having a hydroxyl value of 200 to 800 mgKOH / g from the viewpoint of suppressing hydrolysis and increasing the strength of the polyurethane foam. Polyether polyol, diglycerin polyether polyol, trimethylol propane polyether polyol, pentaerythritol polyether polyol, bisphenol A polyether polyol, Mannich polyether polyol, sugar polyether polyol, sucrose polyether It is preferable that polyol, dextrose-based polyether polyol, and the like are included.

On the other hand, when a polyurethane foam having a density of 20 to 35 kg / m ³ is slightly high, the polyol component contains an aromatic dicarboxylic acid having a hydroxyl value of 200 to 600 mgKOH / g from the viewpoint of enhancing heat resistance and flame retardancy. It is preferable that at least one of acid-based polyester polyol, polyhydric phenol-based polyether polyol, phenol resin-based polyol, and Mannich polyol is included, and the hydroxyl value is 200 to 600 mgKOH / g, phthalic acid, terephthalic acid, or It is more preferable that at least one of phthalic acid-based polyester polyol, Mannich polyol and bisphenol A alkylene oxide adduct using isophthalic acid as a raw material is contained.

  Water is used as a blowing agent. As long as the object of the present invention is not hindered, air, (liquefied) gas such as carbon dioxide, nitrogen, hydrocarbon, hydrochlorofluorocarbon, hydrogenated fluorocarbon, etc. may be used together with water. In view of the above, it is preferable to use only water.

  The amount of water is 4 parts by weight or more, preferably 4 to 100 parts by weight, more preferably 4 to 50 parts by weight, based on 100 parts by weight of the polyol component, from the viewpoint of maintaining the physical properties of the polyurethane foam and reducing the density. Preferably it is 5-30 weight part.

  The fatty acid amine salt having 10 to 24 carbon atoms (hereinafter simply referred to as “fatty acid amine salt”) acts as a compatibilizer for polyol and water, and further enhances the reactivity of the polyol component, water and isocyanate component. Have.

  The number of carbon atoms of the fatty acid used in the fatty acid amine salt is 10 to 24, preferably 10 to 20, from the viewpoint of enhancing the compatibility with the polyol component and water due to its surface activity. The fatty acid used in the fatty acid amine salt is preferably a fatty acid containing an unsaturated group from the viewpoint of handling at low temperatures and compatibility.

  Preferable examples of the fatty acid having 10 to 24 carbon atoms include linear or branched fatty acids such as oleic acid, capric acid, stearic acid, myristic acid, palmitic acid, lauric acid, linoleic acid, linolenic acid, Examples include ricinolenic acid. These can be used alone or in admixture of two or more. Among these, one or more selected from the group consisting of oleic acid, linoleic acid, linolenic acid, and ricinolenic acid is more preferred because of its excellent stability at low temperatures when the fatty acid amine salt is formed.

  The amine compound used for the fatty acid amine salt is a polyamine such as an alkylamine, alkanolamine, alicyclic amine, aromatic amine, diamine or triamine having a primary amino group, secondary amino group or tertiary amino group. These may be used alone or in combination of two or more.

  From the viewpoint of volatilization of the amine compound dissociated from the fatty acid amine salt during the production of the polyurethane foam and the working environment, the amine compound preferably has a hydroxyl group and / or amino group that reacts with an isocyanate group in the molecule. In addition, the amine compound has a tertiary amino group in the molecule from the viewpoint of improving the liquidity (that is, handleability) of the fatty acid amine salt and the reactivity during the production of the polyurethane foam and improving the workability. It is preferable. Furthermore, the molecular weight of the amine compound is preferably 120 or less from the viewpoint of maintaining the concentration of the fatty acid residue as the fatty acid amine salt and improving the compatibility.

  From the above viewpoint, the amine compound is preferably an amine compound having a hydroxyl group and / or amino group that reacts with a tertiary amino group and an isocyanate group in the molecule, and a hydroxyl group that reacts with a tertiary amino group and an isocyanate group. And / or an amine group in the molecule and a molecular weight of 120 or less is more preferred, and the tertiary amino group is more preferably an N, N-dimethylamino group, which will be described later. From the viewpoint of fatty acid exchange with an amine-based catalyst, an amine compound having a primary amino group or a secondary amino group that is more basic is even more preferable.

  Specific examples of suitable amine compounds include N, N-dimethylaminoethanol, N, N-dimethylaminopropanol, N, N-dimethylaminoisopropanol, N, N-dimethylaminobutanol, N, N-dimethylaminopropylamine. , N, N-dimethylaminoethylamine and the like, and these can be used alone or in admixture of two or more. Among these, N, N-dimethylaminoethanol and N, N-dimethylaminopropylamine are preferable from the viewpoints of economy and reaction activity, and these can be used alone or in combination.

  The fatty acid amine salt can be produced by a neutralization reaction between a fatty acid and an amine compound. For example, a fatty acid amine salt can be easily produced by mixing 1 mol of oleic acid and 1 mol of N, N-dimethylaminoethanol and neutralizing it. The mixing ratio of the fatty acid and the amine compound is preferably adjusted so that the fatty acid / amine compound (equivalent ratio of acid to amine) is 1 to 1 / the number of nitrogen atoms of the amine compound.

  Suitable fatty acid amine salts include, for example, fatty acid amine salts obtained by reacting oleic acid with N, N-dimethylaminopropylamine, and fatty acid amine salts obtained by reacting oleic acid with N, N-dimethylaminoethanol. And fatty acid amine salts obtained by reacting ricinoleic acid and N, N-dimethylaminopropylamine, and fatty acid amine salts obtained by reacting ricinoleic acid and N, N-dimethylaminoethanol. In addition, as long as the objective of this invention is in the range which is not inhibited, the other fatty-acid amine salt may contain.

  The amount of the fatty acid amine salt is preferably 1 part by weight or more, more preferably 2 parts by weight or more, and further preferably 3 parts by weight or more with respect to 100 parts by weight of the polyol component, from the viewpoint of increasing the compatibility with the polyol component and water. From the viewpoint of securing the strength and flame retardancy of the polyurethane foam, it is preferably 30 parts by weight or less, more preferably 25 parts by weight or less, and still more preferably 20 parts by weight or less.

  In the present invention, an amine-based catalyst is preferably used as the catalyst from the viewpoint of enhancing the reactivity between water and the isocyanate component and contributing to the compatibilization of the polyol component and water. A catalyst can be used by making it contain in a polyol mixture.

Examples of amine-based catalysts include formula (I):
(CH ₃ ) ₂ N (CH ₂ CH ₂ O) _n -H (I)
(Where n represents a number from 1 to 4)
A compound represented by formula (II):
(CH ₃ ) ₂ N CH ₂ CH ₂ N (CH ₃ ) X (II)
(Wherein X represents a CH ₂ CHYOH group, CH ₂ CH ₂ N (CH ₃ ) ₂ group or CH ₂ CH ₂ N (CH ₃ ) CH ₂ CHYOH group, Y represents a hydrogen atom or a methyl group)
A compound represented by formula (III):
(CH ₃ ) ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ N (CH ₃ ) Z (III)
(Wherein Z is a methyl group or CH ₂ CHYOH group, Y is the same as above)
1,4-diazabicyclo [2.2.2] octane, 2-methyl-1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, N-ethylmorpholine, N- (dimethylaminoethyl) ) Morpholine, dimorpholinodiethyl ether, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N'-tetramethyl- 1,6-hexanediamine, N, N′-dimethylpiperazine, N, N ′, N′-trimethylaminoethylpiperazine, tris (3-dimethylaminopropyl) amine, bis (3-dimethylaminopropyl) amine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, 1,8-diazabicyclo [5.4.0] undecene-7, N, N ', N''-tris (3-dimethylaminopropyl) hexahydro-s-triazine 6-dimethylamino-1-hexanol, 5-dimethylamino-3-methyl-1-pe Butanol, isopropanolamine, N- (3-dimethylaminopropyl) -N-methylaminoethanol, N, N-dimethyl-N, N'-bis (2-hydroxypropyl) -1,3-propanediamine, N, N And tertiary amine catalysts such as bis (3-dimethylaminopropyl) isopropanolamine, 1-methylimidazole, 1-isobutyl-2-methylimidazole, 1,2-dimethylimidazole and their derivatives, etc. These can be used alone or in admixture of two or more.

  Examples of suitable amine-based catalysts include compounds represented by formula (I), compounds represented by formula (II), and formula (III) from the viewpoint of increasing the reactivity between the isocyanate component and water. These can be used, and these can be used alone or in admixture of two or more.

  Among the compounds represented by the formula (I), the compound represented by the formula (II) and the compound represented by the formula (III), 2- (2-dimethylaminoethoxy) ethanol, 2- [2- ( 2-dimethylaminoethoxy) ethoxy] ethanol, N- (2-dimethylaminoethyl) -N-methylethanolamine, N, N, N ', N "-tetramethyl-N" -isopropanol-diethylenetriamine, N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether and N- (2- (2-dimethylaminoethoxy) ethyl) -N-methylethanolamine are preferred. These can be used alone or in admixture of two or more.

  The amount of the amine-based catalyst is preferably 0.5 to 25 parts by weight, more preferably 1 to 20 parts by weight, and still more preferably 1.5 to 100 parts by weight of the polyol component from the viewpoints of reactivity and compatibility. ~ 15 parts by weight.

  The polyol mixture can contain a foam stabilizer. Examples of the foam stabilizer include silicone foam stabilizers such as polyoxyalkylene-polydimethylsiloxane copolymer, polydialkylsiloxane, polyoxyalkylene polyol-modified dimethylpolysiloxane, fatty acid salt, sulfate ester salt, and phosphate ester salt. And anionic surfactants such as sulfonate, and the like. These may be used alone or in admixture of two or more. Of these, polyoxyalkylene-polydimethylsiloxane copolymers are preferred.

  Since the amount of the foam stabilizer varies depending on the type of foam stabilizer, the characteristics of the polyurethane foam, and the like and cannot be determined unconditionally, it is preferable to adjust appropriately according to the type of foam stabilizer.

  In addition, a flame retardant, a crosslinking agent, etc. can be mix | blended with a polyol mixture as needed.

  Examples of flame retardants include tricresyl phosphate, tris (2-chloroethyl) phosphate, tris (2-chloroisopropyl) phosphate, tris (1,3-dichloropropyl) phosphate, tris (2,3-dibromopropyl) phosphate Halogen flame retardants such as these can be used, and these can be used alone or in admixture of two or more. Of these, tris (2-chloroisopropyl) phosphate is preferred.

  The amount of the flame retardant is preferably 5 to 50 parts by weight, more preferably 10 to 40 parts by weight with respect to 100 parts by weight of the polyol component from the viewpoint of imparting flame retardancy to the polyurethane foam and maintaining the properties as the polyurethane foam. Parts by weight.

  Examples of the crosslinking agent include a low molecular compound having two or more active hydrogen-containing groups capable of reacting with a hydroxyl group, a primary amino group, a secondary amino group, and other isocyanate groups. Examples of suitable crosslinking agents include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, glycerin, trimethylolpropane, triethanolamine and the like. Examples include polyamines such as polyhydric alcohol, diethyltoluenediamine, chlorodiaminobenzene, ethylenediamine, and 1,6-hexanediamine. These can be used alone or in admixture of two or more. Among these, propylene glycol and dipropylene glycol are preferable from the viewpoint of further improving the compatibility in the polyol mixture.

  The amount of the crosslinking agent is preferably 0.3 to 10 parts by weight, more preferably 0.5 parts per 100 parts by weight of the polyol component from the viewpoint of securing the strength of the polyurethane foam and improving the compatibility in the polyol mixture. ~ 8 parts by weight.

  Moreover, when manufacturing a polyurethane foam, an auxiliary agent can be used if necessary. As the auxiliary agent, those generally used in the production of polyurethane foam can be used. Examples of the auxiliary agent include stabilizers, pigments, fillers, and viscosity reducing agents. These auxiliaries can be used within a range that does not impair the object of the present invention.

  The polyol mixture of the present invention is a mixture of a polyol component, a predetermined amount of water, a fatty acid amine salt, and, if necessary, an amine catalyst and a foam stabilizer, a flame retardant, a crosslinking agent, and an auxiliary agent. Thus, it can be easily prepared.

  The resulting polyol mixture is transparent and uniform. In the present specification, “transparent” means no turbidity. “Uniform” means that layers are not separated.

  Therefore, the polyol mixture of the present invention is transparent and uniform even when a large amount of water is used as a foaming agent, and reduces the trouble of mixing and stirring the polyol mixture at the time of on-site construction. Not only can the production efficiency of the foam be increased, but also has the advantage that the polyurethane foam with excellent workability can be quickly produced by increasing the reactivity when reacting with the isocyanate component to produce the polyurethane foam. .

  Thus, the reason why the polyol mixture of the present invention exhibits an excellent effect is not clear, but fatty acid amine salts (salts of long chain aliphatic groups and fatty acid carboxylic acid residues and amine compounds) are surface active. It is considered to be based on acting as a compatibilizer between the polyol component and water.

  However, when the fatty acid constituting the fatty acid amine salt is a fatty acid having a carbon number of less than 10 or more than 25, the polyol mixture is phase-separated and a uniform and transparent polyol mixture cannot be obtained. The water content locally fluctuates in the polyol mixture, and density spots and voids due to abnormal foaming appear in the polyurethane foam. This is because if the number of carbon atoms of the fatty acid is small, not only the compatibility with the polyol component decreases, but also the acidity of the fatty acid increases and the hydrophilicity of the fatty acid amine salt becomes stronger. It is thought that it originates in losing the balance.

  In addition, when the polyol mixture of the present invention is used, voids are generated in the polyurethane foam or the cells are disturbed without the trouble of complicated mixing and stirring before the reaction with the isocyanate component. Not only can be suppressed, but also the reactivity with the isocyanate component is enhanced, and a polyurethane foam having excellent workability can be obtained. The reason why such an excellent effect is exhibited is considered to be based on the fact that the polyol mixture has a homogeneous composition and high activity.

  The polyurethane foam of the present invention can be produced by reacting a polyol mixture with an isocyanate component.

  Examples of the isocyanate component include aromatic polyisocyanates such as polymethylene polyphenylene polyisocyanate, tolylene diisocyanate, diphenylmethane diisocyanate, xylylene diisocyanate, and naphthylene diisocyanate; aliphatic polyisocyanates such as hexamethylene diisocyanate and lysine diisocyanate; hydrogenated diphenylmethane. Aliphatic polyisocyanates such as diisocyanates, hydrogenated tolylene diisocyanates, isophorone diisocyanates; the polys containing one or more of urethane bonds, carbodiimide bonds, uretoimine bonds, allophanate bonds, urea bonds, burette bonds, isocyanurate bonds, etc. Isocyanate modified products and the like. These isocyanate components may be used alone or in admixture of two or more. Among the isocyanate components, polymethylene polyphenylene polyisocyanate is preferable from the viewpoint of imparting strength to the polyurethane foam and improving heat resistance.

  The ratio of the polyol mixture and the isocyanate component is usually preferably adjusted so that the isocyanate index is 20 to 300, preferably 30 to 200, more preferably 40 to 150.

  Polyurethane foam, for example, reacts by mixing and stirring a polyol mixture and an isocyanate component with a molding machine etc., injecting them into a mold and reacting them, or spraying them with a spray machine etc. Can be obtained. More specifically, for example, after adjusting the temperature of the polyol mixture to about 20 ° C., the polyol mixture and the isocyanate component are mixed and reacted.

The density of the polyurethane foam of the present invention is not particularly limited, but it is preferably 8 kg / m ³ or more, more preferably 9 kg / m ³ or more from the viewpoint of maintaining physical properties, and a viewpoint of weight reduction and reduction of waste amount. Therefore, it is preferably 35 kg / m ³ or less, more preferably 30 kg / m ³ or less, and still more preferably 20 kg / m ³ or less.

  Thus, according to the production method of the present invention, homogeneous mixing and high reactivity of the polyol mixture and the isocyanate component are realized, the generation of voids is suppressed, the cells are homogenized and stabilized, and the workability is excellent. Polyurethane foam can be obtained quickly.

  The obtained polyurethane foam is, for example, a building material, a freezing warehouse, a heat insulating material such as a bathtub, a pipe, a dew condensation prevention material such as a detached house, an apartment or an industrial pipe, and a building material such as a bay window or a sash to maintain the product shape. It can be suitably used as a lightweight core material or the like packed inside a component or the like.

  In addition, the production method of the present invention can be suitably used particularly when producing a construction material such as a panel or a board on a factory line, especially a heat insulating material and a dew condensation prevention material of a field construction type by a spray method.

Examples 1-6 and Comparative Examples 1-5
As the polyol component, polyoxyalkylene-based polyol [hydroxyl value: 56 mgKOH / g, manufactured by Dow Chemical Co., Ltd., trade name: boranol 3010 (glycerin-based polyoxypropylene triol)] and ethylenediamine-based polyether polyol [hydroxyl value: 768 mgKOH / G, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Actcoal AE-300], 50 parts by weight were used.

  100 parts by weight of polyol component, foam stabilizer [silicone foam stabilizer, manufactured by Toray Dow Silicone Co., Ltd., product number: SF2938F], flame retardant [Tris (2-chloroisopropyl) phosphate, Daihachi Chemical Industry Co., Ltd. ), Product number: TMCPP] 40 parts by weight, 20 parts by weight of water as a blowing agent, and amine catalyst, fatty acid amine salt, surfactant, etc. in the amounts shown in Table 1 are mixed in a lab mixer (mixing conditions: 500 rpm for 1 minute Stirring) to obtain a polyol mixture.

  In addition, the raw material used for the polyol mixture and polyurethane foam obtained by each Example and each comparative example is as follows.

(1) Amine-based catalyst KL-26: 2- (2-dimethylaminoethoxy) ethanol [manufactured by Kao Corporation, trade name: Kao Riser No. 26]
KL-23NP: 2- [2- (2-dimethylaminoethoxy) ethoxy] ethanol [manufactured by Kao Corporation, trade name: Kao Raiser No. 23NP]
KL-28: N- (2-dimethylaminoethyl) -N-methylethanolamine [manufactured by Kao Corporation, trade name: Kao Raiser No. 28]
KL-3: N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine [manufactured by Kao Corporation, trade name: Kao Raiser No. 3]
KL-12P: bis (2-dimethylaminoethyl) ether [manufactured by Kao Corporation, trade name: Kao Raiser No. 12P]
KL-31: Dipropylene glycol solution of 33% triethylenediamine [manufactured by Kao Corporation, trade name: Kao Raiser No. 31]
(2) Fatty acid amine salt / fatty acid amine salt A
A mixture of 141 g (0.5 mol) of a fatty acid mainly composed of oleic acid (trade name: LUNAC OA, manufactured by Kao Corporation) and 51 g (0.5 mol) of N, N-dimethylaminopropylamine And neutralized. The obtained neutralized salt was liquid. This neutralized salt was designated as fatty acid amine salt A.

・ Fatty acid amine salt B
Fatty acid mainly composed of oleic acid (trade name: LUNAC OA, manufactured by Kao Corporation) 141 g (0.5 mol) and N, N-dimethylaminopropylamine 25.5 g (0.25 mol) are mixed. And neutralized. The obtained neutralized salt was liquid. This neutralized salt was designated as fatty acid amine salt B.

・ Fatty acid amine salt C
A mixture of 141 g (0.5 mol) of a fatty acid mainly composed of oleic acid [trade name: LUNAC OA, manufactured by Kao Corporation] and 44.5 g (0.5 mol) of N, N-dimethylaminoethanol And neutralized. The obtained neutralized salt was liquid. This neutralized salt was designated as fatty acid amine salt C.

・ Fatty acid amine salt D
72 g (0.5 mol) of octanoic acid [manufactured by Kao Corporation, trade name: LUNAC 8-98] and 44.5 g (0.5 mol) of N, N-dimethylaminoethanol were mixed and neutralized. . The obtained neutralized salt was liquid. This neutralized salt was designated as fatty acid amine salt D.

(3) Surfactant, etc. ・ Lunac OA: Fatty acid mainly composed of oleic acid [manufactured by Kao Corporation, trade name: Lunac OA]
・ Emulgen 408: Nonionic surfactant (polyoxyethylene (8) oleyl ether) [trade name: Emulgen 408, manufactured by Kao Corporation]
Pelex OT-P: an anionic surfactant based on sodium di (2-ethylhexyl) sulfosuccinate (trade name: Pelex OT-P, manufactured by Kao Corporation)

Next, the compatibility of the obtained polyol mixture was examined by the following method. The result
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(1) Compatibility The compatibility at 20 ° C. of the polyol mixture (after storage at 20 ° C. for 1 day) was visually observed and evaluated based on the following evaluation criteria.
(Compatibility evaluation criteria)
○: Since it is transparent and uniform, compatibility is good. Δ: Some phase separation and turbidity are observed. ×: Phase separation is observed and compatibility is poor.

  Next, the polyol mixture and the isocyanate component (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumidur 44V20) are mixed and stirred at 20 ° C. using a laboratory mixer so that the theoretical isocyanate index is 50. Then, a polyurethane foam was produced using the obtained mixture, and the following characteristics were examined. The results are shown in Table 1.

(2) Reactivity The time required to reach cream time (hereinafter referred to as CT) and rise time (hereinafter referred to as RT) in free foaming of 20 g of the mixture stirred in a 300 mL polycup was measured.

(3) Core density 120 g of the mixture obtained by mixing and stirring the polyol mixture and the isocyanate component is poured into a mold [inner dimensions: 150 mm × 150 mm × 300 mm (height)] to form a polyurethane foam free form. did.

After leaving the polyurethane foam free foam for 1 day, a test piece having a size of 100 mm × 100 mm × 100 mm was cut out from the core portion. The weight of the specimen is measured and the formula:
[Core density] = [weight of specimen] / [volume of specimen]
Based on the above, the core density was determined.

(4) State inside the foam After leaving a free form of polyurethane foam similar to the above for one day, cut at the center along the foaming direction, visually observe the cut surface, and based on the following evaluation criteria evaluated.
〔Evaluation criteria〕
A: The inside of the foam is very good and the cell size is uniform.
○: The inside of the foam is good, and there is some disorder in the cell near the center inside the foam.
Δ: Cell roughness occurs near the center of the foam, or small voids occur.
X: A large void is generated inside the foam.

Examples 7-8 and Comparative Examples 6-7
As the polyol component, phthalate ester-based polyester polyol [hydroxyl value: 315 mgKOH / g, manufactured by Toho Rika Co., Ltd., trade name: phantol PL-305], ethylenediamine-based polyether polyol [hydroxyl value: 768 mgKOH / g Manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Actol AE-300, 30 parts by weight, and polyoxyalkylene polyol [hydroxyl value: 56 mgKOH / g, manufactured by Dow Chemical Co., Ltd. Propylenetriol)] 20 parts by weight were used.

100 parts by weight of polyol component, foam stabilizer [silicone foam stabilizer, manufactured by Toray Dow Silicone Co., Ltd., product number: L-5340], flame retardant [tris (2-chloroisopropyl) phosphate, Daihachi Chemical Industry Co., Ltd., product number: TMCPP] 20 parts by weight, 5 parts by weight of water as a blowing agent, amine catalyst, fatty acid amine salt and surfactant in the amounts shown in Table 2 were mixed in a lab mixer (mixing condition: 1 at 500 rpm) Stirring for a minute) to obtain a polyol mixture.
The compatibility of the obtained polyol mixture was examined by the same method as in Example 1. The results are shown in Table 2.

  Further, the polyol mixture and the isocyanate component [manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumidre 44V20] were mixed and stirred at 20 ° C. using a laboratory mixer so that the theoretical isocyanate index was 105. Polyurethane foams were produced using the obtained mixture, and their properties were examined in the same manner as in Example 1. The results are shown in Table 2.

  From the results shown in Table 1 and Table 2, according to each example, the polyol mixture is uniform and transparent even when a large amount of water is used as a foaming agent when producing polyurethane foam. Therefore, it is possible to reduce the complicated process of mixing and stirring the polyol mixture at the time of on-site construction, and increase the production efficiency of polyurethane foam.

  Moreover, according to each Example, since generation | occurrence | production of a void and a disorder | damage | failure of a cell are few, and also reactivity is high, it turns out that the polyurethane foam (heat insulating material) of the outstanding workability is obtained rapidly.

  The polyurethane foam of the present invention is a building material, a freezing warehouse, a heat insulating material such as a bathtub, a pipe, a dew condensation prevention material such as a detached house, an apartment or an industrial pipe, a building material part such as a bay window or a sash to maintain the product shape, etc. It can be suitably used as a lightweight core material or the like to be packed inside. In addition, the production method of the present invention can be suitably used particularly when producing a construction material such as a panel or a board on a factory line, especially a heat insulating material and a dew condensation prevention material of a field construction type by a spray method.

Claims (9)

Polyol for producing a polyurethane foam containing a polyol component, 4 parts by weight or more of water with respect to 100 parts by weight of the polyol component , and 3 to 20 parts by weight of a fatty acid amine salt having 10 to 24 carbon atoms with respect to 100 parts by weight of the polyol component blend.   The polyol mixture according to claim 1, wherein the fatty acid constituting the fatty acid amine salt contains one or more selected from the group consisting of oleic acid, linoleic acid, linolenic acid and ricinolenic acid.   The polyol mixture according to claim 1 or 2, wherein the amine compound constituting the fatty acid amine salt is an amine compound having a hydroxyl group and / or amino group that reacts with a tertiary amino group and an isocyanate group in the molecule. The polyol mixture in any one of Claims 1-3 whose molecular weight of the amine compound which comprises the fatty-acid amine salt is 120 or less. The polyol mixture in any one of Claims 1-4 containing 5-30 weight part water with respect to 100 weight part of polyol components. The manufacturing method of the polyurethane foam which makes the polyol mixture in any one of Claims 1-5 react with an isocyanate component. The polyurethane foam according to claim 6, wherein the reaction between the polyol mixture and the isocyanate component is carried out using one or more compounds selected from the group consisting of the following formula (I), the following formula (II) and the following formula (III). Manufacturing method.
(CH ₃ ) ₂ N (CH ₂ CH ₂ O) _n -H (I)
(Where n represents a number from 1 to 4)
(CH ₃ ) ₂ N CH ₂ CH ₂ N (CH ₃ ) X (II)
(Where X is CH ₂ CHYOH group, CH ₂ CH ₂ N (CH ₃ ) ₂ Group or CH ₂ CH ₂ N (CH ₃ ) CH ₂ CHYOH group, Y represents a hydrogen atom or a methyl group)
(CH ₃ ) ₂ NCH ₂ CH ₂ OCH ₂ CH ₂ N (CH ₃ ) Z (III)
Wherein Z is a methyl group or CH ₂ CHYOH group, Y is the same as above) Density is 8-20kg / m ³ The method for producing a polyurethane foam according to claim 6 or 7, wherein The heat insulating material which consists of a polyurethane foam obtained by the manufacturing method in any one of Claims 6-8 .