JP5365186B2 - Polyether polyol composition and method for producing rigid polyurethane foam using the same - Google Patents

Description

  The present invention relates to an alkylene oxide addition polymer of a formaldehyde condensate having 1.5 to 3 N-alkylalkanolamino groups in the molecule, and a method for producing a rigid polyurethane foam using the same.

  A rigid polyurethane foam is produced by reacting and foaming a polyol and a polyisocyanate in the presence of a blowing agent, a catalyst, a foam stabilizer, and, if necessary, other auxiliary agents such as a flame retardant and a crosslinking agent. Is widely practiced. This rigid polyurethane foam has a high degree of freedom in molding and has the most excellent heat insulating performance among plastic foams, and is therefore widely used as a heat insulating material for various devices or buildings. Among them, a spray method is often employed when manufacturing a rigid polyurethane foam as a heat insulating material for a building that is particularly large and requires high heat insulation performance.

  Here, the spray method means that a raw material liquid composed of a polyol system liquid and a polyisocyanate compound is fed into a spray gun used for spraying at a high pressure, and these raw material liquids are mixed inside the spray gun to be subjected to construction. It is a method of spraying directly on an object and instantaneously foaming and curing it when it arrives at the construction object, thereby forming a heat insulating material or the like. In this spray method, since it is sprayed in a mist state, it has a feature that a seamless heat insulation layer is formed by filling even a small gap, and at the same time as forming a heat insulation layer, it adheres to the construction object. In addition, there is an advantage that it is possible to reduce the cost by saving labor and shortening the construction period without requiring the ground treatment of the construction object. Furthermore, since it is easy to wipe a construction object having a complicated shape and continuous foaming is possible, it is possible to freely adjust the thickness of the heat insulating layer by spraying repeatedly. For this reason, the multi-layer spraying method is widely used among the spray methods for laminating rigid foams in multiple layers to form a thick heat insulating layer having high heat insulating performance.

  When constructing rigid polyurethane foam by this spray method, it is necessary to quickly foam and harden when the raw material liquid sprayed by the spray gun arrives at the construction object. For this reason, the raw material liquid is required to have high reactivity, and various studies have been made so far.

  Usually, in order to adjust the reactivity of the raw material liquid, it is considered to be a useful means to use a tertiary amine catalyst having excellent catalytic activity alone or in combination with an organometallic catalyst as necessary. .

  By the way, in order to obtain the reactivity suitable for constructing a rigid polyurethane foam by the spray method, it is necessary to use a large amount of these catalysts. However, these tertiary amine catalysts generally have high volatility and strong odor, so when used in a large amount, not only the working environment is significantly deteriorated, but also the resulting product may cause problems such as bad odor. There is sex.

  Therefore, in order to reduce the amount of use of these highly volatile tertiary amine catalysts, Mannich-based polymers produced using the Mannich reaction between phenols, primary or secondary monoamines, and aldehydes are used. Since ether polyols exhibit autocatalytic activity based on tertiary nitrogen atoms in the molecule, they are preferably used in this technical field.

  For example, Patent Document 1 (Japanese Patent Publication No. 2002-524630) discloses a Mannich polyether polyol obtained by adding an alkylene oxide to a condensate of phenol, N, N-diethanolamine and formaldehyde. Patent Document 2 (JP-A-8-301963) discloses a Mannich polyether polyol in which an alkylene oxide is added to a condensate of nonylphenol, N, N-diethanolamine and formaldehyde.

  However, the raw material liquid using the Mannich polyether polyol disclosed in Patent Document 1 and Patent Document 2 described above has a sufficiently satisfactory reactivity for constructing a rigid polyurethane foam by a spray method. Not in.

  Patent Document 3 (Japanese Patent Laid-Open No. 2003-335832) discloses a condensate of phenol, N, N-diethanolamine, alkylamine and formaldehyde. Patent Document 4 (Japanese Patent Application Laid-Open No. 2007-326953) discloses a Mannich polyether polyol in which an alkylene oxide is added to a condensate of phenols, N, N-diethanolamine, alkylamine and formaldehyde. Yes.

  However, the compounds disclosed in Patent Document 3 and Patent Document 4 have a strong odor per se, and the amine compound is generated at a relatively low temperature. Have.

Special Table 2002-524630 JP-A-8-301963 JP 2003-335832 A JP 2007-326953 A

  The present invention has been made in view of the above-mentioned background art, and its purpose is to use a polyol composition that provides high reactivity when a rigid polyurethane foam is applied by a spray method, and by using the polyol composition. An object of the present invention is to provide a method for producing a rigid polyurethane foam in which the amount of a volatile tertiary amine catalyst used can be reduced.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have found that when an alkylene oxide addition polymer of a condensate having an N-alkylalkanolamino group in the molecule is used as the polyol, a volatile tertiary compound is used. The inventors have found that a rigid polyurethane foam can be obtained at a high molding speed without impairing the mechanical strength of the obtained rigid polyurethane foam, and the present invention has been completed.

  That is, this invention is the polyether polyol composition which shows the high autocatalytic activity as shown below, its manufacturing method, and the manufacturing method of a rigid polyurethane foam using the same.

  [1] A phenol compound, N-alkylalkanolamines, and formaldehyde are reacted in a phenol compound: N-alkylalkanolamines: formaldehyde = 1: 1.5-3: 1.5-3 (molar ratio). A polyether polyol composition obtained by adding 1 to 20 moles of alkylene oxide to 1 mole of the phenol compound to the obtained formaldehyde condensate, having a hydroxyl value of 100 to 600 mgKOH / g, and A polyether polyol composition having a viscosity at 25 ° C. of 100 Pa · s or less.

  [2] The phenol compound is phenol, cresol, ethylphenol, xylenol, p-tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol, m-chlorophenol, o-bromophenol, resorcinol, catechol, hydroquinone The polyether polyol composition as described in [1] above, which is one or more selected from the group consisting of phloroglucinol, α-naphthol, β-naphthol, and β-hydroxyanthracene.

  [3] The N-alkylalkanolamines are N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-methylpropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N- The polyether polyol composition as described in [1] or [2] above, which is one or more selected from the group consisting of methyl-2-hydroxybutylamine and N-methylhexanolamine.

  [4] Any one of [1] to [3], wherein the alkylene oxide is one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. The polyether polyol composition described in 1.

[5] The method for producing a polyether polyol composition according to any one of the above [1] to [4], comprising the following steps.
(1) A phenol compound, an N-alkylalkanolamine, and formaldehyde are reacted in a phenol compound: N-alkylalkanolamine: formaldehyde = 1: 1.5-3: 1.5-3 (molar ratio). One step,
(2) A second step in which 1 to 20 mol of alkylene oxide is added to the formaldehyde condensate obtained in the first step with respect to 1 mol of the phenol compound used in the first step.

  [6] In the first step, the phenol compound is phenol, cresol, ethylphenol, xylenol, p-tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol, m-chlorophenol, o-bromophenol, The polyether according to [5] above, wherein the polyether is one or more selected from the group consisting of resorcinol, catechol, hydroquinone, phloroglucinol, α-naphthol, β-naphthol, and β-hydroxyanthracene. Polyol composition.

  [7] In the first step, N-alkylalkanolamines are N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-methylpropanolamine, N-methylisopropanolamine, N-ethyl. The polyether polyol as described in [5] or [6] above, wherein the polyether polyol is one or more selected from the group consisting of isopropanolamine, N-methyl-2-hydroxybutylamine, and N-methylhexanolamine. Composition.

  [8] In the second step, the alkylene oxide to be added to the formaldehyde condensate obtained in the first step is one or more selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. The polyether polyol composition according to any one of [5] to [7] above, which is an alkylene oxide.

  [9] A method for producing a polyurethane foam by reacting a polyol with a polyisocyanate compound in the presence of a foaming agent, wherein the polyol is a polyalkyl group according to any one of the above [1] to [4]. A method for producing a rigid polyurethane foam, comprising an ether polyol composition.

  [10] The above [9], wherein the ratio of the polyether polyol composition according to any one of [1] to [4] to the total amount of polyols used is in the range of 5 to 100% by weight. ] The manufacturing method of the rigid polyurethane foam as described in.

In the present invention, the rigid polyurethane foam refers to a foam that has a highly crosslinked closed cell structure and cannot be reversibly deformed. The physical properties of the rigid polyurethane foam are not particularly limited, but are generally in the range of a density of 10 to 100 kg / m ³ and a compressive strength of 50 to 1000 kPa.

  Since the polyether polyol composition of the present invention has a high degree of autocatalytic activity in urethane formation, it is useful as a polyol for producing rigid polyurethane foam.

  Further, according to the method for producing a rigid polyurethane foam of the present invention, high reactivity capable of being applied to the spray method can be obtained even if the amount of the volatile tertiary amine catalyst used is greatly reduced.

  Furthermore, according to the method for producing a rigid polyurethane foam of the present invention, excellent workability can be obtained in the spray method, particularly in the multilayer spraying method.

  The polyether polyol composition of the present invention comprises a phenol compound, an N-alkylalkanolamine, and formaldehyde, and a phenol compound: N-alkylalkanolamine: formaldehyde = 1: 1.5-3: 1.5-3 ( It is a polyether polyol composition obtained by addition reaction of 1 to 20 mol of alkylene oxide to 1 mol of the phenol compound to a formaldehyde condensate obtained by reacting at a molar ratio).

  The polyether polyol composition of the present invention has a hydroxyl value in the range of usually 100 to 600 mgKOH / g, preferably 200 to 600 mgKOH / g, and its viscosity at 25 ° C. is usually 100 Pa · s or less. , Preferably 70 Pa · s or less.

The manufacturing method of the polyether polyol composition of the present invention includes the following steps.
(1) A phenol compound, an N-alkylalkanolamine, and formaldehyde are reacted in a phenol compound: N-alkylalkanolamine: formaldehyde = 1: 1.5-3: 1.5-3 (molar ratio). One step,
(2) A second step in which 1 to 20 mol of alkylene oxide is added to the formaldehyde condensate obtained in the first step with respect to 1 mol of the phenol compound used in the first step.

  First, the first step of the present invention will be described.

  In the present invention, examples of the phenol compound include compounds having at least one phenolic hydroxyl group bonded to a carbon atom of an aromatic ring.

  The phenol compound may be substituted with a substituent that does not affect the reaction during the reaction for producing the formaldehyde condensate, the addition reaction of the alkylene oxide, the production of the rigid polyurethane foam, or the like.

  Examples of such a substituent include an alkyl group, a cycloalkyl group, an alkoxyl group, a phenoxy group, a nitro group, and a halogen atom. In the present invention, preferred substituents include alkyl groups having 1 to 18 carbon atoms, and more preferred substituents include alkyl groups having 1 to 12 carbon atoms.

  Specific examples of the phenol compound include phenol, cresol, ethylphenol, xylenol, p-tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol, m-chlorophenol, o-bromophenol, resorcinol, Examples include catechol, hydroquinone, phloroglucinol, α-naphthol, β-naphthol, β-hydroxyanthracene, and mixtures thereof. In the present invention, phenol, cresol, octylphenol, nonylphenol, and a mixture thereof are preferable from the viewpoint of easy availability.

  Examples of the N-alkylalkanolamines include N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-methylpropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N- Examples thereof include methyl-2-hydroxybutylamine and N-methylhexanolamine, and N-methylethanolamine is preferable from the viewpoint of imparting high reactivity to the polyether polyol composition of the present invention.

  The form of the formaldehyde is not particularly limited. For example, formalin (37% formaldehyde aqueous solution), methanol solution of formaldehyde, paraformaldehyde and the like are preferably used. In the present invention, when the formaldehyde is used as formalin, a methanol solution of formaldehyde, paraformaldehyde or the like, the amount used is calculated by the number of moles in terms of formaldehyde.

  In the present invention, the molar ratio of the phenol compound and the N-alkylalkanolamine is in the range of 1: 1.5 to 3 mol. When the N-alkylalkanolamine is less than 1.5 moles relative to 1 mole of the phenol compound, the resulting polyether polyol composition has a low viscosity but a low average functional group number. For this reason, when using the obtained polyether polyol composition for manufacture of a rigid polyurethane foam, the obtained rigid polyurethane foam has the fault that it becomes easy to shrink | contract. Moreover, when N-alkyl alkanolamines to be used exceed 3 mol, the reaction point at which the phenol compound can be condensed is exceeded, so that the N-alkylalkanolamines remain unreacted. For this reason, when the polyether polyol composition obtained is used for the production of rigid polyurethane foam, unreacted N-alkylalkanolamines can act as a catalyst to improve the reactivity, but the average number of functional groups decreases. For this reason, the obtained rigid polyurethane foam has a disadvantage that it easily contracts. Therefore, in the present invention, the N-alkylalkanolamines are used in an amount of 1.5 to 3 mol, preferably 1.7 to 3 mol, per 1 mol of the phenol compound.

  In the present invention, the molar ratio of the phenol compound to the formaldehyde is in the range of 1: 1.5 to 3 mol. When the amount of formaldehyde is less than 1.5 moles relative to 1 mole of the phenol compound, the average number of functional groups of the resulting polyether polyol composition becomes small, and the resulting rigid polyurethane foam is likely to shrink. Further, when the amount of formaldehyde exceeds 3 mol, the reaction point exceeds the condensable reaction point of the phenol compound, so that the formaldehyde remains as an unreacted substance or exhibits a crosslinking reaction between the phenol rings. In addition, the rigid polyurethane foam produced using the polyether polyol composition obtained has disadvantages that uniform cells cannot be obtained. Therefore, in the present invention, formaldehyde is used in an amount of 1.5 to 3 mol, preferably 1.7 to 3 mol, per mol of the phenol compound.

  In the present invention, the formaldehyde condensate can be obtained by mixing and reacting the phenol compound, the N-alkylalkanolamines, and formaldehyde at the predetermined molar ratio described above. The order of adding these raw material compounds is not particularly limited. For example, a predetermined amount of a phenol compound and N-alkylalkanolamines are mixed, and while stirring, formaldehyde is controlled to generate heat. However, it is preferably added at a temperature of 90 ° C. or lower. As the addition method at this time, continuous dropping or divided charging is preferred. After completion of the addition of formaldehyde, the mixture is heated at a temperature of usually 40 to 130 ° C., preferably 50 to 100 ° C., for a time sufficient for the unreacted N-alkylalkanolamines to be 5% by weight or less in the reaction mixture. When the reaction temperature is less than 40 ° C., the reaction does not proceed easily, and the amount of unreacted N-alkylalkanolamines is less than 5% by weight in a practical time. Moreover, when reaction temperature exceeds 130 degreeC, there exists a possibility that side reactions, such as high molecularization of a phenol compound and thermal decomposition of a formaldehyde condensate, may occur. The amount of unreacted N-alkylalkanolamines in the reaction mixture can be measured by high performance liquid chromatography.

  In the present invention, in the first step, water is generated by a condensation reaction. When a formalin aqueous solution is used, water is present in the reaction product. In the production method of the present invention, it is preferable to remove water from the reaction product by an appropriate method. As a method for removing water, for example, a method of heating at a temperature of 120 ° C. or less, preferably 100 ° C. or less and dehydrating under reduced pressure can be mentioned.

  Next, the second step of the present invention will be described.

  In the present invention, a polyether polyol composition is produced by adding the above-mentioned predetermined amount of alkylene oxide to the formaldehyde condensate obtained in the first step.

  In the present invention, the alkylene oxide is not particularly limited. For example, one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide are preferably used. .

  In this invention, the quantity of the alkylene oxide added to the said formaldehyde condensate is the range of 1-20 mol with respect to 1 mol of phenol compounds used at the above-mentioned 1st process. When the amount of the alkylene oxide is less than 1 mole relative to 1 mole of the phenol compound used, the resulting polyether polyol composition has a higher hydroxyl value and viscosity. For this reason, the resulting polyether polyol composition is When used in the production of rigid polyurethane foam, poor mixing occurs. In addition, when the amount of alkylene oxide exceeds 20 mol with respect to 1 mol of the phenol compound used, when the resulting polyether polyol composition is used for the production of a rigid polyurethane foam, only a polyurethane foam that is soft and easily shrinks. I can't get it. Therefore, in this invention, 1-20 mol is used with respect to 1 mol of phenolic compounds used at the above-mentioned 1st process, Preferably said alkylene oxide is used 1.5-10 mol.

  In the addition reaction of alkylene oxide to the formaldehyde condensate, for example, the addition form when different types of alkylene oxide are used together may be either a block addition form or a random addition form.

  The addition reaction for adding alkylene oxide to the formaldehyde condensate is usually performed in a temperature range of 60 to 160 ° C, preferably 80 to 130 ° C. When the reaction temperature is less than 60 ° C., a practical reaction rate is difficult to obtain, and when the reaction temperature exceeds 160 ° C., side reactions occur, and in extreme cases, solidification may occur inside the reactor. It is difficult to obtain a polyether polyol composition having desired properties.

  In addition, the addition reaction of alkylene oxide to the formaldehyde condensate has a catalytic action, so that the addition reaction occurs even in the absence of a catalyst. However, in order to obtain a practical reaction rate, a catalyst is used. It may be used. Specific examples include alkali metal hydroxides such as potassium hydroxide and sodium hydroxide, tertiary amines such as dimethylaminoethanol and 1-methylimidazole.

  In the present invention, since unreacted alkylene oxide remains in the addition reaction product, it is preferably removed by stripping or the like. Moreover, when a catalyst is used, it is preferable to remove from a reaction product according to a conventional method.

  The polyether polyol composition of the present invention is suitably used as a polyol for producing rigid polyurethane foam.

  The method for producing a rigid polyurethane foam of the present invention is a method for producing a polyurethane foam by reacting a polyol and a polyisocyanate compound in the presence of a foaming agent, wherein the polyol is the above-described polyether of the present invention. It is characterized by containing a polyol composition.

  In the method for producing a rigid polyurethane foam of the present invention, the polyether polyol composition of the present invention can be used alone as a polyol. Moreover, it can also use together with another polyol. The ratio of the polyether polyol composition of the present invention to the total amount of polyols used is preferably in the range of 5 to 100% by weight.

  The other polyol that can be used in combination with the polyether polyol composition of the present invention may be a polyol generally used in a method for producing a rigid polyurethane foam, and is not particularly limited. For example, ethylene glycol, propylene glycol, butane Polyhydric alcohols such as diol, hexanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sucrose; aliphatic polyether polyols obtained by addition polymerization of alkylene oxide to these polyhydric alcohols; hydroquinone, bisphenol A, aromatic polyether polyols obtained by addition polymerization of alkylene oxide to aromatic compounds such as xylylene glycol; ethylenediamine, diethylenetriamine, triethylene Amine-based polyether polyols obtained by addition polymerization of alkylene oxide using tolamine, aniline, monoethanolamine, diethanolamine, triethanolamine and the like as initiators; aromatic dicarboxylic acids such as terephthalic acid, phthalic acid, and isophthalic acid; Aromatic polyester polyols having a hydroxyl terminal based on glycol with glycol such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, polyoxyethylene glycol having an average molecular weight of 150 to 500, and the like Is mentioned.

  The polyisocyanate compound used in the method for producing a rigid polyurethane foam of the present invention may be a polyisocyanate generally used in the method for producing a rigid polyurethane foam, and is not particularly limited. For example, tolylene diisocyanate ( Hereinafter, abbreviated as TDI), diphenylmethane diisocyanate (hereinafter abbreviated as MDI), aromatic polyisocyanates such as naphthylene diisocyanate and xylylene diisocyanate; hexamethylene diisocyanate (hereinafter abbreviated as HDI), isophorone diisocyanate (hereinafter referred to as “HDI”). , Abbreviated as IPDI.) And the like. Among these, TDI and its derivatives, or MDI and its derivatives are preferable, and these may be used in combination.

  Examples of TDI and its derivatives include a mixture of 2,4-TDI and 2,6-TDI, or a terminal isocyanate prepolymer derivative of TDI. Examples of MDI and its derivatives include a mixture of MDI and its polymer polyphenylpolymethylene diisocyanate, and / or a diphenylmethane diisocyanate derivative having a terminal isocyanate group.

  The mixing ratio of these polyisocyanate compounds and polyols is not particularly limited, but is generally in the range of 60 to 400 in terms of isocyanate index (= isocyanate group / active hydrogen group capable of reacting with isocyanate group). .

  Examples of the foaming agent used in the method for producing the rigid polyurethane foam of the present invention include water, chlorofluorocarbon compounds, low boiling point hydrocarbons, carbon dioxide gas, etc. Among these, water is particularly preferable. Further, chlorofluorocarbon compounds, low-boiling hydrocarbons, carbon dioxide gas and the like may be used in combination with water.

  The fluorocarbon compound may be a conventionally known compound and is not particularly limited. For example, dichloromonofluoroethane (HCFC-141b), 1,1,1,3,3-pentafluoropropane (HFC-245fa) is used. ), 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and the like. Among these, 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) are preferable from the problem of ozone layer destruction. .

  As the low-boiling hydrocarbons, hydrocarbons having a boiling point of 0 to 70 ° C. are usually used, and specific examples include propane, butane, pentane, cyclopentane, cyclohexane, and mixtures thereof.

  In the method for producing the rigid polyurethane foam of the present invention, a catalyst can be used. The catalyst may be a catalyst generally used in the production of polyurethane foam, and is not particularly limited. For example, an organic metal catalyst, a carboxylic acid metal salt catalyst, a tertiary amine catalyst, a quaternary ammonium salt catalyst. Etc.

  The organometallic catalyst may be a conventionally known one, and is not particularly limited. For example, bismuth octoate, bismuth neodecanoate, zinc octoate, zinc neodecanoate, zinc naphthenate, nickel octanoate, nickel naphthenate And cobalt naphthenate. Since heavy metals such as lead, tin, and mercury may cause toxicity problems and environmental problems, it is desirable to use less.

  The carboxylic acid metal salt catalyst may be a conventionally known catalyst and is not particularly limited, and examples thereof include alkali metal salts and alkaline earth metal salts of carboxylic acids. The carboxylic acid is not particularly limited, but examples thereof include aliphatic monocarboxylic acids such as acetic acid, propionic acid, 2-ethylhexanoic acid, and adipic acid, and aromatic monocarboxylic acids such as dicarboxylic acid, benzoic acid, and phthalic acid. Examples thereof include carboxylic acid and dicarboxylic acid. Suitable examples of the metal forming the carboxylate include alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as calcium and magnesium.

  The tertiary amine catalyst may be a conventionally known one, and is not particularly limited. For example, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetra Methylpropylenediamine, 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′-dimethylpipe Gin, dimethylcyclohexylamine, N-methylmorpholine, N-ethylmorpholine, bis (2-dimethylaminoethyl) ether, 1-methylimidazole, 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1-dimethyl And tertiary amine compounds such as aminopropylimidazole.

  The quaternary ammonium salt catalyst may be a conventionally known one, and is not particularly limited. For example, tetraalkylammonium halides such as tetramethylammonium chloride, tetraalkylammonium water such as tetramethylammonium hydroxide salts, and the like. Tetraalkylammonium organics such as oxides, tetramethylammonium 2-ethylhexanoate, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium formate, 2-hydroxypropyltrimethylammonium 2-ethylhexanoate Examples include acid salts.

  In the method for producing a rigid polyurethane foam of the present invention, if necessary, a surfactant can be used as a foam stabilizer. Examples of the surfactant to be used include conventionally known organosilicone surfactants, and specifically, nonionic systems such as organosiloxane-polyoxyalkylene copolymers and silicone-grease copolymers. Surfactant or a mixture thereof may be used. Their use amount is usually in the range of 0.1 to 10 parts by weight per 100 parts by weight of polyols.

  In the method for producing a rigid polyurethane foam of the present invention, a flame retardant can be used if necessary. Examples of the flame retardant used include reactive flame retardants represented by phosphorus-containing polyols such as propoxylated phosphoric acid and propoxylated dibutyl pyrophosphate obtained by addition reaction of phosphoric acid and alkylene oxide; Tertiary phosphate esters such as diphosphate; Halogen-containing tertiary phosphate esters such as tris (2-chloroethyl) phosphate, tris (chloropropyl) phosphate; dibromopropanol, dibromoneopentyl glycol, tetrabromobisphenol A And halogen-containing organic compounds such as antimony oxide, magnesium carbonate, calcium carbonate, and aluminum phosphate. The amount of use varies depending on the required flame retardancy and is not particularly limited, but is usually in the range of 4 to 20 parts by weight with respect to 100 parts by weight of polyols.

  In the method for producing a rigid polyurethane foam of the present invention, a crosslinking agent or a chain extender can be used if necessary. Examples of the crosslinking agent or chain extender include conventionally known low molecular weight polyhydric alcohols such as ethylene glycol, 1,4-butanediol and glycerin; low molecular weight amine polyols such as diethanolamine and triethanolamine; ethylenediamine And polyamines such as xylylenediamine and methylenebisorthochloroaniline.

  In the method for producing the rigid polyurethane foam of the present invention, a coloring agent, an anti-aging agent, and other conventionally known additives can be used as necessary. The type and amount of these additives may be within the normal usage range of the additive used.

  The method for producing the rigid polyurethane foam of the present invention is carried out by rapidly mixing and stirring the mixed solution in which the raw materials are mixed, and then injecting the mixture into a suitable container or mold to perform foam molding. Mixing and stirring may be performed using a general stirrer or a dedicated polyurethane foaming machine. As the polyurethane foaming machine, high-pressure, low-pressure and spray-type devices can be used.

  The method for producing a rigid polyurethane foam of the present invention is suitable for a construction method requiring a quick reaction, particularly a spray method. The spray method is a foaming method in which a raw material liquid composed of a polyol system liquid and a polyisocyanate compound is reacted while sprayed on a construction object. As the spray method, various methods are known and are not particularly limited. For example, a polyol system liquid and a polyisocyanate compound are mixed inside a spray gun and sprayed on an object to be foamed and cured. The preferred formulation is airless spray foaming.

  As a hard polyurethane foam product obtained by the method for producing a rigid polyurethane foam of the present invention, for example, a heat insulating material produced by a spray-type rigid urethane foam is preferable.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not construed as being limited to these examples.

[Example 1]
A 1 L four-necked flask equipped with a reflux condenser was charged with 94.1 g (1.0 mol) of phenol and 225.3 g (3.0 mol) of N-methylethanolamine and stirred at 60 ° C. in a nitrogen atmosphere. The temperature was raised to. Subsequently, 243.5 g of a 37% aqueous formaldehyde solution (3.0 mol in terms of formaldehyde) was added dropwise over about 1 hour so that the internal temperature was 90 ° C. or lower, and an aging reaction was performed at 60 ° C. for 10 hours.

  After completion of the reaction, analysis was performed using high performance liquid chromatography. As a result, it was confirmed that all the starting phenol disappeared and the amount of unreacted N-methylethanolamine was 2.2% by weight.

Subsequently, dehydration was performed under reduced pressure at 90 ° C. to 0.13 kPa, so that the residual water content was 0.3% by weight.
Furthermore, 355.5 g of the formaldehyde condensate obtained in a 1 L autoclave and 9.0 g of 30% potassium hydroxide aqueous solution (0.75% by weight in terms of potassium hydroxide with respect to the formaldehyde condensate) were charged and reacted. After the air in the vessel was replaced with nitrogen, the temperature was raised to 90 ° C. with stirring. The pressure was reduced to 0.13 kPa at 90 ° C. to remove water from the reactor. The reactor was purged with nitrogen again, and the temperature was raised to 100 ° C. with stirring. Then, 285.8 g (4.9 mol) of propylene oxide (4.9 mol) was added at a temperature of 100 ° C. to 2.0 ml. / Min. And a ripening reaction was carried out at 100 ° C. for 4 hours.

After completion of the reaction, the crude polyether polyol containing the resulting catalyst is purified by adding water and an alkaline adsorbent “KYOWARD 600 (manufactured by Kyowa Chemical Industry Co., Ltd.)”, purification by adsorption treatment, filtration and drying. Polyol A was obtained.
As a result of analysis of the polyether polyol A, the hydroxyl value was 431 mgKOH / g, and the viscosity at 25 ° C. was 18.4 Pa · s.

[Examples 2-4], [Comparative Examples 1-2]
Except making the usage-amount (unit: mol) of each raw material as Table 1, it carried out similarly to Example 1 and obtained polyether polyol BF.

なお、表１において、３７％のホルムアルデヒド水溶液におけるホルムアルデヒドのモル数を換算したものを「ホルムアルデヒド」の欄に表示した。

In Table 1, the conversion of the number of moles of formaldehyde in a 37% aqueous formaldehyde solution is displayed in the “Formaldehyde” column.

  Furthermore, the unit of “hydroxyl value” is mgKOH / g, “viscosity” indicates the viscosity at 25 ° C., and the unit is Pa · s.

[Examples 5-8], [Comparative Examples 3-5] Preparation of rigid polyurethane foam.
Each polyol E obtained in Comparative Examples 1 and 2 was taken as an example using a polyol composition consisting of polyols A to D obtained in Examples 1 to 4 and an aromatic polyester polyol as the polyol. , F and an example using a polyol composition comprising an aromatic polyester polyol are shown below as comparative examples.

  Premix A was prepared at the raw material mixing ratio shown in Table 2.

表２で示す配合の各プレミックスＡ６５ｇを３００ｍｌポリエチレンカップに計量し、２０℃に温度調整した。別容器で２５℃に温度調整したイソシアネート液を、イソシアネートインデックス［＝イソシアネート基／ＯＨ基（モル比）×１００］が１００となるように、プレミックスＡのカップの中に入れ、素早く撹拌機にて６０００ｒｐｍで３秒間撹拌した。混合撹拌した混合液を２０℃に温度調節した２Ｌのポリエチレンカップに移し発泡中の反応性を測定した。

65 g of each premix A having the formulation shown in Table 2 was weighed into a 300 ml polyethylene cup, and the temperature was adjusted to 20 ° C. Put the isocyanate liquid adjusted to 25 ° C. in a separate container into the premix A cup so that the isocyanate index [= isocyanate group / OH group (molar ratio) × 100] is 100, and quickly put it in the stirrer. And stirred at 6000 rpm for 3 seconds. The mixed and stirred mixture was transferred to a 2 L polyethylene cup whose temperature was adjusted to 20 ° C., and the reactivity during foaming was measured.

  After 30 minutes from the time when the mixed solution was added, the foam was removed from the mold, a 7 cm × 7 cm × 20 cm core foam was cut out, and the core density was measured. Further, two cubic foams having a side of 4.5 cm were cut out, and the compressive strengths in the horizontal and vertical directions were measured and compared. The results are shown in Table 3. The measurement method for each measurement item is as follows.

（１）測定項目
クリームタイム：フォームが上昇開始する時間を目視にて測定した。

(1) Measurement item Cream time: The time when the foam started to rise was measured visually.

  Gel time: The time required for the reaction to progress to a resinous substance from a liquid substance was measured. It can be said that the shorter the gel time, the faster the molding speed.

  Rise time: The time for the rising of the foam to stop was measured visually.

  Core density: The core density was calculated by cutting the center part of the molded foam into a size of 7 × 7 × 20 cm and measuring the size and weight accurately.

  Compressive strength: A foam having a size of 4.5 × 4.5 × 4.5 cm was cut out from a foam whose core density was measured, and a hardness test was performed according to JIS K 7220. That is, in accordance with JIS K 7220, when a test piece is placed flat on a table of a testing machine, a circular pressure plate having a radius of 10 cm is placed on the upper surface of the test piece, and the load is 0.5 kgf (4.9 N). Was measured as the initial thickness. Next, the compressive stress when the circular pressure plate was pushed in by 25% of the initial thickness was read.

  The foam hardness was calculated using the following formula and was defined as compressive strength.

Foam hardness (N / m ² )
= Compressive stress obtained using a circular pressure plate (N) ÷
The area (m ² ) of the foam part grounded to the circular pressure plate.

  As is clear from Table 3, when the reactivity of Examples 5 to 8 and Comparative Examples 3 and 4 are compared, in Examples 5 to 8, the gel time is short and the molding speed is fast. Moreover, when Example 5-Example 8 and the reactivity of the comparative example 5 which increased the amount of tertiary amine catalysts were compared, the equivalent gel time was shown. That is, polyols A to D using N-methylethanolamine can obtain the same molding speed even if the amount of the tertiary amine catalyst is reduced compared to polyols E and F using N, N-diethanolamine. It was suggested that

  Further, as is apparent from Table 3, when the foam properties of Examples 5 to 8 and Comparative Examples 3 and 4 are compared, the core density, compressive strength (horizontal) and compressive strength (vertical) are the same. there were. That is, it was shown that the polyols A to D using N-methylethanolamine have the same foam physical properties as the polyols E and F using N, N-diethanolamine.

Claims (8)

Phenolic compounds, N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-methylpropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-methyl-2-hydroxybutylamine, and N -One or more N -alkylalkanolamines selected from the group consisting of methylhexanolamine, and formaldehyde, phenol compound: N-alkylalkanolamines: formaldehyde = 1: 1.5-3: 1.5 A polyether polyol composition obtained by adding 1 to 20 moles of alkylene oxide to 1 mole of the phenol compound to a formaldehyde condensate obtained by reacting at ~ 3 (molar ratio). A polyether polyol composition having a viscosity of 100 to 600 mg KOH / g and a viscosity at 25 ° C. of 100 Pa · s or less. The phenol compound is phenol, cresol, ethylphenol, xylenol, p-tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol, m-chlorophenol, o-bromophenol, resorcinol, catechol, hydroquinone, phlorog. The polyether polyol composition according to claim 1, wherein the polyether polyol composition is one or more selected from the group consisting of lucinol, α-naphthol, β-naphthol, and β-hydroxyanthracene. The polyether polyol composition according to claim 1 or 2, wherein the alkylene oxide is one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. object. The manufacturing method of the polyether polyol composition in any one of the Claims 1 thru | or 3 containing the following processes.
(1) Phenol compound, N-methylethanolamine, N-ethylethanolamine, N-isopropylethanolamine, N-methylpropanolamine, N-methylisopropanolamine, N-ethylisopropanolamine, N-methyl-2-hydroxybutylamine And one or more N -alkylalkanolamines selected from the group consisting of N-methylhexanolamine, and formaldehyde, phenol compound: N-alkylalkanolamines: formaldehyde = 1: 1.5-3: 1st process made to react by 1.5-3 (molar ratio),
(2) A second step in which 1 to 20 mol of alkylene oxide is added to the formaldehyde condensate obtained in the first step with respect to 1 mol of the phenol compound used in the first step. In the first step, the phenol compound is phenol, cresol, ethylphenol, xylenol, p-tert-butylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol, m-chlorophenol, o-bromophenol, resorcinol, catechol. The polyether polyol composition according to claim 4, wherein the polyether polyol composition is one or more selected from the group consisting of hydroquinone, phloroglucinol, α-naphthol, β-naphthol, and β-hydroxyanthracene . Manufacturing method . In the second step, the alkylene oxide to be added to the formaldehyde condensate obtained in the first step is one or more alkylene oxides selected from the group consisting of ethylene oxide, propylene oxide, and butylene oxide. The method for producing a polyether polyol composition according to claim 4 or 5, wherein: A method for producing a polyurethane foam by reacting a polyol and a polyisocyanate compound in the presence of a foaming agent, wherein the polyol is a polyether polyol composition according to any one of claims 1 to 3 . A method for producing a rigid polyurethane foam, comprising: The ratio of the polyether polyol composition according to any one of claims 1 to 3 to the total amount of polyols to be used is in the range of 5 to 100% by weight. A method for producing polyurethane foam.