JP2005350555A - Method for producing polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol mixture improving compatibility of a polyol component with a hydrofluorocarbon without using a compound having a risk of adversely affecting human bodies, reducing vapor pressure, suppressing swelling of a drum and avoiding the risk and to provide an additive for the polyol mixture. <P>SOLUTION: The polyol mixture comprises the polyol component, a foaming agent containing the hydrofluorocarbon and a compound represented by formula (I): R<SP>1</SP>-(OCHR<SP>2</SP>CHR<SP>2</SP>)<SB>n</SB>OCOR<SP>3</SP>(I) (wherein, R<SP>1</SP>is a 1-4C alkyl group; R<SP>2</SP>is a hydrogen atom or a methyl group; R<SP>3</SP>is a 1-4C alkyl group; and n is 1-3). <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a method for producing a polyurethane foam. More specifically, the present invention relates to a method for producing a rigid polyurethane foam that can be suitably used as a heat insulating material for building materials, electric refrigerators, refrigerated warehouses, pipes, and the like, and a polyol mixture that can be suitably used for the production method. The manufacturing method of the present invention can be suitably used particularly when manufacturing a construction material such as a panel or a board in a factory line, particularly a heat-insulating material and an anti-condensation material of an on-site construction type by a spray method.

  Rigid polyurethane foam (including isocyanurate ring-containing polyisocyanurate foam; the same applies hereinafter) is used as a heat insulating material for building materials, electric refrigerators, refrigerated warehouses, bathtubs, pipes, etc. because of its good heat insulating properties and flame retardancy Has been.

  For example, when the rigid polyurethane foam is used as a heat insulating material such as a house or building construction material, a foaming agent, a catalyst, It is manufactured by a method of mixing in the presence of other auxiliary agents as required, spraying it on 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, 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3 have been proposed as foaming agents from the viewpoint of avoiding destruction of the ozone layer and global warming in the stratosphere. Hydrofluorocarbons such as 1,3-pentafluorobutane (HFC-365mfc) have been studied.

  However, when they are used, not only the compatibility with the raw materials deteriorates, but in the case of a blowing agent with a high content of HFC-245fa, which has a low boiling point, the vapor pressure becomes high, and the polyol mixture Since the drum you put in will swell, it will be in a dangerous state. In particular, when a phthalic acid-based polyester polyol is used for imparting flame retardancy to the polyol component, the compatibility deteriorates significantly, and not only phase separation between the polyol component and the blowing agent occurs, The polyol component and the isocyanate component cannot be homogeneously mixed, and the polyurethane foam is likely to have spots or voids.

  It is already known to use a phthalic acid ester, a phosphoric acid ester, a cyclic carbonate, an alkylphenol compound or the like as a viscosity reducing agent, a plasticizer or a compatibilizing agent for a polyurethane composition (for example, Patent Document 1 and 2). In addition, nonionic compounds for improving the compatibility of raw materials for polyurethane foam have also been proposed (see, for example, Patent Document 3).

  On the other hand, in order to reduce the vapor pressure when hydrofluorocarbon is used as a foaming agent, it has been proposed to use a halogen-containing compound, a fluorine-containing surfactant, or the like (see, for example, Patent Document 4).

  However, compounds generally used as a viscosity reducing agent or compatibilizing agent for polyurethane are represented by di (2-ethylhexyl) phthalate, tris (2-chloropropyl) phosphate, and polyoxyethylene nonylphenyl ether. In addition, it is often an environmentally hazardous substance, and sufficient compatibility and vapor pressure reduction effects cannot be obtained.

Japanese Patent Laid-Open No. 11-166033 JP 2003-231728 A JP 2002-356528 International Publication No. 03/042268 Pamphlet

  Even when a foaming agent containing hydrofluorocarbon is used, the present invention improves the compatibility between the polyol component and the hydrofluorocarbon without using a compound that may adversely affect the human body, and reduces the vapor pressure. It is an object of the present invention to provide a polyol mixture that can suppress danger by suppressing expansion of the drum by reducing the amount, and an additive for a polyol mixture that can be suitably used for the polyol mixture.

  Another object of the present invention is to provide a method for producing a polyurethane foam which can achieve homogeneous mixing of a polyol component and an isocyanate component, and can achieve homogenization and stabilization of cells.

The present invention
(1) (A) polyol component,
(B) a blowing agent containing a hydrofluorocarbon,
(C) Formula (I):
R ^1- (OCHR ² CHR ² ) _n OCOR ³ (I)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ² is independently a hydrogen atom or a methyl group, and R ³ is a linear or branched chain having 1 to 4 carbon atoms. An alkyl group, n represents a number of 1 to 3)
A compound represented by formula (II):

(In the formula, each R ⁴ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A compound represented by formula (III):

(Wherein R ⁵ represents a hydrogen atom or a methyl group)
And a compound represented by formula (IV):

(In the formula, each R ⁶ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
One or more compounds X selected from the group consisting of the compounds represented by formula (V):
R ⁷ O - [(EO) x · (PO) y ] - (EO) z -H (V )
(In the formula, R ⁷ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. X and z are average additions of oxyethylene groups, respectively. The number of moles is 1 or more, and the sum of x and z is 3 or more, and y is a number of 1 or more that represents the average number of moles of oxypropylene groups added, [(EO) x (Additional form of (PO) y] is random addition, block addition, or a mixed addition thereof, [(EO) x-(PO) y] and (EO) z are block-bonded)
A polyol mixture comprising a nonionic compound represented by:
(2) A process for producing a polyurethane foam in which the polyol mixture is reacted with an isocyanate component, and (3) a compound represented by formula (I), a compound represented by formula (II), and a formula (III) And at least one compound X selected from the group consisting of compounds represented by formula (IV) and a nonionic compound represented by formula (V), and used together with a hydrofluorocarbon The present invention relates to an additive for a polyol mixture.

  According to the polyol mixture additive of the present invention and the polyol mixture in which the polyol mixture is used, the polyol can be used without using a compound that may adversely affect the human body even when a foaming agent containing hydrofluorocarbon is used. The compatibility between the component and the hydrofluorocarbon can be improved, the vapor pressure can be reduced, and the expansion of the drum can be suppressed to avoid danger.

  In addition, according to the method for producing a polyurethane foam of the present invention, homogeneous mixing of the polyol component and the isocyanate component can be realized, and the cells can be homogenized and stabilized.

  In the polyol mixture of the present invention, a group consisting of a compound represented by formula (I), a compound represented by formula (II), a compound represented by formula (III) and a compound represented by formula (IV) One or more selected compounds X (hereinafter simply referred to as compound X) and a nonionic compound represented by formula (V) (hereinafter simply referred to as nonionic compound) and a hydrofluorocarbon are used in combination. There is a big feature in that. Thus, in the present invention, since the compound X and the nonionic compound and the hydrofluorocarbon are used in combination, the compatibility between the polyol component and the hydrofluorocarbon is remarkably improved, and the vapor pressure is further reduced. Can do.

  The reason why such a remarkably excellent effect is manifested is not clear, but Raul's law is generally sought for reducing the vapor pressure, but this law applies to diluted solutions and ideals. This is in the case of a solution, and in most cases this is not the case with a polyol mixture containing a hydrofluorocarbon as in the present invention.

However, compound X is common in that all of them contain no aromatic ring or hydroxyl group and have an ester group. Further, in the compounds represented by formulas (I), (II) and (IV), R ¹ , R ³ , R ⁴ and R ⁶ are short chain alkyl groups having 4 or less carbon atoms, and in the compound represented by the formula (III), the alkylene group having R ⁵ is a short chain alkylene having 2 or 3 carbon atoms. Since it is common in that it is a group, it is considered that the ester group is derived from the fact that some action acts on the hydrofluorocarbon to lower the vapor pressure. In addition, it cannot be said that a highly compatible compound is necessarily effective in reducing the vapor pressure, but the compatibility between the polyol component and the hydrofluorocarbon to some extent, which is not sufficient for the compound X, is also involved in the reduction of the vapor pressure. It is thought that.

  Therefore, all of the compounds X have the common property that the compatibility between the polyol component and the hydrofluorocarbon is not sufficient, but is improved to some extent and the vapor pressure is reduced.

  Furthermore, in the present invention, since a nonionic compound is used, the compatibility between the polyol component and the hydrofluorocarbon is improved, and as a synergistic effect, the effect of reducing the vapor pressure of the compound X is further exhibited. It is considered a thing.

  The additive for polyol mixture of the present invention contains compound X and a nonionic compound.

In the compound represented by the formula (I), R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ² is independently a hydrogen atom or a methyl group, and R ³ is 1 to 4 carbon atoms. A linear or branched alkyl group, n represents a number of 1 to 3.

Among the compounds represented by formula (I), R ³ is a methyl group or an ethyl group from the viewpoint of increasing the flash point of the compound itself, increasing the compatibility between the polyol component and the hydrofluorocarbon, and reducing the vapor pressure. A group, preferably a methyl group, and n is preferably 2.

  Specific examples of the compound represented by the formula (I) include ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monoisopropyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether. Acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol monobutyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monoisopropyl ether acetate, propylene glycol monobutyl ether acetate, dipropylene glycol Solution monomethyl ether acetate, dipropylene glycol monoethyl ether acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol monobutyl ether acetate, triethylene glycol monomethyl ether acetate, triethylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether pro Pionate, ethylene glycol monobutyl ether propionate, diethylene glycol monoethyl ether propionate, diethylene glycol monobutyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol monobutyl ether propionate, dipropylene glycol monoethyl ether propionate And dipropylene glycol monobutyl ether propionate, diethylene glycol monomethyl ether butyrate, diethylene glycol monoethyl ether butyrate, diethylene glycol monomethyl ether valerate, diethylene glycol monoethyl ether valerate, and the like. The above can be mixed and used.

  Specific examples of the preferred compound represented by formula (I) include diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monoisopropyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether. Acetate, dipropylene glycol monoisopropyl ether acetate, dipropylene glycol monobutyl ether acetate and the like can be mentioned, and these can be used alone or in admixture of two or more.

In the compound represented by the formula (II), each R ⁴ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.

  Specific examples of the compound represented by the formula (II) include triglyceride acetate (also known as triacetin), triglyceride propionate and the like, and these can be used alone or in admixture of two or more. Among these, triglyceride acetate is preferable from the viewpoint of the effect of reducing the vapor pressure.

In the compound represented by the formula (III), R ⁵ represents a hydrogen atom or a methyl group.
Specific examples of the compound represented by the formula (III) include ethylene carbonate and propylene carbonate. Among these, propylene carbonate is preferable from the viewpoint of handleability (which is a room temperature liquid).

In the compound represented by the formula (IV), each R ⁶ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.

  Specific examples of the compound represented by the formula (IV) include trimethyl phosphate, triethyl phosphate, triisopropyl phosphate, tri n-propyl phosphate, triisobutyl phosphate, tri n-butyl phosphate, and the like. Or a mixture of two or more. Among these, triethyl phosphate, triisopropyl phosphate, tri n-propyl phosphate and triisobutyl phosphate are preferable from the viewpoints of compatibility between the polyol component and the hydrofluorocarbon, an effect of reducing vapor pressure, and hydrolysis stability.

  The content of the compound X in the additive for polyol mixture of the present invention is preferably 20 to 90% by weight, more preferably 30 to 90% by weight, from the viewpoint of the compatibility between the polyol component and the hydrofluorocarbon and the effect of reducing the vapor pressure. %, More preferably 40 to 80% by weight.

  The nonionic compound further improves the compatibility between the polyol component and the hydrofluorocarbon, and not only exhibits an effect of lowering the vapor pressure when used in combination with the compound X, but also at the time of producing the polyurethane foam, It is a component that improves compatibility with fluorocarbons and improves homogenization and stabilization of cells of polyurethane foam.

In the nonionic compound represented by the formula (V), R ⁷ represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and these groups are each present alone. In addition, two or more kinds may be mixed. Among R ⁷ , an alkyl group having 8 to 18 carbon atoms is preferable from the viewpoints of surface active effect, oxidation resistance stability, and economical efficiency (low cost and easy availability).

  EO represents an oxyethylene group. PO represents an oxypropylene group. x and z are each a number of 1 or more indicating the average number of added moles of the oxyethylene group, but x is a number from 1 to 10 and z is 1 from the viewpoint of the surface active effect, room temperature properties and handling viscosity. It is preferably a number of ˜20, more preferably x is a number of 1 to 5 and z is a number of 1 to 10. Although the sum of x and z is 3 or more, the number of 3-20 is preferable and the number of 3-10 is more preferable from the viewpoint of homogenization and stabilization of the cells of the polyurethane foam.

  y is a number of 1 or more indicating the average number of added moles of the oxypropylene group, but from the viewpoint of the surface active effect and the handling viscosity, the number of 1 to 10 is preferable, and the number of 1 to 7 is more preferable.

  The addition form of [(EO) x. (PO) y] is random addition, block addition, or a mixed addition of them. [(EO) x. (PO) y] and (EO) z are block combinations. doing. “Mixed addition” refers to an addition form in which random addition and block addition are added at an arbitrary ratio.

The nonionic compound has the formula (VI):
R ⁷ —OH (VI)
(Wherein R ⁷ is the same as above)
Can be obtained by adding ethylene oxide and propylene oxide randomly or in blocks, and then adding ethylene oxide. Examples of the method of adding alkylene oxide to the alcohol represented by the formula (VI) include, for example, a method of adding in the presence of a catalyst such as sodium hydroxide or potassium hydroxide using a known alkoxylation method. Is mentioned.

In the nonionic compound, R ⁷ in the formula (V) is an alkyl group having 8 to 18 carbon atoms, x is a number of 1 to 10, y is a number of 1 to 10, and z is a number of 1 to 20. It is preferable from the viewpoint of the surface active effect on each of the polyol component, the isocyanate component and the hydrofluorocarbon, and the handling property of the nonionic compound.

Representative examples of suitable nonionic compounds include those of formula (Va):
_{^{R 7 O- (EO) x -}} (PO) y - (EO) z -H (Va)
[Wherein, R ⁷ , EO, PO, x, y and z are the same as above. (EO) _x , (PO) _y, and (EO) _z are linked in this order, respectively]
The nonionic compound represented by these is mentioned.

  In the additive for polyol mixture of the present invention, the compound X / nonionic compound (weight ratio) is preferably used from the viewpoint of improving the compatibility between the polyol component and the hydrofluorocarbon, and homogenizing and stabilizing the cells of the polyurethane foam. Is 90/10 to 20/80, more preferably 90/10 to 30/70, still more preferably 80/20 to 40/60.

  The additive for the polyol mixture is used together with the hydrofluorocarbon, and can be suitably used for the polyol mixture.

  The polyol mixture of the present invention contains a polyol component, a blowing agent containing a hydrofluorocarbon, compound X and a nonionic compound.

  As a polyol component, what is conventionally used when manufacturing a polyurethane foam is illustrated.

  Representative examples of the polyol component include, for example, polyester polyols and ethylenediamine-based polyether polyols described in “Polyurethane Resin Handbook” edited by Keiji Iwata (published on September 25, 1987, published by Nikkan Kogyo Shimbun). Examples include ether polyols, polymer polyols, phenol resin polyols, and Mannich polyols. These can be used alone or in admixture of two or more.

  Among the polyol components, aromatic dicarboxylic acid polyester polyols, polyhydric phenol polyether polyols, phenol resin polyols and Mannich polyols are preferred from the viewpoints of heat resistance and flame retardancy, and phthalic acid, terephthalic acid or isophthalic acid. More preferred are phthalic polyester polyols, Mannich polyols and alkylene oxide adducts of bisphenol A, and more preferred are phthalic polyester polyols.

  The content of the polyester polyol in the polyol component is preferably 50 to 100% by weight, more preferably 60 to 90% by weight from the viewpoints of strength maintenance, heat resistance and flame retardancy.

  The content of the polyol component in the polyol mixture is preferably 40 to 90% by weight, more preferably 50 to 80% by weight.

  A foaming agent containing hydrofluorocarbon is used as the foaming agent. A foaming agent may consist of hydrofluorocarbon and water, and may contain another foaming agent within the range in which the object of the present invention is not inhibited.

  Examples of the hydrofluorocarbon include 1,1,1,2-tetrafluoroethane (HFC-134a), 1,1-difluoroethane (HFC-152a), 1,1,1,2,3,3,3-hepta. Fluoropropane (HFC-227ea), 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), 1,1, 2,3,3-pentafluoropropane (HFC-245ea), 1,1,2,2,3-pentafluoropropane (HFC-245ca), 1,1,1,2,2-pentafluoropropane (HFC- 245cb), 1,1,2,2,3,3-hexafluoropropane (HFC-236ca), 1,1,1,4,4,4-hexafluorobutane (HFC-356mffm) and the like. Can be used alone or in admixture of two or more. Of these, 1,1,1,2,3,3,3-heptafluoropropane (HFC-227ea), 1,1,1,3,3- Pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) are preferable, and from the viewpoint of suppressing the occurrence of flash point, 1,1,1,3,3 -Pentafluoropropane (HFC-245fa) alone and 1,1,1,3,3-pentafluoropropane (HFC-245fa) and 1,1,1,3,3-pentafluorobutane (HFC-365mfc) Is more preferable.

  The amount of hydrofluorocarbon varies depending on the density and isocyanate index of the rigid polyurethane foam and cannot be determined unconditionally. However, from the viewpoint of improving the thermal conductivity of the rigid polyurethane foam and economical efficiency, it is based on 100 parts by weight of the polyol component. The amount is preferably 10 to 50 parts by weight, more preferably 10 to 40 parts by weight.

  The amount of water varies depending on the density and isocyanate index of the rigid polyurethane foam and cannot be determined unconditionally. From the viewpoint of suppressing hydrolysis of the polyester polyol contained in the polyol component and improving the thermal conductivity of the foam, Preferably it is 0.3-5 weight part with respect to 100 weight part of polyol components, More preferably, it is 0.5-3 weight part.

  Other foaming agents may be used as long as they do not impair the object of the present invention. From the viewpoint of protecting the global environment, other foaming agents are preferably low-boiling hydrocarbons such as cyclopentane, normal pentane, isopentane, normal butane, and isobutane, air, carbon dioxide, and the like.

  The amount of the other foaming agent varies depending on the type and the density of the target rigid polyurethane foam, and cannot be determined unconditionally. Therefore, it is preferable to adjust appropriately according to these.

  As the compound X, the same compounds as those used for the additive for polyol mixture can be used.

  The amount of compound X varies depending on the amount of hydrofluorocarbon and cannot be determined unconditionally. However, the compatibility between the polyol component and the hydrofluorocarbon is improved, the vapor pressure is reduced, and the flame retardancy of the polyurethane foam and From the viewpoint of improving the physical properties of the foam, the amount is preferably 2 to 30 parts by weight, more preferably 3 to 25 parts by weight, and still more preferably 5 to 20 parts by weight with respect to 100 parts by weight of the polyol component.

  As the nonionic compound, the same compounds as those used for the additive for polyol mixture can be used.

  The amount of the nonionic compound is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the polyol component from the viewpoint of improving the compatibility between the polyol component and the hydrofluorocarbon and homogenizing and stabilizing the cells of the polyurethane foam. More preferably, it is 2 to 25 parts by weight, still more preferably 2 to 20 parts by weight.

  Thus, a polyol mixture is obtained by mixing the polyol component, the foaming agent containing hydrofluorocarbon, the compound X and the nonionic compound. The obtained polyol mixture can be suitably used as a raw material in the production of rigid polyurethane foam.

  The polyol mixture of the present invention improves the compatibility between the polyol component and the hydrofluorocarbon without using a compound that may adversely affect the human body even when a foaming agent containing hydrofluorocarbon is used. Since the vapor pressure can be reduced and the drum expansion can be suppressed to avoid danger, it can be suitably used in the production of polyurethane foam.

  The polyurethane foam can be obtained by reacting a polyol component, a foaming agent containing hydrofluorocarbon, a polyol mixture containing Compound X and a nonionic compound, and an isocyanate component.

  A catalyst can be used when producing the polyurethane foam. The catalyst can be used by being contained in a polyol mixture.

  Examples of the catalyst include 1,4-diazabicyclo [2.2.2] octane, 2-methyl-1,4-diazabicyclo [2.2.2] octane, N-methylmorpholine, N-ethylmorpholine, N- (dimethylaminoethyl ) Morpholine, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylpropylenediamine, N, N, N ', N'-tetramethyl-1,6-hexane Diamine, N, N-dimethylpiperazine, N, N ', N'-trimethylaminoethylpiperazine, tris (3-dimethylaminopropyl) amine, N, N-dimethylcyclohexylamine, N, N-dimethylbenzylamine, N, N, N ', N' ', N' '-Pentamethyldiethylenetriamine, bis (2-dimethylaminoethyl) ether, 1,8-diazabicyclo [5.4.0] undecene-7, N, N', N ''- Tris (3-dimethylaminopropyl) hexahydro-s-triazine, 6-dimethylamino-1-hexanol, 5- Methylamino-3-methyl-1-pentanol, N, N-dimethylethanolamine, N, N-dimethylaminoethoxyethanol, N, N-dimethylaminoethoxyethoxyethanol, N- (3-dimethylaminopropyl) -N Tertiary amine catalysts such as 1-methylaminoethanol, N- (2-dimethylaminoethyl) -N-methylaminoethanol, 1-methylimidazole, 1-isobutyl-2-methylimidazole, 1,2-dimethylimidazole, and the like Derivatives thereof, salts of these with acids such as carboxylic acid and carbonic acid; organotin compounds such as tin dibutyldiacetate, tin dibutyldilaurate, tin di (2-ethylhexyl) dilaurate, di (2-ethylhexanoate) tin And organometallic catalysts represented by di (2-ethylhexanoic acid) lead.

  Further, in the present invention, for the purpose of imparting flame retardancy to the polyurethane foam, a potassium salt such as potassium acetate or potassium octylate or an isocyanurate catalyst represented by a quaternary ammonium salt is used as the catalyst. You may use together. These catalysts can be used alone or in admixture of two or more.

  The amount of the catalyst cannot be determined unconditionally because the reaction mechanism and reaction characteristics differ depending on the type of the catalyst, and therefore it is desirable to appropriately adjust the amount according to the type.

  Examples of the isocyanate component include aromatic polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylene polyisocyanate, 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 above polys containing one or more of urethane bonds, carbodiimide bonds, uretimine 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, from the viewpoint of heat resistance and flame retardancy, one or more of polymethylene polyphenylene polyisocyanate, urethane bond, carbodiimide bond, uretoimine bond, allophanate bond, urea bond, burette bond, isocyanurate bond, etc. A polyisocyanate-modified product having a bond is preferred.

  The ratio of the polyol component and the isocyanate component is appropriately adjusted according to the degree of flame retardancy of the intended rigid polyurethane foam. In general, the ratio of the polyol component to the isocyanate component is preferably adjusted so that the isocyanate index is preferably 80 to 500, more preferably 100 to 300, and still more preferably 110 to 250.

  When producing a rigid polyurethane foam, a foam stabilizer can be used as necessary. As a foam stabilizer, what is generally used when manufacturing a polyurethane foam can be used.

  Representative examples of foam stabilizers include silicone surfactants such as dimethylpolysiloxane and polyoxyalkylene-modified dimethylpolysiloxane, anionic surfactants such as fatty acid salts, sulfate ester salts, phosphate ester salts, and sulfonate salts. Etc. These foam stabilizers can be used alone or in admixture of two or more.

  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.

  Moreover, when manufacturing a rigid polyurethane foam, another auxiliary agent can be used if necessary. Examples of other auxiliaries include auxiliaries generally used in the production of polyurethane foams, such as crosslinking agents, flame retardants, stabilizers, pigments, fillers, and the like. These auxiliaries can be used within a range that does not impair the object of the present invention.

  The rigid polyurethane foam is prepared by mixing, for example, a polyol component, a foaming agent containing a hydrofluorocarbon, a compound X, a nonionic compound, a catalyst, if necessary, a foam stabilizer and other auxiliary agents, and an obtained polyol mixture and an isocyanate. The components can be obtained by mixing and stirring with a molding machine or the like, injecting them into a mold and reacting them. More specifically, for example, after the temperature of the polyol mixture is adjusted to 5 to 20 ° C. using a tank or the like, the polyol mixture is By reacting with an isocyanate component, a rigid polyurethane foam can be obtained.

  Thus, according to the production method of the present invention, the polyol component and the isocyanate component are homogeneously mixed by using the polyol component, the foaming agent containing hydrofluorocarbon, and the polyol mixture containing compound X and the nonionic compound. Thus, a rigid polyurethane foam in which the cells are homogenized and stabilized can be obtained. The obtained rigid polyurethane foam can be suitably used as, for example, a heat insulating material such as a building material, an electric refrigerator, a freezer warehouse, and a pipe.

  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.

Production Example Alcohol and water wherein R ⁷ is an alkyl group having 12, 12, or 16 carbon atoms in the formula (VI) in a 5 L rotary stirring autoclave equipped with two measuring tanks for ethylene oxide and propylene oxide. After potassium oxide was charged and nitrogen gas substitution was performed, the temperature was raised to 110 ° C. and dehydration was performed under a reduced pressure of 5.33 kPa for 1 hour.

  Subsequently, ethylene oxide, propylene oxide, and further ethylene oxide were subjected to a block addition reaction in this order to obtain a nonionic compound having a predetermined addition mole number. At that time, the alkylene oxide reaction was carried out at a reaction temperature of 150 ° C. in the case of addition reaction of ethylene oxide, and at a reaction temperature of 120 ° C. in the case of addition reaction of propylene oxide.

As described above, in the formula (Va), R ⁷ is an alkyl group having 12 carbon atoms, x is 2.0, y is 2.0, z is 3.0 (hereinafter referred to as REPE-1), R ⁷ is carbon number 14 alkyl groups, a compound in which X is 2.0, Y is 2.0 and Z is 3.0 (hereinafter referred to as REPE-2), and R ⁷ is an alkyl group having 16 carbon atoms, x is 6.0, y is 5.0, and z is 6.0. A compound (hereinafter referred to as REPE-3) was obtained.

Examples 1-7 and Comparative Examples 1-8
(1) Preparation of polyol mixture As polyol component, phthalate ester-based polyester polyol [hydroxyl value: 315 mgKOH / g, manufactured by Toho Rika Co., Ltd., trade name: Phanthol PL-305] and ethylenediamine-based polyether polyol [Hydroxyl value: 760 mgKOH / g, manufactured by Mitsui Takeda Chemical Co., Ltd., trade name: Polyol AE-300] A mixture of 20 parts by weight was used.

  100 parts by weight of a polyol component, 40 parts by weight of HFC-245fa (1,1,1,3,3-pentafluoropropane) as a blowing agent and 1.0 part by weight of water, and the amounts of Compound X and nonionic amount shown in Table 1 Compound, etc., silicone foam stabilizer [manufactured by Nihon Unicar Co., Ltd., trade name: L-5340] 1.0 part by weight, catalyst [manufactured by Kao Corporation, trade name: Kao Raiser No. 31] 2.5 parts by weight Were mixed to obtain a polyol mixture.

  The compatibility of the obtained polyol mixture at 10 ° C. was visually observed and evaluated based on the following evaluation criteria. Further, the vapor pressure of the polyol mixture at 50 ° C. was measured and evaluated based on the following evaluation criteria. The results are also shown in Table 1.

[Measurement of vapor pressure]
Based on JIS K2240 5.3, the sample mixture of the vapor pressure tester is filled with the polyol mixture, placed in a constant temperature water bath at 50 ° C, the reading of the pressure gauge when the pressure becomes constant, and the value is taken as the vapor pressure. .

[Compatibility Evaluation Criteria]
○: Compatibility is good because it is homogeneously dissolved △: Some phase separation is observed ×: Phase separation is observed and compatibility is poor

[Evaluation criteria for vapor pressure]
○: Vapor pressure is less than 0.180 MPa ×: Vapor pressure is 0.180 MPa or more

The abbreviations listed in Table 1 mean the following.
[Compound X]
(Compound represented by formula (I))
-ECA: Diethylene glycol monoethyl ether acetate-EBA: Diethylene glycol monobutyl ether acetate-MDP-Ac: Dipropylene glycol monomethyl ether acetate (compound represented by formula (II))
・ TAG: Triacetin (compound represented by formula (III))
・ PC: Propylene carbonate (compound represented by formula (IV))
・ TBP: Triisobutyl phosphate

[Other thinning agents, compatibilizers, etc.]
・ DOP: Di (2-ethylhexyl) phthalate
・ TCPP: Tris (2-chloroisopropyl) phosphate (Daihachi Chemical Industry Co., Ltd., trade name: TMCPP)
・ Emulgen 908: Polyoxyethylene (8) nonylphenyl ether (trade name: Emulgen 908, manufactured by Kao Corporation)

  From the results shown in Table 1, it can be seen that the polyol mixture obtained in each Example is excellent in compatibility and excellent in the effect of reducing the vapor pressure as compared with each Comparative Example. In particular, in the comparison between Example 5 and Comparative Examples 3 and 4, it can be seen that the synergistic effect by the combined use of Compound X and the nonionic compound is significant.

(2) Production of Rigid Polyurethane Foam The polyol mixture obtained in each Example and each Comparative Example and an isocyanate component (manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumijour 44V20) have an isocyanate index of 105 Thus, 220 g of the resulting mixture was poured into a mold [inner dimensions: 150 mm × 150 mm × 300 mm (height)] to form a rigid polyurethane foam free form.

  The resulting polyurethane foam free form was cut and the internal state was observed and evaluated based on the following evaluation criteria. The results are shown in Table 1.

[Void evaluation criteria]
○: Voids with a diameter of 2 mm or more are not observed. If the diameter is 2 mm or less, it is difficult to distinguish the void from the cell.
Δ: Small voids with a diameter of about 2-3 mm are observed.
×: Deep void generation with a diameter of 3 mm or more is observed.

[Cell homogeneity]
(Double-circle): There is no disorder of the cell of a foam and it is homogeneous.
◯: There is a slight disturbance of the foam cell, but it is almost homogeneous.
X: The part where the cell of the form was disturbed in part has occurred.

  From the results shown in Table 1, it can be seen that in the polyurethane foams obtained in the respective examples, the generation of voids is not observed because of the excellent compatibility of the polyol mixture, and the cell homogeneity is also good.

  The additive for polyol mixture of the present invention can be suitably used for, for example, a polyol mixture which is a raw material of polyurethane foam and the like, and the polyol mixture can be suitably used for producing polyurethane foam. is there.

  The polyurethane foam of the present invention can be suitably used as a heat insulating material for building materials, electric refrigerators, refrigerated warehouses, pipes and 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.

Claims (4)

(A) polyol component,
(B) a blowing agent containing a hydrofluorocarbon,
(C) Formula (I):
R ^1- (OCHR ² CHR ² ) _n OCOR ³ (I)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ² is independently a hydrogen atom or a methyl group, and R ³ is a linear or branched chain having 1 to 4 carbon atoms. An alkyl group, n represents a number of 1 to 3)
A compound represented by formula (II):

(In the formula, each R ⁴ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A compound represented by formula (III):

(Wherein R ⁵ represents a hydrogen atom or a methyl group)
And a compound represented by formula (IV):

(In the formula, each R ⁶ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
One or more compounds X selected from the group consisting of the compounds represented by formula (V):
R ⁷ O - [(EO) x · (PO) y ] - (EO) z -H (V )
(In the formula, R ⁷ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. X and z are average additions of oxyethylene groups, respectively. The number of moles is 1 or more, and the sum of x and z is 3 or more, and y is a number of 1 or more that represents the average number of moles of oxypropylene groups added, [(EO) x (Additional form of (PO) y] is random addition, block addition, or a mixed addition thereof, [(EO) x-(PO) y] and (EO) z are block-bonded)
The polyol mixture formed by containing the nonionic compound represented by these.   The polyol mixture according to claim 1, wherein the polyol component contains 50% by weight or more of polyester polyol.   A process for producing a polyurethane foam comprising reacting the polyol mixture according to claim 1 or 2 with an isocyanate component. Formula (I):
R ^1- (OCHR ² CHR ² ) _n OCOR ³ (I)
(In the formula, R ¹ is a linear or branched alkyl group having 1 to 4 carbon atoms, R ² is independently a hydrogen atom or a methyl group, and R ³ is a linear or branched chain having 1 to 4 carbon atoms. An alkyl group, n represents a number of 1 to 3)
A compound represented by formula (II):

(In the formula, each R ⁴ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms)
A compound represented by formula (III):

(Wherein R ⁵ represents a hydrogen atom or a methyl group)
And a compound represented by formula (IV):

(In the formula, each R ⁶ independently represents a linear or branched alkyl group having 1 to 4 carbon atoms.)
One or more compounds X selected from the group consisting of compounds represented by formula (V):
R ⁷ O - [(EO) x · (PO) y ] - (EO) z -H (V )
(In the formula, R ⁷ is a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, EO is an oxyethylene group, and PO is an oxypropylene group. X and z are average additions of oxyethylene groups, respectively. The number of moles is 1 or more, and the sum of x and z is 3 or more, and y is a number of 1 or more that represents the average number of moles of oxypropylene groups added, [(EO) x (Additional form of (PO) y] is random addition, block addition, or a mixed addition thereof, [(EO) x-(PO) y] and (EO) z are block-bonded)
The additive for polyol mixtures which contains the nonionic compound represented by these, and is used with hydrofluorocarbon.