JP4731821B2 - Production method of polyurethane foam - Google Patents

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 foams (including polyisocyanurate foams containing isocyanurate rings; the same applies hereinafter) have good heat insulating properties and flame retardancy, and as a heat insulating material for building materials, electric refrigerators, freezer warehouses, bathtubs, pipes, etc. in use.

  Rigid polyurethane foam, for example, when used as a heat insulating material for houses, building materials, etc., by 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 necessary Depending on the situation, it is produced by a method of mixing in the presence of other auxiliaries, spraying 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 1,1,1,4, as a foaming agent, from the viewpoint of avoiding ozone layer destruction and global warming in the stratosphere Hydrofluorocarbons such as 4-pentafluorobutane (HFC-365mfc) are being 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 Because the drum that I put in swells, it becomes a dangerous situation. 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 that are generally used as a viscosity reducer or compatibilizer 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 the effect of reducing vapor pressure 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 drum expansion to avoid danger 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) polyol component and formula (I):
R ¹ -OCOR ² COO-R ¹ (I)
Wherein R ¹ is independently a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms, R ² is a direct bond or a linear or branched alkylene group having 1 to 8 carbon atoms, or Represents an alkenylene group)
A polyol mixture containing a dibasic acid ester represented by formula (II) and a blowing agent containing a hydrofluorocarbon,
(2) Further, the formula (II):
R ³ O - [(EO) x · (PO) y ] - (EO) z -H (II )
(In the formula, R ³ 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 according to the above (1), which contains a nonionic compound represented by:
(3) A method for producing a polyurethane foam in which the polyol mixture according to (1) or (2) is reacted with an isocyanate component, and
(4) The present invention relates to an additive for a polyol mixture which contains a dibasic acid ester represented by the formula (I) and is used together with a hydrofluorocarbon.

  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 drum expansion 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.

  The polyol mixture of the present invention has a great feature in that a dibasic acid ester represented by the formula (I) (hereinafter simply referred to as “dibasic acid ester”) and a hydrofluorocarbon are used in combination. Thus, in the present invention, since the dibasic acid ester and the hydrofluorocarbon are used in combination, the compatibility between the polyol component and the hydrofluorocarbon is remarkably improved, and the vapor pressure can be further reduced.

The reason why such a remarkably excellent effect is manifested is not clear, but the dibasic acid ester does not contain an aromatic ring, has two ester groups, and R ¹ is linear or It is a branched lower alkyl group or alkenyl group, and is considered to be derived from the fact that the linear or branched alkylene group or alkenylene group of R ² is relatively short, so that it is easily dissolved in both the hydrofluorocarbon and the polyol component. It is done.

  On the other hand, regarding the reduction of vapor pressure, Raoul's law is generally sought, but this law is applicable to dilute solutions and ideal solutions. In the polyol mixture containing hydrofluorocarbon as in the present invention, In most cases this is not the case. Although the cause of the excellent effect of dibasic acid ester in suppressing the decrease in vapor pressure is not clear, there is no interaction such as a direct hydrogen bond due to a hydroxyl group or an electronic effect due to an aromatic ring. In addition, it is considered that some action acts on the ester group and the hydrofluorocarbon, resulting in a decrease in vapor pressure. Furthermore, since the dibasic acid ester has a relatively low molecular weight and has two ester groups in the molecule, it is considered that the fact that the ratio of the ester groups in the molecule is high is also a factor that shows a remarkable effect.

  In the present invention, by further using a nonionic compound represented by the formula (II) (hereinafter simply referred to as “nonionic compound”), the compatibility is further improved, and the dibasic acid ester and the nonionic compound are non-reactive. Since the total amount with the ionic compound can be reduced, it is considered to work advantageously on the flame retardancy of the polyurethane foam.

  The additive for polyol mixture of the present invention contains a dibasic acid ester and is used together with a hydrofluorocarbon.

In the dibasic acid ester, R ¹ in the formula (I) is each independently a linear or branched alkyl group or alkenyl group having 1 to 8 carbon atoms. R ² is a direct bond or a linear or branched alkylene group having 1 to 8 carbon atoms or an alkenylene group.

From the viewpoint of reduction in vapor pressure and compatibility, R ¹ is preferably independently a linear or branched alkyl group or alkenyl group having 1 to 4 carbon atoms, and R ² is a direct bond or carbon. More preferably, it is a linear or branched alkylene group or alkenylene group of 1 to 4.

  Preferred examples of the dibasic acid ester include dimethyl oxalate, diethyl oxalate, dipropyl oxalate, dibutyl oxalate, dimethyl malonate, diethyl malonate, dipropyl malonate, dimethyl succinate, diethyl succinate, dipropyl succinate. , Dimethyl glutamate, diethyl glutarate, dibutyl glutamate, dimethyl adipate, diethyl adipate, dibutyl adipate, diisobutyl adipate, dimethyl pimelate, diethyl pimelate, dipropyl pimelate, dimethyl suberate, diethyl suberate , Dibutyl suberate, dimethyl azelate, diethyl azelate, diisobutyl azelate, dimethyl sebacate, diethyl sebacate, dibutyl sebacate, dimethyl maleate, diethyl maleate, Examples include dibutyl inmate, dimethyl fumarate, diethyl fumarate, dibutyl fumarate, dimethyl citraconic acid, diethyl citraconic acid, dibutyl citraconic acid, dimethyl mesaconic acid, and diethyl mesaconic acid. These may be used alone or in combination of two or more. Can be used.

  Among these dibasic acid esters, dibutyl oxalate, dimethyl malonate, diethyl malonate, dimethyl succinate, diethyl succinate, and glutane from the viewpoints of handleability (liquid at room temperature), flash point, and vapor pressure reduction effect. More preferred are dimethyl acid, diethyl glutamate, dimethyl adipate, diethyl adipate, dibutyl adipate, diisobutyl adipate, dimethyl maleate, diethyl maleate, dibutyl maleate, diethyl fumarate and dibutyl fumarate, dimethyl succinate, More preferred are diethyl succinate, dimethyl glutamate, diethyl glutamate, dimethyl adipate and diethyl adipate alone or mixtures thereof.

  In the polyol mixture additive of the present invention, “contains a dibasic acid ester” means that the polyol mixture additive is composed of a dibasic acid ester and is within the range that does not impair the object of the present invention. This means that non-ionic compounds, various additives, and the like may be contained.

  The polyol mixture of the present invention contains a polyol component, a dibasic acid ester, and a blowing agent containing a hydrofluorocarbon.

  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 polyol, ethylenediamine-based polyether polyol, and the like 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 polyol, polyhydric phenol polyether polyol, phenol resin polyol and Mannich polyol are preferable from the viewpoint 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 amount of the dibasic acid ester is preferably 5 to 40 parts by weight with respect to 100 parts by weight of the polyol component from the viewpoint of reducing the vapor pressure and improving the compatibility, and improving the flame retardancy and foam properties. More preferably, it is 10-35 weight part, More preferably, it is 10-30 weight part.

  In addition, the amount of the dibasic acid ester is improved in compatibility when used in combination with a desired amount of a nonionic compound, from the viewpoint of reducing the vapor pressure and from the viewpoint of improving flame retardancy and foam properties. The amount is preferably 3 to 30 parts by weight, more preferably 5 to 30 parts by weight, and still more preferably 8 to 25 parts by weight with respect to 100 parts by weight of the polyol component.

  In the present invention, 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. However, from the viewpoint of inhibiting hydrolysis of the polyester polyol contained in the polyol component and the thermal conductivity of the foam, the polyol component Preferably it is 0.3-5 weight part with respect to 100 weight part, 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.

  The polyol mixture of the present invention preferably further contains a nonionic compound. When the polyol mixture further contains a nonionic compound, not only the compatibility between the polyol component and the hydrofluorocarbon is further improved, but also when the polyurethane foam is produced, the isocyanate component and the hydrofluorocarbon are mixed. Since the compatibility is also improved, the total amount of the dibasic acid ester and the nonionic compound can be reduced to increase the flame retardancy of the polyurethane foam, and at the same time, the cells can be homogenized and stabilized. Can do.

In the nonionic compound, R ³ in the formula (II) represents a linear or branched alkyl group or alkenyl group having 8 to 20 carbon atoms, and these groups may be used alone or in combination of two or more. Can be used. Among R ³ , 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 moles added of the oxypropylene group, but from the viewpoint of the surface active effect and handling viscosity, a number of 1 to 10 is preferable, and a 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. is doing. “Mixed addition” refers to an addition form in which random addition and block addition are added at an arbitrary ratio.

In the nonionic compound, R ³ in the formula (II) 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 (IIa):
_{^{R 3 O- (EO) x -}} (PO) y - (EO) z -H (IIa)
[Wherein R ³ , 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.

  The amount of the nonionic compound is preferably 1 to 30 parts by weight, more preferably 2 to 25 parts based on 100 parts by weight of the polyol component, from the viewpoint of improving compatibility and homogenizing and stabilizing the cells of the polyurethane foam. Part by weight, more preferably 2 to 20 parts by weight.

  The total amount of the dibasic acid ester and the nonionic compound is preferably 5 with respect to 100 parts by weight of the polyol component from the viewpoint of improving the compatibility, reducing the vapor pressure, and improving the foam characteristics. It is -40 weight part, More preferably, it is 8-35 weight part, More preferably, it is 10-30 weight part.

  The ratio between the dibasic acid ester and the nonionic compound varies depending on the type of polyol and the amount of the foaming agent and cannot be determined unconditionally. However, the viewpoint of improving the compatibility and reducing the vapor pressure and the foam characteristics From the viewpoint of improving the quality, the dibasic acid ester / nonionic compound (weight ratio) is preferably 80/20 to 20/80, more preferably 80/20 to 30/70, and 75 / More preferably, it is 25-40 / 60.

  Thus, a polyol mixture is obtained by mixing a polyol component, a dibasic acid ester, a foaming agent containing a hydrofluorocarbon, and a nonionic compound if necessary. 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 is preferably obtained by reacting a polyol component, a dibasic acid ester, a foaming agent containing a hydrofluorocarbon, a polyol mixture containing a nonionic compound if necessary, and an isocyanate component. it can.

  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 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 isocyanate components, from the viewpoint of heat resistance and flame retardancy, one or more of polymethylene polyphenylene polyisocyanate, isocyanurate bond, carbodiimide bond, uretimine bond, allophanate bond, urea bond, burette bond, isocyanurate bond, etc. A polyisocyanate-modified product having a bond of

  The ratio of the polyol component to 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 rigid 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 dibasic acid ester, a foaming agent containing a hydrofluorocarbon, if necessary, a nonionic compound, a catalyst, a foam stabilizer and other auxiliary agents, and the resulting polyol mixture. It can be obtained by mixing and stirring the isocyanate component with a molding machine or the like, pouring the mixture into a mold, and reacting. More specifically, for example, the temperature of the polyol mixture is adjusted to 5 to 20 ° C. using a tank or the like, and then the polyol mixture is used with a foaming machine such as an automatic mixing injection type foaming machine or an automatic mixing injection type foaming machine. By reacting with an isocyanate component, a rigid polyurethane foam can be obtained.

  Thus, according to the production method of the present invention, by using a polyol mixture containing a polyol component, a dibasic acid ester, and a blowing agent containing a hydrofluorocarbon, homogeneous mixing of the polyol component and the isocyanate component is realized. 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.

Examples 1 to 5 and Comparative Examples 1 to 6 ( Examples 1 and 2 are reference examples)
(1) Preparation of polyol mixture Dibasic acid ester and nonionic compound shown in Table 1 and polyol A as a polyol component [phthalate ester polyester polyol (hydroxyl value: 315 mgKOH / g, manufactured by Toho Rika Co., Ltd., (Product name: Phanthol PL-305)]] 80 parts by weight and polyol B [Ethylenediamine-based polyether polyol (hydroxyl value: 760 mgKOH / g, manufactured by Mitsui Takeda Chemical Co., Ltd., product name: Polyol AE-300)]] 20 parts by weight , 40 parts by weight of HFC-245fa (1,1,1,3,3-pentafluoropropane) as a foaming agent and 1.0 part by weight of water, a silicone-based foam stabilizer [manufactured by Nippon Unicar Co., Ltd., trade name: L-5340 A polyol mixture was obtained by mixing 1.0 part by weight and 1.0 part by weight of a catalyst [trade name: Kao Riser No. 1 manufactured by Kao Corporation].

  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.

[Compatibility Evaluation Criteria]
○: Compatibility is good due to homogeneous mixing. Δ: 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 ×: Vapor pressure is 0.180 or more

In addition, each abbreviation described in Table 1 means the following.
[Dibasic acid ester]
DMA: Dimethyl adipate DMG: Mixture consisting of 19% by weight dimethyl succinate, 64% by weight dimethyl glutamate and 17% by weight dimethyl adipate

[Nonionic compounds]
・ REPE-1: In the formula (II), R ³ is an alkyl group having 12 carbon atoms, X is 2, Y is 2, Z is 3 ・ REPE-2: In the formula (II), R ³ is carbon A compound in which the number 14 alkyl group, X is 2, Y 2 and Z is 3. REPE-3: In the formula (II), R ³ is an alkyl group having 16 carbon atoms, X is 6, Y is 5, Z Is a compound of which 6 is

[Other thinning agents, compatibilizers, etc.]
-TCPP: Tris (2-chloropropyl) phosphate (Daihachi Chemical Industry Co., Ltd., trade name: TMCPP)
・ D-400: Tris (isobutyl) phosphate [Daiha Chemical Industry Co., Ltd., trade name: DAIGUARD-400]
・ DOP: Di (2-ethylhexyl) phthalate
・ Emulgen 908: Polyoxyethylene (8) nonylphenyl ether, manufactured by Kao Corporation, trade name: Emulgen 908
・ MDP-Ac: Dipropylene glycol monomethyl ether acetate

  From the results shown in Table 1, since the dibasic acid ester represented by the formula (I) is used in the polyol mixture obtained in each example, it has better compatibility than each comparative example, and the vapor mixture It can be seen that the pressure reducing effect is also excellent.

  Moreover, in Examples 3-5, since dibasic acid ester and a nonionic compound are used together, it turns out that compatibility improves markedly and the usage-amount of both can be reduced. This means that flame retardancy can be increased.

(2) Production of Rigid Polyurethane Foam The polyol mixture obtained in Examples 1 to 5 and Comparative Examples 1 to 6 and the isocyanate component [manufactured by Sumika Bayer Urethane Co., Ltd., trade name: Sumijour 44V20] were used as the isocyanate index. The mixture was stirred and stirred at 10 ° C with a lab mixer at 10 ° C, and 220 g of the resulting mixture was poured into a mold (inner dimensions: 150 mm x 150 mm x 300 mm (height)) to form a rigid polyurethane foam free form. Molded.

  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, in the polyurethane foams obtained in each Example, since the compatibility of the polyol mixture using the dibasic acid ester is excellent, generation of voids is not recognized, and further, the cell homogeneity. It turns out that it is also favorable.

  Moreover, in Examples 3-5, since the dibasic acid ester and the nonionic compound are used together, it turns out that the homogeneity of a cell is still more excellent.

  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 (3)

Polyol component and formula (I):
R ¹ -OCOR ² COO-R ¹ (I)
(Wherein R ¹ represents a methyl group, R ² represents a direct bond or a linear or branched alkylene group having 1 to 4 carbon atoms or an alkenylene group)
And a foaming agent containing 1,1,1,3,3-pentafluoropropane, a formula (II):
R ³ O - [(EO) x · (PO) y ] - (EO) z -H (II )
(In the formula, R ³ 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 the formula: wherein the total amount of the dibasic acid ester and the nonionic compound is 8 to 35 parts by weight with respect to 100 parts by weight of the polyol component; And the polyol mixture whose dibasic acid ester / nonionic compound (weight ratio) is 80 / 20-30 / 70.   The polyol mixture according to claim 1, wherein the polyol component contains 50% by weight or more of polyester polyol. Formula (I):
R ¹ -OCOR ² COO-R ¹ (I)
(Wherein R ¹ represents a methyl group, R ² represents a direct bond or a linear or branched alkylene group having 1 to 4 carbon atoms or an alkenylene group)
And a dibasic acid ester represented by formula (II):
R ³ O - [(EO) x · (PO) y ] - (EO) z -H (II )
(In the formula, R ³ 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)
And an additive for a polyol mixture used together with 1,1,1,3,3-pentafluoropropane, comprising the dibasic acid ester and the nonionic compound For a polyol mixture in which the total amount of is 8 to 35 parts by weight with respect to 100 parts by weight of the polyol component, and the dibasic acid ester / nonionic compound (weight ratio) is used at 80/20 to 30/70 Additive.