JP2007084761A - Polyol composition for spray-foamed rigid polyurethane foam and method for producing spray-foamed rigid polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition for spray-foamed rigid polyurethane foam having a reduced lateral elongation and also having excellent adhesion to a face material, flame retardancy and operability while using an HFC compound such as HFC-245fa and HFC-365mfa and water as a foaming agent; and to provide a rigid polyurethane foam using the polyol composition, and a method for producing the rigid polyurethane foam. <P>SOLUTION: The polyol composition for spray-foamed rigid polyurethane foam contains a polyol compound, a foaming agent, a foam stabilizer and a catalyst, and is used for forming the rigid polyurethane foam by being mixed and reacted with a polyisocyanate component by a spray device. The polyol compound contains an ester polyol, and the foaming agent contains the 1,1,1,3,3-pentafluoropropane (HFC-245fa), the 1,1,1,3,3-pentafluorobutane (HFC-365mfc) and the water. The catalyst contains an amine catalyst and a quaternary ammonium salt catalyst. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a spray-foamed polyol composition for rigid polyurethane foam which forms a highly heat-insulating rigid polyurethane foam, and a method for producing a rigid polyurethane foam using the polyol composition.

  Rigid polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. Such a rigid polyurethane foam is formed by mixing a polyol composition containing a polyol compound and a foaming agent as essential components and a polyisocyanate component, and foaming and curing. In the past, fluorocarbon compounds such as CFC-11 have been used as foaming agents, but CFC compounds are prohibited because they cause the destruction of the ozone layer. At present, rigid polyurethane foams are roughly divided into three types of foaming agents. Is manufactured and used.

  The first blowing agent is water, and a foam is formed by carbon dioxide gas generated by the reaction between water and an isocyanate group. The rigid polyurethane foam obtained by water foaming contains carbon dioxide in the bubbles immediately after production, but the carbon dioxide diffuses into the atmosphere over time, and nitrogen and the like are present in the bubbles. It becomes like this. As a result, it is difficult to lower the thermal conductivity of the water-foamed rigid polyurethane foam as much as other foaming agents, and it cannot be used for applications requiring high heat insulation.

  The second blowing agent is pentanes such as cyclopentane and iso-pentane, and foams using such pentanes are excellent in heat insulation, but in the production because the pentane is highly flammable. Has a problem that a facility for preventing fire is necessary, and a conventional apparatus for producing rigid polyurethane foam cannot be used as it is, and remodeling or new installation is very expensive. In particular, in the case of spray foaming, if pentane is used as a foaming agent, it is volatilized during the spraying operation, so that it is practically impossible to use.

  As the third blowing agent, an HFC compound having an ozone layer depletion coefficient of zero is known, and volatilization of the blowing agent in the polyol composition when using HFC-245fa having a boiling point of 15 ° C. is prevented. A technique for adding a compatibilizing agent such as ε-caprolactone to prevent swelling of containers such as drums and petroleum cans containing the polyol composition is known (for example, Patent Document 1).

  However, since HFC compounds such as HFC-245fa and HFC-365mfa do not contain chlorine or bromine, they do not have the effect of improving the flame retardancy of the foam. This improves the compatibility of the foaming agent in the polyol composition contained as the agent with the polyol compound and lowers the vapor pressure, and does not give consideration to flame retardancy. For this reason, especially for construction, etc., improvement in the flame retardancy of the rigid polyurethane foam obtained from such a polyol composition is required.

  As a means for enhancing the flame retardancy of a rigid polyurethane foam using an HFC compound as a foaming agent, an aromatic ester polyol is used as a polyol compound constituting the raw material polyol composition, and at the same time, the amount of the isocyanate component is increased. It is conceivable to increase the NCO / OH reaction ratio (NCO index) by increasing the blending amount of the isocyanurate ring concentration in the foam-constituting resin.

  However, it has been found that when the amount of the aromatic ester polyol is increased as described above and the NCO index is increased and the rigid polyurethane foam is produced by the spray foaming method, the adhesiveness to the face material and the substrate is lowered.

  In general, HFC compounds are expensive, and it is difficult to adjust the reactivity mildly compared to the conventional formulation using HCFC-141b, and it is necessary to spray hard polyurethane foam with spray foaming formulation. In a refrigerated warehouse, etc., there is a problem in that workability is poor because it cannot blow smoothly. In addition, when water is used as the foaming agent, carbon dioxide gasification is fast, and it has been found that leveling is particularly difficult when spraying thickly with a spray foaming formulation and there are problems with workability (for example, patents) Reference 2). Further, it has also been found that when an attempt is made to milden such reactivity, the adhesion with a face material or a substrate is lowered.

  Furthermore, in the production of rigid polyurethane foam, the lateral elongation of the rigid polyurethane foam may occur greatly due to the addition of a catalyst. In such a case, there is a problem that the peeling of the end portion, the adhesive performance, and the workability deteriorate. is there.

JP 2004-107439 A JP-A-11-130830

  Accordingly, an object of the present invention is to suppress lateral elongation while using HFC compounds such as HFC-245fa and HFC-365mfa and water as foaming agents in order to solve the problems in conventional rigid polyurethane foams, It is to provide a polyol composition for rigid polyurethane foam excellent in adhesion, flame retardancy, and workability, a rigid polyurethane foam using the polyol composition, and a method for producing the same.

  As a result of intensive studies to solve the above problems, the present inventors have found that the above object can be achieved by the following polyol composition for spray foamed rigid polyurethane foam, and have completed the present invention.

That is, the polyol composition for spray foamed rigid polyurethane foam of the present invention contains a polyol compound, a foaming agent, a foam stabilizer and a catalyst, and is mixed with a polyisocyanate component by a spray device and reacted to form a rigid polyurethane foam. A composition comprising:
The polyol compound contains an ester polyol,
The foaming agent contains 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), and water,
The catalyst includes an amine catalyst and a quaternary ammonium salt catalyst.

Also, the method for producing a spray foamed rigid polyurethane foam of the present invention comprises a polyol composition containing a polyol compound, a foaming agent, a foam stabilizer and a catalyst, and a polyisocyanate component mixed by a spray device and reacted to form a rigid polyurethane foam. A method for producing a rigid polyurethane foam comprising:
The polyol compound contains an ester polyol,
The blowing agent includes HFC-245fa, HFC-365mfc, and water;
The catalyst includes an amine catalyst and a quaternary ammonium salt catalyst.

  According to the present invention, as shown in the results of Examples, by using the polyol compound having the above-described configuration as the polyol composition for the rigid polyurethane foam, the obtained rigid polyurethane foam suppresses the lateral elongation, and the face material Excellent adhesion, flame retardancy, and workability. Although the details of the reason why the rigid polyurethane foam has such an effect are not clear, the reactivity of the polyurethane foam is appropriately controlled and the lateral elongation is increased by combining the composition ratio of the polyol compound and the specific blowing agent and catalyst. Therefore, it is presumed that the adhesion performance and workability are improved and the flame retardancy is exhibited in a well-balanced manner.

  Furthermore, by using the polyol composition, an increase in the finished density of the resulting rigid polyurethane foam can be suppressed, and the amount of the stock solution such as the polyol composition used can be reduced by the conventional formulation (HCFC-141b or HFC compound). Reduction is possible compared to the prescription used). Although the details of the reason for this effect are not clear, it is presumed that the improvement of the finished density was suppressed as a result of the reduction of the loss of the gas acting as the foaming agent because the reactivity could be appropriately controlled in a balanced manner.

  In the polyol composition, it is preferable that 5 to 50 parts by weight of the ester polyol is contained in 100 parts by weight of the polyol compound. By using the ester polyol, combustibility is improved.

  In the present invention, the polyol composition preferably contains the amine catalyst and the quaternary ammonium salt catalyst in a weight ratio of 4/1 to 2/1. By using at the above weight ratio, the reaction balance can be optimized.

  Furthermore, it is preferable that 0.01 to 0.15 parts by weight of lead octenoate is further contained in the polyol composition. By using the above lead octenoate, it can be sprayed without dropping even by spray foaming on the ceiling surface where higher workability is required, and the workability is further improved.

  On the other hand, the production method of the present invention is characterized by using a polyol composition for rigid polyurethane foam having any one of the above-described configurations. By using such a production method, it is possible to produce a rigid polyurethane foam that suppresses lateral elongation and is excellent in adhesion to a face material, flame retardancy, and workability by a spray method.

  Hereinafter, embodiments of the present invention will be described in detail.

The polyol composition for spray foamed rigid polyurethane foam of the present invention contains a polyol compound, a foaming agent, a foam stabilizer and a catalyst, and is mixed with a polyisocyanate component by a spray device and reacted to form a rigid polyurethane foam. Because
The polyol compound contains an ester polyol,
The foaming agent contains 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), and water,
The catalyst includes an amine catalyst and a quaternary ammonium salt catalyst.

  As the polyol compound of the present invention, those containing an ester polyol are used, but those containing Mannich polyol are also preferred, and those containing polyether polyol are also preferred. By using the ester polyol, combustibility is improved.

  In the polyol composition, in 100 parts by weight of the polyol compound, the ester polyol is preferably contained in an amount of 5 to 50 parts by weight, more preferably 15 to 40 parts by weight, and further preferably 20 to 35 parts by weight. preferable.

  Especially, it is preferable that ester polyol 15-40 weight part, Mannich polyol 20-60 weight part, and polyether polyol 0-65 weight part are contained in 100 weight part of polyol compounds, and ester polyol 20 is contained in 100 weight part of polyol compounds. More preferably, 35 parts by weight, 20 to 40 parts by weight of Mannich polyol, and 30 to 60 parts by weight of polyether polyol are included.

  In the polyol composition and the method for producing a rigid polyurethane foam of the present invention, it is preferable to use an ester polyol having a functional group number of 1.8 to 2.5 and a hydroxyl value of 200 to 600 mgKOH / g as the polyol compound.

  Further, in the polyol composition for spray foamed rigid polyurethane foam of the present invention, a Mannich polyol having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4 is converted into an ester polyol / Mannich polyol = 15/40 to 20/60 (weight). It is more preferable to contain so that it may become ratio.

  With such a configuration, it is possible to produce a rigid polyurethane foam having more excellent flame retardancy. The ester polyol may be 100. The weight ratio of ester polyol / Mannich polyol is more preferably 15/40 to 20/60. If the ratio of Mannich polyol is too large, the flame retardancy is lowered.

  The ester polyol preferably contains an aromatic dicarboxylic acid glycol ester and a fatty acid compound having 8 to 22 carbon atoms.

  By using a fatty acid compound having 8 to 22 carbon atoms as the polyol compound, the compatibility of the HFC compound as a foaming agent as the polyol composition is improved.

  Examples of the aromatic dicarboxylic acid glycol ester include terephthalic acid, phthalic acid, isophthalic acid and the like, ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, polyoxyethylene glycol having an average molecular weight of 300 to 500, and the like. Examples thereof include ester polyols having a hydroxyl group terminal based on glycol. Among these, the use of an ester polyol of terephthalic acid is preferable because a rigid polyurethane foam excellent in flame retardancy can be formed.

  As the fatty acid compound having 8 to 22 carbon atoms, a fatty acid compound having 8 to 22 carbon atoms or a reaction product of oil and fat containing the fatty acid and glycol can be used. As fatty acids having 8 to 22 carbon atoms, as fatty acids obtained from nature, caprylic acid, capric acid, linoleic acid, linolenic acid, oleic acid, stearic acid, palmitic acid, lauric acid, myristic acid, ricinoleic acid, tall oil fatty acid Etc. are exemplified.

  Examples of the synthetic fatty acid having 8 to 22 carbon atoms include isocaprilic acid, 2-ethylhexanoic acid, isononanoic acid, isocapriic acid, isolauric acid, isopalmitic acid, and isostearic acid.

  Fats and oils containing the above fatty acids include corn oil, cottonseed oil, olive oil, peanut oil, rapeseed oil, safflower oil, sesame oil, soybean oil, coconut oil, palm oil, linseed oil, tall oil, and other vegetable oils, beef fat, pork Animal fats and oils such as fat and whale oil are exemplified.

  The ester polyol of the present invention may be an alkyl ester such as the above fatty acid or its methyl ester, and an oil or fat mainly composed of the above fatty acid may be allowed to react with a glycol in the presence of the ester polyol in the presence of an aromatic dicarboxylic acid. The fatty acid compound obtained by reacting glycol in advance may be added to an aromatic ester polyol composed of an aromatic dicarboxylic acid and glycol. The above naturally-derived fatty acids and synthetic fatty acids may be used alone or in combination of two or more.

  The ester polyol containing a fatty acid compound can be produced by a known method. For example, a known esterification reaction catalyst such as a titanium compound obtained by mixing a predetermined amount of an aromatic dicarboxylic acid such as terephthalic acid and a fatty acid having 8 to 22 carbon atoms or an oil and fat of the fatty acid and adding glycol. It can manufacture by heating to 200 to 230 degreeC in nitrogen stream in presence.

  The content of the fatty acid compound in the ester polyol is preferably 1 to 20% by weight, and more preferably 1 to 10% by weight. If the amount is less than 1% by weight, the effect of improving the compatibility of the HFC compound is small, and if it is too much, the flame retardancy of the resulting foam is lowered.

  Mannich polyol is obtained by ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide on an active hydrogen compound obtained by the Mannich reaction of phenol and / or its alkyl-substituted derivative, formaldehyde and alkanolamine. It is a polyol compound having a hydroxyl value of 250 to 550 mgKOH / g and having 2 to 4 functional groups. A commercially available product of such a polyol compound is, for example, DK-3810 (manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) and can be used.

  The polyol compound of the present invention may further contain at least one polyol compound (amine polyol) having a hydroxyl value of 200 to 500 mgKOH / g selected from aliphatic amine polyols and aromatic amine polyols.

  Examples of the aliphatic amine polyol include alkylene diamine polyols and alkanol amine polyols. These polyol compounds are polyfunctional polyol compounds having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using alkylene diamine or alkanol amine as an initiator.

  As the alkylene diamine, known compounds can be used without limitation. Specifically, for example, use of alkylene diamine having 2 to 8 carbon atoms such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, and neopentyl diamine is preferable. Among these, the use of alkylenediamine having a small number of carbon atoms is more preferable, and the use of a polyol compound starting from ethylenediamine or propylenediamine is particularly preferable.

  In the alkylene diamine-based polyol, the alkylene diamine as the initiator may be used alone or in combination of two or more. The number of functional groups of the polyol compound using alkylenediamine as an initiator is 4.

  Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. The number of functional groups of the polyol compound using alkanolamine as an initiator is 3.

  The aromatic amine-based polyol is a polyfunctional polyether polyol compound having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using an aromatic diamine as an initiator.

  As the initiator, known aromatic diamines can be used without limitation. Specific examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4′-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, and the like. . Of these, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine, or a mixture thereof) is particularly preferred in that the rigid polyurethane foam obtained has excellent properties such as heat insulation and strength.

  When the amine polyol is used in combination, the weight ratio of (ester polyol + Mannich polyol) / amine polyol is preferably 100/0 to 35/65, and more preferably 70/30 to 40/60. If the amount of amine polyol used is too large, the flame retardancy of the resulting foam will be reduced.

  You may use a crosslinking agent as a component which comprises the polyol composition for rigid polyurethane foams of this invention. As the crosslinking agent, low molecular weight polyhydric alcohols used in the technical field of polyurethane can be used. Specifically, for example, trimethylolpropane, glycerin, pentaerythritol, triethanolamine and the like are exemplified.

  The blowing agent used in the method for producing the polyol composition and the rigid polyurethane foam of the present invention contains HFC-245fa and HFC-365mfc in water. By using such a foaming agent, a rigid polyurethane foam having excellent heat insulating properties can be obtained.

  The ratio of HFC-245fa / HFC-365mfc is preferably 95/5 to 60/40. The addition amount of the HFC compound is preferably 20 to 50 parts by weight, and more preferably 25 to 40 parts by weight with respect to 100 parts by weight of the total polyol compound.

  The HFC compound / water ratio is preferably 99.5 / 0.5 to 95/5. Moreover, it is preferable that it is 0.5-5 weight part with respect to a polyol compound total 100 weight part, and, as for the addition amount of water, it is more preferable that it is 1-2 weight part. By adding water, the vapor pressure of the blowing agent of the polyol composition can be reduced.

  In the polyol composition of the present invention, an amine catalyst and a quaternary ammonium salt catalyst are used in combination as the catalyst.

  Examples of the amine catalyst include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine (Kaorizer No. 1), N, N, N ′, N'-alkylpolyalkylenepolyamines such as N ', N "-pentamethyldiethylenetriamine (Kaorizer No. 3), N, N-dimethylcyclohexylamine (polycat-8), triethylenediamine, N-methylmorpholine and the like These amine catalysts may be used alone or in combination of two or more.

  In this invention, it is preferable that 2-7 weight part of the said amine catalyst is contained with respect to 100 weight part of said polyol compounds, It is more preferable that a weight part is contained, It is more preferable that 2-4 weight part is contained. .

  Examples of the quaternary ammonium salt catalyst include N- (2-hydroxypropyl) -N- (2-hydroxyethyl) -N, N-dimethylammonium octylate, N-hydroxyalkyl-N, N, N. In addition to -trialkylammonium salts, quaternary ammonium salt catalysts disclosed in JP-A-9-104734 can be used. Of these, hydroxyalkylammonium is preferably used. Moreover, as a commercial item, the kaolinizer 420 (made by Kao Corporation) etc. can be used, for example. These quaternary ammonium salt catalysts may be used alone or in admixture of two or more.

  In the present invention, the quaternary ammonium salt catalyst is preferably contained in an amount of 0.5 to 2 parts by weight, more preferably 0.5 parts by weight, based on 100 parts by weight of the polyol compound. More preferably, 5 parts by weight is contained.

  Furthermore, in the present invention, the polyol composition preferably contains the amine catalyst and the quaternary ammonium salt catalyst in a weight ratio of 4/1 to 2/1, preferably in a weight ratio of 4/1 to 3/1. More preferably it is included. By using at the above weight ratio, the reaction balance can be optimized.

  In the polyol composition of the present invention, it is preferable that lead octenoate which is an organometallic catalyst is further used as a catalyst. The lead octenoate in the present invention refers to an organometallic salt composed of octenoic acid and lead. In addition, isomers can be appropriately used for the octenoic acid. These compounds may be used alone or in combination of two or more. If the above lead octenoate is not used, there is no problem with spray foaming on the wall or floor surface, but spray foam on the ceiling surface may spill, but by using the above lead octenoate Even spray foaming on the ceiling surface where higher workability is required can be sprayed without dripping, and the workability is further improved.

  In the present invention, the lead octenoate is generally used at 0.75 or less with respect to 100 parts by weight of the polyol compound, but is preferably contained in an amount of 0.01 to 0.15 parts by weight, More preferably, 0.13 part by weight is contained, and 0.05 to 0.1 part by weight is more preferred.

  In the production of the rigid polyurethane foam of the present invention, in addition to the above components, other catalysts, flame retardants, viscosity reducing agents, colorants, antioxidants and the like well known to those skilled in the art can be used.

  The use of a catalyst that forms an isocyanurate bond that contributes to improvement in flame retardancy in the structure of the polyurethane molecule is also preferred, and examples thereof include potassium acetate and potassium octylate. Some of the above-mentioned tertiary amine catalysts also promote the isocyanurate ring formation reaction. A catalyst that promotes the formation of isocyanurate bonds and a catalyst that promotes the formation of urethane bonds may be used in combination.

  As the foam stabilizer, a known foam stabilizer used in the technical field of rigid polyurethane foam can be used without limitation. Specifically, for example, B-8465 (manufactured by Goldschmidt), SH-192, SH-193 (manufactured by Toray Dow Corning Silicon), S-824-02, SZ-1704, SZ-1923 (Nihon Unicar) And the like. These compounds may be used alone or in combination of two or more.

  In the present invention, addition of a flame retardant is also a preferred embodiment. Examples of suitable flame retardants include metal compounds such as halogen-containing compounds, organic phosphate esters, antimony trioxide, and aluminum hydroxide. Is done. These compounds may be used alone or in combination of two or more.

  Organophosphates are suitable additives because they also have an action as a plasticizer, and thus have an effect of improving the brittleness of the rigid polyurethane foam. It also has the effect of reducing the viscosity of the polyol composition. As such organic phosphate esters, halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like can be used. Specifically, for example, tris (β-chloroethyl) phosphate is used. (CLP, manufactured by Daihachi Chemical Co., Ltd.), tris (β-chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical Co., Ltd.), tributoxyethyl phosphate (TBXP, manufactured by Daihachi Chemical Co., Ltd.), tributyl phosphate, triethyl phosphate, cresyl Examples thereof include phenyl phosphate and dimethylmethylphosphonate, and one or more of these can be used. The addition amount of the organic phosphates is 40 parts by weight or less, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total polyol compound. If this range is exceeded, there may be cases where the plasticizing effect and the flame retardant effect cannot be sufficiently obtained, or the mechanical properties of the foam are deteriorated.

  In the present invention, it is also preferable to add a viscosity reducing agent. Examples of suitable viscosity reducing agents include trischloroethyl phosphate and tributoxyethyl phosphate as flame retardants. These compounds may be used alone or in combination of two or more.

  The viscosity of the polyol composition of the present invention is preferably 1000 mPa · s (20 ° C.) or less, and preferably 800 mPa · s (20 ° C.) or less, from the viewpoint of easily producing a rigid polyurethane foam by a spray method. More preferred.

  The polyisocyanate compound that forms a rigid polyurethane foam by mixing and reacting with the polyol composition is easy to handle, fast in reaction, excellent in the physical properties of the resulting rigid polyurethane foam, and low in cost. Therefore, it is preferable to use liquid MDI. As liquid MDI, Crude MDI (c-MDI) (Sumijoule 44V-10, Sumijoule 44V-20, etc. (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR-200 (Nippon Polyurethane Industry)), uretonimine-containing MDI (Millionate) MTL; manufactured by Nippon Polyurethane Industry Co., Ltd.) is used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination. As the polyisocyanate compound used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

  In the above-mentioned method for producing a rigid polyurethane foam, the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixing of the polyol composition and the polyisocyanate component is 1.2 to 1.6, more preferably 1.3 to 1.5, more preferably 1.35 to 1.45. More preferably, the NCO index can be adjusted to the above equivalence ratio, and the catalyst contains a trimerization catalyst.

With this configuration, it is possible to produce a rigid polyurethane foam in which many isocyanurate bonds are formed in the resin constituting the rigid polyurethane foam and the flame retardancy is further improved. The density of the rigid polyurethane foams produced by the present invention ^is preferably ^{25kg / m 3 ~50kg / m 3} , more preferably ^{30kg / m 3 ~40kg / m 3} . In particular, application to applications using high-density rigid polyurethane foam such as refrigerator applications is preferred.

Also, the method for producing a spray foamed rigid polyurethane foam of the present invention comprises a polyol composition containing a polyol compound, a foaming agent, a foam stabilizer and a catalyst, and a polyisocyanate component mixed by a spray device and reacted to form a rigid polyurethane foam. A method for producing a rigid polyurethane foam comprising:
The polyol compound contains an ester polyol,
The blowing agent includes HFC-245fa, HFC-365mfc, and water;
The catalyst includes an amine catalyst, a quaternary ammonium salt catalyst, and lead octenoate.

  More specifically, the present invention is characterized by using a polyol composition for rigid polyurethane foam having any one of the above-mentioned configurations. By using such a production method, it is possible to produce a rigid polyurethane foam that suppresses lateral elongation and is excellent in adhesion to a face material, flame retardancy, and workability by a spray method.

  In the production method of the present invention, a generally known spray foaming / molding apparatus for polyurethane is appropriately used and molded into a shape corresponding to the application.

  The rigid polyurethane foam of the present invention is generally spray-foamed so that the thickness of the hard polyurethane foam after curing is 100 to 300 mm, but in the present invention, it is spray-foamed to be 20 to 400 mm. In particular, it is preferably used for spray foaming so as to be 100 to 300 mm. By using the polyol composition of the present invention, a hard material having a good balance between workability and smoothness even when the thickness is about 250 to 300 mm, which is generally poor in workability and difficult to smooth. A polyurethane foam is obtained.

  Since the rigid polyurethane foam obtained by the present invention has the above-mentioned configuration, it suppresses lateral elongation and has excellent adhesion to the face material, flame retardancy, and workability. It becomes suitable for a heat insulating molded body (or a heat insulating board or the like) such as a refrigerated warehouse.

  Examples and the like specifically showing the configuration and effects of the present invention will be described below. In addition, the evaluation methods, such as a physical property in an Example etc., are as follows.

[Raw material of polyurethane composition]
A polyol composition was prepared with the composition described in the upper part of Table 1 (table describing the raw material blending ratio). The contents and suppliers of the polyurethane composition used in the production of the polyurethane foam are as follows.
-Polyol A: ethylenediamine-based polyol, Ex 450ED (Asahi Glass Co., Ltd.)
Polyol B: Mannich polyol, DK-3810 (Daiichi Kogyo Seiyaku Co., Ltd.)
Polyol C: Polyester polyol, Terol 693 (manufactured by Sakai Kogyo Co., Ltd.)
-Flame retardant: Trischloropyruphosphate-Foam stabilizer: SH-193 (Toray Industries, Inc.)
・ Amine catalyst: Triethylenediamine ・ Quaternary ammonium salt catalyst: Kao Raiser 420 (manufactured by Kao Corporation)
・ Lead octenoate: manufactured by Dainippon Ink

[Production conditions for rigid polyurethane foam]
In Examples and Comparative Examples, a polyol composition was prepared by blending a polyol compound described in the upper column of Table 1. The polyol compound blend is 100 parts by weight of the total amount of the polyol compound, 22 parts by weight of a flame retardant (manufactured by Akzo, Pyrol PCF), and the blowing agent is HFC-245fa / HFC-365mfc = 80/20 (weight ratio) 37 parts by weight and 1 part by weight of water were used.

  In the production of rigid polyurethane foam, the polyol composition and the polyisocyanate component are mixed with a laboratory stirrer so that the isocyanate index (NCO / OH equivalent ratio) is the ratio described in the upper column of Table 1, A foam was manufactured by casting into a 20 cm × 20 cm × 20 cm mold laid with kraft paper as a face material. The evaluation described below was performed, and the results are shown in the lower part of Table 1.

[Evaluation of rigid polyurethane foam]
Various characteristics of the rigid polyurethane foam produced in Examples and the like were evaluated as described below.

(Evaluation of lateral elongation)
About 100 g of a liquid obtained by mixing a polyol composition prepared in Examples and the like and a polyisocyanate component was sprayed on a flat surface, and the ratio of thickness to width was measured when free foaming was performed to evaluate lateral elongation.

(Evaluation of reactivity)
The reactivity in the production process of the rigid polyurethane foam in Examples and the like was evaluated as follows.

The produced rigid polyurethane foam was compared under each condition of the temperature setting of the blowing foaming machine, the atmospheric temperature, and the temperature of the object to be sprayed. The evaluation criteria were as follows.
・ If the surface is smooth and smooth: ○
・ If there are relatively few irregularities: △
・ If the unevenness is too large to be sprayed smoothly: ×

(Evaluation of stock solution usage)
Using the value obtained by calculating the total amount of stock solution used for spraying construction quantity (m ² × spraying thickness) and dividing it by construction volume (m ³ ) (stock solution usage / construction volume [kg / m ³ ]) evaluated. The evaluation criteria were as follows.
・ If it is 55 kg / m ³ or less: ○
・ When it is 55-60 kg / m ³ : △
・ If it is 60 kg / m ³ or more: ×

(Evaluation of flame retardancy)
Using the rigid polyurethane foam produced in Examples and the like, the test was conducted in accordance with the combustion test of JIS A 9511, and the flame retardancy was evaluated.
・ When the combustion distance is within 40 mm and the time is within 120 seconds: ○
・ If the combustion distance is within 60 mm and the time is within 120 seconds: △
・ When the combustion distance is 60 mm or more and the time is 120 seconds or more: ×

(Evaluation of thermal insulation)
Measure the thermal conductivity with an anacometer or auto lambda measuring instrument, and test the heat insulation of the rigid polyurethane foam produced in the examples etc. according to the combustion test of JIS A 9526 to evaluate the flame retardancy. went. The evaluation criteria were as follows.
・ When the standard value is 0.022 w / m / k or less: ○
・ When the standard value exceeds 0.022 w / m / k: ×

(Adhesive evaluation)
Using the rigid polyurethane foam produced in Examples and the like, the adhesiveness was evaluated by vertical tension (JIS A 9526, measuring method of self-adhesive strength) by autograph. The following criteria were used as evaluation criteria.
・ If the foam breaks: ○
・ When interface breaks: ×

(Examples and comparative examples)
The evaluation results of the obtained rigid polyurethane foam are shown in the lower column of Table 1.

From these results, in any of Examples 1 to 5 having the configuration of the present invention, lateral elongation is suppressed, adhesion to a face material, flame retardancy, heat insulation, and workability (stock solution use amount, reaction) It has been found that a rigid polyurethane foam having excellent properties can be obtained. On the other hand, in Comparative Examples 1 and 2 that do not have the configuration of the present invention, in any of the obtained rigid polyurethane foams, suppression of lateral elongation, adhesion to a face material, heat insulation, flame retardancy, and workability Could not stand side by side.

  As described above, by using the polyol composition for spray foamed rigid polyurethane foam of the present invention, a highly heat-insulating rigid polyurethane foam that suppresses lateral elongation and has excellent adhesion to the face material, flame retardancy, and workability is obtained. It was confirmed that it was obtained.

Claims (8)

A polyol composition comprising a polyol compound, a foaming agent, a foam stabilizer and a catalyst, mixed with a polyisocyanate component by a spray device and reacted to form a rigid polyurethane foam,
The polyol compound contains an ester polyol,
The foaming agent contains 1,1,1,3,3-pentafluoropropane (HFC-245fa), 1,1,1,3,3-pentafluorobutane (HFC-365mfc), and water,
A polyol composition for spray foamed rigid polyurethane foam, wherein the catalyst comprises an amine catalyst and a quaternary ammonium salt catalyst.   2. The polyol composition for spray foamed rigid polyurethane foam according to claim 1, wherein 5 to 50 parts by weight of the ester polyol is contained in 100 parts by weight of the polyol compound.   The polyol composition for spray-foamed rigid polyurethane foam according to any one of claims 1 to 2, wherein the amine catalyst and the quaternary ammonium salt catalyst are contained in a weight ratio of 4/1 to 2/1.   The polyol composition for spray-foamed rigid polyurethane foam according to any one of claims 1 to 3, further comprising 0.01 to 0.15 parts by weight of lead octenoate with respect to 100 parts by weight of the polyol compound. object. A method for producing a rigid polyurethane foam comprising mixing a polyol composition containing a polyol compound, a foaming agent, a foam stabilizer and a catalyst and a polyisocyanate component by a spray device and reacting the mixture to form a rigid polyurethane foam,
The polyol compound contains an ester polyol,
The blowing agent includes HFC-245fa, HFC-365mfc, and water;
A method for producing a spray foamed rigid polyurethane foam, wherein the catalyst contains an amine catalyst and a quaternary ammonium salt catalyst.   The method for producing a spray-foamed rigid polyurethane foam according to claim 5, wherein 5 to 50 parts by weight of the ester polyol is contained in 100 parts by weight of the polyol compound.   The method for producing a spray foamed rigid polyurethane foam according to any one of claims 5 to 6, wherein the amine catalyst and the quaternary ammonium salt catalyst are contained in a weight ratio of 4/1 to 2/1.   The method for producing a spray-foamed rigid polyurethane foam according to any one of claims 5 to 7, further comprising 0.01 to 0.15 parts by weight of lead octenoate with respect to 100 parts by weight of the polyol compound. .