JP2009040961A - Polyol composition for spray blowing hard polyurethane foam and method for producing spray blowing hard polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition using water as a blowing agent, forming a spray blowing hard polyurethane foam with excellent flame retardancy, suppressing problems on eye-rainbow and excellent in preservation stability, and to provide a method for producing spray blowing hard polyurethane foam using the polyol composition. <P>SOLUTION: The polyol composition for spray blowing hard polyurethane foam consists of a polyol compound, a blowing agent and a catalyst and the composition is mixed with a polyisocyanate component by a spray device to react therewith to form the hard polyurethane foam, wherein the blowing agent is water, the catalyst contains a trimerization promoting catalyst and a reactive amine catalyst in which the weight ratio of the trimerization promoting catalyst and the reactive amine catalyst is 0.7/1-1.3/1. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyol composition for spray-foamed rigid polyurethane foam that forms a rigid polyurethane foam using water as a foaming agent, and a method for producing a spray-foamed 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. Among these, rigid polyurethane foams formed by a spray foaming method are widely used particularly as heat insulating materials for houses and refrigerators.

  As for the spray foaming method, HCFC-141b was used in place of the CFC compound in applications requiring high flame retardancy (for example, Patent Document 1 below). However, since the use of HCFC-141b is currently prohibited, such a rigid polyurethane foam cannot be manufactured.

  In place of HCFC-141b, there is no problem in the working environment and the global environment, and water is known as a low-cost foaming agent, and rigid polyurethane foam using water as the foaming agent is known. In such a rigid polyurethane foam, it is necessary to use a large amount of water in order to increase the expansion ratio to form a low-density rigid polyurethane foam. In addition, the spray foaming method is used in various environments and may be applied at a low temperature of 0 ° C. or lower. For this reason, in water-foamed rigid polyurethane foams formed by the spray foaming method, a highly active amine catalyst or a lead compound such as lead octylate has usually been used as a catalyst in order to maintain high reactivity (for example, Patent Document 2) below.

  However, a highly active amine catalyst generally may cause eye itchiness (eye rainbow) and the like, and when a rigid polyurethane foam is formed by a spray foaming method in a narrow construction environment, eye rainbow becomes a particular problem. On the other hand, when a lead compound is used as a catalyst, particularly when water is used as a foaming agent, hydrolysis of esters in the polyol composition containing the catalyst and water is caused, resulting in poor storage stability of the polyol composition. There is. In addition, lead is highly toxic and it is preferable to avoid the use of lead compounds in view of recent environmental problems.

JP-A-8-53565 JP 2000-256434 A

  The present invention has been made in view of the above circumstances, the purpose of which is to use water as a foaming agent, can form a spray foamed rigid polyurethane foam excellent in flame retardancy, further suppress the problem of eye rainbow, It is another object of the present invention to provide a polyol composition having excellent storage stability and a method for producing a spray foamed rigid polyurethane foam using the polyol composition.

  The above object can be achieved by the present invention as described below. That is, the polyol composition for spray foamed rigid polyurethane foam according to the present invention comprises a polyol compound, a foaming agent and a catalyst, and is mixed with a polyisocyanate component by a spray device and reacted to form a rigid polyurethane foam. A foam composition for foam, wherein the blowing agent is water, the catalyst contains a trimerization promoting catalyst and a reactive amine catalyst, and the weight ratio of the trimerization promoting catalyst / the reactive amine catalyst is 0. 7/1 to 1.3 / 1.

  The polyol composition for spray foamed rigid polyurethane foam having such a structure contains a catalyst comprising a trimerization promoting catalyst and a reactive amine catalyst, and the weight ratio of the trimerization promoting catalyst / the reactive amine catalyst is 0.7 / 1 to 1. .3 / 1. By including such a catalyst, the problem of eye rainbow is suppressed in this polyol composition, and the storage stability is excellent. Furthermore, when this polyol composition is used, even if only water is used as a foaming agent, a spray foamed rigid polyurethane foam having excellent flame retardancy can be formed. Such trimerization-promoting catalyst and reactive amine catalyst may be used singly, but in consideration of the problem of eye rainbow and workability at the time of spray foaming, it is preferable to use two or more different catalyst activities in combination. .

  In the above polyol composition for spray foamed rigid polyurethane foam, the polyol compound contains an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a polyether polyol containing resin fine particles, and the polyoxyethylene glycol has an average molecular weight of 150. The aromatic dicarboxylic acid is orthophthalic acid, or is composed of orthophthalic acid and terephthalic acid, and the molar percentage of the orthophthalic acid exceeds 95 mol%. The ether polyol weight ratio is preferably 90/10 to 55/45.

  The polyol composition having such a configuration is excellent in storage stability, and when this polyol composition is used, it is possible to form a spray-foamed rigid polyurethane foam which is particularly excellent in flame retardancy and has small thermal shrinkage due to aging.

  Here, when the average molecular weight (according to the terminal group determination method) of the polyoxyethylene glycol constituting the ester polyol is less than 150, the hydrolysis resistance is lowered, and the storage stability of the polyol composition becomes insufficient. Exceeding the above will reduce the combustion resistance of the rigid polyurethane foam obtained.

  Further, when the weight ratio of the ester polyol and the resin polyol-containing polyether polyol exceeds 90/10 and the weight ratio of the ester polyol is large, the shrinkage of the foam due to the diffusion of the carbon dioxide gas as the foaming gas increases. If it exceeds 45 and the weight ratio of the resin polyol-containing polyether polyol is large, the closed cell ratio is lowered and the thermal conductivity is increased. The weight ratio of the ester polyol to the resin fine particle-containing polyether polyol is more preferably 90/10 to 60/40, and still more preferably 90/10 to 70/30.

  Further, the aromatic dicarboxylic acid is characterized by being composed of orthophthalic acid or orthophthalic acid and terephthalic acid, and the mole% of orthophthalic acid is more than 95 mole%. The polyol composition having such a structure has practical storage stability to the extent that a rigid polyurethane foam can be produced even after market distribution just after production, and the rigid polyurethane foam excellent in flame retardancy. Can be manufactured. When the molar ratio of terephthalic acid / orthophthalic acid exceeds 5/95 and the ratio of terephthalic acid is large, shrinkage may occur in the produced rigid polyurethane foam.

  Another method for producing a spray foamed rigid polyurethane foam according to the present invention is a spray foaming in which a polyol composition containing a polyol compound, a foaming agent and a catalyst is mixed with a polyisocyanate component and reacted to form a rigid polyurethane foam. A method for producing a rigid polyurethane foam, wherein the blowing agent is water, the catalyst contains a trimerization promoting catalyst and a reactive amine catalyst, and the weight ratio of the trimerization promoting catalyst / the reactive amine catalyst is It is 0.7 / 1 to 1.3 / 1.

  According to the manufacturing method having such a configuration, it is possible to manufacture a spray-foamed rigid polyurethane foam excellent in flame retardancy even if the problem of eye rainbow is suppressed and only water is used as a foaming agent.

  In the production method of the spray foamed rigid polyurethane foam, the polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol, and the polyoxyethylene glycol has an average molecular weight of 150 to 500, and the aromatic dicarboxylic acid is orthophthalic acid, or is composed of orthophthalic acid and terephthalic acid, and the mole percentage of the orthophthalic acid exceeds 95 mole%, and the ester polyol / the resin fine particle-containing polyether It is preferable that the weight ratio of polyol is 90/10 to 55/45.

  According to the manufacturing method having such a configuration, spray foaming hard that suppresses the problem of eye rainbow and has excellent flame retardancy and small thermal shrinkage due to aging even when only water is used as a foaming agent. Polyurethane foam can be produced.

  In the polyol composition for spray foamed rigid polyurethane foam and the method for producing spray foamed rigid polyurethane foam according to the present invention, the trimerization promoting catalyst and the reactive amine catalyst are contained, and the weight ratio of the trimerization promoting catalyst / the reactive amine catalyst. A catalyst having a ratio of 0.7 / 1 to 1.3 / 1 is used. Considering the problem of eye rainbow, the storage stability of the polyol composition and the flame retardancy of the resulting rigid polyurethane foam, the weight ratio of the trimerization promoting catalyst / reactive amine catalyst is 0.8 / 1 to 1.2 / 1 is preferable, and 0.9 / 1 to 1.1 / 1 is more preferable.

  Trimerization promoting catalysts include potassium metal acetate, potassium propionate, potassium 2-ethylhexanoate (potassium octylate), and the like, and N- (2-hydroxypropyl). -N- (2-hydroxyethyl) -N, N-dimethylammonium octylate, N-hydroxyalkyl-N, N, N-trialkylammonium salt, etc., compounds disclosed in JP-A-9-104734 And quaternary ammonium salt catalysts such as Dabco-TMR, Dabco-TMR-2, and Polycat 41 (Air Products).

  The reactive amine catalyst contains a compound having an active hydrogen group in the molecule. For example, dimethylmethanolamine, dimethylethanolamine, 2- [methyl [2- (dimethylamino) ethyl] amino] ethanol (TMAEEA), 2- [2- (dimethylamino) ethoxy] ethanol (DMAEE), 1,3-bis (dimethylamino) -2-propanol (TMHPDA), 4-methylpiperazine-1-ethanol, 3,3 ′-[3- (Dimethylamino) propylimino] bis (2-propanol) (Thancat-DPA), 2-morpholinoethanol, commercially available Polycat 16, Polycat 17, DabcoWT (Air Products), TOYOCAT-RX-7 (Tosoh), etc. Is mentioned. In the present invention, the reactive amine catalyst includes not only those exhibiting foaming reaction activity but also those exhibiting both foaming reaction activity and resinification reaction activity.

  In this invention, you may add the catalyst well-known to those skilled in the art which shows foaming reaction activity and / or resinification reaction activity as needed.

  Examples of the polyol compound contained in the polyol composition of the present invention include those containing an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol.

  The ester polyol is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid, the polyoxyethylene glycol has an average molecular weight of 150 to 500, the aromatic dicarboxylic acid consists of orthophthalic acid, or orthophthalic acid and terephthalic acid, And the mol% of orthophthalic acid exceeds 95 mol%. The polyoxyethylene glycol having an average molecular weight of 150 to 500 may contain diethylene glycol or triethylene glycol. Diethylene glycol is preferably not included. For example, when polyoxyethylene glycol having a relatively broad molecular weight distribution including triethylene glycol (molecular weight 150) is used, since crystallization does not occur, liquid property stability is good and preferable. Such an ester polyol can be produced by the same production method as an ester polyol composed of an aromatic dicarboxylic acid and ethylene glycol or diethylene glycol which are generally used conventionally. The bifunctional polyoxyethylene glycol constituting the ester polyol can also be produced by a conventional method, and a commercially available product such as PEG400 may be used.

  The resin polyol-containing polyether polyol can be produced by a known method. For example, a resin produced by a bulk polymerization method or a solution polymerization method is pulverized into fine particles, and if necessary, a resin fine powder obtained by classification is added to and mixed with a polyol compound, a resin obtained by an emulsion polymerization method Examples include a method of adding an emulsion containing fine particles as it is, a method in which a monomer is dissolved or dispersed in a polyol compound, a radical polymerization initiator such as AIBN or BPO is added, heated, and polymerized to obtain a resin fine particle polyol compound. The Among these, the method of polymerizing in a polyol compound to form resin fine particles is most preferable because the particles are less likely to settle even when left for a long period of time and a stable polyol composition is obtained.

  As the resin fine particles, known resin fine particles contained in a polyol for polyurethane foam can be used. Specifically, single weights such as acrylonitrile, methacrylonitrile, α-ethylacrylonitrile, styrene, vinyl acetate, acrylic monomers, and the like can be used. Copolymer fine particles and copolymer fine particles of two or more monomers selected from these monomers can be used. Moreover, it is preferable that the resin fine particle in the polyol compound whole quantity which comprises a polyol composition is 0.2 to 1.0 weight%.

  In the present invention, the resin fine particle-containing polyether polyol is preferably a Mannich polyether polyol having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4 and containing resin fine particles.

  By using the polyol composition having such a configuration, a rigid polyurethane foam having further excellent flame retardancy can be formed.

  Mannich polyol constituting the resin polyol-containing polyether polyol is an active hydrogen compound obtained by a Mannich reaction of phenol and / or its alkyl-substituted derivative, formaldehyde and alkanolamine, or at least one of ethylene oxide and propylene oxide in this compound. An active hydrogen compound obtained by ring-opening addition polymerization.

  Commercially available products can be used as the resin polyol-containing polyether polyol, and specific examples include Asahi Glass Urethane Co., Ltd. products.

  The polyol composition of the present invention may further contain at least one polyol compound 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, 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 having ethylenediamine or propylenediamine as an initiator 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. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. The number of functional groups of the polyol compound using alkylene diamine as the initiator is 4, and the number of functional groups of the polyol compound using alkanolamine as the 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 obtained rigid polyurethane foam has excellent properties such as heat insulation and strength.

  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, trimethylolpropane, glycerin, pentaerythritol, triethanolamine and the like are exemplified.

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

  As the foam stabilizer, known foam stabilizers used in the technical field of rigid polyurethane foam can be used without limitation. Specifically, foam stabilizers such as B-8465 (Gold Schmidt), SH-193, S-824-02, SZ-1704 (Toray Dow Corning Silicon) can be used. Two or more foam stabilizers may be used.

  In the present invention, addition of a flame retardant is also a preferred embodiment, and examples of suitable flame retardants include metal compounds such as halogen-containing compounds, organophosphates, antimony trioxide, and aluminum hydroxide. .

  Organophosphates are suitable additives because they also have an action as a plasticizer and thus have an effect of improving the brittleness of rigid polyurethane foam. It also has the effect of reducing the viscosity of the polyol composition. Examples of the organic phosphate esters include halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like. Specifically, tris (β-chloroethyl) phosphate (CLP, Daihachi Chemical), Tris (β-chloropropyl) phosphate (TMCPP, Daihachi Chemical), Tributoxyethyl phosphate (TBXP, Daihachi Chemical), Tributyl phosphate, Triethyl phosphate, Cresyl phenyl phosphate, Dimethyl methylphosphonate Etc., and one or more of these can be used. The amount of the organic phosphate ester added is 60 parts by weight or less, preferably 5 to 55 parts by weight, based on 100 parts by weight of the polyol compound. If this range is exceeded, problems such as insufficient plasticization and flame retardant effects and deterioration of the mechanical properties of the foam may occur.

  The viscosity of the polyol composition of the present invention is preferably 500 mPa · s (20 ° C.) or less, and preferably 300 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. For this reason, liquid MDI is used. As liquid MDI, Crude MDI (c-MDI) (Sumijoule 44V-10, Sumijoule 44V-20, Sumijoule H-420, etc. (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR-200 (Nippon Polyurethane Industry)) Uretonimine-containing MDI (Millionate MTL; manufactured by Nippon Polyurethane Industry) and the like are 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 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 1.1 to 2.5, more preferably 1.5. It is -2.2, More preferably, it is 1.8-2.0.

  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.

(Polyol composition)
A polyol composition was prepared with the composition described in the upper part of Table 1. The contents and characteristics of the raw materials used are as follows.
a) Polyol A
Ester polyol (Hitachi Kasei Polymer) prepared from orthophthalic acid, which is an aromatic carboxylic acid, and glycol containing bifunctional polyoxyethylene glycol (PEG) having an average molecular weight of 400 by a conventional method; hydroxyl value = 150 mgKOH / g, viscosity = 2500 mPa・ Sec (25 ℃)
b) Polyol B
Polyol in which resin fine particles are dispersed in a Mannich polyether polyol compound (Asahi Glass); hydroxyl value = 380 mgKOH / g
c) Flame retardant TMCPP: Phosphorus flame retardant (plasticizer) (Daihachi Chemical Industry)
TBXP: Phosphorus flame retardant (plasticizer) (Daihachi Chemical Industry)
d) Catalyst (A): Trimerization promoting catalyst Perlon 9540 (potassium octylate) (Perlon)
(B): Trimerization promoting catalyst Polycat 41 (Air Products)
(C): Reactive amine catalyst (TOYOCat-RX-7) (Tosoh)
(D): Tertiary amine catalyst (NIAX-A-1) (Union Carbide)
(E): Tin octylate (Dabco T-9) (Air Products)
e) Foam stabilizer (A): Organosilicon compound F701 (Shin-Etsu Chemical)
(B): Silicon-based surfactant F501 (Shin-Etsu Chemical)
f) Foaming agent: water g) Polyisocyanate component: Sumijour 44V-20 (Suika Bayer Urethane), NCO% = 31.0%

(Evaluation)
1) Foam density (kg / m ³ )
A foaming stock solution composition is prepared by stirring with a mixer, freely foamed using a mold of 200 mm × 200 mm, depth of 200 mm, and 100 mm × 100 mm in thickness from the core layer obtained by removing the skin layer from the obtained rigid polyurethane foam. A 100 mm foam sample was cut out and weighed to calculate the density (kg / m ³ ).

2) Storage stability of the polyol composition A sample having the same shape as the sample used for the measurement of the foam density by producing a free-foam foam by leaving the polyol composition in a sealed state for 1 month at a temperature of 40 ° C. Was left for 48 hours under high temperature and high humidity conditions (temperature 70 ° C., relative humidity 95%), and the dimensional change rate (%) of the core in the vertical direction of foaming was measured. When a polyol composition with poor storage stability is used, the dimensional change rate increases. Those with a dimensional change rate of less than 5% were evaluated as ◎, those with 5-10% as ○, 10% or less but accompanied by distorted deformations as Δ, and those not retaining the shape as X.

3) Workability A polyol composition and a polyisocyanate component are sprayed and foamed and cured at 0 ° C on a kraft paper face material that is attached to a plywood installed vertically using a commercially available spray foaming device. A 20 to 25 mm rigid polyurethane foam was formed. The occurrence of dripping at the time of spray foaming was visually observed to evaluate the reactivity. The results are shown as “Good” for those with no dripping, “Δ” for those with little reactivity, “B” for those with little occurrence, and “x” for those with large dripping and low reactivity, which are impractical.

4) Flame retardancy A sample was cut out from the rigid polyurethane foam formed by spray foaming (however, the spraying temperature was room temperature) in 3) above, and flame retardancy was evaluated in accordance with JIS A 1321.

5) Eye rainbow evaluation Using a container that can be sealed, a gas detector (manufactured by Gastec Co., Ltd.) was used to measure the gas concentration (ppm) of amines filled with 50% urethane foam in the space. A sample in which the concentration of amines was less than 50 ppm and did not cause eye rainbow in the worker was rated as ◯, and a concentration of amines was 50 ppm or more and in the worker was causing eye rainbow in ×.

(Examples and comparative examples)
In Examples and Comparative Examples, a polyol composition was prepared by blending a polyol compound described in the upper part of Table 1. In the production of rigid polyurethane foam, the polyol composition and the polyisocyanate component are mixed so that the isocyanate index (NCO / OH equivalent ratio) is the ratio described in Table 1 to obtain a foamed stock solution composition, which is foam-cured. To produce a rigid polyurethane foam. The evaluation described above was performed, and the results are shown in the lower part of Table 1. The isocyanate index is calculated for other OH groups, with 2 equivalents of NCO groups consumed by 1 mol of water.

  From the results shown in Table 1, the polyol composition of Example 1 was excellent in storage stability while ensuring good workability while suppressing the problem of eye rainbow. In addition, when a hard polyurethane foam obtained using such a polyol composition was evaluated for flame retardancy in accordance with JIS A 1321, the classification was flame retardant grade 3 and was suitable for the surface test. It was. On the other hand, when a rigid polyurethane foam was produced using the polyol composition of Comparative Example 1, the problem of eye rainbow occurred. Moreover, it turned out that the polyol composition of Comparative Example 2 has poor storage stability.

Claims (4)

A polyol composition for a spray foamed rigid polyurethane foam comprising a polyol compound, a foaming agent and a catalyst, mixed with a polyisocyanate component by a spray device and reacted to form a rigid polyurethane foam,
The blowing agent is water;
The catalyst contains a trimerization promoting catalyst and a reactive amine catalyst, and the weight ratio of the trimerization promoting catalyst / the reactive amine catalyst is 0.7 / 1 to 1.3 / 1. Polyol composition for spray foamed rigid polyurethane foam. The polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid is composed of orthophthalic acid, or orthophthalic acid and terephthalic acid, and the mol% of the orthophthalic acid exceeds 95 mol%,
The polyol composition for spray-foamed rigid polyurethane foam according to claim 1, wherein the weight ratio of the ester polyol / the resin fine particle-containing polyether polyol is 90/10 to 55/45. A method for producing a spray foamed rigid polyurethane foam comprising mixing a polyol composition containing a polyol compound, a foaming agent and a catalyst and a polyisocyanate component by a spray device and reacting the mixture to form a rigid polyurethane foam,
The blowing agent is water;
The catalyst contains a trimerization promoting catalyst and a reactive amine catalyst, and the weight ratio of the trimerization promoting catalyst / the reactive amine catalyst is 0.7 / 1 to 1.3 / 1. Manufacturing method of spray foamed rigid polyurethane foam. The polyol compound includes an ester polyol of polyoxyethylene glycol and an aromatic dicarboxylic acid and a resin polyol-containing polyether polyol,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid is composed of orthophthalic acid, or orthophthalic acid and terephthalic acid, and the mol% of the orthophthalic acid exceeds 95 mol%,
The method for producing a spray foamed rigid polyurethane foam according to claim 3, wherein a weight ratio of the ester polyol / the resin fine particle-containing polyether polyol is 90/10 to 55/45.