JPWO2019022077A1 - Polyol composition for rigid polyurethane foam, composition for rigid polyurethane foam, and method for producing rigid polyurethane foam - Google Patents

Abstract

The polyol composition for rigid polyurethane foam of the present invention contains at least a polyol compound, a foaming agent, a catalyst and an acid component, and is mixed with and reacted with a polyisocyanate component to form a rigid polyurethane foam. And containing at least 1-chloro-3,3,3-trifluoropropene as a blowing agent, at least one selected from the group consisting of an amine catalyst and a metal catalyst as a catalyst, and an acid component It is a polyol composition containing an organic acid. ADVANTAGE OF THE INVENTION According to this invention, the polyol composition for rigid polyurethane foams excellent in storage stability, the composition for rigid polyurethane foams, and the manufacturing method of rigid polyurethane foam can be provided.

Description

  The present invention relates to a polyol composition for a rigid polyurethane foam containing at least 1-chloro-3,3,3-trifluoropropene (hereinafter also referred to as "HFO-1233zd") as a foaming agent, and a hard composition containing the polyol composition. The present invention relates to a composition for polyurethane foam and a method for producing a rigid polyurethane foam using the polyol composition as a raw material.

  Following the adoption of the Montreal Protocol on Substances that Deplete the Ozone Layer in Canada in 1987, the “Ozone Layer Protection Act” was enacted in Japan in 1988, and the production and import of fluorocarbons are restricted. . For this reason, development of alternative materials such as regulated CFCs has been promoted, and hydrofluoroolefins (hereinafter also referred to as "HFO") are considered to be promising as useful alternative materials. Among HFOs, HFO-1233zd is widely used in the market as a foaming agent for rigid polyurethane foam.

  By the way, in general, rigid polyurethane foam is divided into raw materials into a two-component system, the polyisocyanate component and the component compatible with it are P liquid, and the polyol composition containing at least a polyol compound, a foaming agent and a catalyst is R liquid. , P and R are mixed, stirred, reacted and cured. Here, Liquid P and Liquid R are usually prepared and stored in advance before manufacturing rigid polyurethane foam, but in the case where Liquid R contains HFO-1233zd as a foaming agent, In the case where it takes time to produce a rigid polyurethane foam after the preparation of the R solution, there may occur a problem such as a partial deactivation of the catalyst contained in the R solution together with the foaming agent. Such problems lead to productivity deterioration or product failure due to delayed gel time at the time of production of rigid polyurethane foam or insufficient progress of foam foaming. For this reason, there has been a demand in the market to improve the storage stability of a polyol composition containing at least a polyol compound, HFO-1233zd and a catalyst.

  In US Pat. No. 5,956,015, a composition is described comprising a hydrohaloolefin blowing agent and a catalyst system comprising at least one precipitation resistant metal catalyst and at least one amine catalyst.

  Patent Document 2 below describes a catalyst composition containing a blowing agent containing a halogenated hydroolefin, a polyol, an amine catalyst, a non-amine catalyst, or a mixture of these catalysts, and a polyol premix composition containing an antioxidant. It is done.

Japanese Patent Application Publication No. 2014-506947 Japanese Patent Application Publication No. 2015-529738

  However, the inventors of the present invention have made intensive studies and found that there is room for improvement in the storage stability of the polyol composition containing at least a polyol compound, a blowing agent and a catalyst in the above-mentioned prior art. The present invention has been made in view of the above situation, and its object is to contain a polyol compound, a catalyst, and at least 1-chloro-3,3,3-trifluoropropene as a foaming agent, and is excellent in storage stability. It is an object of the present invention to provide a polyol composition for rigid polyurethane foam, a composition for rigid polyurethane foam, and a method for producing rigid polyurethane foam.

  The above object can be achieved by the present invention as described below. That is, the present invention is a polyol composition for rigid polyurethane foam, which contains at least a polyol compound, a foaming agent, a catalyst and an acid component, and is mixed and reacted with a polyisocyanate component to form a rigid polyurethane foam, Containing at least 1-chloro-3,3,3-trifluoropropene as an agent, at least one selected from the group consisting of an amine catalyst and a metal catalyst as the catalyst, and containing an organic acid as the acid component The present invention relates to a polyol composition for rigid polyurethane foam characterized by

  In the polyol composition for a rigid polyurethane foam, it is preferable to contain an organic acid having an aromatic ring as the acid component.

  The present invention also relates to a composition for a rigid polyurethane foam comprising the above-mentioned polyol composition and a polyisocyanate component.

  The present invention is also a method for producing a rigid polyurethane foam, wherein a polyol composition containing at least a polyol compound, a foaming agent, a catalyst and an acid component is mixed and reacted with a polyisocyanate component, wherein the polyol composition is the foam Containing at least 1-chloro-3,3,3-trifluoropropene as an agent, at least one selected from the group consisting of an amine catalyst and a metal catalyst as the catalyst, and containing an organic acid as the acid component The present invention relates to a method for producing a rigid polyurethane foam characterized by:

  In the method for producing a rigid polyurethane foam, it is preferable that the acid component contains an organic acid having an aromatic ring.

  In the polyol composition for a rigid polyurethane foam containing a polyol compound, a catalyst, and at least HFO-1233zd as a foaming agent, the inventor describes the cause of the deterioration in storage stability caused by partial deactivation of the catalyst, etc. I studied earnestly. As a result, it was found that the deactivation of the catalyst was caused by the interaction between HFO-1233zd and the catalyst.

  The polyol composition for rigid polyurethane foam according to the present invention comprises, as an acid component, a foaming agent containing at least HFO-1233zd and a catalyst containing at least one selected from the group consisting of an amine catalyst and a metal catalyst. Contains an organic acid. For this reason, the catalyst activated under basicity can be shifted to acidity, and the activity of the catalyst can be suppressed. As a result, the catalyst with reduced activity loses affinity with HFO-1233zd, and the deactivation of the catalyst due to the interaction between HFO-1233zd and the catalyst can be prevented. As a result, the polyol composition for rigid polyurethane foam according to the present invention has improved storage stability.

  As mentioned above, since the polyol composition for rigid polyurethane foam concerning the present invention is excellent in storage stability, in the manufacturing method of the rigid polyurethane foam which uses this as a raw material, it is excellent in production stability.

  The polyol composition for rigid polyurethane foam according to the present invention contains at least a polyol compound, HFO-1233zd as a foaming agent, a catalyst and an acid component.

  As the polyol compound, polyols known to those skilled in the art can be used, and polyether polyols, polyester polyols and the like can be mentioned.

  The polyether polyol is a polyoxyalkylene polyol obtained by subjecting an alkylene oxide to ring-opening addition polymerization to an initiator having 2 to 4 active hydrogen atoms. Specific examples of the initiator include aliphatic polyhydric alcohols (eg, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-butanediol, 1,6-hexane). Diols, glycols such as neopentyl glycol, cyclohexylene glycol, cyclohexanedimethanol, triols such as trimethylolpropane and glycerin, tetrafunctional alcohols such as pentaerythritol), aliphatic amines (eg, ethylene diamine, propylene diamine, butylene) Diamines, alkylene diamines such as hexamethylene diamine and neopentyl diamine, alkanolamines such as monoethanolamine and diethanolamine, aromatic amines (for example, 2) 4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine, etc.) and the like, each of which may be used alone You may use or you may use 2 or more types together. It is preferable to use an aliphatic alcohol as the initiator, more preferably to use triols, and it is particularly preferable to use glycerin. The polyether polyol preferably has an average number of functional groups of 2 to 4, and more preferably 2.5 to 3.5. Furthermore, as for a polyether polyol, it is more preferable that weight average molecular weights are 3000-5000.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide and the like. Among these, it is preferable to carry out ring-opening addition polymerization to the above-mentioned initiator using ethylene oxide and propylene oxide in combination. At that time, the ratio of ethylene oxide ((ethylene oxide) / (ethylene oxide + propylene oxide)) is preferably 5% to 30%.

  The hydroxyl value of the polyether polyol is preferably 200 to 1000 mg KOH / g, more preferably 300 to 600 mg KOH / g. When the hydroxyl value is less than 200 mg KOH / g, the viscosity ratio of the polyol composition to the polyisocyanate component becomes high, which leads to poor stirring at the time of mixing. On the other hand, if it exceeds 1000 mg KOH / g, it will be difficult to impart adequate toughness to the obtained polyurethane foam. A hydroxyl value is a value measured based on JISK155-1: 2007.

  Examples of polyester polyols include aromatic polyester polyols and aliphatic polyester polyols, but in consideration of the flame retardancy of the resulting rigid polyurethane foam, it is preferable to use aromatic polyester polyols. The aromatic polyester polyol is a condensate of an aromatic dicarboxylic acid and a glycol such as phthalic acid, isophthalic acid, terephthalic acid and naphthalene dicarboxylic acid, and has an average functional group number of 1.8 to 2.5, more preferably 1.9. It is a polyol compound of -2.3 and a hydroxyl value of 100 to 400 mg KOH / g. Although it does not specifically limit as glycol which comprises aromatic polyester polyol, It is preferable to use the low molecular-weight aliphatic glycol well-known as a component of polyester polyols, such as ethylene glycol, propylene glycol, diethylene glycol. In the case of a condensation product of an aromatic dicarboxylic acid and a glycol, the number of functional groups is about 2, but the number of functional groups may be increased to 2 or more by substituting a part of the glycol with a polyfunctional alcohol such as trimethylolpropane. With this configuration, the physical properties of the resulting foam can be adjusted.

  At least HFO-1233zd is used as blowing agent. However, other hydrofluoroolefins (HFO) may be used in combination as long as the object of the present invention is not impaired. As such HFO, for example, 1,3,3,3-tetrafluoropropene, 1,1,3,3-tetrafluoropropene, 1,2,3,3,3-pentafluoropropene, 1,1,1- Trifluoropropene, 1,1,1,3,3-pentafluoropropene, 1,1,2,3,3-pentafluoropropene, (Z) -1,1,1,2,3-pentafluoropropene, And 1,1,1,4,4,4-hexafluorobut-2-ene and the like.

The content of the foaming agent in the polyol composition for rigid polyurethane foam can be varied as appropriate depending on the target density of the finally produced rigid polyurethane foam. For example, when the free foaming density of rigid polyurethane foam is 25 to 35 kg / m ³ , the content of the foaming agent is preferably 10 to 50 parts by weight when the total amount of the polyol compound is 100 parts by weight, More preferably, it is 15 to 40 parts by weight.

  In the present invention, at least one selected from the group consisting of an amine catalyst and a metal catalyst is used as a catalyst. As the amine catalyst, N, N, N ', N'-tetramethylethylenediamine, N, N, N', N'-tetramethylhexamethylenediamine, N, N, N ', N', N'-pentamethyl Tertiary such as N-alkyl polyalkylene polyamines such as diethylenetriamine, diazabicycloundecene (DBU), N, N-dimethylcyclohexylamine, triethylenediamine, N-methylmorpholine, bis (2-dimethylaminoethyl) ether Amines include, etc. Further, examples of the metal catalyst include trimerization catalysts such as potassium acetate and potassium octylate.

  In the present invention, the term "rigid polyurethane foam" refers to a foam-constituting polymer formed by mixing and reacting a polyol composition and a polyisocyanate component and having substantially only urethane bonds (hereinafter also referred to as "PUR") In addition to the above, the foam-constituting polymer also includes one having a nurate bond (hereinafter also referred to as "PIR"). When PUR is produced as a rigid polyurethane foam, it is preferable to contain 0.1 to 8% by weight, and more preferably 0.1 to 4% by weight, based on 100% by weight of the total amount of polyol compounds. . When PIR is produced as a rigid polyurethane foam, when the total amount of the polyol compound is 100% by weight, it contains, for example, 0.1 to 8% by weight of a metal catalyst or a quaternary amine catalyst as a trimerization (nuration) catalyst It is more preferable to contain 0.1 to 4 weight%.

In the present invention, the organic acid as the acid component suppresses the activity of the catalyst and prevents the deactivation of the catalyst by the interaction between HFO and the catalyst, thereby improving the storage stability of the polyol composition for rigid polyurethane foam. Have an action to
Examples of organic acids that can be used in the present invention include aliphatic organic acids and organic acids having an aromatic ring.
The aliphatic organic acid is not particularly limited, and may be saturated or unsaturated, and may be linear or branched. Examples of the aliphatic organic acid include aliphatic organic acids having a hydrocarbon group having 1 to 10 carbon atoms, and examples thereof include formic acid, acetic acid, propionic acid, butyric acid and valeric acid.
As an organic acid which has an aromatic ring, the organic acid which has a monocyclic (non-polycyclic) aromatic ring, and the organic acid which has a polycyclic aromatic ring can be illustrated.
Examples of organic acids having a monocyclic (non-polycyclic) aromatic ring include benzoic acid, phthalic acid (orthophthalic acid, isophthalic acid, and terephthalic acid) and salicylic acid.
As an organic acid having a polycyclic aromatic ring, naphthoic acid, anthronic acid and the like can be mentioned.
As the organic acid having an aromatic ring, an organic acid having a monocyclic (non-polycyclic) aromatic ring is preferable, and among these, benzoic acid and phthalic acid are more preferable.

  In the present invention, when an organic acid having an aromatic ring is used as the organic acid, there is less odor compared to a low molecular weight organic acid, and corrosion to a foamer / mixer used in producing a rigid polyurethane foam It is preferable because there is less contamination. The content of the organic acid is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 0.3 parts by weight or more, still more preferably 0.5 parts by weight or more, more preferably 100 parts by weight of the polyol compound. Is preferably 1 part by weight or more, and preferably 15 parts by weight or less, more preferably 10 parts by weight or less, still more preferably 8 parts by weight or less, still more preferably 5 parts by weight or less.

  In addition to the polyol compound, the foaming agent, the catalyst and the acid component, a flame retardant, a foam stabilizer, a coloring agent and an antioxidant may be added to the polyol composition for rigid polyurethane foam according to the present invention.

  As the flame retardant, metal compounds such as organic phosphoric acid esters, halogen-containing compounds, aluminum hydroxide and the like can be mentioned, and in particular, organic phosphoric acid esters are preferable because they have the effect of lowering the viscosity of the polyol composition. Examples of organic phosphoric acid esters include halogenated alkyl esters of phosphoric acid, alkyl phosphoric acid esters, aryl phosphoric acid esters and phosphonic acid esters. Specifically, tris (chloropropyl) phosphate (TMCPP, manufactured by Daihachi Chemical), tributoxyethyl phosphate (TBEP), tributyl phosphate, triethyl phosphate, trimethyl phosphate, cresyl phenyl phosphate and the like can be mentioned. The compounding amount of the flame retardant is preferably 1 to 30 parts by weight, and more preferably 3 to 25 parts by weight with respect to 100 parts by weight of the polyol compound.

  As a foam stabilizer, the graft copolymer of polyoxyalkylene glycol which is a polymer of ethylene oxide or a propylene oxide, and a polydimethylsiloxane is mentioned, for example among the foam stabilizers for rigid polyurethane foams, A silicone foam stabilizer having an oxyethylene group content of 70 to 100 mol% in polyoxyalkylene is preferably used. Specifically, SH-193, SZ-1671, SF-2937F, SF-2938F (Toray Dow Corning B-8465, B-8467, B-8481 (manufactured by Evonik Degussa Japan), L-6900 (manufactured by Momentive), and the like. The blending amount of the foam stabilizer is preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polyol compound.

The above-mentioned polyol composition can be used as a composition for rigid polyurethane foam containing a polyol composition and a polyisocyanate component. The rigid polyurethane foam composition can be used to produce rigid polyurethane foams.
The composition for rigid polyurethane foam can be obtained by mixing the polyol composition and the polyisocyanate component, and the mixing of both in this case may preferably follow the isocyanate index described later.
As a polyisocyanate component to be mixed and reacted with the above-mentioned polyol composition to form a rigid polyurethane foam, various polyisocyanate compounds such as aromatic, alicyclic and aliphatic having two or more isocyanate groups may be used. Can. Preferably, liquid diphenylmethane diisocyanate (MDI) is used because of ease of handling, speed of reaction, excellent physical properties of the resulting polyurethane foam, and low cost. As liquid MDI, crude MDI (c-MDI) (44V-10, 44V-20, etc. (made by Sumika Kobesutra Urethane Co., Ltd.), Millionate MR-200 (Nippon Polyurethane Industry)), uretone imine containing MDI (Millionate MTL; Japan Polyurethane industry) and the like. In addition to liquid MDI, other polyisocyanate compounds may be used in combination, and as polyisocyanate compounds used in combination, polyisocyanate compounds known in the technical field of polyurethane can be used without limitation.

  In the method for producing a rigid polyurethane foam according to the present invention, a polyol composition containing at least a polyol compound, a foaming agent, a catalyst and an acid component is mixed and reacted with a polyisocyanate component. The blowing agent contains at least one hydrofluoroolefin having 3 to 6 carbon atoms, the catalyst contains at least one member selected from the group consisting of an amine catalyst and a metal catalyst, and contains an organic acid as the acid component. Do.

  In the above production method, the isocyanate index (NCO Index) when mixing and reacting the polyol composition and the polyisocyanate component differs depending on whether PUR or PIR is to be produced. In the case of PUR, it is preferably 100 to 140, and more preferably 110 to 120. On the other hand, in the case of PIR, it is preferably 150 to 700, and more preferably 200 to 500. Here, the isocyanate index refers to the equivalent ratio of the isocyanate group of the polyisocyanate component to all active hydrogen groups (calculated as water as a foaming agent as a bifunctional active hydrogen compound) contained in the polyol composition as a percentage (Equivalent ratio of isocyanate group to 100 equivalents of active hydrogen group) is meant.

The density of the rigid polyurethane foam obtained by the production method is preferably 20~40kg / ^{m 3,} more preferably from 25~35kg / ^{m 3.} The foam density is a value measured in accordance with JIS K7222.

  In the method for producing the above-mentioned rigid polyurethane foam, it may be produced continuously in a continuous line or may be produced in a batch system. Further, a spray method in which the composition is sprayed onto a constituent substrate of a building by spraying, an injection method in which a mixture of a polyol composition and a polyisocyanate component is injected into voids formed by the construction substrate, and the like are mentioned.

  Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

(Preparation of Polyol Composition)
The polyol composition was prepared according to the formulation described in Table 1 below. The details of each component in Table 1 are as follows.

Examples 1 to 6 and Comparative Example 1
(1) Polyols Polyether-based polyol A; trade name "ACTOCOR GR84" (manufactured by Mitsui Chemicals, Inc.)
Polyether-based polyol B; trade name "ACTOCOR GR40A" (manufactured by Mitsui Chemicals, Inc.)
(2) Flame Retardant Tris (β-chloropropyl) phosphate; trade name "TMCPP" (made by Daihachi Chemical Co., Ltd.)
(3) Foam control agent Polyalkylene glycol based foam control agent; trade name "SH-193" (manufactured by Toray Dow Corning Silicone Co., Ltd.)
(4) Catalyst Amine catalyst A: (N, N, N ', N'-tetramethylethylenediamine or N, N, N', N'-tetramethylhexamethylenediamine); trade name "Kaolyzer No. 1" ( Kao Corporation)
Amine catalyst B; (bis (2-dimethylaminoethyl) ether); trade name "NIAX A-1" (manufactured by Momentive)
(5) Organic acid Acetic acid (Kanto Chemical Co., Ltd.), formic acid (Kanto Chemical Industry Co., Ltd.), benzoic acid (Kanto Chemical Industry Co., Ltd.),
(0-) Phthalic acid (Kanto Chemical Industry Co., Ltd.)
However, benzoic acid was dissolved in methanol and used (concentration 50 wt%), and (0-) phthalic acid was dissolved in methanol and used (concentration 20 wt%).
(6) Foaming agent HFO-1233zd; trade name "Solstice LBA" (manufactured by Honeywell)
water

Examples 7 to 10 and Comparative Example 2
(1) Polyols Phthalate-based polyester polyol; trade name "Maximol RFK-556" (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
(2) Flame Retardant Tris (β-chloropropyl) phosphate; trade name "TMCPP" (made by Daihachi Chemical Co., Ltd.)
(3) Foam control agent Polyalkylene glycol based foam control agent; trade name "SH-193" (manufactured by Toray Dow Corning Silicone Co., Ltd.)
(4) Catalyst Amine catalyst A: (N, N, N ', N'-tetramethylethylenediamine or N, N, N', N'-tetramethylhexamethylenediamine); trade name "Kaolyzer No. 1" ( Kao Corporation)
Amine catalyst B; (bis (2-dimethylaminoethyl) ether); trade name "NIAX A-1" (manufactured by Momentive)
Metal catalyst; Octylic acid potassium salt; trade name "Percat 9540" (manufactured by Sakai Industry Co., Ltd.)
(5) Organic acid acetic acid (Kanto Chemical Industry Co., Ltd.), formic acid (Kanto Chemical Industry Co., Ltd.), benzoic acid (Kanto Chemical Industry Co., Ltd.), (0-) phthalic acid (Kanto Chemical Industry Co., Ltd.)
However, benzoic acid was dissolved in methanol and used (concentration 50 wt%), and (0-) phthalic acid was dissolved in methanol and used (concentration 20 wt%).
(6) Foaming agent HFO-1233zd; trade name "Solstice LBA" (manufactured by Honeywell)
water

(Lab evaluation)
Each prepared polyol composition (Examples 1 to 10, Comparative Examples 1 and 2) was mixed with a polyisocyanate component and reacted according to a conventional method to prepare a rigid polyurethane foam. As the polyisocyanate component, c-MDI (Sumidur 44V-20, manufactured by Sumika Kobethurourethane, NCO%: 31%) is used, and the isocyanate index (NCO Index) is as described in Tables 1 and 2. did. However, the methanol used to dissolve the organic acid was excluded from the index calculation. The following evaluations were made, and the results are shown in Table 1.

[Storage stability evaluation]
The time (seconds) at which thickening occurs and gel strength begins to appear after mixing of the liquid is defined as gel time. The gel time when producing a rigid polyurethane foam using the polyol composition immediately after being adjusted with the composition described in Table 1 is "initial gel time (seconds)", using the polyol composition after leaving at 40 ° C for 1 week Gel time at the time of producing rigid polyurethane foam is "gel time after 40 ° C-1 week (second)", difference between "gel time after 40 ° C-1 week (second)" and "initial gel time (second)""Reactive delay (seconds)". The shorter the second of the reactivity delay, the more the deactivation of the catalyst due to the interaction between the HFO and the catalyst can be prevented, which means that the storage stability of the polyol composition is excellent.

[Odor evaluation]
The polyol compositions of Examples and Comparative Examples were determined for the presence or absence of an odor (stimulous odor) of the polyol compositions under conditions of a liquid temperature of about 20 ° C. and an ambient temperature of about 23 ° C.

[Corrosion test]
110 mL of the polyol compositions of Examples and Comparative Examples are placed in a glass screw bottle, and iron nails (about 74 mm in length, about φ 3.3 mm) are charged therein, and rusted after storage for 1 year at room temperature for 1 year June We confirmed the presence or absence of

  From the results of Tables 1 and 2, it is understood that the polyol compositions according to Examples 1 to 10 have a short number of seconds for the reactivity delay, and are excellent in the storage stability of the polyol composition. In addition, when an organic acid having an aromatic ring is used as the organic acid, it is understood that there is little irritating odor and the corrosion resistance is also excellent.

Claims (5)

A polyol composition for rigid polyurethane foam, which contains at least a polyol compound, a blowing agent, a catalyst and an acid component, and is mixed and reacted with a polyisocyanate component to form a rigid polyurethane foam,
At least 1-chloro-3,3,3-trifluoropropene as the blowing agent,
The catalyst includes at least one selected from the group consisting of an amine catalyst and a metal catalyst as the catalyst,
A polyol composition for a rigid polyurethane foam, comprising an organic acid as the acid component.   The polyol composition for a rigid polyurethane foam according to claim 1, containing an organic acid having an aromatic ring as the acid component.   A composition for rigid polyurethane foam comprising the polyol composition according to claim 1 and a polyisocyanate component. A method for producing a rigid polyurethane foam, which comprises mixing and reacting a polyol composition containing at least a polyol compound, a blowing agent, a catalyst and an acid component with a polyisocyanate component,
The polyol composition is
At least 1-chloro-3,3,3-trifluoropropene as the blowing agent,
The catalyst includes at least one selected from the group consisting of an amine catalyst and a metal catalyst as the catalyst,
An organic acid is contained as said acid component, The manufacturing method of the rigid polyurethane foam characterized by the above-mentioned.   The manufacturing method of the rigid polyurethane foam of Claim 4 containing the organic acid which has an aromatic ring as said acid component.