JP2003201329A - Hard polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To suppress flyability of a hard polyurethane foam made of a hydrofluorocarbon as a foaming agent. <P>SOLUTION: The polyurethane foam is made by mixing a polyisocyanate component, a polyol, a foaming agent containing the hydrofluorocarbon, a catalyst, a foaming regulator and the other auxiliary agents, and by expanding it. The polyol contains an ester compound, of at least 5 wt.% in the total polyol, obtained by reacting at least one selected from the group consisting of a fatty acid, a fatty acid ester and a fatty acid anhydride, with at least one of a hydroxyl compound and its ester. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a rigid polyurethane foam, and more particularly, to a mixed liquid containing a polyisocyanate component, a hydroxy component, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, which is mixed with a mixing head. It is a rigid polyurethane foam suitable for airless spray foaming, and has extremely excellent flame retardancy while suppressing the flyability when hydrofluorocarbon (HFC), which does not cause ozone layer depletion, is used as a foaming agent. A rigid polyurethane foam obtainable.

[0002]

2. Description of the Related Art Rigid polyurethane foam is widely used as a heat insulating material for houses, refrigerators and the like because it has excellent heat insulating properties and self-adhesive properties.

Rigid polyurethane foams used in these applications are generally airless in which a compounding liquid containing a polyisocyanate component, a hydroxy component, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries is mixed with a mixing head to foam. Obtained by spray foaming, this method is a simple work of spraying directly on the construction object,
A good insulating layer of rigid polyurethane foam can be formed.

In the rigid polyurethane foam, dichloromonofluoroethane (HCFC-141b), which is currently used as a main blowing agent, has a problem of ozone layer depletion. For this reason, hydrofluorocarbons (HFCs), which do not destroy the ozone layer, are listed as candidates as a next-generation foaming agent to replace them. HFCs include tetrafluoroethane (HFC134a), 1,
1,1,3,3-Pentafluoropropane (HFC24
5fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), 1,1,1,2,3,3,3
-Heptafluoropropane (HFC227) and the like, and among them, there is also a compound which has no ozone depletion property and is considered to be a promising foaming agent after HCFC is completely abolished.

By the way, one of the most important performances required for a rigid polyurethane foam for a heat insulating material is flame retardancy. Conventionally, in order to enhance flame retardancy, a hydroxy compound and an o-phthalate are used as a hydroxy component. It has been proposed to use a polyester polyol obtained by an esterification reaction with an aromatic acid component such as an acid.

[0006]

In a hard polyurethane foam using hydrofluorocarbon as a foaming agent, flyability is likely to occur. The flyability means that the foam is brittle, bulky, and easily broken. When the flyability occurs, there is a problem that the foam easily peels off. In particular, in order to improve flame retardancy, when a polyester polyol obtained by esterifying a hydroxy compound and an aromatic acid component such as o-phthalic acid is used as the hydroxy component, flyability is improved. Is more likely to occur.

It is an object of the present invention to solve the above-mentioned conventional problems and to suppress flyability when hydrofluorocarbon is used as a foaming agent and to provide a high quality rigid polyurethane foam.

[0008]

The rigid polyurethane foam of the present invention is obtained by mixing and foaming a polyisocyanate component, a hydroxy component, a blowing agent containing a hydrofluorocarbon, a catalyst, a foam stabilizer and other auxiliaries. In the rigid polyurethane foam, the hydroxy component is an ester compound obtained by reacting at least one selected from the group consisting of fatty acids, fatty acid esters, and fatty acid anhydrides with a hydroxy compound and at least one ester thereof, 5% by weight in all hydroxy components
It is characterized by including the above.

An ester compound obtained by reacting at least one selected from the group consisting of fatty acids, fatty acid esters, and fatty acid anhydrides as a hydroxy component with at least one of a hydroxy compound and its ester (hereinafter referred to as "fatty acid-based compound""Polyesterpolyol") is used in an amount of 5% by weight or more in the total hydroxy component, whereby the flyability can be suppressed.

In the present invention, the reason why the effect of suppressing flyability is obtained by using the above specific fatty acid type polyester polyol is not clear, but it is presumed as follows.

That is, the hydrofluorocarbon is difficult to dissolve in the hydroxy component and the usual isocyanate component, and it hardly dissolves particularly when the aromatic component concentration in the hydroxy component becomes high. When the solubility of the hydrofluorocarbon is poor as described above, the plasticity of the obtained foam is impaired and the flyability is exhibited.

On the other hand, by using the above-mentioned specific fatty acid type polyester polyol used in the present invention, the compatibility with hydrofluorocarbon can be improved, the obtained foam can have appropriate plasticity, and the flyability can be improved. Is suppressed.

Dichloromonofluoroethane (HC
In FC-141b), a part of the foam remains dissolved in the hydroxy component without being used for foaming, and the resulting foam has appropriate plasticity, so that flyability is suppressed. That is, flyability is a problem peculiar to using hydrofluorocarbon (HFC) as a foaming agent, and in this case, a hydroxy component having a high aromatic component concentration is used to improve flame retardancy. Although more prominent, this problem can be solved by using the specific fatty acid-based polyester polyol according to the present invention.

In the rigid polyurethane foam of the present invention, in order to improve the flame retardancy, the hydroxy component contains o-.
By reacting at least one selected from the group consisting of phthalic acid, m-phthalic acid, p-phthalic acid, esters of these acids, and anhydrides of these acids with at least one of a hydroxy compound and its ester. It is preferable to include the ester compound thus obtained (hereinafter sometimes referred to as “phthalic acid-based polyester polyol”).

Similarly, in order to improve flame retardancy, the hydroxy component preferably contains an ester compound in which the phenol component and / or its derivative is a hydroxy compound (and / or its ester).

Further, as the polyisocyanate component, it is preferable to use a polyisocyanate having a characteristic that, when mixed with a large amount of hydrofluorocarbon, the hydrofluorocarbon is uniformly dispersed and emulsified.

As the hydrofluorocarbon, 1,1,1,3,3-pentafluoropropane (H
FC245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), and 1,1,1,
2,3,3,3-heptafluoropropane (HFC22
It is preferable to use one or more selected from the group consisting of 7).

In particular, the present invention is an airless spray for foaming by mixing a polyisocyanate component and a blending liquid containing a hydroxy component, a blowing agent containing hydrofluorocarbon, a catalyst, a foam stabilizer and other auxiliaries with a mixing head. It is suitable for rigid polyurethane foam obtained by foaming.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the rigid polyurethane foam of the present invention will be described in detail below.

First, the raw materials for producing the rigid polyurethane foam of the present invention will be described.

(1) Polyisocyanate Component As the polyisocyanate component, aromatic polyisocyanate compounds such as diphenylmethane diisocyanate and tolylene diisocyanate, alicyclic polyisocyanates such as isophorone diisocyanate, and aliphatic type polyisocyanates such as hexamethylene diisocyanate. One kind or two or more kinds of polyisocyanates and the like can be used. Especially, in order to suppress flyability, even when mixed with a large amount of hydrofluorocarbon, the hydrofluorocarbon is uniformly dispersed and emulsified. Those having characteristics are preferable.

Here, the large amount means 35% by weight or more of the weight of the polyisocyanate compound.

When a normal polyisocyanate component and hydrofluorocarbon are mixed and stirred, when the proportion of hydrofluorocarbon is small, the hydrofluorocarbon is dissolved in the polyisocyanate component to form a uniform solution. Quickly separates. In the present invention, preferably,
A polyisocyanate component that is stably emulsified and dispersed without being separated even when mixed with a large amount of hydrofluorocarbon and stirred. By using the polyisocyanate component excellent in dispersion stability with hydrofluorocarbons in this manner, flyability can be suppressed more reliably.

The isocyanate index is 100 to 25.
It is preferably 0. It is also preferable to obtain an isocyanurate foam in the presence of a trimerization catalyst.

(2) Hydroxy component As the hydroxy component, a fatty acid polyester polyol, that is, a fatty acid or a fatty acid ester as an acid component,
And at least one selected from the group consisting of fatty acid anhydrides
A compound containing an ester compound obtained by reacting a seed with at least one of a hydroxy compound and its ester is used. Suitable fatty acids of the acid component of the fatty acid-based polyester polyol include fatty acids having about 8 to 9 carbon atoms such as octylic acid and nonanoic acid.

The hydroxy component used in the present invention further comprises
Phthalates polyester polyol, that is, one or two selected from the group consisting of o-phthalic acid, m-phthalic acid, p-phthalic acid as the acid component, esters of these acids, and anhydrides of these acids. It is preferable that 5% by weight or more of the ester compound obtained by reacting one or more of the above with at least one of the hydroxy compound and the ester thereof is contained from the viewpoint of improving the flame retardancy of the obtained foam.

The preferred hydroxyl value of such fatty acid type polyester polyol and phthalic acid type polyester polyol is 150 to 450 mg-KOH / g.

If the proportion of such a fatty acid type polyester polyol in the hydroxy component is too small, a sufficient flyability suppressing effect cannot be obtained, so the content in the hydroxy component is 5% by weight or more. However, when the content is excessively high, the foam strength is lowered, so that the hydroxy component is contained in an amount of particularly 5 to 80% by weight, particularly 40 to 40% by weight.
It is preferably contained at 70% by weight.

If the proportion of the phthalic acid type polyester polyol in the hydroxy component is too small, a sufficient effect of improving flame retardancy cannot be obtained, so the content in the hydroxy component is preferably 5% by weight or more. . However, if the content is excessively large, the reaction becomes slow and it becomes difficult to foam. Therefore, it is preferable that the hydroxy component is contained in an amount of 5 to 95% by weight, particularly 40 to 70% by weight.

The ratio of the fatty acid type polyester polyol to the total of the fatty acid type polyester polyol and the phthalic acid type polyester polyol is 7 to 25% by weight, particularly about 10% by weight, and the balance is phthalic acid type polyester polyol. preferable.

Examples of the hydroxy compound constituting the polyester polyol such as fatty acid type polyester polyol and other ester compounds include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol and trimethylolpropane. Especially higher HF
In order to improve the solubility with C245fa or HFC365mfc, it is preferable to use diethylene glycol, propylene glycol, dipropylene glycol, triethylene glycol or the like.

In order to further suppress flyability, the hydroxy component preferably contains an ester compound containing propylene glycol as a hydroxy compound.

In order to further improve the flame retardancy,
The hydroxy component preferably contains an ester compound in which phenol and / or its derivative is a hydroxy compound (and / or its ester).

As the hydroxy component, in addition to the above-mentioned fatty acid type polyester polyol and phthalic acid type polyester polyol, a polyether polyol obtained by Mannich modification of phenol and / or its derivative (hereinafter referred to as "Mannich modified polyol"). That is, phenol or a phenol derivative such as alkylphenol such as nonylphenol is subjected to Mannich modification with a secondary amine such as formaldehyde and diethanolamine, ammonia, or a primary amine to open an alkylene oxide such as ethylene oxide or propylene oxide. You may use the polyether polyol obtained by addition polymerization. Such Mannich-modified polyol is
Since the self-reactive activity is high and the flame retardancy is relatively high, by using the Mannich-modified polyol, for example,
In the airless spray foaming rigid polyurethane foam, the reaction can be promptly advanced without significantly impairing the flame retardant performance at the time of blowing and foaming. However, the Mannich-modified polyol in the hydroxy component is 80% by weight.
When the content of the Mannich-modified polyol is increased, the proportion of the hydroxy component in the hydroxy component is 70% by weight or less, preferably 20 to 50% by weight.

Further, a fatty acid type polyester polyol,
In addition to the phthalic acid-based polyester polyol component and the Mannich-modified polyol, ethylenediamine, tolylenediamine, sucrose, aminoalcohol, diethylene glycol, and other Mannich-modified polyols having a different initiator polyol compound from the range not impairing the object of the present invention are hydroxy. You may use together in the range of 40 weight% or less in a component.

(3) Catalyst As the catalyst, amine catalysts such as triethylenediamine, pentamethyldiethylenetriamine and tetramethylhexamethylenediamine, and urethanes such as organometallic catalysts such as dibutyltin dilaurate, lead octylate and stannas octoate. Examples include chemical catalysts. Further, flame retardancy can be improved by using a trimerization catalyst such as potassium octylate (potassium 2-ethylhexylate) or potassium acetate. These catalysts can use 1 type (s) or 2 or more types.

(4) Foaming agent A foaming agent containing hydrofluorocarbon is used. As the hydrofluorocarbon, especially 1,1,1,3,3-pentafluoropropane (HFC
245fa), 1,1,1,3,3-pentafluorobutane (HFC365mfc), and 1,1,1,2,
3,3,3-Heptafluoropropane (HFC227)
It is preferable to use one kind or two or more kinds selected from the group consisting of, in particular, 1,1,1,3,3-pentafluoropropane and / or 1,1,1,3,3-pentafluorobutane. It is preferably used. In this case, 1,
1,1,3,3-pentafluoropropane and 1,1,
The usage ratio of 1,3,3-pentafluorobutane is 1,
5-95% by weight of 1,1,3,3-pentafluoropropane and 9% of 1,1,1,3,3-pentafluorobutane
5 to 5% by weight, particularly 20 to 80% by weight of 1,1,1,3,3-pentafluoropropane, 1,1,1,3,3-
Pentafluorobutane is preferably 80 to 20% by weight. If the amount of 1,1,1,3,3-pentafluorobutane exceeds the above range, there are problems such as reduced flame retardancy and soaring prices, and conversely 1,1,1,3,3-pentafluorobutane. When the amount of butane is low, the internal pressure of the compounding liquid and the viscosity of the compounding liquid increase due to the increase in the concentration of the low boiling point blowing agent.

Further, as the foaming agent, 1, 1, 1,
Hydrofluorocarbons such as 2-tetrafluoroethane may be used in combination, and when 1,1,1,2-tetrafluoroethane is used, it may be added to the compounding liquid together with another foaming agent, or the third component Alternatively, it may be directly mixed with a mixing head or the like.

In the present invention, by using a hydrofluorocarbon having a boiling point of 0 ° C. or less at room temperature and atmospheric pressure as a foaming agent, the density of the obtained foam is further lowered, and the effect of being excellent in economic efficiency is exhibited. But
In this case, it is preferable to directly inject this low boiling HFC into the mixing head or into the introduction conduit for other components to the mixing head, particularly in airless spray foaming, in order to ensure workability during spraying.

In this case, the amount of the low boiling point HFC used is such that the polyisocyanate component, the hydroxy component, the
It is preferably 0.5 to 10% by weight with respect to the reactive polyurethane raw material consisting of a foaming agent, a catalyst and other auxiliary agents. If the amount used is less than the above range, the effect of lowering the foam density and improving workability cannot be sufficiently obtained,
If it is too large, the vaporizing power of the low boiling point blowing agent will be too strong and the bubbles will not be stable.

This low boiling HFC has a boiling point of −26 ° C.
1,1,1,2-tetrafluoroethane is preferably used.

In addition to the above hydrofluorocarbons, water can be used together as a foaming agent. That is, by using carbon dioxide gas generated by reacting water and isocyanate as a foaming agent, it is possible to reduce the density of the foam,
It is possible to suppress the amount of expensive HFC input and improve the economic efficiency. However, if water is added more than necessary, the amount of carbon dioxide gas generated will increase and the heat insulating property of the foam will decline, so the reactive polyurethane raw material consisting of polyisocyanate component, hydroxy component, blowing agent, catalyst and other auxiliary agents Water content is 0.01 to 3% by weight, preferably 0.01 to
1.5% by weight.

(5) Foam Stabilizer As the foam stabilizer, any foam stabilizer effective for producing rigid polyurethane foam can be used. For example, a silicone-based polymer such as polysiloxane or an alkylene oxide adduct thereof can be used.

Further, in the present invention, any components other than the above, such as flame retardants and fillers, may be used within the range not impeding the object of the present invention.

When the rigid polyurethane foam of the present invention is produced by airless spray foaming using a mixing head, 30 parts of the above polyisocyanate component and a compounded liquid containing a hydroxy component, a foaming agent, a catalyst and other auxiliaries are mixed. Mix using a mixing head at ~ 50 ° C, spray on the surface to be constructed at a discharge pressure of 3.9 to 7.8 MPa,
It can be manufactured by repeating spraying until a predetermined thickness is reached and foaming.

The rigid polyurethane foam of the present invention preferably has a core density of 20 to 45 kg / m ³ . Core density (core density) is 20 kg / m ³
If it is less than 45%, the strength will be significantly reduced and the product will shrink,
When it exceeds m ³ , the amount of combustion of the rigid polyurethane foam is increased due to the high density, and the flame retardancy is remarkably lowered. Therefore, the core density is 20 to 45 kg / m ^3, preferably 25 to 45 kg / m ^3.
40 kg / m ³ . The core density is the average density of the portion of the polyurethane foam surface excluding the dense layer, and can be measured, for example, according to JIS A 9526: 1994.

[0047]

EXAMPLES The present invention will be described more specifically below with reference to experimental examples, examples and comparative examples.

The raw materials used for the evaluation in the following experimental examples and the production of the rigid polyurethane foams in the examples and comparative examples are as follows.

[0049]   Polyol A: Mannich modified polyether polio manufactured by Dai-ichi Kogyo Seiyaku Co., Ltd.                   (Nonylphenol and diethanolamine and formal                   The terminal modified group obtained by the Mannich modification with a                   Ring-Opening Addition Polymerization of Tylene Oxide and Propylene Oxide                   Polyether polyol obtained by                   Hydroxyl value: 750 mg-KOH / g   Polyol B: Toho Rika Co., Ltd. phthalate / nonanoic acid-based polyester resin                   Liol (diethylene glycol and phthal as an acid component)                   Polyester polyol obtained from acid and nonanoic acid. Po                   Ratio of nonanoic acid-based polyester polyol in Liol B                   In the case of 20% by weight, the balance is polyester polyester based on phthalic acid.                   It's all. )                   Hydroxyl value: 270 mg-KOH / g   Polyol C: Toho Rika Co., Ltd. o-phthalic acid based polyester polio                   "PL-2001"                   Hydroxyl value: 260 mg-KOH / g   Polyol D: Toho Rika Co., Ltd. diethylene glycol and nonylpheno                   And a polyester poly obtained from m, p-phthalic acid                   All "PL JP-801"                   Hydroxyl value: 295 mg-KOH / g   Polyisocyanate A: manufactured by Nippon Polyurethane Industry Co., Ltd.                           Crude diphenylmethane diisocyanate "Coroney                           1156 "(NCO%: 30.5)   Polyisocyanate B: manufactured by Nippon Polyurethane Industry Co., Ltd.                           Crude diphenylmethane diisocyanate "DRC6                           94 "(NCO%: 30.5)   Flame retardant: "TCPP" (Tris monochloropropyl phos) manufactured by Daihachi Chemical Co., Ltd.             Fate)   Foam stabilizer: "SH193" manufactured by Toray Dow Corning Silicon Co., Ltd.             (Block copolymer of dimethyl siloxane and polyether)   Catalyst A: Kao Corporation Tetramethylhexamethylenediamine "Kaolizer"             -No. 1 "   Catalyst B: Nippon Kagaku Sangyo Co., Ltd. potassium octylate solution "Pucat 15             G "   Catalyst C: Dioctyl phthalate solution of lead octylate manufactured by Nippon Kagaku Sangyo Co., Ltd.             Nikka Octix "(lead concentration 17% by weight)   Foaming agent A: 1,1,1,3,3-pentafluoropropane manufactured by Asahi Glass Co., Ltd.               (HFC245fa)   Foaming agent B: 1,1,1,3,3-pentafluorobutane manufactured by Solvay Co., Ltd.               (HFC365mfc)   Foaming agent C: Asahi Glass Co., Ltd. 1,1,1,2-tetrafluoroethane (HF               C134a)

Experimental Example 1 100 of each of the above polyols A, B, C and D was placed in a beaker.
g Weigh and add the foaming agent A (HFC245fa) or the foaming agent B (HFC365mfc) and mix with stirring. The amount of the foaming agent added is determined as a part by weight, and the result is shown in Table 1. Indicated.

[0051]

[Table 1]

From Table 1, the polyol B containing a fatty acid is
It can be seen that the solubility of hydrofluorocarbon as a foaming agent is remarkably excellent.

Experimental Example 2 Isocyanate A or Isocyanate B and Blowing Agent B
And were mixed at the ratios shown in Table 2, the state of the mixed solution was examined, and the results are shown in Table 2.

[0054]

[Table 2]

From Table 2, the isocyanate B is the foaming agent B.
The foaming agent B is in a floating state in which the foaming agent B is uniformly dispersed, however, in the isocyanate A, the foaming agent B is dispersed.
If the ratio of the
It can be seen that when the ratio of is large, the particles are separated and a uniform dispersed state cannot be obtained.

In Table 2, No. 2 and No. The mixing ratio of 7 is isocyanate A in Examples 1 and 2 described below.
Alternatively, it corresponds to the mixing ratio of the isocyanate B and the foaming agent B.

Examples 1 to 3 and Comparative Example 1 According to the compounding recipe shown in Table 3, the compounding liquid A was first prepared, and the foaming agent C and the polyisocyanate A or B were prepared. Next, a gasmer model HF1600 unit (manufactured by Gasmer Co.) was used as an airless mixing type high pressure spray foaming machine system. The mixture was pressure-fed at the mixing ratios shown, and spray-foamed on a calcium silicate plate having a length of 910 mm, a width of 910 mm, and a thickness of 10 mm at room temperature (8 to 10 ° C.). The discharge temperature of the raw material was set to 35 ° C., the air pressure of the air pump was set to 0.5 MPa, and the temperature of the calcium silicate plate was set to be equal to the ambient temperature. In addition, for rigid polyurethane foam, the thickness of one layer of spray is 5-10m.
The total thickness is 25.
It was sprayed so as to have a size of about mm.

The isocyanate index and the proportion (% by weight) of the fatty acid type polyester polyol and the phthalic acid type polyester polyol in the hydroxy component are as shown in Table 3.

With respect to the obtained rigid polyurethane foam, the core density was measured and the presence or absence of flyability was examined, and the results are shown in Table 3. The core density is JI
It measured based on SA9526: 1994. Also,
The degree of flyability was visually evaluated.

[0060]

[Table 3]

[0061]

As described above in detail, according to the present invention, it is possible to suppress the flyability of a rigid polyurethane foam using hydrofluorocarbon as a foaming agent, and to have a remarkably excellent flame retardancy and a flyability. A high-quality rigid polyurethane foam is provided without any problems.

Claims (6)

[Claims] 1. A rigid polyurethane foam obtained by mixing and foaming a polyisocyanate component, a hydroxy component, a foaming agent containing a hydrofluorocarbon, a catalyst, a foam stabilizer and other auxiliaries, wherein the hydroxy component is a fatty acid, At least one selected from the group consisting of fatty acid esters and fatty acid anhydrides,
A rigid polyurethane foam comprising an ester compound obtained by reacting at least one of a hydroxy compound and its ester in an amount of 5% by weight or more in the total hydroxy component. 2. The hydroxy component according to claim 1, wherein the hydroxy component is at least selected from the group consisting of o-phthalic acid, m-phthalic acid, p-phthalic acid, esters of these acids, and anhydrides of these acids. A rigid polyurethane foam, comprising an ester compound obtained by reacting one compound with at least one of a hydroxy compound and an ester thereof. 3. The rigid polyurethane foam according to claim 1 or 2, wherein the ester compound contains an ester compound in which the hydroxy compound is at least one selected from the group consisting of phenol and its derivatives. 4. The polyisocyanate according to any one of claims 1 to 3, wherein the polyisocyanate component has a property that, when mixed with a large amount of hydrofluorocarbon, the hydrofluorocarbon is uniformly dispersed and emulsified. A rigid polyurethane foam characterized by being used. 5. The hydrofluorocarbon according to claim 1, wherein the hydrofluorocarbon is 1,1,1,1.
3,3-pentafluoropropane, 1,1,1,3,3
-Pentafluorobutane, and 1,1,1,2,3,
A rigid polyurethane foam containing one or more selected from the group consisting of 3,3-heptafluoropropane. 6. The mixing solution according to claim 1, wherein the polyisocyanate component is mixed with a hydroxy component, a blowing agent containing hydrofluorocarbon, a catalyst, a foam stabilizer and other auxiliary agents. Rigid polyurethane foam obtained by airless spray foaming, which mixes and foams at the head.