JPH0597956A - Production of spray type rigid polyurethane foam - Google Patents

Abstract

(57) [Summary] [Objective] To provide a rigid polyurethane foam excellent in adhesiveness and mechanical properties especially at low temperature by a spray-type production method. [Structure] When a urethane foam is produced by a spray method by reacting a polyisocyanate component and a polyol component, part or all of the polyol component has a tertiary amino group in the molecular skeleton and hydroxyl groups at both ends of the molecule. Using a tertiary amino alcohol having
Furthermore, a specific amount of water is used as a foaming agent. Also, the third
It is also possible to use a tertiary amino alcohol and a tertiary amino alcohol having a hydroxyl group only at one end thereof in combination.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a spray-type rigid polyurethane foam. More specifically, the present invention relates to a method for producing a spray-type rigid polyurethane foam which is capable of sufficiently advancing a reaction between a polyol and an isocyanate even at a low temperature and is excellent in mechanical properties and adhesiveness.

[0002]

2. Description of the Related Art Rigid polyurethane foams have excellent heat insulating properties, self-adhesiveness, ease of production and versatility, and are therefore used in various fields. Generally, rigid polyurethane foam is often used for inner walls and ceilings. On the other hand, spray-type rigid polyurethane foam is used for house insulation, tank insulation, etc. because it can be installed locally. A dedicated foaming machine is used for foaming work of spray-type rigid polyurethane foam. The air spray foaming machine is a system that introduces compressed air into the mixing gun, and the airless foaming machine is a system that introduces the undiluted solution into the mixing gun using a lightweight compression pump and sprays it. Using these foaming machines, spray a mixture of polyol component and isocyanate component on the surface to be sprayed, and use the property of rapidly increasing the viscosity, foaming, and increasing the molecular weight of it to insulate hard polyurethane foam on the surface to be sprayed. Allow the layers to form. As the spray-type rigid polyurethane foam which is useful as described above has been used in various applications and increased in amount, various problems have occurred. One of them is that the adhesive strength with the surface material to be adhered is low. After the construction, since the adhesive strength with the face material is low, peeling may occur or fall off, and the thermal conductivity and the dew condensation are likely to occur. Further, in recent years, due to the problem of global environmental pollution, the amount of water blended as a foaming agent tends to increase due to restrictions on the use of CFCs such as trichlorofluoromethane, and this problem is exacerbated. That is, when the content of water is increased to reduce the amount of regulated CFCs, the urea bond generated by the reaction of water and isocyanate undergoes severe aggregation, and the heat of reaction is generated at the boundary with the adhered surface of the urethane foam or the surface of the foam. Since it is difficult to accumulate, the spray-type rigid polyurethane foam has the drawbacks that the most important physical properties are insufficient self-adhesive strength and increased brittleness. Furthermore, this tendency becomes remarkable when spraying is performed at a relatively low temperature of 5 ° C. or less.

[0003]

The inventors of the present invention have conducted extensive studies to solve the above-mentioned problems, and as a result, in the production of a spray-type rigid polyurethane foam, a catalyst having a catalytic action in the molecular skeleton as a polyol component has been obtained. By using a tertiary amino alcohol having a tertiary amino group and a hydroxyl group capable of reacting with an isocyanate group at both ends of the molecule and using a specific amount of water as a foaming agent, a low temperature of a spray-type rigid polyurethane foam can be obtained. The inventors have found that the self-adhesive strength below is improved and have reached the present invention.

That is, according to the present invention, when a polyisocyanate component and a polyol component are reacted to produce a spray-type rigid polyurethane foam, water is used as a blowing agent in an amount of 2 to 8 parts by weight based on 100 parts by weight of the total amount of the polyol component. The following general formula (I) is used for a part or all of the polyol component.

[0005]

[Chemical 3]

[In the formula, R ₁ has the same or different carbon number 2 to 2]
24 linear or branched alkylene group, alicyclic alkylene group, cycloalkylene group, arylene group, aralkylene group or-(CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ ) _q- (where p is 0 Or a positive number, q is a positive number), R ₂ represents the same or different linear or branched alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms, and the average degree of polymerization n Indicates a positive number from 1 to 50. ] A method for producing a spray-type rigid polyurethane foam characterized by using at least one kind of a tertiary amino alcohol represented by the above formula.

Since the tertiary amino alcohol represented by the general formula (I) used in the present invention has a tertiary amino group in the molecule, it has catalytic performance for the reaction between the polyisocyanate compound and the active hydrogen compound. Since it has a terminal hydroxyl group, it itself reacts with an isocyanate group, is incorporated into the polyurethane skeleton, and since it is a diol type, it does not hinder the increase in the molecular weight of the polyurethane resin and does not deteriorate the final physical properties. It has the feature. Therefore, the reaction between the polyol component containing the tertiary amino alcohol represented by the general formula (I) and the isocyanate can complete the reaction rate early in proportion to the blending amount, and the reaction rate of 5 ° C. or lower can be achieved. The reaction can proceed even at low temperatures. As described above, the reaction sufficiently proceeds even at a low temperature, so that the necessary mechanical properties and adhesive strength are maintained, and the heat insulating layer does not peel off or fall off from the adhered surface after spraying. Furthermore, the amount of regulated CFCs such as trichlorofluoromethane is reduced, and the desired adhesive strength can be obtained even with a polyol component using a large amount of water as a foaming agent, and the heat insulating layer is peeled off even at a low temperature of 5 ° C. or lower. Never fell out. Also,
Compared with ordinary tertiary amine catalysts, the tertiary amino alcohol represented by the general formula (I) according to the present invention has a terminal hydroxyl group and has a certain molecular weight, and therefore has no odor of its own. In addition, since there is no scattering of catalyst components and no offensive odor during spraying work, it also has the advantage of providing a favorable working environment.

The tertiary amino alcohol represented by the general formula (I) used in the present invention has various structures and molecular weights by changing the kinds of diol and primary amine which are raw materials for production. be able to. As the diol, a linear or branched one having 2 to 24 carbon atoms is used, and examples thereof include 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexane. Examples include diols, 1,9-nonanediol, 1,10-decanediol, diethylene glycol, triethylene glycol, tetraethylene glycol, 1,4-cyclohexanedimethanol, 1,4-hydroquinone, and the mixture thereof. You can also Also,
Examples of the primary amine include linear or branched primary amines having 1 to 24 carbon atoms or aromatic amines having two active hydrogens, such as methylamine, propylamine, isopropylamine and butylamine. 2-Ethylhexylamine, heptylamine, octylamine, decylamine, dodecylamine, cetylamine, stearylamine, docosylamine, oleylamine, benzylamine, phenethylamine, aniline and the like can be mentioned, and a mixture thereof can also be used.

The method for producing the tertiary amino alcohol according to the present invention will be described in more detail. First with the above diol
In producing a tertiary amino alcohol by reacting with a primary amine, a catalyst containing copper-noble metal as a main component, for example, copper-
Nickel-group 8 platinum group element, copper-chromium-group 8 platinum group element, copper-zinc-group 8 platinum group element, copper-manganese-
A catalyst having a composition of Group 8 platinum group element, copper-iron-Group 8 platinum group element, copper-cobalt-Group 8 platinum group element, etc. is used, and water generated by the reaction in the presence of these catalysts is used. The object is achieved by continuously or intermittently removing it to the outside of the reaction system and stirring and reacting at a temperature of 150 to 250 ° C. under atmospheric pressure or pressure. At this time, the diol may be continuously added during the reaction, or may be charged from the beginning, or a predetermined amount may be divided and charged. When the primary amine is a gas, it may be continuously or intermittently blown during the reaction, or a predetermined amount may be charged at once under pressure. When the primary amine is a liquid, it may be charged continuously, or a predetermined amount may be charged from the beginning. Here, the molar ratio of amine to diol needs to be 0.7 times or more, preferably 1 times, and in the case of a gaseous amine, an excessively charged gas together with hydrogen may be recovered and recycled.

In the method for producing a tertiary amino alcohol according to the present invention, it is preferable that the water produced by the reaction between the diol and the primary amine is taken out of the reaction system. If the generated water is not taken out of the system, the catalytic activity and selectivity are often lowered. For example, when the reaction is carried out without removing the produced water, the disproportionation product of the amine may increase, and the yield of the intended tertiary amino alcohol may decrease. However, the amine disproportionate is usually represented by the following general formula (II)

[0011]

[Chemical 4]

[In the formula, R ₃ has the same or different carbon number 2 to
24 linear or branched alkylene group, alicyclic alkylene group, cycloalkylene group, arylene group, aralkylene group or-(CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ ) _q- (where p is 0 Or a positive number, and q is a positive number), R ₄ represents the same or different straight-chain or branched-chain alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms, and the average degree of polymerization m Indicates a positive number from 1 to 50. ] A tertiary amino alcohol represented by the following formula is produced, and a mixture containing the tertiary amino alcohol represented by the general formula (II) can be used in the present invention. If the amount of disproportionation product is within the range, it is not necessary to remove water. The water may be removed continuously or continuously, and the produced water does not exist in the reaction system for a long time and may be appropriately removed, but the produced water is continuously removed each time. It is desirable to do. Specifically, it is common to introduce an appropriate amount of hydrogen gas into the reaction system during the reaction and distill the produced water together with the hydrogen gas.By concentrating and separating the produced water in a condenser, the hydrogen gas is circulated. It can also be used. It is also possible to add an appropriate solvent during the reaction and distill the produced water by azeotropic distillation with this solvent, or to add an inert solvent for the purpose of lowering the viscosity of the product.

In the method for producing the tertiary amino alcohol represented by the general formula (I) according to the present invention, a catalyst previously reduced with hydrogen gas may be used separately, but it may be used together with a diol as a reaction raw material. The catalyst before reduction is placed in a reactor, and when the hydrogen gas or the amine that reacts is a gaseous amine, the catalyst is reduced by raising the temperature to the reaction temperature while introducing a mixed gas of hydrogen gas and gaseous amine. Is preferred.

The tertiary amino alcohol used in the present invention has a structure represented by the general formula (I), and R ₁ is the same or different straight or branched chain having 2 to 24 carbon atoms. Alkylene group, alicyclic alkylene group, cycloalkylene group, arylene group, aralkylene group or-(CH ₂ CH
₂ O) _p − (CH ₂ CH ₂ ) _q − (where p is 0 or a positive number, preferably a positive number from 0 to 15, and more preferably a positive number from 0 to 10. q is A positive number, preferably a positive number of 1 to 15), preferably the same or different carbon number of 6 to
9 is a linear or branched alkylene group. The cycloalkylene group and the arylene group may have a substituent, for example, the cycloalkylene group having a total carbon number of 4 to 24 and the arylene group having a total carbon number of 7 to 24 are used. R ₂ is the same or different linear or branched alkyl group having 1 to 24 carbon atoms, an aryl group or an aralkyl group, wherein the aralkyl group has an aromatic ring such as a benzyl group or a phenethyl group. Refers to an alkyl group. Also,
The aralkylene group represented by R ₁ is a divalent group obtained by removing one hydrogen atom from an aralkyl group. R ₂ is preferably the same or different linear or branched alkyl group having 1 to 4 carbon atoms, and particularly preferably methyl group. The average degree of polymerization n is a positive number of 1 to 50, preferably 1 to 30, and particularly preferably 2 to 18. When the carbon number of R ₁ is larger than 24 and the average degree of polymerization n is larger than 50, the molecular weight of the obtained tertiary amino alcohol becomes large, and the viscosity becomes high depending on the carbon number and structure of R ₂ and it becomes difficult to use. On the other hand, when the carbon number of R ₁ is smaller than 2 and the average degree of polymerization n is smaller than 1, the content of the tertiary amino group in the molecular skeleton becomes too small, and the expected catalyst performance cannot be obtained.

Examples of the tertiary amino alcohol represented by the general formula (I) used in the present invention include those in the formula (I).
R ₁ is the same or different and has a linear or branched alkylene group having 2 to 20 carbon atoms, an alicyclic alkylene group, an aralkylene group or-(CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ ) _q- ( However, p is 0 or an integer, q is an integer), R ₂ is the same or different linear or branched alkyl group having 1 to 20 carbon atoms or aralkyl group, and the average degree of polymerization n is A tertiary amino alcohol which is an integer of 2 to 50, a linear or branched alkylene group having 6 to 9 carbon atoms in which R ₁ in the general formula (I) is the same or different, and a carbon number 1 in which R ₂ is the same or different. To a linear or branched alkyl group, a tertiary amino alcohol having an average degree of polymerization n of an integer of 2 to 18, R ₁ in the general formula (I) having the same or different carbon number of 6 to 9 linear or branched alkylene group, a linear or branched alkyl group having 1 to 4 carbon atoms R ₂ is identical or different, positive average polymerization degree n is 1-30 Tertiary amino alcohols and the like are can be given.

As described above, the tertiary amino alcohol represented by the general formula (II) may be produced depending on the reaction conditions. In the present invention, the tertiary amino alcohol represented by the general formula (I) is used in combination with one or more tertiary amino alcohols represented by the general formula (II) as a third component. You can also The third component represented by the general formula (II) is 30 in the total amount of the tertiary amino alcohol represented by the general formula (I) and the tertiary amino alcohol represented by the general formula (II). It is preferably used in the range of not more than wt%. Regarding the tertiary amino alcohol represented by the general formula (II), R ₃ in the general formula (II) is R ₁ in the general formula (I) and R ₄ in the general formula (II) is the general formula (II). The R _{2 in} I) and the average degree of polymerization m in the general formula (II) may be different from n in the general formula (I), but those in the same range are preferable.

Thus, by selecting the tertiary amino group content and molecular weight in the molecular skeleton and the molecular weight and structure of the side chain within the range that satisfies the performance as a polyol,
Tertiary amino alcohols with various catalytic properties adapted to the required reactivity are obtained, which makes it possible to produce rigid polyurethane foams by spraying, essentially without the use of catalyst components.

In the present invention, the tertiary amino alcohol represented by the general formula (I) is used as a part or the whole of the polyol component and can be used in an arbitrary ratio with other polyols, but the preferred range of use (general) The total amount of the tertiary amino alcohol represented by the formula (II) when used together is 1 to 50% by weight, preferably 10 to 30% by weight, based on the total amount of the polyol component. As other polyols, polyester polyols, polyether polyols and the like which are commonly used in the production of rigid polyurethane foams can be used. For example, polyester polyols produced from ordinary dibasic acid and polyhydric alcohol, glycol, glycerin, pentaerythritol,
Trimethylolpropane, polyhydric alcohols such as sucrose and triethylenediamine, 1,3 propanediamine, polyether polyols obtained by adding ethylene oxide and / or propylene oxide to polyamines such as isophoronediamine. it can. These polyols can be used alone or as a mixture of two or more kinds.

The polyisocyanate compound used in the present invention is an aromatic, aliphatic or alicyclic polyisocyanate having two or more isocyanate groups, a mixture of two or more thereof, and a modified one thereof. There is a modified polyisocyanate obtained. For example, polyisocyanates such as tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl polyisocyanate (crude MDI), xylylene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate and modified polyisocyanates thereof, for example, carbodiimide modified products and burette modified products. There are dimers, trimers and the like, and examples thereof include a terminal isocyanate group prepolymer of these polyisocyanates and active hydrogen compounds.

Further, in the production method of the present invention, water is used as a foaming agent, and the amount thereof is the total amount of the polyol component.
It is 2 to 8 parts by weight with respect to 100 parts by weight. Further, it is preferable to use trichlorofluoromethane or other foaming agent which is usually used in combination.

In the present invention, in addition to the polyisocyanate component and the polyol component, if necessary, a catalyst,
Surfactants and / or foam stabilizers, colorants, flame retardants, stabilizers and the like can be used. Regarding the type and the amount of these additives, they can be used sufficiently in the types and the range of use that are usually used.

By using the tertiary amino alcohol represented by the general formula (I) according to the present invention as all or at least a part of the polyol component, it is substantially unnecessary to use the catalyst component, but the blending thereof is required. When the amount is small, a metal catalyst can be used together for controlling the reaction at low temperature. A catalyst can be used depending on the application. Such a catalyst is not particularly limited, but conventionally known amine catalysts and metal catalysts can be used.
These catalysts may be used alone or as a mixture of two or more species in the third catalyst.
It can be used in combination with a primary amino alcohol.

[0023]

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited to these examples. In the examples, “part” is based on weight unless otherwise specified.

Reference Example A 600 g of 1,6-hexanediol and Cu were placed in a 1 liter flask equipped with a condenser and a separator for separating produced water.
/ Ni / Pd catalyst 36g (6% by weight to diol) was charged,
The inside of the system was replaced with nitrogen while stirring and the temperature rise was started. When the temperature in the system reaches 100 ° C, use the flow meter to add hydrogen gas.
It was blown into the system at a flow rate of 10 liters / hr and the temperature was raised to 180 ° C. At this temperature, a mixed gas of monomethylamine and hydrogen gas was blown into the reaction system at a flow rate of 40 liters / hr, and the reaction was monitored by amine value and hydroxyl value. The reaction was carried out for about 4 hours. After completion of the reaction, the catalyst was separated by filtration to obtain a light brown viscous liquid.

Reference Example B The reaction was carried out for 4 hours under the same conditions as in Reference Example A except that the flow rate of hydrogen gas was 5 liters / hr and the flow rate of the mixed gas of monomethylamine and hydrogen gas was 35 liters / hr.

Table 1 shows the analytical values of the tertiary amino alcohols A and B obtained in the above reference example.

[0027]

[Table 1]

Comparative Example 1 A conventional spray type rigid polyurethane foam as shown in Table 2 was blended and foamed by the following method. That is, Table 2
In the formulation, the raw materials excluding crude MDI were premixed and kept at 5 ° C, and then a prescribed amount of the polyol component premixed with crude MDI heated to 5 ° C was reacted by hand mixing foaming to obtain a reaction rate, The mechanical properties of the foam were measured. The self-adhesion strength was measured by a method according to JIS 9526. That is, the sample preparation is a crude MD
The raw materials except I are premixed and kept at 5 ° C. Then, a specified amount of the polyol component premixed with crude MDI heated to 5 ° C. was hand-mixed, and the mixed solution was sprayed on plywood kept at 5 ° C. to foam and cure. The environmental temperature during the foaming process was kept at 5 ° C. The results are shown in Table 3.

Examples 1 to 4 The tertiary amino alcohol A of the present invention obtained in Reference Example,
Using B, foaming was carried out in the same manner as in Comparative Example with the formulation shown in Table 2, and each physical property of the polyurethane foam was measured.
The results are shown in Table 3.

Example 5 and Comparative Example 3 A foaming test was carried out at a low temperature (0 ° C.). The operation was performed under the same conditions as in Comparative Example 1 and Example 1. However,
The raw material temperature was kept at 0 ° C, and the temperature of the self-adhesive strength test body and room temperature were also kept at 0 ° C. The results are shown in Table 3.

[0031]

[Table 2]

[0032]

[Table 3]

[0033]

As is apparent from the examples, when the tertiary amino alcohol according to the present invention is used, a conventional amine catalyst is not required, and particularly the reaction rate at 0 ° C. is greatly delayed in the conventional compounding. On the other hand, when the tertiary amino alcohol of the present invention is blended, the reaction rate delay is small,
Since the increase in free-form density is small, it is considered that the reaction at low temperature is progressing smoothly. Also JIS 9
It was also clarified that the self-adhesive strength of 526 was significantly improved, which enables construction at low temperatures, which was difficult to perform by conventional spray construction, and is also effective for formulations containing a large amount of water.

─────────────────────────────────────────────────── ───

[Procedure amendment]

[Submission date] August 7, 1992

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] 0020

[Correction method] Change

[Correction content]

Further, in the production method of the present invention, water is used as a foaming agent, and the amount thereof is the total amount of the polyol component.
It is 2 to 8 parts by weight with respect to 100 parts by weight. Further, it is preferable to use trichlorofluoromethane or other foaming agent which is usually used in combination. As other foaming agents, for example
Difluorochloromethane (F-22), 1,1-difluoroethane
(F-152a), 1,1,1,2-tetrafluoroethane (F-134a),
1,1,1,2,2-Pentafluoroethane (F-125), 1,1-di
Lolo-2,2,2-trifluoroethane (R-123), 2,2-di
Chloro-2-fluoroethane (R-141b), 1-chloro-1,
1-difluoroethane (R-142b) and the like can be mentioned.

[Procedure Amendment 2]

[Document name to be amended] Statement

[Name of item to be corrected] 0022

[Correction method] Change

[Correction content]

By using the tertiary amino alcohol represented by the general formula (I) according to the present invention as all or at least a part of the polyol component, it is substantially unnecessary to use the catalyst component, but the blending thereof is required. When the amount is small, a metal catalyst can be used together for controlling the reaction at low temperature. A catalyst can be used depending on the application. Such a catalyst is not particularly limited, but conventionally known amine catalysts and metal catalysts can be used.
As the amine catalyst, N, N-dimethylcyclohexyl acetate is used.
Min, N, N-dimethylbenzylamine, triethylami
N, N-methylmorpholine, N-ethylmorpholine, N,
N, N ', N'-Tetramethylethylenediamine, N, N, N', N '
-Tetramethyl-1,3-propanediamine, N, N, N ', N'
-Tetramethylhexanediamine, bis-2-dimethyl
Aminoethyl ether, N, N, N ', N', N ''-pentamethyl
Diethylenetriamine, tetramethylguanidine, tri
Ethylenediamine, N, N'-dimethylpiperazine, N-me
Cyl-N'-dimethylaminoethyl-piperazine, N-
(2-Dimethylaminoethyl) morpholine, 1-methyl
Imidazole, 1,2-dimethylimidazole, N, N-di
Methylaminoethanol, N, N, N'-trimethylaminoe
Cylethanolamine, N-methyl-N '-(2-hydro
Xyethyl) piperazine, N- (2-hydroxyethyl)
Le) Morpholine, 1- (2-hydroxypropyl) imi
Dazole, 2,4,6-tris (dimethylaminomethyl) phenyl
Enol, N, N-Dimethylaminohexanol, N, N-
Dimethylaminoethoxyethoxy ethanol, 1,4-bi
Sus (2-hydroxypropyl) -2-methylpiperazi
, Triethanolamine, N, N ', N''-tris (3-di
Methylaminopropyl) hexahydro-S-triazine
Etc. Also, as a metal-based catalyst, octane
Stannate, dibutyltin dilaurate, lead octoate, o
Examples include lead dibutyl citrate and the like. These catalysts can be used alone or as a mixture of two or more kinds in combination with the tertiary amino alcohol.

─────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area // (C08G 18/28 101: 00) C08L 75:04

Claims (7)

[Claims] 1. When a polyisocyanate component and a polyol component are reacted to produce a spray-type rigid polyurethane foam, water is used as a blowing agent in an amount of 2 to 8 parts by weight per 100 parts by weight of the total amount of the polyol component. Part or all of the components may be represented by the following general formula (I): [In the formula, R ₁ is the same or different linear or branched alkylene group having 2 to 24 carbon atoms, alicyclic alkylene group, cycloalkylene group, arylene group, aralkylene group or-(CH ₂ C
H ₂ O) _p- (CH ₂ CH ₂ ) _q- (where p is 0 or a positive number and q is a positive number) and R ₂ is the same or different and has 1 to 24 carbon atoms.
Of a linear or branched alkyl group, aryl group or aralkyl group, and the average degree of polymerization n is a positive number of 1 to 50. ]
A method for producing a spray-type rigid polyurethane foam, which comprises using at least one kind of a tertiary amino alcohol represented by: 2. A linear or branched alkylene group, alicyclic alkylene group, aralkylene group, or-(CH ₂ CH ₂ O) in which R _{1 s} in the general formula (I) are the same or different and are the same or different. ) _p − (CH ₂
CH ₂ ) _q- (where p is 0 or an integer, and q is an integer)
Wherein R ₂ is the same or different and is a linear or branched alkyl group having 1 to 20 carbon atoms or an aralkyl group, and the average degree of polymerization n is an integer of 2 to 50. Polyurethane foam manufacturing method. 3. A straight-chain or branched alkylene group having 6 to 9 carbon atoms in which R ₁ is the same or different in the general formula (I), and a straight-chain or branched chain having 1 to 4 carbon atoms in which R ₂ is the same or different. The method for producing a rigid polyurethane foam of a spray type according to claim 1, wherein the alkyl group and the average degree of polymerization n are integers of 2-18. 4. A straight-chain or branched alkylene group having 6 to 9 carbon atoms in which R ₁ is the same or different in the general formula (I), and a straight-chain or branched chain having 1 to 4 carbon atoms in which R ₂ is the same or different. 2. The method for producing a spray-type rigid polyurethane foam according to claim 1, wherein the alkyl group and the average degree of polymerization n are positive numbers of 1 to 30. 5. Further, in addition to the tertiary amino alcohol represented by the general formula (I), as a third component, a compound represented by the general formula (II): [In the formula, R ₃ are the same or different linear or branched alkylene groups having 2 to 24 carbon atoms, alicyclic alkylene groups, cycloalkylene groups, arylene groups, aralkylene groups or-(CH ₂ C
H ₂ O) _p- (CH ₂ CH ₂ ) _q- (where p is 0 or a positive number and q is a positive number), and R ₄ is the same or different and has 1 to 24 carbon atoms.
Is a linear or branched alkyl group, aryl group or aralkyl group, and the average degree of polymerization m is a positive number from 1 to 50. ]
The method for producing a spray-type rigid polyurethane foam according to any one of claims 1 to 4, wherein at least one tertiary amino alcohol represented by the formula (1) is used. 6. The tertiary component represented by the general formula (II) is a tertiary amino alcohol represented by the general formula (I) and the tertiary amino alcohol represented by the general formula (II). The method for producing a spray-type rigid polyurethane foam according to claim 5, wherein the spray-type rigid polyurethane foam is used in a range of 30% by weight or less based on the total amount of alcohol. 7. A linear or branched alkylene group having 6 to 9 carbon atoms, wherein R ₁ in the general formula (I) and / or R ₃ in the general formula (II) are the same or different, In formula (I)
R ₂ and / or R ₄ in the general formula (II) is the same or different linear or branched alkyl group having 1 to 4 carbon atoms, and the average polymerization degree n and n in the general formula (I) are / Or the general formula
The method for producing a spray-type rigid polyurethane foam according to claim 5 or 6, wherein the average degree of polymerization m in (II) is a positive number of 1 to 30.