JP2994823B2 - Production of rigid polyurethane foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a polyurethane foam. More specifically, the present invention relates to a method for producing a rigid polyurethane foam having excellent heat insulation performance and low-temperature dimensional stability.

[0002]

2. Description of the Related Art Rigid polyurethane foams are used in various fields by taking advantage of their excellent properties. Particularly, since it is the most excellent heat insulating material, it is widely used as a heat insulating material for refrigerators, freezer warehouses and the like. The heat insulating properties of these heat insulating materials are largely due to the fact that the rigid polyurethane foam uses trichlorofluoromethane (hereinafter referred to as R-11) as a foaming agent.

[0003]

In recent years, the use of chlorofluorocarbons for protecting the ozone layer in the atmosphere has been regulated. Since R-11 is also included in this regulation, the development of a foaming agent to replace it has been urgent. As a result, in view of various physical properties, 1,1-dichloro-2,2,2-trifluoroethane (hereinafter, referred to as R-123) or 2,2-dichloro-2-fluoroethane (hereinafter, R-141) is used. b) is considered a potential alternative. However, it has been confirmed that the use of these compounds as a foaming agent deteriorates the performance in the following points. That is, 1) the reactivity is greatly reduced. 2) The dimensional stability at low temperature is poor. 3) The heat insulation performance is poor. As means for solving the above points, it is conceivable to increase the density, increase the amount of the catalyst, etc.
This is not a practical method for producing a rigid polyurethane foam.

[0004]

The present inventors have conducted intensive studies to solve the above problems, and as a result, have a tertiary amino group having a catalytic action in the molecular skeleton and an isocyanate at both ends of the molecule. A tertiary amino alcohol having a hydroxyl group capable of reacting with a hydroxyl group is used, and one or more compounds selected from polyfunctional alcohols, aliphatic amines and aromatic amines having a hydroxyl value of 1,000 or more, particularly a hydroxyl value
The inventors have found that a rigid polyurethane foam exhibiting excellent heat insulating performance and low-temperature dimensional stability can be obtained by using 1000 or more polyfunctional alcohols in combination, and have reached the present invention.

That is, the present invention relates to a method for producing a rigid polyurethane foam by reacting a polyisocyanate component and a polyol component in the presence of a blowing agent, wherein the polyol component is represented by the following general formula (I): 3
Using a secondary amino alcohol, and a polyfunctional alcohol having a hydroxyl value of 1000 or more, one or more compounds selected from aliphatic amines and aromatic amines, and particularly preferably a polyfunctional alcohol having a hydroxyl value of 1,000 or more is used in combination. It is intended to provide a method for producing a rigid polyurethane foam characterized by the above.

[0006]

Embedded image

Wherein R ₁ is the same or different and has 2 to 2 carbon atoms.
24 linear or branched alkylene groups, alicyclic alkylene groups, cycloalkylene groups, arylene groups, aralkylene groups or-(CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ ) _q- (where p is 0 R ₂ represents the same or different linear or branched alkyl, aryl or aralkyl group having 1 to 24 carbon atoms, and the average degree of polymerization n Represents a positive number of 1 to 50. ].

The tertiary amino alcohol represented by the general formula (I) used in the present invention has 1 to 50 tertiary amino alcohols in the molecule.
Since it has a tertiary amino group, it has the same catalytic activity as a commonly used tertiary amine catalyst, and since hydroxyl groups at both ends of the molecule can react with isocyanate groups, tertiary amino alcohols The reaction between the polyisocyanate and the isocyanate component has priority and has a catalytic action on other polyol components and water. Moreover, it surprisingly promotes the reaction between the polyol component and the isocyanate group as compared with the usual tertiary amine catalyst. In addition, it has a strong so-called resinification catalytic activity, but has a feature that it accelerates the resinification reaction particularly at the initial stage of the reaction.

On the other hand, in order to improve the filling property, it is important to balance the rate of gas generation by the reaction with the rate of curing of the resin. When the rate of gas generation is faster than the rate of curing of the resin, the gas is contained in the resin. It is not sufficiently taken in, the required foam volume cannot be obtained, and the filling property is poor. When the curing speed of the resin is higher than the gas generation speed, the resin viscosity increases, so-called liquid flow decreases, and the filling property of the polyurethane foam decreases.

Even when water and trichlorofluoromethane are used in a normal ratio, if the curing rate of the resin is increased by changing the ratio of polyol, catalyst, etc. for the purpose of improving productivity, etc. The balance between the generation rate of the resin and the curing rate of the resin is lost, and the filling property of the polyurethane foam is reduced. However, when the tertiary amino alcohol represented by the general formula (I) according to the present invention is used as all or a part of the polyol component, resinification at the initial stage of the reaction is promoted and gasification of trichlorofluoromethane is promoted at the same time. Therefore, the balance between the gas generation speed required for filling and the curing speed of the resin is maintained, and the filling is further improved.

[0011] In addition, in the freon-reducing formulation in which the use amount of trichlorofluoromethane is reduced, the filling property of the polyurethane foam is reduced due to a rapid foaming hardening reaction due to the large amount of water used. When the tertiary amino alcohol represented by the general formula (I) according to the present invention is used in such a chlorofluorocarbon-reducing formulation, a catalyst component usually used is unnecessary, and the tertiary amino alcohol (I) according to the present invention is used. Due to the characteristics described above, since the reaction between water and isocyanate groups is suppressed, the filling properties of the polyurethane foam are not impaired.

Furthermore, instead of trichlorofluoromethane, 1,1-dichloro-2,2,2-trifluoroethane or 2,2
When using 2-dichloro-2-fluoroethane,
The drawbacks of these are that the filling property is reduced due to the difference in boiling point from trichlorofluoromethane and the reduction in the rate of resinification reaction due to solubility in the resin and the delay in the generation of CFCs associated therewith. Formula (I)
By using the tertiary amino alcohol represented by the formula (1), the resinification reaction rate is promoted, and a decrease in the filling property of the polyurethane foam can be prevented.

The tertiary amino alcohol represented by the general formula (I) used in the present invention has various structures and molecular weights by changing the types of the dihydric alcohol and the primary amine which are the raw materials for production. You can get things. As the dihydric alcohol, a linear or branched one having 2 to 24 carbon atoms is used. For example, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 6-hexanediol, 1,9-nonanediol, 1,10-decanediol, diethylene glycol,
Triethylene glycol, tetraethylene glycol,
1,4-cyclohexanedimethanol, 2-ethyl-
Examples thereof include 1,3-hexanediol, 3-methyl-1,5-pentanediol, and 1,4-hydroquinone, and a mixture thereof can also be used. Examples of the primary amine include a linear or branched C1-C24 primary or aromatic amine having two active hydrogens such as methylamine, propylamine, isopropylamine, and the like. Examples include butylamine, 2-ethylhexylamine, heptylamine, octylamine, decylamine, dodecylamine, cetylamine, stearylamine, docosylamine, oleylamine, benzylamine, phenethylamine, aniline, and the like, and mixtures thereof.

The method for producing the tertiary amino alcohol represented by the general formula (I) according to the present invention will be described in more detail. In producing the tertiary amino alcohol by reacting the above dihydric alcohol with the primary amine, a catalyst containing copper-noble metal as a main component, for example, copper-nickel-group VIII platinum group element, copper-chromium -Group 8 platinum group element, copper-zinc-
Group VIII platinum group element, copper-manganese-Group VIII platinum group element,
Using a catalyst having a composition of copper-iron-group 8 platinum group element, copper-cobalt-group 8 platinum group element, etc., water generated by the reaction in the presence of these catalysts is continuously or intermittently produced. 150-250 ℃ at atmospheric pressure or under pressure while removing outside the reaction system
The object is achieved by stirring and reacting at a temperature of.
At this time, the dihydric alcohol may be added continuously during the reaction, charged from the beginning, or may be charged in a predetermined amount. When the primary amine is a gas, it may be blown continuously or intermittently during the reaction, or may be charged at a time under a predetermined 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 the amine to the dihydric alcohol needs to be 0.7 times or more, preferably 1 time. In the case of gaseous amines, the gas charged in excess with hydrogen is recovered and recycled. Is also good. In the method for producing a tertiary amino alcohol according to the present invention, it is preferable that water generated by the reaction between the dihydric alcohol and the primary amine is taken out of the reaction system. If the produced water is not taken out of the system, the catalytic activity and selectivity often decrease. For example, when the reaction is carried out without removing the generated water, the amount of amine disproportionate increases and the desired general formula (I)
May decrease the yield of the tertiary amino alcohol represented by the formula: However, as the amine disproportionate, the following general formula (III)

[0016]

Embedded image

[Wherein R ₄ is the same or different and has 2 to 2 carbon atoms.
24 linear or branched alkylene groups, alicyclic alkylene groups, cycloalkylene groups, arylene groups, aralkylene groups or-(CH ₂ CH ₂ O) _p- (CH ₂ CH ₂ ) _q- (where p is 0 R ₅ represents the same or different linear or branched alkyl group, aryl group or aralkyl group having 1 to 24 carbon atoms, and an average degree of polymerization m Represents a positive number of 1 to 50. To produce a tertiary amino alcohol represented by the general formula (III):
Since a mixture containing a secondary amino alcohol can also be used, it is not necessary to particularly remove water as long as the amount of disproportionate generated is within a range where the desired polyurethane can be obtained. The removal of water may be carried out continuously or continuously, and the produced water may be removed as appropriate without being present in the reaction system for a long 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 off the generated water together with the hydrogen gas.The hydrogen gas is circulated by concentrating and separating the generated water with a condenser. Can also be used. Further, a suitable solvent may be added during the reaction, and the produced water may be distilled off by azeotropic distillation with this solvent, or an inert solvent may be added for the purpose of lowering the viscosity of the product.

In the method for producing a 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. At the same time, the catalyst before reduction is put into the reactor, and when the hydrogen gas or the amine to be reacted is a gaseous amine, the catalyst is raised by raising the temperature to the reaction temperature while introducing a mixed gas of hydrogen gas and the gaseous amine. It is preferred to reduce.

The tertiary amino alcohol used in the present invention has the structure represented by the general formula (I), wherein R ₁ is the same or different and has a 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 of 0 to 15, more preferably a positive number of 0 to 10. q is A positive number, preferably a positive number of 1 to 15), and preferably 6 to 6 carbon atoms of the same or different.
And 9 linear or branched alkylene groups. The cycloalkylene group and the arylene group may have a substituent. For example, a cycloalkylene group having a total carbon number of 4 to 24 and an 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 for R ₁ is a divalent group obtained by removing one hydrogen atom from an aralkyl group. The aralkylene group has 0 to 6, preferably 0, carbon atoms in the alkylene group substituted on the aromatic ring.
To 3 are mentioned. R ₂ is preferably the same or different linear or branched alkyl group having 1 to 4 carbon atoms, particularly preferably a methyl group. The average degree of polymerization n is 1
It is a positive number of -50, preferably 1-30, particularly preferably a positive number of 2-18. If the carbon number of R ₁ is greater than 24 and the average degree of polymerization n is greater than 50, the molecular weight of the tertiary amino alcohol obtained will increase, and the viscosity will increase due to the carbon number and structure of R ₂ , making it difficult to use. On the other hand, if 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 catalytic performance cannot be obtained.

Examples of the tertiary amino alcohol represented by formula (I) used in the present invention include compounds represented by formula (I)
A tertiary amino alcohol wherein the average degree of polymerization n is an integer of 2 to 50; a linear or branched alkylene group having 3 to 9 carbon atoms in which R ₁ is the same or different in the general formula (I); ₂ is the same or different, a linear or branched alkyl group having 1 to 4 carbon atoms, a tertiary amino alcohol having an average polymerization degree n of an integer of 2 to 18, and R ₁ in the general formula (I) is the same or different straight-chain or branched-chain alkylene group having a carbon number of 6-9, a straight-chain or branched alkyl group having 1 to 4 carbon atoms R ₂ is identical or different, the average polymerization degree n is 1-30 positive And tertiary amino alcohols.

As described above, the tertiary amino alcohol represented by the general formula (III) may be produced depending on the reaction conditions. In the present invention, one or more tertiary amino alcohols represented by the general formula (III) are used in combination with the tertiary amino alcohol represented by the general formula (I) as a third component. You can also. The third component represented by the general formula (III) accounts for 30% of the total amount of the tertiary amino alcohol represented by the general formula (I) and the tertiary amino alcohol represented by the general formula (III). It is preferable to use not more than% by weight. In the tertiary amino alcohol represented by the general formula (III), R ₄ in the general formula (III) is the same as R ₁ in the general formula (I).
And R ₅ in the general formula (III) may be different from R ₂ in the general formula (I), and the average degree of polymerization m in the general formula (III) may be different from n in the general formula (I). Are preferably in the same range.

As described above, by selecting the tertiary amino group content in the molecular skeleton, the molecular weight, the molecular weight of the side chain, and the structure within the range satisfying the performance as a polyol,
A tertiary amino alcohol having various catalytic performances suitable for the required reactivity can be obtained, and it becomes possible to produce a rigid polyurethane foam having excellent filling properties without substantially using a catalyst component. General formula (I) according to the present invention
The tertiary amino alcohol represented by the formula (when the tertiary amino alcohol represented by the general formula (III) is used in combination) is 1 to 50% by weight based on the total amount of the polyol component used.
It is preferably used.

The tertiary amino alcohol used in the present invention is a divalent diol as shown by the general formula (I). Therefore, it is necessary to introduce an intramolecular or intermolecular cross-linked structure in order to achieve the resin strength required for improving the low-temperature dimensional stability. Based on this, the present inventors have conducted various studies, and as a result, the polyfunctional alcohol having a hydroxyl value of 1000 or more as a part of
It has been found that the intended physical properties are exhibited when a rigid polyurethane foam is produced by using it together with a secondary amino alcohol. As polyfunctional alcohols, aromatic amine polyols, sugar-based polyether polyols,
Glycerin-based polyether polyols and the like can be mentioned.
Particularly, ethylene glycol and glycerin are preferred. The use amount of these polyfunctional alcohols is preferably 1 to 50% by weight based on the total amount of the polyol component.

Usually, when producing a rigid polyurethane foam, diphenylmethane diisocyanate is mainly used as an isocyanate, and a polyol having a hydroxyl value of 300 to 700 is used as a polyol, and a polyol having a number of functional groups of 3 to 8 is used. Is used.

In the present invention, in addition to the tertiary amino alcohols represented by the above general formulas (I) and (III) and the polyfunctional alcohols having a hydroxyl value of 1000 or more, polyols usually used in the production of polyurethane foams Can be used in combination. As such polyols, generally known polyester polyols, polyether polyols, and the like used in the production of rigid polyurethane foams can be used. For example, polyester polyols produced from ordinary dibasic acids and polyhydric alcohols, glycols, glycerin, pentaerythritol, trimethylolpropane, polyhydric alcohols such as sucrose and triethylenediamine, 1,3 propanediamine, isophoronediamine and the like And polyether polyols obtained by adding ethylene oxide and / or propylene oxide to the polyvalent amine. These polyols can be used alone or as a mixture of two or more.

As the polyisocyanate compound used in the present invention, an aromatic, aliphatic or alicyclic polyisocyanate having two or more isocyanate groups, a mixture of two or more 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, buret modified products And dimer and trimer, and further include prepolymers of terminal isocyanate groups of these polyisocyanates and active hydrogen compounds.

Further, the blowing agent is at least one selected from the group consisting of water, trichlorofluoromethane, 1,1-dichloro-2,2,2-trifluoroethane and 2,2-dichloro-2-fluoroethane. Preference is given to using different blowing agents, particularly preferably 1,1-dichloro-2,2,2-trifluoroethane and / or 2,2-dichloro-2-fluoroethane, or water and 1,1-dichloromethane. It is a combination of -2,2,2-trifluoroethane and / or 2,2-dichloro-2-fluoroethane. In some cases, methylene chloride, pentane, n-hexane or the like can be used in combination for the purpose of reducing the amount of trichlorofluoromethane used. Examples of foaming agents other than the above foaming agents include:
For example, difluorochloromethane (F-22), 1,1-difluoro
Tan (F-152a), 1,1,1,2-tetrafluoroethane (F-134
a), 1,1,1,2,2-pentafluoroethane (F-125), 1-c
Use rolo-1,1-difluoroethane (R-142b), etc.
Can also be.

In the present invention, in addition to the above-mentioned polyisocyanate component and polyol component, a surfactant and / or a foam stabilizer, a coloring agent, a flame retardant, a stabilizer and the like can be used, if necessary. The types and amounts of these additives can be sufficiently used within the types and usage ranges usually used. Above all, it is desirable to use a surfactant in order to more sufficiently exert the effects of the present invention, and examples of the surfactant include a silicone-based surfactant.

In the present invention, an aliphatic amine and / or an aromatic amine can be used together with the tertiary amino alcohol. These amines act as catalysts, and in particular, triethanolamine, tolylenediamine, or the following general formula (II) H ₂ N—R ₃ —NH ₂ (II) wherein R ₃ has 2 to 8 carbon atoms Shows a linear or branched alkylene group. ] Are preferred. The amount of amine catalyst used is the total amount of polyol components
1 to 30 parts by weight per 100 parts by weight is preferred. These amine catalysts can be used alone or as a mixture of two or more kinds with a tertiary amino alcohol and a polyfunctional alcohol having a hydroxyl value of 1,000 or more. In addition, polyurethane foil
Use common amine catalysts used in the production of
Can be Such amine catalysts include N, N
-Dimethylcyclohexylamine, N, N-dimethylben
Jilamine, triethylamine, N-methylmorpholine
, N-ethylmorpholine, N, N, N ', N'-tetramethyl
Ethylenediamine, N, N, N ', N'-tetramethyl-1,3-
Propanediamine, N, N, N ', N'-tetramethylhexane
Diamine, bis-2-dimethylaminoethyl ether,
N, N, N ', N', N ''-pentamethyldiethylenetriamine,
Tetramethylguanidine, triethylenediamine, N, N '
-Dimethylpiperazine, N-methyl-N'-dimethylamido
Noethyl-piperazine, N- (2-dimethylaminoethyl
G) morpholine, 1-methylimidazole, 1,2-dim
Tilimidazole, N, N-dimethylaminoethanol,
N, N, N'-trimethylaminoethylethanolamine, N
-Methyl-N ′-(2-hydroxyethyl) piperazine,
N- (2-hydroxyethyl) morpholine, 1- (2-
(Hydroxypropyl) imidazole, 2,4,6-tris
(Dimethylaminomethyl) phenol, N, N-dimethyl
Aminohexanol, N, N-dimethylaminoethoxy
Toxicethanol, 1,4-bis (2-hydroxypropyl
) -2-methylpiperazine, N, N ', N''-tris (3-
Dimethylaminopropyl) hexahydro-S-triazi
And the like. In addition, as a metal-based catalyst, octa
Tinate, dibutyltin dilaurate, lead octanoate,
And dibutyl lead octanoate. These catalysts can be used alone or as a mixture of two or more of the catalysts of the present invention.
It can be used in combination with a graded amino alcohol.

[0030]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to reference examples of tertiary amino alcohols used in the present invention.
The present invention is not limited to only these examples. In the examples, “parts” are 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 for separating produced water and a separator.
/ G / Ni / Pd catalyst 24g (based on diol 4% by weight)
The system was replaced with nitrogen while stirring, and the temperature was raised. When the temperature in the system reaches 100 ° C, hydrogen gas is
It was blown into the system at a flow rate of 10 liter / 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 liter / Hr, and the reaction was monitored by amino value and hydroxyl value. The reaction was carried out for about 4 hours, and after completion of the reaction, the catalyst was separated by filtration to obtain a pale brown viscous liquid (hereinafter referred to as tertiary amino alcohol A).

Reference Example B The reaction was carried out under the same conditions as in Reference Example A except that the flow rate of hydrogen gas was changed to 5 L / Hr, and the flow rate of a mixed gas of monomethylamine and hydrogen gas was changed to 35 L / Hr. (Hereinafter referred to as tertiary amino alcohol B).

Reference Example C n-Butylamine was used as the amine at a reaction temperature of 185 ° C.
The reaction was carried out for 40 hours under the same conditions as in Reference Example B except that the tertiary amino alcohol was obtained (hereinafter referred to as tertiary amino alcohol C).

Reference Example D A reaction was carried out for 30 hours under the same conditions as in Reference Example B except that benzylamine was used as the amine to obtain a tertiary amino alcohol (hereinafter referred to as tertiary amino alcohol D).

Reference Example E The reaction was carried out for 8 hours under the same conditions as in Reference Example B except that the reaction temperature was 210 ° C., 1,9-nonanediol was used as a dihydric alcohol, and the catalyst was 2% by weight. A tertiary amino alcohol was obtained (hereinafter referred to as tertiary amino alcohol E).

Reference Example F A tertiary amino alcohol was obtained under the same conditions as in Reference Example B except that the reaction temperature was 220 ° C. and triethylene glycol was used as a dihydric alcohol for 20 hours (hereinafter referred to as “tertiary amino alcohol”).
Tertiary amino alcohol F).

The tertiary amino alcohols obtained in Reference Examples AF are shown in Table 1.

[0038]

[Table 1]

N and m in Table 1 mean the average degree of polymerization, and were calculated by measuring the hydroxyl value and calculating the composition ratio by ¹ H-NMR.

Examples 1 to 28 and Comparative Examples 1 to 8 The raw materials for the production of rigid polyurethane foams were formulated as shown in Tables 2 and 3 and urethane foaming was carried out according to the usual procedure. That is, polyol, foaming agent,
Mix and stir foam stabilizer, catalyst and polyisocyanate,
It was poured into a mold of 20 × 20 × 5 cm kept at 40 ° C., demolded after 10 minutes, and a rigid polyurethane foam was obtained as samples for various evaluations. The rigid polyurethane foam obtained by the above method was stored at −30 ° C. for 24 hours, the dimensional change was measured, and the foam was cut out to 18 × 18 × 2.5 cm to measure the thermal conductivity. Also, in Tables 2 and 3, the amount of resin destruction is one of the indicators of adhesiveness. Five minutes after injecting the agitated rigid polyurethane foam raw material into the above-mentioned mold kept at 40 ° C. by measuring flyability, which is one of the indices of adhesiveness. It shows the amount of resin adhered to the mold when the mold was removed. The results are shown in Tables 2 and 3.
In Tables 2 and 3, polyol A is 70 parts of an aromatic amine polyol (OHV = 450) manufactured by Asahi Ohlin Co., Ltd.
A mixture obtained by mixing 20 parts of a sugar-based polyether polyol (OHV = 530) manufactured by Sumitomo Bayer Urethane Co., Ltd. and 10 parts of a glycerin-based polyether polyol (OHV = 235) manufactured by Mitsui Toatsu Chemicals, Inc. was used. Also, as a foam stabilizer,
Table 2 uses 1.5 parts of L-5340 manufactured by Nippon Unicar Co., Ltd.
The amount of tetramethylhexamethylenediamine (Kaorizer No. 1) manufactured by Kao Corporation shown in FIG. 3 was used. As the polyisocyanate component, TR manufactured by Mitsui Toatsu Chemicals, Inc.
-50BX (isocyanate weight% = 30.7) with NCO / O
H = 1.05 was used. Glycerin used as a polyfunctional alcohol is purified glycerin (OHV manufactured by Kao Corporation).
= 1830).

[0041]

[Table 2]

[0042]

[Table 3]

Examples 29 to 34 The raw materials for the production of rigid polyurethane foams were as shown in Table 4 and urethane foaming was carried out in the same manner as described above to obtain rigid polyurethane foams, which were used as samples for various evaluations. The same test as described above was performed using this sample. Table 4 shows the results. In Table 4, polyol A and L-5340 were the same as described above, and the same catalyst and polyisocyanate component were used. As the ethylene glycol used as the polyfunctional alcohol, Katayama Chemical reagent grade 1 (OHV = 1810) was used. Also, 1,6
-Hexanediamine used was Katayama Chemical's first grade reagent.

[0044]

[Table 4]

[0045]

As specifically shown in the examples,
Using a tertiary amino alcohol according to the present invention, and having a hydroxyl value of 1000 or more polyfunctional alcohols, one or two or more compounds selected from aliphatic amines and aromatic amines, especially a hydroxyl value of 1000 or more The use of trichlorofluoromethane, which is regulated for the purpose of protecting the ozone layer, as well as making it possible to produce rigid polyurethane foam with excellent filling properties for large and complicated injection targets by using polyfunctional alcohols together Even when the amount is reduced, it becomes possible to produce a rigid polyurethane foam having improved filling properties. In addition, the rigid polyurethane foam produced according to the present invention has excellent low-temperature dimensional stability and heat insulation performance.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification symbol FI C08G 101: 00) C08L 75:04 (56) References JP-A-56-67329 (JP, A) JP-A-56-67331 ( JP, A) Special Table 61-501372 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C08G 18/32 C08G 18/50 C08G 18/64 C08J 9/02

Claims (12)

(57) [Claims] 1. A method for producing a rigid polyurethane foam by reacting a polyisocyanate component and a polyol component in the presence of a foaming agent, wherein a tertiary amino alcohol represented by the following general formula (I) is used as the polyol component: A method for producing a rigid polyurethane foam, characterized by using one or more of the above and in combination with one or more compounds selected from polyfunctional alcohols having a hydroxyl value of 1000 or more, aliphatic amines and aromatic amines . Embedded image (In the formula, R ₁ is the same or different and is a linear or branched alkylene group having 2 to 24 carbon atoms, an alicyclic alkylene group, a cycloalkylene group, an arylene group, an 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 carbon number of 1 to 24
And an average degree of polymerization n is a positive number of 1 to 50. ] 2. An average polymerization degree n in the general formula (I) is 2 to 50.
The method for producing a rigid polyurethane foam according to claim 1, which is an integer of: 3. In the general formula (I), R ₁ is the same or different and is a straight-chain or branched-chain alkylene group having 3 to 9 carbon atoms, R ₂ is the same or different straight-chain or 1 to 4 carbon atoms or The method for producing a rigid polyurethane foam according to claim 1, wherein the branched alkyl group and the average degree of polymerization n are integers of 2 to 18. 4. In the formula (I), R ₁ is the same or different and is a straight-chain or branched alkylene group having 6 to 9 carbon atoms, R ₂ is the same or different straight-chain or 1 to 4 carbon atoms or The method according to claim 1, wherein the branched alkyl group and the average degree of polymerization n are positive numbers of 1 to 30. 5. The method for producing a rigid polyurethane foam according to claim 1, wherein the polyfunctional alcohol is at least one selected from ethylene glycol and glycerin. 6. The aliphatic amine and / or aromatic amine is one or more selected from triethanolamine, tolylenediamine, or a diamine represented by the following general formula (II). The method for producing a rigid polyurethane foam according to any one of the above. H ₂ N—R ₃ —NH ₂ (II) wherein R ₃ represents a linear or branched alkylene group having 2 to 8 carbon atoms. ] 7. The foaming agent is water, 1,1-dichloro-2,2,2.
2. One or more kinds selected from -trifluoroethane and 2,2-dichloro-2-fluoroethane.
The method for producing a rigid polyurethane foam according to any one of claims 6 to 6. 8. The use amount of the tertiary amino alcohol represented by the general formula (I) is 1 to 50% by weight in the total amount of the polyol component, and the use amount of the polyfunctional alcohol is in the total amount of the polyol component. 1 to 50% by weight of the aliphatic amine and / or
Or the amount of aromatic amine used is the total amount of polyol component 100
The method for producing a rigid polyurethane foam according to any one of claims 1 to 7, wherein the amount is 1 to 30 parts by weight based on parts by weight. 9. The method for producing a rigid polyurethane foam according to claim 1, wherein the tertiary amino alcohol represented by the general formula (I) and a polyfunctional alcohol having a hydroxyl value of 1,000 or more are used as essential components. Manufacturing method. 10. In addition to the tertiary amino alcohol represented by the general formula (I), a tertiary amino alcohol represented by the general formula (II)
I) (In the formula, R ₄ 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 ₅ is the same or different carbon number of 1 to 24
And a linear or branched alkyl group, aryl group or aralkyl group having an average degree of polymerization m of 1 to 50. ]
The method for producing a rigid polyurethane foam according to any one of claims 1 to 9, wherein one or more tertiary amino alcohols represented by the formula (1) are used. 11. The tertiary amino alcohol represented by the general formula (III) is combined with a tertiary amino alcohol represented by the general formula (I) and a tertiary amino alcohol represented by the general formula (III). 11. The method for producing a rigid polyurethane foam according to claim 10, wherein the rigid polyurethane foam is used in a range of 30% by weight or less of the total amount with the quaternary amino alcohol. 12. A linear or branched alkylene group having 6 to 9 carbon atoms wherein R ₁ is the same or different in the general formulas (I) and / or (III), and R ₂ is the same or different carbon number. A straight-chain or branched-chain alkyl group of 1 to 4;
12. The process for producing a rigid polyurethane foam according to claim 10, wherein the average degree of polymerization n in Formula (III) and / or the average degree of polymerization m in Formula (III) is a positive number of 1 to 30.