JP2003335832A - Foamable composition for polyurethane foam and polyurethane foam prepared by foaming and curing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foamable composition which has a low viscosity hardly changing with time, has an improved compatibility with a substitutive blowing agent HCFC-141b, and contains a Mannich polyol especially suitable as a foam material; and a polyurethane foam prepared by foaming and curing the composition. <P>SOLUTION: The composition comprises a polyol component consisting of a Mannich polyol and a polyol added as necessary, a polyisocyanate, a blowing agent, a foam stabilizer, and other additives as necessary. The Mannich polyol is prepared by reacting a phenol, an aldehyde, and a monoamine component in an amount of 1.0-2.0 mol based on 1 mol of the phenol. The monoamine component consists of at least one monoamine selected from primary and secondary alkanolamines and at least one monoamine selected from primary and secondary alkylamines in a molar ratio of the alkanolamine to the alkylamine of (1:0.3) to (1:2.4). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a highly reactive Mannich-type polyol having a low viscosity and a small change in viscosity with time, and having a self-catalytic ability suitable for in-situ foaming or injection foaming, particularly as a raw material of a foam. The present invention relates to a foamable composition for polyurethane-based foams, in which a polyol is added as necessary to a polyol component, and a polyurethane-based foam formed by foaming and curing the same.

[0002]

2. Description of the Related Art Mannich-type polyols produced by the Mannich reaction of phenols, aldehydes, and primary or secondary monoamines are capable of promoting a base-catalyzed reaction based on a tertiary nitrogen atom in the molecule. Therefore, it is known that it is useful as a curing agent for epoxy resin or the like for producing a polyurethane molded article or a polyurethane foam by a reaction injection molding method, an in-situ foaming method, an injection foaming method or the like.

However, since this Mannich-type polyol is generally high in viscosity and inferior in mixing property, when it is used as a polyol raw material for foam, for example, it is generally alkylated or alkoxylated as disclosed in Patent Documents 1 and 2. The viscosity has been lowered due to this. Further, the Mannich-based polyol has a problem that the viscosity tends to increase with the passage of time. Further, depending on the type of the phenols, there is a drawback that it is difficult to use due to lack of compatibility with an alternative freon-based foaming agent, particularly HCFC-141b (dichlorofluoroethane).

[0004]

[Patent Document 1] Japanese Patent Application Laid-Open No. 2-132115 (claims and others)

[Patent Document 2] Japanese Patent Laid-Open No. 3-121113 (claims and others)

[0005]

Under the circumstances described above, the present invention has a low viscosity, a small change in viscosity over time, and an improved compatibility with the alternative CFC-based blowing agent HCFC-141b. In particular, the present invention has been made for the purpose of providing a foamable composition for polyurethane foam containing a Mannich polyol suitable as a raw material for foam, and a polyurethane foam obtained by foaming and curing the same.

[0006]

Means for Solving the Problems As a result of intensive studies to achieve the above-mentioned object, the inventors of the present invention have used alkanolamine and alkylamine as primary and secondary monoamines in a specific molar ratio. And, the desired Mannich-type polyol can be efficiently obtained by reacting these with phenols and aldehydes in a range of a specific molar ratio with respect to phenols, and foaming properties using this as a component. The present inventors have found that the composition is suitable for polyurethane-based foams, and have completed the present invention based on this finding.

That is, according to the present invention, phenols, aldehydes, and 1.0 to 2.0 per mol of phenols are used.
Mol of at least one selected from primary and secondary monoamines consisting of alkanolamine and alkylamine, and the molar ratio of alkanolamine and alkylamine is from 1: 0.3 to 1: A Mannich-based polyol obtained by reacting the monoamines of 2.4 with a polyol component if necessary,
It is intended to provide a foamable composition for polyurethane foam, which is obtained by mixing a polyisocyanate, a foaming agent, a foam stabilizer and an additive component used as necessary.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the composition of the present invention, a Mannich-based polyol obtained by the following method is added with a conventionally used polyol such as a polyether polyol, a polyester polyol or a phenol resin, if necessary. The polyol component is mixed with a polyisocyanate, a foaming agent, a foam stabilizer, and other optional components used as necessary, for example, by a high-pressure collision mixer to prepare a liquid foamable composition. This composition is then
For example, after spray coating with a spray gun, etc. on the surface of the structure of the building where heat insulation is required, or
After pouring and filling into a space such as a refrigerator or a honeycomb structure, and foaming and curing at room temperature, a polyurethane foam layer is formed on the surface of the body or inside the space. Further, by utilizing the high reactivity and autocatalytic ability of the Mannich-based polyol, the curability can be improved by blending it with a conventional polyol. Specifically, first, conventionally used polyols, Mannich-based polyols, polyisocyanates, foaming agents, foam stabilizers and other additive components used as necessary are mixed by, for example, a high-speed stirring mixer. A liquid foamable composition is prepared. Then, the composition is applied, for example, on a face material (eg, polyethylene sheet, kraft paper, calcium silicate plate, shaped metal thin plate, etc.) continuously conveyed by upper and lower endless conveyor devices, or in a horizontal formwork. After being supplied onto a glass fiber or rock wool fiber mat, a single foam or a composite of polyurethane foam is produced by a continuous foaming method in which foaming and hardening are performed at room temperature or under heating, an impregnation foaming method, or the like.

The method for obtaining the above-mentioned Mannich-based polyol is to use phenols, aldehydes and phenols 1
It is at least one selected from primary and secondary monoamines consisting of alkanolamine and alkylamine, and the molar ratio of alkanolamine and alkylamine is 1.0 to 2.0 mol per mol. Is a monoamine having a ratio of 1: 0.3 to 1: 2.4.

In this reaction, primary and secondary monoamines composed of phenols, aldehydes and a combination of alkanolamines and alkylamines are used as raw materials. The phenols include at least one phenolic hydroxyl group bonded to a carbon atom of an aromatic ring and at least one ortho or para position with respect to the hydroxyl group.
A phenolic compound having a reactive hydrogen atom at a position and having no substituent at the ortho position, the meta position or the para position or having a non-reactive substituent such as an alkyl group, an aryl group or a halogen atom is preferable. Used. Examples of such phenolic compounds include phenol, cresol, ethylphenol, xylenol, p-tertiarybutylphenol, octylphenol, nonylphenol, dodecylphenol, p-phenylphenol, m-chlorophenol, o-bromophenol,
Resorcinol, catechol, hydroquinone, phloroglicinol, bisphenol A [2,2-bis (4-
Hydroxyphenyl) propane], bisphenol F
(4,4'-dihydroxydiphenylmethane), α-naphthol, β-naphthol, β-hydroxyanthracene and resorcinol, catechol, bisphenol A, bisphenol F, and other phenolic compound purification residues, and mixtures thereof, etc. Phenols, alkylphenols and mixtures thereof are typically used.

Suitable aldehydes are, for example, formaldehydes such as formalin, paraformaldehyde, polyoxymethylene, trioxane and tetraoxane, glyoxal and mixtures thereof, but formalin, paraformaldehyde and mixtures thereof are generally preferred. used.

The alkanolamines and alkylamines are aliphatic primary or secondary monoamines having one or two alkanol groups or alkyl groups bonded to the nitrogen atom. Examples of such alkanolamines include monoethanolamine, methylethanolamine, ethylethanolamine, isopropanolamine, methylisopropanolamine, ethylisopropanolamine, monoalkanolamines such as methyl-2-hydroxybutylamine, diethanolamine, ethanolisopropanolamine, Examples include dialkanolamines such as diisopropanolamine, ethanol-2-hydroxybutylamine, isopropanol-2-hydroxybutylamine, and mixtures thereof. Of these, dialkanolamines, especially diethanolamines, are particularly preferred because they have a large effect of imparting a high degree of reactivity to Mannich polyols.

On the other hand, examples of the alkylamine include monoalkylamines such as methylamine, ethylamine, propylamine, butylamine and pentylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, dipentylamine, methylethylamine,
Examples include dialkylamines such as methylpropylamine and methylbutylamine, and mixtures thereof. Of these, dialkylamines, especially diethylamine, are particularly preferable in terms of the effect of reducing the viscosity of Mannich-based polyols.

Regarding the use ratio of each raw material in the above method, alkanolamine and alkylamine are used in a molar ratio of 1: 0.3 to 1: 2.4.
When the amount of alkylamine used is less than the above range,
The resulting Mannich-type polyol may not exhibit the effect of lowering the viscosity and the effect of suppressing the change with time of viscosity sufficiently, and if it is more than the above range, the foam characteristics will deteriorate when used in the production of a polyurethane-based foam, which is not preferable. . Considering the viscosity-lowering effect of Mannich-based polyols, the effect of suppressing viscosity change over time, and foam characteristics,
A particularly preferred ratio of the alkanolamine and the alkylamine used is in the range of 1: 0.5 to 1: 1.5 by molar ratio.

The amount of the monoamine mixture used is
It is in the range of 1.0 to 2.0 mol per mol of phenols. If the amount of this monoamine mixture used is less than 1.0 mol, the resulting foam will become brittle when reacted with polyisocyanate, and if it exceeds 2.0 mol, uniform mixing with polyisocyanate will be poor and good quality will be obtained. I can't get the form. On the other hand, the amount of the aldehyde used is substantially stoichiometric with respect to the monoamine mixture in order to prevent the viscosity from increasing and the viscosity changing with time due to a complicated reaction due to the residual aldehyde.

There are no particular restrictions on the reaction system in the above method, but it is advantageous to use the reaction system shown below. First, required amounts of phenols and alkanolamine are mixed, and aldehydes are added to the mixture while stirring, while controlling the heat generation, preferably at a temperature of 40 ° C. or lower. As a method of addition at this time, continuous dropping or divided addition is advantageous. After the addition of the aldehydes is completed, it varies depending on the type of raw material and the ratio of use, but generally 40 to 1
After continuing the reaction for about 0.5 to 5 hours at a temperature of 00 ° C, preferably 50 to 80 ° C, 25 to 3
Cool to about 5 ° C. Then, while stirring the reaction solution, a required amount of alkylamine is added thereto, and the remaining aldehydes are added in the same manner as described above to carry out the reaction. After completion of the reaction, the reaction mixture is heated and concentrated under reduced pressure, preferably at a temperature of 130 ° C. or lower, until the water content thereof is preferably 1% by weight or lower, more preferably 0.5% by weight or lower, The desired Mannich-based polyol is obtained. In the above method, the order of adding the alkanolamine and the alkylamine may be reversed.

As another method, for example, a method in which an aldehyde is added to a mixture of phenols, an alkanolamine and an alkylamine by the above-mentioned method to react, and phenols, aldehydes, an alkanolamine and an alkylamine are simultaneously charged. To react with,
Examples include a method of previously reacting an alkanolamine and an alkylamine with an aldehyde and then reacting with a phenol.

The Mannich-based polyol thus obtained has a low viscosity, a small change in viscosity over time, a good reactivity with isocyanate, and a base-catalyzed reaction accelerating ability (autocatalytic ability) such as epoxy. It has the property of promoting the ring-opening reaction of resins and the addition reaction of polyols and polyisocyanates. Therefore, the reaction injection molding method,
It is extremely useful as a polyol for the production of polyurethane-based molded articles and polyurethane-based foams by the in-situ foaming method, injection foaming method, etc., or as a curing agent for epoxy resins.

This Mannich type polyol or the one to which a conventionally commonly used polyol is added, if necessary, has excellent mixability based on low viscosity and excellent workability and formability based on high reactivity and autocatalytic activity. Therefore, it is suitably used as the polyol component of the polyurethane foam by the in-situ foaming method or the injection foaming method in which such properties are important.

Examples of the polyether polyols among the conventionally used polyols are polyhydric alcohols such as ethylene glycol, propylene glycol, glycerin, trimethylolpropane, sorbitol and sucrose, monoethanolamine, diethanolamine,
Ethylenediamine, diethylenetriamine, aniline,
Examples thereof include polyether polyols obtained by reacting two or more active hydrogen-containing compounds such as amines such as phenylenediamine, xylylenediamine, and tolylenediamine with alkylene oxide (eg, ethylene oxide, propylene oxide, butylene oxide). .
Examples of polyester polyols include polyhydric alcohols such as succinic acid, adipic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, trimellitic acid,
Examples thereof include polyester polyols obtained by reacting a polycarboxylic acid such as dimer acid and lactone-based polyester polyols obtained by ring-opening polymerization of lactones.

As the phenol resin, a benzyl ether type phenol resin, an alkylene oxide, a cyclic carbonic acid ester (eg ethylene carbonate,
Modified benzyl ether type phenols obtained by reacting or mixing arbitrary modifying compounds such as propylene carbonate), epoxy compounds such as epoxy resins, nitrogen-containing compounds such as urea resins, melamine resins, polyamide resins, xylene resins, etc. Resins are preferred. In some cases, a resol-type phenol resin, a phenol resin in which a methylol group or a dimethylene ether group is introduced into a novolac-type phenol resin, a novolac-type phenol resin, and a modified phenol resin obtained by subjecting these resins to the modification treatment. Can be used alone or in combination with the benzyl ether type phenol resin.

The polyisocyanate to be reacted with the Mannich-type polyol obtained by the above method is an organic isocyanate compound having two or more isocyanate groups in the molecule, and examples thereof include diphenylmethane diisocyanate, triphenylmethane triisocyanate and polymethylene polyisocyanate. Phenyl isocyanate (common name, crude MDI), tolylene diisocyanate (common name, TD)
I), mixed TDI, aromatic polyisocyanates such as xylylene diisocyanate, and urethane-modified polyisocyanate prepolymers obtained by reacting these aromatic polyisocyanates with polyols.
Further, if necessary, isophorone diisocyanate, alicyclic polyisocyanate such as hydrogenated methylene diphenyl diisocyanate, aliphatic polyisocyanate such as hexamethylene diisocyanate, isocyanurate modification,
A modified polyisocyanate such as buret-modified or carbodiimide-modified polyisocyanate is used. The amount of these polyisocyanates used varies depending on the type of the foam (urethane type, urethane nurate type, nurate type), physical properties and applications, but generally, the isocyanate group (NCO group) of the polyisocyanate and the hydroxyl group (OH) of the polyol are used. The equivalent ratio of (group) (NCO group / OH group, hereinafter referred to as NCO index) is selected in the range of 0.5 to 5.0.

As a foaming agent for forming a foam, dichlorofluoroethane (alternative CFC H) is usually used.
CFC-141b), dichloropentafluoropropane (alternative Freon HCFC-225), trifluoroethane, tetrafluoroethane, pentafluoropropane,
Halogenated hydrocarbons such as perfluorohexane, perfluoropentane and methylene chloride, aliphatic hydrocarbons such as pentane and hexane, reactive blowing agents utilizing the reaction of polyisocyanate with hydrogen peroxide and water, amines Decomposition type foaming agents such as carbon dioxide adducts and combinations thereof are used, but if necessary, aliphatic ethers such as diethyl ether and diisopropyl ether, paratoluenesulfonyl hydrazide, oxybisbenzenesulfonyl hydrazide, azobis. Pyrolysis type foaming agents such as isobutyronitrile, gas bodies such as air, nitrogen, carbon dioxide and butane are also used. The amount of foaming agent used varies depending on the foam density, type of foaming agent, etc.
Generally, it is selected in the range of 0.5 to 50 parts by weight per 100 parts by weight of polyol.

As the foam stabilizer, a nonionic surfactant is preferably used, but in some cases, another surfactant such as an anionic surfactant is used alone or in combination with a nonionic surfactant. Used. Examples of the nonionic surfactant include polysiloxane oxyalkylene copolymer, polyoxyethylene sorbitan fatty acid ester, castor oil ethylene oxide adduct, alkylphenol ethylene oxide adduct, lauryl fatty acid ethylene oxide adduct, lauryl alcohol ethylene oxide adduct and these. And the like. The amount of the foam stabilizer used is usually selected in the range of 0.3 to 10 parts by weight per 100 parts by weight of the polyol.

Further, as an additive component used as necessary, for example, tertiary amine, dibutyltin dilaurate, ethylmorpholine, triethylenediamine, tetramethylhexamethylenediamine, hydroxyalkyl quaternary ammonium salt, lead naphthenate, octyl. Curing catalysts such as potassium acid, sodium acetate, hexahydrotriazine, γ-aminopropyltriethoxysilane, γ-
Silane coupling agents such as glycidoxypropyltrimethoxysilane, curing accelerators such as resorcin, urea,
Formaldehyde scavengers such as melamine, bubble refiners such as trimethylmethoxysilane, melamine compounds,
Examples thereof include phosphorus-containing compounds, halogen-containing compounds, flame retardants such as aluminum hydroxide, and further plasticizers, antioxidants, fungicides, colorants, fillers, reinforcing base materials and the like.

[0026]

EXAMPLES The present invention will now be described in more detail with reference to examples, but the present invention is not limited to these examples.

Example 1 1222 g of phenol and 819 g of diethanolamine were placed in a reaction vessel equipped with a thermometer, an agitator and a reflux condenser.
498g of 47% by weight formalin under stirring
Was added dropwise while controlling the heat generation so as not to exceed 40 ° C.
After the dropping was completed, the temperature was raised to 60 ° C, the reaction was carried out at the same temperature for 1 hour, and then the temperature was cooled to 30 ° C. Continue to diethylamine 38
After adding 0 g and dropping 332 g of 47 wt% formalin by the same operation as above, the reaction was carried out at 60 ° C for 1 hour and then cooled to 40 ° C. Then, the pressure in the reaction system is reduced to about 20 to 60 mmHg under stirring, and 100
Mannich-based polyol A was prepared by heating and condensing to ° C. The Mannich polyol A thus obtained had a water content (Karl Fischer method) of 0.4% by weight and a hydroxyl value (J
IS K0070) is 500 mgKOH / g, cone plate viscometer CV-1S (trade name, manufactured by Toa Kogyo Co., Ltd., viscosity is cone type rotor No. 5 starts rotation at 94 rpm 30
It is a value calculated by multiplying the display value after seconds by 8) 84.5 poise / 30 ° C., the viscosity after standing at 45 ° C. for 3 days is 46.0 poise / 30 ° C., The change in viscosity with time was slight. In addition, the maximum amount (by weight) of the CFC substitute foaming agent HCFC141b in the Mannich-based polyol was 44%.

100 parts by weight of the Mannich-type polyol A thus obtained, 2 parts by weight of a silicone-based nonionic surfactant as a foam stabilizer, and an alternative CFC HCF as a foaming agent
40 parts by weight of C-141b and 10 parts by weight of a phosphorus-based flame retardant were mixed to prepare a polyol composition having a viscosity of 4.4 poise / 20 ° C. 33.1 g of this polyol composition
After weighing 26.9 g of crude MDI (manufactured by Mitsui Toatsu Chemicals, Inc., trade name: Cosmonate M100, NCO content 31% by weight) whose temperature was adjusted to 20 ° C. as a polyisocyanate in a paper cup (capacity 500 cc), High-speed stirring and mixing with a homodisper (trade name, manufactured by Tokushu Kika Kogyo Co., Ltd.) to prepare a foamable composition, which is foamed and cured to a density of 24.7 kg /
A polyurethane foam of m ³ (JIS A9511) was produced. Mixing of the polyisocyanate and the polyol composition was carried out with an NCO index of 1.05, and the miscibility of both components was judged from the state of the foam obtained, and the admixability was good. Further, the reactivity of the foamable composition is such that the cream time (CT) is 2 seconds and the gel time (G) is
T) was 4 seconds, tack free time (TFT) was 6 seconds, and rise time (RT) was 23 seconds.

Here, CT is the time from the start of mixing of the polyisocyanate and the polyol composition to the start of foaming, and GT is the time from the start of mixing of the above components to the tackiness of the surface of the foam that enables stringing. , TFT is the time from the start of mixing the above components until the surface tackiness of the foam disappears, and RT is the time from the start of mixing the above components to the end of foaming. In addition, the surface hardness of the foam (J
IS K6911, Bacol hardness meter 934-1 type used)
Was 15 after 30 seconds and 25 after 60 seconds from the start of mixing the components. The presence or absence of brittleness of the foam was confirmed by touch. Regarding shrinkage of the foam, after foaming and curing in the cup was left for 24 hours at an ambient temperature of 25 ° C, the upper edge of the cup was sliced into rings and the presence or absence of foam shrinkage from the peripheral edge of the cup was visually observed. confirmed. The results are shown in Table 1.

Comparative Example 1 1000 g of phenol was placed in the same reaction vessel as described in Example 1.
Then, 1117 g of diethanolamine was charged, and 679 g of 47% by weight formalin was added dropwise under stirring while controlling the heat generation so as not to exceed 40 ° C. After completion of the dropping, the temperature was raised to 60 ° C, the reaction was carried out at the same temperature for 1 hour, and then the temperature was cooled to 40 ° C. Then, the inside of the reaction system is stirred for 20 to 60 mmH.
A Mannich-type polyol B was prepared by reducing the pressure to about g and heating and concentrating it to 90 ° C. The Mannich polyol B thus obtained had a water content of 0.5% by weight, a hydroxyl value of 800 mgKOH / g, an initial viscosity of 112 poise / 30 ° C., and a viscosity after standing at 45 ° C. for 3 days of 375 poise / 30 ° C. The change in viscosity with time was large. Further, the maximum amount of dissolution (weight basis) of the foaming agent HCFC141b was 5% or less.

2 parts by weight of the silicone-based nonionic surfactant used in Example 1, 10 parts by weight of a phosphorus-based flame retardant and 100 parts by weight of the Mannich-based polyol B thus obtained, a blowing agent HCFC- Although 141 b was added and mixed at a ratio of 40 parts by weight, a uniform polyol composition could not be obtained, such as showing a white turbid state and causing phase separation when left standing, and a polyurethane foam could not be manufactured. The results are shown in Table 2.

Examples 2 to 4 and Comparative Examples 2 to 4 The same as Example 1 except that the 47 wt% formalin amount, diethanolamine amount and diethylamine amount were changed as shown in Tables 1 and 2. To produce Mannich-based polyols (A _{1 to} A ₃ and B _{1 to} B ₃ ). According to the method described in Example 1, the Mannich-based polyol has a hydroxyl value, a water content, a viscosity (initial and after aging),
The maximum dissolution amount of the blowing agent HCFC141b, the viscosity of the polyol composition, the miscibility of the polyol composition with the polyisocyanate, the reactivity of the foamable composition, and the characteristics of the polyurethane foam obtained using the same (density, surface hardness, brittleness) , Shrinkage) was measured and evaluated. These results are shown in Table 1 or Table 2.
Shown in.

[0033]

[Table 1]

[0034]

[Table 2]

Example 5 60 parts by weight of the Mannich-type polyol A ₁ obtained in Example 2 and 60 parts by weight of the phthalic acid-type polyester polyol and 1 part of the silicone-type nonionic surfactant used in Example 1 were used.
Parts by weight, 20 parts by weight of phosphorus flame retardant and HCFC blowing agent
45 parts by weight of -141b and an amine-based curing catalyst were mixed at a ratio of 3 parts by weight to prepare a polyol composition having a viscosity of 1.8 poise / 30 ° C. 30 g of this polyol composition and crude MDI30 used in Example 1 adjusted to 20 ° C.
g was weighed in a paper cup (capacity: 500 cc) and mixed by high speed stirring with a homodisper to prepare a foamable composition, which was foamed and cured to produce a polyurethane foam having a density of 24.8 kg / m ³ . When the polyisocyanate and the polyol composition were mixed with an NCO index of 1.60, the mixing properties of both components were good. Further, the reactivity of the foamable composition measured by the method described in Example 1 is CT2.
Seconds, GT 3 seconds, TFT 4 seconds, RT 15 seconds, and the surface hardness of the foam was 22 after 30 seconds and 38 after 60 seconds. Furthermore, the ambient temperature for foam shrinkage is 25 ° C.
And 5 ° C., no shrinkage was observed at any temperature. Further, the brittleness of the foam was not recognized. The results are shown in Table 3.

Example 6 and Comparative Example 5 Example 6 is the same as Example 5 except that the combination of Mannich polyol A ₁ and other polyols and the compounding ratio thereof and the amount of amine curing catalyst are changed as shown in Table 3. A foamable composition was prepared in the same manner as in No. 5, and was foamed and cured to produce a polyurethane-based foam having a density of 24.1 kg / m ³ . Further, the mixing property of the polyol composition and the polyisocyanate, the reactivity of the foamable composition and the foam property [surface hardness, brittleness, shrinkage (25 ° C. and 5 ° C.)] were measured and evaluated by the method described in Example 1. went. The results are shown in Table 3.

[0037]

[Table 3]

[0038]

INDUSTRIAL APPLICABILITY According to the present invention, a Mannich-based polyol and a blowing agent HC which are obtained by using an alkanolamine and an alkylamine in combination and have a low viscosity and a small viscosity change with time.
Since Mannich-based polyols with improved compatibility with FC141b have low viscosity, high reactivity, and autocatalytic activity, on-site foaming in which the workability is most important as the polyol component of the foamable composition It is possible to provide a polyurethane-based foam that can be suitably applied to a foam molding method such as injection foaming, and that does not shrink, particularly at low temperatures, and is not brittle.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Koji Tani             No.26 Niitsu, Nanfu, Fuso, Niwa-gun, Aichi             Local 4 Asahi Organic Materials Co., Ltd. Aichi factory (72) Inventor Isao Kai             No.26 Niitsu, Nanfu, Fuso, Niwa-gun, Aichi             Local 4 Asahi Organic Materials Co., Ltd. Aichi factory F term (reference) 4J034 CA04 CB03 CB07 CC12 CC62                       CC65 CD01 CD04 HA01 HA07                       HA08 HC12 HC61 HC64 HC67                       HC71 HC73 NA01 NA02 NA03                       NA05 NA06 NA07 NA08

Claims (3)

[Claims] 1. At least one selected from phenols, aldehydes, and primary and secondary monoamines consisting of alkanolamines and alkylamines in an amount of 1.0 to 2.0 mol per mol of phenols. A Mannich-based polyol obtained by reacting one type of monoamine having a molar ratio of alkanolamine and alkylamine of 1: 0.3 to 1: 2.4 with a polyol added, if necessary. A foamable composition for polyurethane foam, which is obtained by mixing the above polyol component with a polyisocyanate, a foaming agent, a foam stabilizer and an additive component used as necessary. 2. The foamable composition according to claim 1, wherein the alkanolamine is diethanolamine and the alkylamine is diethylamine. 3. A polyurethane foam obtained by foaming and curing the foamable composition according to claim 1.