Polyol and rigid polyurethane foam

Abstract

The present invention relates to a polyol, polyurethane resin, rigid polyurethane foam, preparation process thereof and a preparation process of a rigid polyurethane foam composite. The polyol comprises an epoxy resin based polyol, which may be combined with a phenol resin based polyol component and/or an aromatic amine based polyol component. The polyurethane resin, foam and composite using the polyol as a raw material has resistance to dissolution in a hydrochlorofluorocarbon and a hydrofluorocarbon which are foaming agents having very low public environmental hazards and can be used as a thermal insulation material or a thermal insulation structure for refrigerators, freezers, insulation panels, ships and vehicles.

Description

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a polyol, polyurethane resin, rigid polyurethane foam, preparation process thereof and a preparation process of a rigid polyurethane foam composite.

More particularly the polyol mixture of the present invention comprising an epoxy resin based polyol and a polyol component initiated with a single compound or a mixture thereof selected from phenol resin, aliphatic polyhydroxy compound, alkanolamine and aromatic amine is a raw material for preparing polyurethane resin having resistance to dissolution in hydrochlorofluorocarbons (hereinafter abbreviated as HCFC) and hydrofluorocarbons (hereinafter abbreviated as HFC) which are foaming agents causing very low public hazards. The polyol can provide rigid polyurethane foam and its composites thereof by using the above foaming agents.

The rigid polyurethane foam among them obtained above has excellent properties equivalent to those of conventional polyurethane foams obtained by the use of chlorofluorocarbons (hereinafter abbreviated as CFC) as foaming agents. Hence, the rigid polyurethane foam of the present invention is extremely useful for insulating materials or insulating structural materials of electric refrigerators, freezing warehouses, insulation panels, ships and vehicles.

2. Description of the Prior Art

In the present manufacturing process of polyurethane foams, CFC such as CFC-11 (trichlorofluoromethane) and CFC-12 (dichlorodifluoromethane) are generally used as foaming agents. These compounds have recently been recognized as materials causing environmental destruction such as disruption of the ozone layer or enhancement of the greenhouse effect. Accordingly, restriction has recently been imposed upon the manufacture and use of these compounds.

At the same time, HCFC such as HCFC-123 (2,2-dichloro-1,1,1-trifuluoroethane), HCFC-141b (1,1-dichloro-1-fluoroethane) HCFC-142b(1-chloro-1,1-difluoroethane), HCFC-22(1-chloro-1,1-difluoromethane) and additionally HFC such as HFC-134a (1,1,1,2-tetrafluoroethane) and HFC-152a (1,1-difluoroethane) which cause much less environmental destruction have been focused on as substitutes for CFC-11 and CFC-12 and the like. However, it was found that HCFC and HFC have higher dissolving powers for rigid polyurethane resins as compared with CFC, and hence have disadvantages of severely deteriorating the properties of the resulting rigid polyurethane foams, for example, reduction of closed cell content and foam strengths. Particularly it has been confirmed by the present inventors that in the manufacture of rigid polyurethane foams, HCFC and HFC dissolve the cell walls of closed cells in the course of foaming and drastically lower the heat insulation effect which is a characteristic property of rigid polyurethane foams.

Consequently, a novel polyurethane resin has been desired. The conventional polyoxyalkylene polyol (hereinafter abbreviated as polyol) used as the raw material for polyurethane resins decreases viscosity according to an increase in the amount of alkylene oxide added. As a result, operations in polyurethane resin production can be conducted with ease. However, excess addition of alkylene oxide leads to dissolution of polyurethane resin in HCFC and HFC, and tends to made application of these foaming agents substantially impossible. On the other hand, when the amount of alkylene oxide added is reduced, the polyol becomes solid or extremely viscous and solubility of polyol in other raw materials becomes poor. Thus the polyol is very difficult to handle.

As mentioned above, in order to maintain resistance to dissolution in HCFC and HCF, the operational efficiency in the rigid polyurethane foam production must be greatly sacrificed. Polyol which has a viscosity suitable for the foaming operation, good resistance to dissolution in HCFC and HFC and which is excellent in the mixing and dispersing ability in HCFC and HFC has never been found.

Tokkai-Sho 50-6698 (1975) has disclosed polyurethane foam which has good resistance to high temperatures using epoxy resin, polyol having hydroxyl value of from 300 to 550 mgKOH/g and CFC as the foaming agent.

Tokkai-Sho 63-139908 (1988) has disclosed an epoxy resin modified polyol having a molecular weight of from 2000 to 7000 and a flexible polyurethane foam for packing using CFC and low boiling point hydrocarbon as the foaming agent.

Tokkai-Hei 2-86613 (1990) has disclosed a flexible polyurethane foam using modified polyol obtained by reacting epoxy resin with polyamine or dialkanolamine in a polyol, which is subsequently reacted with organic polyisocyanate.

SUMMARY OF THE INVENTION

The present invention relates to a polyol, polyurethane resin, rigid polyurethane foam, preparation process thereof and a preparation process of a rigid polyurethane foam composite.

The polyol used in the present invention comprises an epoxy resin based polyol, which may be combined with a phenol resin based polyol component and/or aromatic amine based polyol component.

The above polyurethane resin, foam and composite using the above polyol as a raw material has resistance to dissolution in a hydrochlorofluorocarbon and a hydrofluorocarbon which are foaming agents having very low public environmental hazards.

The above-mentioned foam products have excellent physical properties equivalent to those of conventional polyurethane foams obtained by using chlorofluorocarbons, and hence are very useful as a thermal insulation material or a thermal insulation structure for refrigerators, freezers, insulation panels, ships and vehicles.

DETAILED DESCRIPTION OF THE INVENTION

The primary object of the present invention is to provide a polyol which gives equivalent operation efficiency in polyurethane foaming operations, particularly in the production of a rigid polyurethane foam, and equivalent foam properties compared with conventional CFC, even though HCFC and/or HFC having very low public environmental hazards are used.

As a result of an intensive investigation in order to achieve the above object, the present inventors have completed the present invention.

That is, the aspect of the present invention is illustrated by the following (1) to (6).

(1) A polyol (A) comprising polyol component (a) and polyol component (b); said polyol component (a) having a number average molecular weight of from 500 to 1800 and an average functionality of from 4 to 12 and being obtained by the addition of an alkylene oxide to a polymer (g2) resulting from the reaction of an active hydrogen containing compound(g) or an alkylene oxide adduct thereof(g1) with an epoxy resin represented by the formula (I): ##STR1## wherein R.sub.1 is a hydrogen atom, alkyl having from 1 to 9 carbon atoms, chlorine, bromine, fluorine or a hydroxy, m is an integer of from 1 to 3, R.sub.2 is a glycidyloxy or a glycidylamino, n is an integer of from 0 to 4, X and Y may be the same or different, and are a divalent group selected from the group consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and sulfonyl, or may be a combination of the above-mentioned groups; said polyol component (b) being obtained by the addition of an alkylene oxide to an active hydrogen containing compound(j),

(2) A polyol (D) comprising the polyol (A) described in (1) and phenol resin based polyol component (B) and/or aromatic amine based polyol component (C).

(3) A polyurethane resin obtained by the reaction of a polyol with an organic polyisocyanate comprising using the polyol (A) or polyol (D) described in (1) or (2).

(4) A rigid polyurethane foam obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst, cell regulator and, where necessary, other additives, said polyol comprising the polyol (A) or polyol (D) described in (1) or (2), said foaming agent comprising one or more compounds selected from a hydrochlorofluorocarbon and a hydrofluorocarbon and additionally an auxiliary foaming agent, if necessary.

(5) A preparation process for the rigid polyurethane foam described in (4).

(6) A preparation process for a rigid polyurethane foam composite by reacting an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst, cell regulator and, where necessary, other additives to form a rigid polyurethane foam on a facing material or in a cavity surrounded by a plurality of facing material, comprising using the polyol (A) or polyol (D) described in (1) or (2) and one or more of the foaming agents selected from the group consisting of a hydrochlorofluorocarbon and a hydrofluorocarbon and additionally an auxiliary foaming agent, if necessary.

Polyol (A) of the invention is mixture of polyol components (a) and (b). Polyol component (a) is initiated from polymer (g2) which is obtained by reacting the epoxy resin of the following formula (I) with a below described active hydrogen containing component (g) or an alkylene oxide adduct thereof (g1). An alkylene oxide is added to the polymer (g2) to obtain polyol component (a). Separately an alkylene oxide is added to a hydrogen containing compound (j) to obtain polyol component (b). The active hydrogen containing compounds (g) and (j) may be the same or different. The polyol components (a) and (b) thus obtained are then mixed to prepare polyol (A).

The epoxy resin used for the raw material of the epoxy resin base polyol (A) of the present invention is a compound represented by the formula (I): ##STR2## wherein R.sub.1 is a hydrogen atom, alkyl having from 1 to 9, chlorine, bromine, fluorine or a hydroxy, m is an integer of from 1 to 3, R, is a glycidyloxy or a glycidylamino; n is an integer of from 0 to 4, and X and Y may be the same or different and are a divalent group selected from the group consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and sulfonyl, or may be a combination of the above-mentioned groups; said polyol component (b) being obtained by the addition of an alkylene oxide to an active hydrogen containing compound (j) which may be the same as or different from polyol(g).

The epoxy resin can be obtained, for example, by reacting epichlorohydrin with phenol derivatives such as bis(hydroxyphenyl)propane, bis(hydroxytolyl)propane, bis(ethylhydroxyphenyl)propane, bis(propylhydroxyphenyl)propane, bis(isopropylhydroxyphenyl)propane, bis(butylhydroxyphenyl)propane, bis(pentylhydroxyphenyl)propane, bis(chlorohydroxyphenyl)propane, bis(hydroxyphenyl)methane, bis(hydroxyphenyl)ethane, bis(hydroxyphenyl)propane, bis(hydroxyphenyl)butane, bis(hydroxyphenyl)pentane, bis(hydroxyphenyl)hexane, bis(hydroxyphenyl)heptane, bis(hydroxyphenyl)octane, bis(hydroxyphenyl)nonane, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)sulfone, and novolak resin.

Particularly, bis(hydroxyphenyl)propane, bis(hydroxyphenyl)methane, bis(chlorohydroxyphenyl)propane, and novolak resin are preferable.

Other epoxy resins having glycidylamino groups can be obtained by reacting epichlorohydrin with the following compounds, for example, diphenylmethanediamine, bis(aminochlorophenyl)methane, polymethylenepolyphenylpolyamine, polyphenylpolyxylylenepolyamine, tolylenediamine, phenylenediamine, propylphenylenediamine, isopropylphenylenediamine butylphenylenediamine, aminophenol, diaminophenol, triaminophenol, aminohydroquinone, diaminohydroquinone, triaminohydroquinone, 2,2-(4-aminophenyl-4'-hydroxyphenyl) propane, tetraglycidyldiaminodiphenylmethane. Particularly desirable compounds among them are aminophenol, diphenylmethanediamine, tolylenediamine, phenylenediamine.

The alkylene oxide for use in the invention includes ethylene oxide, proxylene oxide and butylene oxide. These alkylene oxides may be used as a mixture.

Polymer (g2) which is the starting material of polyol component (a) can be obtained by reacting one equivalent of epoxy resin with 0.5 to 2.0 moles of aliphatic polyhydroxy compounds such as glycols polyhydric alcohols and polysaccharides having a functionality of 2 to 8, active hydrogen containing compounds (g) such as alkanolamine, or adducts thereof (g1) obtained by adding 3 moles or less of an alkylene oxide to one equivalent of the active hydrogen containing compounds (g)

When the above epoxy resin contains less than 2 epoxy groups in a molecule, the average functionality of the polymer (g2) is too small and reduces the strength of the resulting foam. An epoxy resin containing more than 6 epoxy groups has an increased functionality. However, the viscosity of the polymer (g2) increases and impairs operation efficiency.

The alkylene oxide addition number to the active hydrogen containing compound (g) is less than 3 moles per equivalent of active hydrogen. Alkylene oxide addition exceeding 3 moles reduces viscosity of the polymer (g2), but impairs physical properties of the foam.

Polyol component (a) for use in the invention can be prepared by the addition of from 0.5 to 3.0 moles of an alkylene oxide to 1 equivalent of active hydrogen in the above polymer (g2). It is preferable that polyol component (a) has a number average molecular weight (hereinafter abbreviated as Mn) of from 500 to 1800 and an average functionality of from 4 to 12. Alkylene oxide addition less than 0.5 mole causes unfavorable reduction in the properties of the resulting polyurethane foam. On, the other hand, when the alkylene oxide is added in an amount of more than 3 moles, the resulting polyurethane foam lowers resistance to dissolution in HCFC or HFC and has inferior physical properties of foam, although viscosity is reduced and dispersibility in HCFC and HFC is improved.

A number average molecular weight (Mn) less than 500 leads to too high a viscosity of polyol component (a). A number average molecular weight exceeding 1800 causes lowering of foam strengths. An average functionality less than 4 results in reduction of foam strengths. An average functionality exceeding 12 causes too high a viscosity of polyol component (a).

Any kind of active hydrogen containing compound which is commonly used for preparing a polyol as a raw material for polyurethane can be used. An aliphatic polyhydroxy compound or alkanolamine is preferred.

The aliphatic polyhydroxy compound used for the present invention is a single compound or a mixture of two more compounds selected from the group consisting of glycols polyhydric alcohols and polysaccharides having 2 to 8 a functionality of 2 to 8. Exemplary aliphatic polyhydroxy compounds include glycols such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, cyclohexane dimethanol and cyclohexane tetramethanol; polyhydric alcohols such as glycerol, trimethylolethane, trimethylolpropane, and pentaerythritol; and polysaccharides such as methylglucoside, sorbitol, mannitol, dulcitol and sucrose.

The alkanolamine for use in the present invention is represented by the formula (II):

NR.sub.3 R.sub.3 R.sub.4 (II) wherein R.sub.3 and R.sub.4 are individually a hydrogen atom, hydroxyethyl or hydroxyisopropyl, (they may be the same or different) excluding the case wherein both R.sub.3 and R.sub.4 are hydrogen atoms. Exemplary alkanolamines include monoethanolamine, diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine and triisopropanolamine.

Polyol component (b) used in the epoxy resin base polyol (A) of the invention is obtained by the addition of from 0.5 to 3.0 moles of an alkylene oxide to 1 equivalent of active hydrogen in the active hydrogen containing compounds (j) including polyhydroxy compounds such as the above glycols, polyhydric alcohols and polysaccharides and alkanolamines. Here, compounds (j) and afore-mentioned compound (g) may be the same or different.

When the alkylene oxide addition is less than 0.5 mole per equivalent of the active hydrogen in said active hydrogen containing compound, the crosslinking activity of said active hydrogen containing compound remains and hence deteriorates the physical properties of the resulting polyurethane foam. The amount of the alkylene oxide exceeding 3.0 moles also decreases foam properties even in a polyol mixing ratio (a)/(b) of 4.0 by weight as described below. The resulting polyurethane foam cannot be practically used.

The above polyol components (a) and (b) are preferably mixed in a ratio (a)/(b) of from 0.1 to 4.0 by weight. A mixing ratio exceeding 4.0 causes high viscosity and poor dispersibility in HCFC and HFC and also leads to operational problems in the preparation of the polyurethane resin. On the other hand, the mixing ratio less than 0.1 is unsuitable because of inferior properties of the resulting polyurethane foams.

Another polyol (D) of the invention comprises the above polyol (A) and phenol resin polyol component (B) and/or, aromatic amine polyol component (C). The above polyol component (B) comprises polyol component (a1) obtained by the addition of alkylene oxide to the phenol resin represented by the formula (III) illustrated below and polyol component (b1) obtained by the addition of alkylene oxide to the above alkanolamine or polyol component (c1) obtained by the addition of alkylene oxide to the above aliphatic polyhydroxy compound. ##STR3## wherein R.sub.5 is a hydrogen atom, alkyl having from 1 to 9 carbon atoms, chlorine, bromine, fluorine or hydroxy, l is an integer of from 1 to 3, S is an integer of from 1 to 6, and V and W are the same or different divalent group selected from the group consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and sulfonyl, or may be a combination of the above-mentioned groups.

The phenol resin generally used in the preparation of polyol component (a1) which is one component constituting phenol resin initiated polyol component (B) has Mn of from 650 to 1400 and an average functionality of from 3 to 8, and includes, for example, reaction products of phenols such as phenol, cresol, ethylphenol, propylphenol, isopropylphenol, butylphenol, pentylphenol, hexylphenol, heptylphenol, octylphenol, nonylphenol, chlorophenol, dichlorophenol, resorcinol, hydroquinone, catechol, guaiacol, bis(hydroxyphenyl)propane, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)sulfone, with aldehydes such as aldehydes or .alpha.,.alpha.'-dimethoxyxylene, .alpha.,.alpha.'-dichloroxylene or sulfur. The reaction is carried out by known methods.

Preferred phenol resins include, for example, novolak resins having (Mn) of from 650 to 900 and an average functionality of from 3 to 8 in the formula (III), and a softening point of from 75.degree. to 115.degree. C.

When the molar amount of alkylene oxide addition to obtain polyol component (a1) is increased, resistance to dissolution) in HCFC and HFC is generally decreased.

When the (Mn) of the phenol resin is less than 650, the polyurethane resin derived from the phenol resin dissolves in HCFC and HFC, even though the molar addition is 1 mole per equivalent of hydroxyl group in the phenol resin. A (Mn) of the phenol resin exceeding 1400 leads to high viscosity in any mixing ratio, poor dispersibility in HCFC and HFC, inferior operational efficiency in the reaction, and complex handling procedures required for uniform admixture Of polyol containing alkanolamine initiated polyol component (b1) or aliphatic polyhydroxy compound initiated polyol component (c1) with an organic polyisocyanate. Resistance of the polyurethane resin to dissolution in HCFC or HFC is unfavorably poor.

The polyol component (a1) of the invention is obtained by the addition of 1.0 to 4.5 moles of alkylene oxide to 1 equivalent of the hydroxyl group in the phenol resin and has a hydroxyl value of 145 to 350 mgKOH/g. Alkylene oxide of less than 1.0 mole per equivalent of phenolic hydroxyl group, that is, an excess of remaining hydroxyl groups leads to unfavorable deterioration of physical properties in the resulting polyurethane foam. On the other hand, alkylene oxide addition exceeding 4.5 moles eliminates resistance of polyurethane resin to dissolution in HCFC or HFC, although viscosity is reduced and dispersibility in HCFC or HFC increases.

When the phenol resin has an average functionality of less than 3, the polyurethane resin prepared by reacting an organic polyisocyanate with a polyol containing alkanolamine initiated polyol component (b1) or aliphatic polyhydroxy compound initiated polyol component (c1) decreases resistance to dissolution in HCFC or HFC. On the other hand, an average functionality exceeding 8 leads to a disadvantage of rendering the polyurethane resin brittle.

The alkanolamine used for the polyol component (b1) of the invention is represented by the above formula (II).

The polyol component (b1) is obtained by the addition of 0.5 to 3.0 moles of alkylene oxide to 1 equivalent of active hydrogen in the alkanolamine and has a hydroxyl value of 240 to 800 mgKOH/g.

When the amount of alkylene oxides is less than 0.5 mole per equivalent of active hydrogen in alkanolamine, crosslinking activity of alkanolamine remains and hence deteriorates physical properties of resulting polyurethane foam. The amount of alkylene oxide exceeding 3.0 moles also decreases foam properties to render the foam impossible to use.

The mixing ratio (a1)/(b1) by weight, that is, the ratio of polyol component (a1) to that of (b1) in polyol component (B) is preferably 0.25 to 4.0. A mixing ratio exceeding 4.0 leads to a high viscosity and deterioration of dispersibility in HCFC and HFC, and causes unfavorable problems on operational efficiency in the preparation of the polyurethane resin.

The aliphatic polyhydroxy compound which is the starting material of polyol components (c1) is as described above.

Preferred polyol component (c1) has an alkylene oxide addition number Of 0.5 to 6.5 moles per equivalent of hydroxyl group in the aliphatic polyhydroxy compound and a hydroxyl value of 130 to 750 myKOH/g. An amount of less than 0.5 mole makes the polyurethane foam brittle. On the other hand, an amount exceeding 6.5 moles decreases resistance of the polyurethane resin to dissolution in HCFC or HFC.

A mixing ratio (a1)/(c1) by weight, that is, the ratio of phenol resin initiated polyol component (a1) to aliphatic polyhydroxy compound initiated polyol (c1) in polyol component (B) in the invention is preferably 0.1 to 4.0. A mixing ratio less than 0.1 decreases resistance to dissolution in HCFC and HFC of the polyurethane resin obtained in the presence of a catalyst. A mixing ratio exceeding 4.0 leads to too high a viscosity and hence results in the disadvantage of poor operational efficiency in preparing the polyurethane resin.

The aromatic amine used for a raw material of the aromatic amine based polyol component (C) is a compound represented by the formula (IV) or (V): ##STR4## wherein E is methylene, xylylene or ethylidene, R is a hydrogen atom, aliphatic hydrocarbon group having from 1 to 10 carbon atoms or alicyclic hydrocarbon group, and U is an integer of from 0 to 5, ##STR5## wherein R.sub.o is a hydrogen atom, chlorine, bromine, fluorine, aliphatic hydrocarbon group having from 1 to 10 carbon atoms or alicyclic hydrocarbon group, t is an integer of from 1 to 3, and p is an integer of from 0 to 2.

Exemplary aromatic amines include diphenylmethanediamine, bis(aminochlorophenyl)methane, polymethylenepolyphenylpolyamine, polyphenylpolyxylylenepolyamine, tolylenediamine, phenylenediamine, propylphenylenediamine, iso-propylphenylenediamine, butylphenylenediamine, pentylphenylenediamine, hexylphenylenediamine, heptylphenylenediamine, octylphenylenediamine, nonylphenylenediamine, cyclohexylphenylenediamine, aminophenol, diaminophenol, triaminophenol, aminohydroquinone, diaminohydroquinone, triaminohydroquinone.

Preferable compounds are diphenylmethanediamine, polymethylenepolyphenylpolyamine, polyphenylpolyxylylenepolyamine, tolylenediamine, aminophenol.

Polyol component (a2) of the invention is obtained by the addition of 1.0 to 9.0 moles of alkylene oxide to 1 equivalent of the active hydrogen in the above aromatic amine. The hydroxyl value of polyol (a2) is 50.about.600 mgKOH/g. Alkylene oxide of less than 1.0 mole, that is, an excess of remaining phenolic hydroxyl groups causes difficult control of the foaming reaction and unfavorable reduction of the physical properties in the resulting polyurethane foam. On the other hand, alkylene oxide addition exceeding 9.0 moles deteriorates physical properties of the resulting polyurethane foam, although viscosity is reduced and dispersibility in HCFC and HFC increases.

Polyol component (b1) used in the invention is obtained by the addition of 0.5 to 3.0 moles of alkylene oxide to 1equivalent of active hydrogen in the alkanolamine.

When the amount of alkylene oxide is less than 0.5 mole per equivalent of active hydrogen of alkanolamine, the crosslinking activity of the alkanolamine remains and hence deteriorates the physical properties of the resulting polyurethane foam.

When the amount of alkylene oxide is in excess of 3.0 moles, foam properties are decreased even though the mixing ratio of polyol components (a2) and (b1) in polyol component (C), namely the ratio (a2)/(b1) by weight (P.S) exceeds 4.0, and the resulting foam cannot be used.

Polyol component (a2) and (b1) of polyol component (C) used in the invention are preferably used in a mixing ratio (a2)/(b1) of 0.25 to 4.0 by weight. A mixing ratio exceeding 4.0 causes high viscosity and poor dispersiblity in HCFC and HFC and also leads to unfavorable operational problems on the preparation of the polyurethane resin. On the other hand, a mixing ratio less than 0.25 is unsuitable because of inferior properties of the resulting polyurethane foams.

The aliphatic polyhydroxy compound used as a starting material for polyol component (c1) in the present invention can be the afore-mentioned compound.

Preferred mole amounts of alkylene oxide addition are from 0.5 to 6.5 moles per equivalent of the hydroxyl in the aliphatic polyhydroxy compound. Alkylene oxide addition of less than 0.5 mole makes the resultant polyurethane foam brittle. On the other hand, an amount exceeding 6.5 moles lowers resistance to dissolution in HCFC and HFC of the polyurethane resin obtained.

The polyol components (a2) and (c1) which are initiated with the aromatic amine and the aliphatic polyhydroxy compound, respectively, are preferably mixed in the ratio (a2)/(c1) of 0.1 to 4.0 by weight. A mixing ratio less than 0.1 reduces resistance to dissolution in HCFC and HFC of the polyurethane resin prepared by reacting in the presence of a catalyst. On the other hand, a mixing ratio exceeding 4.0 leads to the disadvantage of poor operational efficiency due to too high a viscosity in the preparation of the polyurethane resin.

The mixing ratios of polyol component (B) and/or polyol component (C) which are mixed with polyol (A) used in the present invention, that is, the ratios (B)/(A), (C)/(A) or [(B)+(C)]/(A) are in the range of from 0.1 to 4.0 by weight. Polyol (D) of the invention which contains polyol (A) and additionally polyol component (B) and/or polyol component (C) in the above weight ratio provides heat conductivity of the resulting foam almost equal to that of polyol (A) alone. However, a weight ratio exceeding 4.0 increases heat conductivity. The addition of polyol component (B) and/or polyol component (C) to polyol (A) further improves the strength low temperature dimensional stability of the foam derived from polyol (A) alone. However, a weight ratio less than 0.1 has a small effect. Consequently, the above range of weight ratio is preferred.

The proportion between polyol component (B) and polyol component (C) in admixture with polyol (A) is (B)=100-(C) by weight. Since the effect of polyol component (B) and polyol component (C) on the foam property is similar, either one or both of the polyol components may be mixed in the above range of proportion by weight.

The catalysts which can be used in the alkylene oxide addition for the preparation of polyol components (a), (a1), (a2), (b), (b1), (c1) and (g1), i.e., polyol components for constituting polyol (A), polyol (B) and components (C) are an amine catalyst and an alkali metal hydroxide catalyst.

The amine catalyst is represented by the formula (VI) or the formula (VII):

NR.sub.6 R.sub.6 R.sub.7 (VI) R.sub.6 R.sub.7 N(CH.sub.2).sub.i NR.sub.6 R.sub.7 (VII) wherein R.sub.6 and R.sub.7 are a hydrogen atom or a group selected from a group consisting of alkyl group having from 1 to 6 carbon atoms, hydroxyethyl and hydroxyisopropyl, but R.sub.6 and R.sub.7 cannot be hydrogen atoms at the same time in the formula (VI), and i is an integer of from 1 to 6.

Exemplary amine compounds include dibutylamine, ethylenediamine, tetramethylenediamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, triethylamine, tri-n propylamine, di-n-propylamine, n-propylamine, n-amylamine, N,N-dimethylethanolamine, isobutylamine, isoamylamine and methyldiethylamine.

Alkali metal hydroxide can also be used as the catalyst for the above addition reaction. Representative examples of alkali metal hydroxide include lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide and barium hydroxide.

The above amine and alkali metal hydroxide catalysts can be used singly or in combination.

The amount of the above catalyst used for the invention is from 0.1 to 2.0 parts by weight per 100 parts by weight of the sum of the starting materials of polyol components (a), (a1), (a2), (b), (b1), (c1 ) or (g1).

In the case of using an alkali metal hydroxide catalyst, the reacted solution is neutralized by the acidic aqueous solution such as phosphoric acid aqueous solution.

In the preparation process for the polyol used in the invention, a single compound or a mixture thereof selected from phenol resin, aromatic amine, alkanolamine and aliphatic polyhydroxy compound is charged in an autoclave and used as a starting material. Epoxy resin is previously reacted with alkanolamine or aliphatic polyhydroxy compound and the reaction product is used as a starting material.

Then alkylene oxide is gradually fed to the autoclave to conduct a addition reaction. Preferred reaction temperature is 90.degree. to 130.degree. C. The temperature of lower than, 90.degree. C. results in a slow reaction. On the other hand, a temperature exceeding 130.degree. C. is liable to cause side reactions.

No particular restriction is imposed upon the organic polyisocyanate used in the process of the invention.

Conventionally known organic polyisocyanates, for example, aromatic, aliphatic and alicyclic polyisocyanates and their modified products can be used. Exemplary polyisocyanates which are suitable for use include phenylenediisocyanate, diphenylmethanediisocyanate, crude diphenylmethanediisocyanate, tolylenediisocyanate, crude tolylenediisocyanate, xylylenediisocyanate, hexamethylenediisocyanate, isophoronediisocyanate, hydrogenated di phenylmethanediisocyanate, hydrogenated tolylenediisocyanate, triphenylmethanetriisocyanate, tolylenetriisocyanate, polymethylenepolyphenylpolyisocyanate, modified polyisocyanates such as carbodiimide modified diphenylmethane diisocyanate, and isocyanate terminated prepolymers which can be obtained by reacting the above polyisocyanate with polyol or polymer polyol in a NCO/active hydrogen equivalent ratio of from 2 to 20 and have an isocyanate content of from 5 to 35% by weight.

These polyisocyanates can be used singly or in combination.

The equivalent ratio of the polyisocyanate to the hydroxyl group in the resin premix is in the range of from 0.8 to 5.0. An equivalent ratio exceeding 5.0 leads to unreacted polyisocyanate. On the other hand, an equivalent ratio less than 0.8 results in unreacted polyol. Hence the above range is preferable.

The foaming agent for use in the invention is HCFC or HFC.

Exemplary HCFC's include HCFC-123, HCFC-141b, HCFC-142b or HCFC-22. Exemplary HFC's include HFC-134a, or HFC-152a. These foaming agents can be used singly or in combination.

When necessary, water and/or low boiling point compound and other auxiliary foaming agents can be used in combination.

Water is usually used in an amount of from 0.5 to 5.0 parts by weight per 100 parts by weight of the resin premix. Exemplary low boiling point compound includes methylene chloride and other low boiling point hydrocarbons (boiling point is from 10.degree. to 50.degree. C.) and their mixtures. Conventional CFC can also be used in combination.

The catalyst which can be used for the preparation of the rigid polyurethane foam of the invention includes, for example, amine catalyst such as triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N,N-dimethylethanolamine, diethylenetriamine, N,N,N',N'-tetramethylethylenediamine, N,N,N',N'-tetramethylpropylenediamine, N,N,N',N'-tetramethylbutanediamine, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N,N',N'-tetramethylhexamethylenediamine, bis [2-(N,N-dimethylamino)ethyl] ether, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N,N',N",N"-pentamethyldiethylenetriamine, triethylenediamine, formic acid and other acid salts of triethylenediamine, oxyalkylene adducts of amino groups in primary and secondary amines, aza ring compounds such as N,N-dialkylpiperazines, and various N,N',N"-trialkylaminoalkylhexahydrotriazines such as .beta.-aminocarbonyl catalyst disclosed in Japanese Tokko-SHO 52-043517 (1977) and .beta.-aminonitrile catalysts disclosed in Japanese Tokko-SHO 53-014279 (1978); and organometallic urethane catalysts such as tin acetate, stannous octoate, stannous oleate, stannous laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate and cobalt naphthenate.

These catalysts can be used singly or in combination. The amount of the catalyst for use is in the range of from 0.0001 to 10.0 parts by weight per 100 parts of the polyol.

The cell regulator for use in the present invention is a conventionally known organic silicone surfactant. Exemplary cell regulators include products of Nippon Unicar Co., Ltd. which are L-520, L-540, L-5340, L-5410, L-5420, L-5710, and L-5720, products of Toray Silicone Co., Ltd. which are SH-190, SH-192, SH-193, SH-194, and SH-195, products of Shinetsu Silicone Co., Ltd. which are F-305, F-306, F-317, F-341 and F 345, and a product of Toshiba Silicone Co., Ltd. which is TFA 4200.

The amount of the cell regulator used is in the range of from 0.1 to 20 parts by weight per 100 parts by weight of the sum of the polyol and the organic polyisocyanate.

Flame retardants which can be used are tris(2-chloroethyl)-phosphate, tris(dichlopropyl)phosphate, tris(dibromopropyl)-phosphate, products of Daihachi Chemical Co., Ltd. which are CR-505 and CR-507, and a product of Akuzo Japan Co., Ltd. which is Fyrol-6.

Other additives usually employed in polyurethane, for example, plasticizers, fillers, stabilizers such as antioxidants, ultraviolet absorbers and colorants can also be added, if necessary.

In order to practice the present invention, the polyol, catalyst, cell regulator, flame retardant, foaming agent such as HCFC or HFC and other additives are mixed in a prescribed amount to form a premix.

Using a polyurethane dispensing machine, the resin premix is rapidly and continuously mixed with the organic polyisocyanate at a constant ratio so as to obtain a NCO/active hydrogen equivalent ratio of from 0.8 to 5.0.

The mixture obtained is successively poured into a cavity or a mold, or spread on a plate. After pouring or spreading, liquid raw material of the rigid polyurethane foam is foamed and cured in a several minutes.

The rigid polyurethane foam obtained in the present invention is used for heat insulation material or structural material for refrigerators, heat-insulating panels, ships and vehicles.

EXAMPLE

The present invention will hereinafter be illustrated further in detail by way of examples and comparative examples. [Polyol preparation] (Table 1-Table 4)

Polyol A-1 (Table 1)

To a 2 l autoclave, 374 g of bisphenol-A diglycidylether (Trademark; Epikote 828, a product of Yuka Shell Epoxy Co.) and 210 g of diethanolamine were charged. After replacing the atmosphere with nitrogen, 2.2 g of triethylamine was added and reacted at 100.degree. for 2 hours. After finishing the reaction, 174 g of propylene oxide was gradually added and reacted for 3 hours. After finishing the reaction, unreacted propylene oxide was removed from the reaction system. Polyol component (a-1) thus obtained was 758 g and had a hydroxyl value of 444 mgKOH/g.

To a 2 l autoclave, 745 g of triethanolamine was charged and the atmosphere was replaced by nitrogen. Then 435 g of propylene oxide was gradually charged at 120.degree. and reacted for 3 hours. Unreacted propylene oxide was removed from the reaction mixture to obtain polyol component (b-1) having a hydroxyl value of 713 mgKOH/g.

The propylene oxide addition number was 0.5 mole in both polyol component (a-1) and polyol component (b-1).

Polyol components (a-1) and (b-1) were mixed in a ratio (a-1)/(b-1)=1.0 by weight. Polyol (A-1) thus obtained had a hydroxyl value of 483 mgKOH/g, and a viscosity of 15700 cp/25.degree. C.

By the same procedure as described in the polyol A-1 preparation, various polyols were obtained. Preparation conditions and physical properties are indicated in Tables 1.about.4.

TABLE 1__________________________________________________________________________Polyol (A)__________________________________________________________________________ ExampleMixed polyol (mark) A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8Polyol component (a)Epoxy resin (g) 374 374 374 374 374 374 801 422(No.: indicated in Note) (1) (1) (1) (1) (1) (1) (2) (3)Active hydrogen containg compound (g)Dietholamine 210 210 210 210 525 420Glycerol 184Mitsui polyol (a) 612Mitsui polyol (b)Active hydrogen radical/Epoxy radical 1.0 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.Alkylene oxide (g)Propylene oxide 174 696 696 696 696 696 1740 2234Alkylene oxide addition amount (mol/OHEq.) 0.5 2.0 2.0 2.0 2.0 2.0 2.0 2.0OH-value (mgKOH/g) 444 263 263 263 268 200 275 293Polyol component (b) (g)Triethanolamine 745 745 745 745 745Pentaerythritol 384 384Glycerol 644Alkylene oxide (g)Propylene oxide 435 870 870 1392 609 870 1392 435Alkylene oxide addition amount (mol/OHEq.) 0.5 1.0 4.0 3.0 0.5 1.0 3.0 0.5OH-value (mgKOH/g) 713 521 521 253 940 521 253 713Mixed Polyol (a) + (b) = (A)Mixing ratio (a)/(b) 1.0 1.0 4.0 0.1 2.0 1.0 3.0 3.0OH-value (mgKOH/g) 483 392 314 254 492 361 270 398Viscosity (cp/25.degree. C.) 15700 17800 14200 21500 15600 19700 13200 12700__________________________________________________________________________ Comparative ExampleMixed polyol (mark) A-9 A-10 A-11 A-12 A-13 A-14 A-15Polyol component (a)Epoxy resin (g) 374 374 374 374 374 374 374(No.: indicated in Note) (1) (1) (1) (1) (1) (1) (1)Active hydrogen containg compound (g)Dietholamine 210 210 210 210 210GlycerolMitsui polyol (a) 612Mitsui polyol (b) 2000Active hydrogen radical/Epoxy radical .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.Alkylene oxide (g)Propylene oxide 174 70 1396 174 174 174 696Alkylene oxide addition amount (mol/OHEq.) 0.5 2.0 4.0 0.5 0.5 0.5 2.0OH-value (mgKOH/g) 132 514 170 444 444 444 200Polyol component (b) (g)Triethanolamine 745 745 745 745 149 745 745PentaerythritolGlycerolAlkylene oxide (g)Propylene oxide 435 435 435 350 696 435 870Alkylene oxide addition amount (mol/OHEq.) 0.5 0.5 0.5 4.0 4.0 0.5 1.0OH-value (mgKOH/g) 713 713 713 770 199 713 521Mixed Polyol (a) + (b) = (A)Mixing ratio (a)/(b) 1.0 3.0 1.0 1.0 4.0 5.0 0.05OH-value (mgKOH/g) 440 560 441 607 395 489 505Viscosity (cp/25.degree. C.) 19000 21000 9900 10000 18600 52000 1200__________________________________________________________________________ Note: (1) Bisphenol based epoxy resin (2) Novolak resin based resin (3) Tetraglycidyldiaminodiphenylmethane Mitsui polyol (a): MN300 Molecular weight 300 Mitsui polyol (b): NM1000 Molecular weight 1000 Eq.: Equivalent Mixing ratio is indicated by weight (hereinafter the same) TABLE 28__________________________________________________________________________Polyol component (B) ExampleMixed polyol (mark) B-1 B-2 B-3 B-4 B-5 B-6__________________________________________________________________________Polyol component (a1)Phenol resin (g) 500 500 500 500 500 500(No.: indicated in Note) (2) (2) (3) (2) (2) (1)Alkylene oxide (g) 821 247 547 821 300 1231Propylene oxideAlkylene oxide addition amount (mol/OHEq.) 3.1 1.0 1.9 3.1 1.1 4.4OH-value (mgKOH/g) 198 339 250 198 320 153Polyol component (b1) (g)Triethanolamine 500 500 500 500 500 500Alkylene oxidePropylene oxide 292 292 1348 292 1752 1752Alkylene oxide addition amount (mol/OHEq.) 0.5 0.5 2.3 0.5 3.0 3.0OH-value (mgKOH/g) 713 713 327 713 253 253Mixed polyol (a1) + (b1) = (B)Mixing ratio (a1)/(b1) 0.25 1.0 0.43 4.0 2.0 1.5OH-value (mgKOH/g) 615 532 298 302 295 193Viscosity (cp/25.degree. C.) 3600 19700 9670 28000 32500 18900__________________________________________________________________________ Note: OHvalue: hydroxyl value, JIS K 1557 Viscosity: JIS K 1557 (hereinafter the same) (1) Novolak #1000HS a product of Mitsui Toatsu Chemicals, Inc. (2) Novolak #2000 a product of Mitsui Toatsu Chemicals, Inc. (3) Novolak #9000 a product of Mitsui Toatsu Chemicals, Inc. (hereinafter the same) TABLE 3______________________________________Polyol component (B) ExampleMixed polyol (mark) B-7* B-8 B-9______________________________________Polyol component (a1)Phenol resin (g) 500 500 500(No.: indicated in Table 2 (2) (4) (2)Alkylene oxide (g) 821 305 300Propylene oxideAlkylene oxide addition amount 3.1 1.2 1.1(mol/OHEq)OH-value (mgKOH/g) 198 296 320Polyol component (c1)Glycerol (g) 500 500Trimethylolpropane (g) 500Alkylene oxide (g) 832 832 4230Propylene oxideAlkylene oxide addition amount 0.8 0.8 6.2(mol/OHEq)OH-value (mgKOH/g) 730 730 141Mixed polyol (a1) + (c1) = (B)Mixing ration (a1)/(c1) 1.0 4.0 1.5OH-value (mgKOH/g) 460 320 245Viscosity (cp/25.degree. C.) 6300 12700 4900______________________________________ Note: *Mixture of phenol resin (2) and glycerol is used as starting material (4 Cresol/Novolak type resin TABLE 4__________________________________________________________________________Polyol component (C)__________________________________________________________________________ ExampleMixed polyol (mark) C-1 C-2 C-3 C-4 C-5 C-6 C-7 C-8Polyol component (a2) (g)Aromatic amine 594 198 530 594 795 792 198 265(No.: indicated in Note) (1) (1) (2) (1) (2) (1) (1) (2)Alkylene oxide (g)Propylene oxide 696 1044 302 696 464 1044 1357Ethylene oxide 686Alkylene oxide addition amount 2.0 9.0 1.0 2.0 2.0 1.0 9.0 9.0(mol/OHEq.)OH-value (mgKOH/g) 520 180 701 520 590 723 186 182Polyol component (b1), (c1) (g)Glycerol 368 92 400 276Triethanolamine 200 596 596 596Alkylene oxide (g)Propylene oxide 696 1131 1508 389 348 1044 1044Ethylene oxide 396Alkylene oxide addition amount 1.0 6.5 6.5 0.5 1.0 0.5 1.5 1.5(mol/OHEq.)OH-value (mgKOH/g) 630 140 132 940 633 713 410 410Mixed polyol (a2) + (c1) or (a2) + (c1)Mixing ratio (a2)/(c1) or (a2)/(b1) 4.0 0.1 1.0 4.0 4.0 4.0 3.0 3.0OH-value 542 144 416 604 599 721 242 241Viscosity (cp/25.degree. C.) 15000 11200 18300 22500 18500 23000 6500 7800__________________________________________________________________________ ExampleMixed polyol (mark) C-9 C-10 C-11 C-12 C-13 C-14 C-15 C-16Polyol component (a2) (g)Aromatic amine 530 530 895 895 448 895 895 327(No.: indicated in Note) (2) (2) (3) (3) (3) (3) (3) (4)Alkylene oxide (g)Propylene oxide 777 327 654 1437 327 1044Ethylene oxide 590 497Alkylene oxide addition amount 256 258 1.0 2.0 9.0 1.0 2.0 2.0(mol/OHEq.)OH-value (mgKOH/g) 451 516 518 408 164 518 455 368Polyol component (b1), (c1) (g)Glycerol 92 460Triethanolamine 596 596 1043 298 1043 1043Alkylene oxide (g)Propylene oxide 696 1044 1131 696 609 1044 609 609Ethylene oxideAlkylene oxide addition amount 1.0 1.5 6.5 0.8 0.5 3.0 0.5 0.5(mol/OHEq.)OH-value (mgKOH/g) 529 410 137 727 713 250 713 713Mixed polyol (a2) + (c1) or (a2) + (c1)Mixing ratio (a2)/(c1) or (a2)/(b1) 1.0 1.0 4.0 2.0 0.5 2.0 3.0 1.0OH-value 490 463 441 514 536 429 519 541Viscosity (cp/25.degree. C.) 21500 19400 22500 10700 7500 8600 21500 9600__________________________________________________________________________ Note: (1) MDA 220, a product of Mitsui Toatsu Chemicals, Inc. (MDA: polymethylenepolyphenylpolyamine) (2) MDA 150, a product of Mitsui Toatsu Chemicals, Inc. (3) Anilix .RTM.:Polyphenylpolyxylylenepolyamine based; a product of Mitsui Toatsu Chemicals, Inc. (4) Aminophenol

Polyurethane Resin Preparation (Table 5.about.Table 9)

Polyurethane resin was prepared by reacting 12.00 g of polyol obtained in the examples and the comparative examples with an organic polyisocyanate MD1-CR (a product of Mitsui Toatsu Chemicals, Inc. having NCO content of 31.0%) in the presence of an amine catalyst Kaolizer No. 1 (trademark of Kao Co.) at room temperature according to the formulation illustrated in Table 5 to Table 9.

HCFC absorption was measured on the polyurethane resin thus obtained. Results are illustrated in Table 5 to Table 9.

TABLE 5__________________________________________________________________________Polyurethane resin (Polyol (A) only)__________________________________________________________________________ Example 1 2 3 4 5 6 7 8__________________________________________________________________________Polyol (A) A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8OH-value (mg/KOH/g) 483 392 314 254 492 361 270 398Viscosity (cp/25.degree. C.) 15700 17800 14200 24500 15600 19700 13200 12700Formulation (g)Polyol 12.00 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.MDI-CR 14.07 11.42 9.14 7.49 14.33 10.51 7.86 11.59Kaolizer No. 1 0.12 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.HCFC absorptionHCFC-1230 hr 36.07 23.41 21.15 19.40 26.33 22.51 19.86 23.5924 hr 36.09 23.46 21.23 19.40 26.33 22.58 19.94 23.69Absorption (%) 0.1 0.2 0.4 0.0 0.0 0.3 0.4 0.4HCFC-141b0 hr 36.07 23.42 21.15 19.40 26.33 22.51 19.86 23.5924 hr 36.09 23.44 21.23 19.40 26.33 22.60 19.96 23.66Absorption (%) 0.1 0.1 0.3 0.0 0.0 0.4 0.5 0.3__________________________________________________________________________ Comparative Example 1 2 3 4 5 6 7__________________________________________________________________________Polyol (A) A-9 A-10 A-11 A-12 A-13 A-14 A-15OH-value (mg/KOH/g) 440 560 441 607 395 489 505Viscosity (cp/25.degree. C.) 19000 21000 9900 10000 18600 52000 1200Formulation (g)Polyol .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.MDI-CR 12.82 16.31 12.84 17.68 11.50 14.24 14.71Kaolizer No. 1 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.HCFC absorptionHCFC-1230 hr 24.82 28.31 24.84 29.68 23.50 26.24 26.7124 hr 25.19 28.91 25.84 29.83 25.10 26.37 26.90Absorption (%) 1.5 2.1 4.0 0.5 6.8 0.5 0.7HCFC-141b0 hr 24.82 28.31 24.84 29.68 23.50 26.24 26.7124 hr 25.14 28.88 25.71 29.83 24.75 26.37 26.92Absorption (%) 1.3 2.0 3.5 0.5 5.3 0.5 0.8__________________________________________________________________________ Note: MDICR: Crude diphenylmethanediisocyanate, a product of MITSUI TOATSU CHEMICALS, INC. Kaolizer No. 1: Amine based catalyst, a product of Kao Comp. Absorption: Weight increase rate of a specimen of polyurethane resin having dimensions of 40 .times. 40 .times. 7.about. 17 mm after immersion in 50 g of HCFC. TABLE 6__________________________________________________________________________Polyurethane resin (Polyol (A) + Polyol component (B)) Example 9 10 11 12 13 14 15 16 17 18 19 20 21__________________________________________________________________________Polyol (A) A-6 A-6 A-6 A-1 A-1 A-1 A-4 A-4 A-4 A-2 A-2 A-5 A-5Polyol component (B) B-2 B-2 B-2 B-7 B-7 B-7 B-7 B-7 B-7 B-8 B-8 B-8 B-8Mixing ratio (B)/(A) 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 1.0 2.0OH-value 447 475 480 472 468 465 357 391 420 356 393 406 397(mgKOH/g)Viscosity (cp/25.degree. C.) 19700 19800 19800 14100 11900 9200 20000 13100 9500 16800 14100 13400 12900Formulation (g)Polyol 12.00 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.MDI-CR 12.90 13.71 13.86 13.63 13.51 13.42 10.40 11.39 12.23 10.37 9.99 11.83 10.98Kaolizer No. 1 0.12 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.HCFC absorptionHCFC-1230 hr 25.02 25.83 25.98 25.75 25.63 25.54 22.40 22.39 24.23 22.37 21.99 23.83 22.9824 hr 25.04 25.89 26.01 25.75 25.68 25.54 22.47 23.41 24.35 22.37 22.00 23.87 23.00Absorption (%) 0.1 0.2 0.1 0.0 0.2 0.0 0.3 0.1 0.5 0.0 0.5 0.2 0.1HCFC-141b0 hr 25.02 25.83 25.98 25.75 25.63 25.54 22.40 22.39 24.23 22.37 21.99 23.83 22.9824 hr 25.04 25.89 25.98 25.75 25.68 25.54 22.42 23.39 24.33 22.37 22.03 23.85 22.98Absorption (%) 0.1 0.2 0.0 0.0 0.2 0.0 0.1 0.0 0.4 0.0 0.2 0.1 0.0__________________________________________________________________________ TABLE 7__________________________________________________________________________Polyurethane resin (Polyol (A) + Polyol component (C)) Example 22 23 24 25 26 27 28 29 30 31 32 33__________________________________________________________________________Polyol (A) A-1 A-1 A-1 A-5 A-5 A-5 A-1 A-1 A-1 A-5 A-5 A-5Polyol component (C) C-1 C-1 C-1 C-1 C-1 C-1 C-3 C-3 C-3 C-3 C-3 C-3Mixing ratio (C)/(A) 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0OH-value (mgKOH/g) 512 522 530 517 524 532 450 438 429 454 441 431Viscosity (cp/25.degree. C.) 15600 15200 15200 15400 15300 15800 16200 16900 15900 16800 17000Formulation (g)Polyol 12.00 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.MDI-CR 14.91 15.20 15.44 15.06 15.26 15.00 12.99 12.64 12.37 13.10 12.72 12.43Kaolizer No. 1 0.12 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.HCFC absorptionHCFC-1230 hr 26.91 27.20 27.44 27.06 27.26 27.50 25.11 24.76 24.49 25.22 24.84 24.5524 hr 27.90 27.31 27.49 27.06 27.34 27.55 25.11 24.86 24.49 25.32 24.94 24.58Absorption (%)HCFC-141b0 hr 26.91 27.20 27.44 27.06 27.26 27.50 25.11 24.76 24.49 25.22 24.84 24.5524 hr 27.05 27.31 27.49 27.06 27.34 27.58 25.11 24.83 24.49 25.30 24.92 24.55Absorption (%) 0.5 0.4 0.2 0.0 0.3 0.3 0.0 0.3 0.0 0.3 0.3 0.0__________________________________________________________________________ TABLE 8__________________________________________________________________________Polyurethane resin (Polyol (A) + Polyol component (C)) Example 34 35 36 37 38 39 40 41 42__________________________________________________________________________Polyol (A) A-8 A-8 A-8 A-6 A-6 A-6 A-3 A-3 A-3Polyol component (C) C-10 C-10 C-10 C-12 C-12 C-12 C-15 C-15 C-15Mixing ratio (C)/(A) 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0OH-value 431 441 450 438 463 483 417 450 478(mgKOH/g)Viscosity (cp/25.degree. C.) 13200 15100 17000 18000 16500 13100 15600 18700 19500Formulation (g)Polyol 12.00 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.MDI-CR 12.55 12.84 13.11 12.64 13.37 13.95 12.15 13.11 13.92Kaolizer No. 1 0.12 .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw. .rarw.HCFC absorptionHCFC-1230 hr 24.55 24.84 25.11 24.76 25.49 26.07 24.15 25.11 25.9224 hr 24.58 24.87 25.12 24.81 25.51 26.07 24.17 25.11 25.97Absorption (%) 0.1 0.1 0.3 0.2 0.1 0.0 0.1 0.0 0.2HCFC-141b0 hr 24.55 24.84 25.11 24.76 25.49 26.07 25.15 25.11 25.9224 hr 24.58 24.87 25.16 24.78 25.49 26.07 25.15 25.11 25.95Absorption (%) 0.1 0.1 0.2 0.1 0.0 0.0 0.0 0.0 0.1__________________________________________________________________________ TABLE 9______________________________________Polyurethane resin (Polyol (A) +Polyol component (B) + Polyol component (C)) Example 43 44 45 46______________________________________Polyol (A) A-1 A-1 A-1 A-5Polyol component (B) B-2 B-2 B-7 B-8Polyol component (C) C-10 C-10 C-12 C-12Mixing (parts by weight)Polyol (A) 50 50 50 50Polyol component (B) 25 40 25 25Polyol component (C) 25 10 25 25OH-value (mgKOH/g) 490 501 485 455Viscosity (cp/25.degree. C.) 17200 16300 11000 14200Formulation (g)Polyol 12.00 .rarw. .rarw. .rarw.MDI-CR 14.27 14.59 14.13 13.25Kaolizer No. 1 0.12 .rarw. .rarw. .rarw.HCFC absorptionHCFC-1230 hr 26.27 26.59 26.12 25.2524 hr 26.30 26.62 26.15 25.28Absorption (%) 0.1 0.1 0.1 0.1HCFC-141b0 hr 26.27 26.59 26.12 25.2524 hr 26.27 26.62 26.15 25.28Absorption (%) 0.0 0.1 0.1 0.1______________________________________ Comparative Example 8 9 10 11Polyol (A) A-6 A-1 A-1 A-8Polyol component (B) or B-2 C-1 C-3 C-10Polyol component (C)Mixing ratio [(B) or (C)]/(A) 5.0 5.0 5.0 5.0OH-value (mgKOH/g) 506 532 427 452Viscosity (cp/25 .degree.C.) 19900 15100 17100 17500Formulation (g)Polyol 12.00 .rarw. .rarw. .rarw.MDI-CR 14.74 15.50 12.44 13.17Kaolizer No. 1 0.12 .rarw. .rarw. .rarw.HCFC absorptionHCFL-1230 hr 26.74 27.50 24.44 25.1724 hr 26.79 27.52 24.46 25.22Absorption (%) 0.2 0.1 0.1 0.2HCFC-141b0 hr 26.74 27.50 24.44 25.1724 hr 26.79 27.52 24.46 25.22Absorption (%) 0.2 0.1 0.1 0.1______________________________________

Rigid Polyurethane Foam Preparation (Table 10.about.Table 14)

To 100 g of the polyol thus obtained, 1.0 g of water, 1.5 g of silicone surfactant L-5420 (a product of Nippon Unicar Co., Ltd.), 3.0 g of amine catalyst Kaolizer No. 1 (a product of Kao Co., Ltd.) and each amount of CFC or HCFC illustrated in Table 10-Table 14 were added and mixed to obtain a premix. The premix thus obtained was mixed and reacted with each amount of polyisocyanate (MDI-CR, crude diphenylmethanediisocyanate, a product of Mitsui Toatsu Chemicals, Inc.) illustrated in the same tables at the room temperature and poured into a mold to prepare a rigid polyurethane foam.

In the step of preparing the resin premix, mixing and dispersing ability (operational efficiency) between CFC or HCFC and polyol was observed and the closed cell content of the rigid polyurethane foam were measured. Results are illustrated in the same tables.

TABLE 10__________________________________________________________________________Rigid polyurethane foam (polyol (A) only)__________________________________________________________________________ Example47 48 49 50 51 52 53 54Polyol (A) A-1 A-2 A-3 A-4 A-5 A-6 A-7 A-8OH-value (mgKOH/g) 483 392 314 254 492 361 270 398Viscosity (cp/25.degree. C.) 15700 17800 14200 21800 15600 19700 13200 12700Formulation (g)Polyol 100.0H.sub.2 O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 29 26 24 22 30 25 22 27MDI-CR 143 120 99 83 146 111 87 121Operational efficiencyCFC-11 all goodHCFC-123HCFC-141bClosed cell (%)CFC-11 89.2 89.1 89.0 89.5 89.0 88.9 88.7 89.0HCFC-123 88.1 89.0 88.7 88.4 88.9 88.7 88.4 88.5HCFC-141b 88.0 89.0 88.5 89.2 88.9 88.8 88.5 88.4 Comparative Example12 13 14 15 16 17 18Polyol (A) A-9 A-10 A-11 A-12 A-13 A-14 A-15OH-value (mgKOH/g) 440 560 441 607 395 489 505Viscosity (cp/25.degree. C.) 19000 21000 9900 10000 18600 52000 1200Formulation (g)Polyol 100.0H.sub.2 O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 28 32 28 33 26 29 30MDI-CR 132 164 132 176 120 145 149Operational efficiencyCFC-11 good good good good good not good goodHCFC-123HCFC-141bClosed cell (%)CFC-11 85.2 85.3 84.2 86.2 83.2 85.2 83.9HCFC-123 83.2 84.3 83.5 83.1 83.1 82.9 82.1HCFC-141b 83.6 83.7 84.1 84.5 83.9 83.0 83.1__________________________________________________________________________ Note: L5420: Silicon based regulator Closed cell content: Beckman air compariosn hydrometer (a product of Toshiba Backmann Comp.) Foaming agent: 3 foaming tests using CFC11, HCFC123 and HCFC141b were carried out respectively according to the formulation in Table 10. Same amount of foaming agent was used. Operational efficiency and closed cell content of foams obtained were measured respectively. Table 11.about.14 are the same as Table 10. TABLE 11__________________________________________________________________________Rigid polyurethane foam (polyol (A) .degree. polyol component (B)) Example 55 56 57 58 59 60 61 62 63 64 65 66 67__________________________________________________________________________Polyol (A) A-6 A-6 A-6 A-1 A-1 A-1 A-4 A-4 A-4 A-2 A-2 A-5 A-5Polyol component (B) B-2 B-2 B-2 B-7 B-7 B-7 B-7 B-7 B-7 B-8 B-8 B-8 B-8Mixing ratio ((B)/(A)) 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 1.0 2.0OH-value 447 475 480 472 468 465 357 391 420 356 344 406 377(mgKOH/g)Viscosity (cp/25.degree. C.) 19700 19800 19800 14100 11900 9200 20000 13100 9500 16800 14100 13400 12900Formulation (g)Polyol 100.0H.sub.2 O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 28 29 29 29 29 29 25 26 27 25 25 27 26MDI-CR 134 141 143 141 140 139 110 119 127 110 107 123 116Operational efficiency all goodCFC-11HCFC-123HCFC-141bClosed cell (%)CFC-11 89.9 89.4 89.1 89.7 89.1 89.1 89.7 89.6 89.2 89.9 88.9 88.9 89.3HCFC-123 88.2 88.4 88.5 88.5 88.4 89.0 88.5 88.9 87.9 89.7 88.3 88.4 89.0HCFC-141b 87.3 88.2 88.6 88.5 88.1 89.0 88.5 89.0 88.3 89.2 88.1 88.5 89.2__________________________________________________________________________ TABLE 12__________________________________________________________________________Rigid polyurethane foam (polyol (A) + polyol component (C) Example 68 69 70 71 72 73 74 75 76 77 78 79__________________________________________________________________________Polyol (A) A-1 A-1 A-1 A-5 A-5 A-5 A-1 A-1 A-1 A-5 A-5 A-5Polyol component (C) C-1 C-1 C-1 C-1 C-1 C-1 C-3 C-3 C-3 C-3 C-3 C-3Mixing ratio ((C)/(A)) 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0OH-value (mgKOH/g) 513 522 530 517 525 532 450 438 429 454 441 431Viscosity (cp/25.degree. C.) 15600 15200 15200 15400 15300 15300 15800 16200 16900 15900 16800 17000Formulation (g)Polyol 100.0Hphd 2O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 30 30 31 30 31 31 28 28 28 28 28 28MDI-Cr 151 154 156 152 155 156 135 132 129 136 132 130Operational efficiency all goodCFC-11HCFC-123HCFC-141bClosed cell (%)CFC-11 89.2 89.1 89.9 89.8 89.2 89.3 89.5 89.4 89.1 89.3 89.1 89.3HCFC-123 88.1 88.2 88.4 88.4 88.3 88.2 88.3 88.4 88.9 88.9 88.7 88.9HCFC-141b 88.2 88.2 88.5 88.4 88.5 88.3 88.5 88.0 88.9 88.9 88.6 88.9__________________________________________________________________________ TABLE 13__________________________________________________________________________Rigid polyurethane foam (polyol (A) .degree. polyol component (C)) Example 80 81 82 83 84 85 86 87 88__________________________________________________________________________Polyol (A) A-8 A-8 A-8 A-6 A-6 A-6 A-3 A-3 A-3Polyol component (C) C-10 C-10 C-10 C-12 C-12 C-12 C-15 C-15 C-15Mixing ratio ((C)/(A)) 1.0 2.0 4.0 1.0 2.0 4.0 1.0 2.0 4.0OH-value 461 441 450 438 463 483 417 451 498(mgKOH/g)Viscosity (cp/25.degree. C.) 13200 15100 17000 18000 16500 13100 15600 18700 19500Formulation (g)Polyol 100.0H.sub.2 O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 28 28 28 28 29 29 27 28 29MDI-CR 130 132 135 132 138 143 126 135 142Operational efficiency all goodCFC-11HCFC-123HCFC-141bClosed cell (%)CFC-11 89.3 89.2 89.3 89.1 89.2 89.5 89.1 89.7 89.0HCFC-123 87.9 87.9 88.3 88.6 87.9 88.6 88.7 88.4 88.9HCFC-141b 89.0 89.1 89.0 88.9 89.1 89.3 89.0 89.4 89.0__________________________________________________________________________ TABLE 14______________________________________Rigid polyurethane foam (polyol (A) +polyol component (B) + polyol component (C) Example 89 90 91 92______________________________________Polyol (A) A-1 A-1 A-1 A-5Polyol component (B) B-2 B-2 B-7 B-8Polyol component (C) C-10 C-10 C-12 C-12Mixing (parts by weight)Polyol (A) 50 50 50 50Polyol component (B) 25 40 25 25Polyol component (C) 25 10 25 25OH-value (mgKOH/g) 490 501 485 455Viscosity (cp/25 .degree.C.) 17200 16300 11000 14200Formulation (g)Polyol 100.0H.sub.2 O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 29 30 29 30MDI-CR 145 148 144 136Operational efficiencyCFC-11 all goodHCFC-123HCFC-141bClosed cell (%)CFC-11 89.0 89.2 89.3 89.7HCFC-123 88.6 88.5 88.4 88.9HCFC-141b 88.8 88.6 88.4 88.7______________________________________ Comparative Example 19 20 21 22______________________________________Polyol (A) A-6 A-1 A-1 A-8Polyol comp. (B) or comp. (C) B-2 C-1 C-3 C-10Mixing ratio [(B) or (C)]/(A) 5.0 5.0 5.0 5.0OH-value (mgKOH/g) 506 532 472 452Viscosity (cp/25 .degree.C.) 19900 15100 17100 17500Formulation (g)Polyol 100H.sub.2 O 1.0L-5420 1.5Kaolizer No. 1 3.0Foaming agent 30 31 27 28MDI-CR 150 156 129 135Operational efficiencyCFC-11 all goodHCFC-123HCFC-141bClosed cell (%)CFC-11 87.2 87.3 86.9 87.4HCFC-123 84.2 86.3 84.9 84.7HCFC-141b 84.3 86.5 85.0 85.0______________________________________ Note: comp.: component

(Polyols A-2.about.A-15, Polyol components) B-1.about.B-9, Polyol components C-1.about.C16)

The same procedures as described in polyol(A-1) were carried out. When alkali metal hydroxide was used as a catalyst, the reaction mixture was neutralized with acid. Autoclaves having a content of 2 to 5 l were used depending upon the amount of raw materials.

Polyols A-2 to A-15 (Table 1) are epoxy resin based polyols, polyol components B-1 to B-9 (Tables 2 and 3) are phenol resin initiated polyoI components and polyol components C-1 to C-16 (Table are aromatic amine initiated polyol components.

As seen in Table 10 to Table 14, it is found that a single polyol or a mixture thereof obtained by reacting alkylene oxide with a starting material selected from epoxy resin, phenol resin and aromatic amine can maintain, in the polyurethane foam production using HCFC or HFC as a foaming agent, equivalent operational efficiency and foam properties as compared with conventional foam production using a CFC. Rigid polyurethane foam production (Table 15 to Table 24)

Resin premix was prepared according to the formulation illustrated in Tables 15 to Table 24. The resin premix was rapidly mixed at 5000 rpm for 6 seconds with a prescribed amount of an organic polyisocyanate as illustrated in above Tables. The mixture obtained was immediately poured into vertical wooden boxes having dimensions of 200.times.200.times.200 mm and 380.times.380.times.35 (thickness) mm.

Specimens having dimensions of 80.times.80.times.30 mm in size were cut from the former mold and density, compressive strength and low temperature dimensional stability were measured in accordance with JIS A 9514.

A specimen having dimensions of 200.times.200.times.25 mm in size were cut from the latter mold and heat conductivity were measured in accordance with JIS A 1412.

Results are illustrated in Tables 15 to 24.

TABLE 15__________________________________________________________________________Rigid polyurethane foam (polyol (A) only)__________________________________________________________________________ Example 93 94 95__________________________________________________________________________Low material (g)MDI-CR 152 128 107Polyol (1) 100Polyol (2) 100Polyol (3) 100Polyol (4)Polyol (5)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 2.0 2.0 1.8Foaming agentCFC-11 38 34 33HCFC-123 45 41 37HCFC-141b 32 28 26HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 25.9 25.8 25.6 25.8 25.2 25.7 25.3 25.4 25.0Compressive strength (kg/cm.sup.3) 1.62 1.42 1.38 1.64 1.50 1.52 1.63 1.39 1.45Raw temperature dimensional -0.7 -2.1 -2.0 -0.5 -2.2 -1.9 -0.4 -1.4 -1.6stability (%, -30.degree. C. .times. 24 hr.)Heat conductivity (kcal/mhr .degree.C.) 0.0161 0.0163 0.0164 0.0162 0.0164 0.0163 0.0163 0.0165 0.0165__________________________________________________________________________ Example 96 97__________________________________________________________________________ Low material (g) MDI-CR 91 154 Polyol (1) Polyol (2) Polyol (3) Polyol (4) 100 Polyol (5) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 3.0 3.0 Foaming agent CFC-11 29 38 HCFC-123 34 46 HCFC-141b 24 32 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 26.1 26.0 26.1 26.1 25.9 25.1 Compressive strength (kg/cm.sup.3) 1.56 1.36 1.39 1.53 1.37 1.33 Raw temperature dimensional -0.4 -1.6 -1.5 -0.5 -1.7 -1.4 stability (%, -30.degree. C. .times. 24 hr.) Heat conductivity (kcal/mhr .degree.C.) 0.0160 0.0162 0.0162 0.0159 0.0163 0.0163__________________________________________________________________________ TABLE 16__________________________________________________________________________Rigid polyurethane foam (polyol (A) .degree. polyol component (B)) Example 98 99 100 101 102__________________________________________________________________________Low material (g)MDI-CR 120 96 129 152 152Polyol (1) 100Polyol (2) 100Polyol (3) 100Polyol (4) 100Polyol (5) 100H.sub.2 O 1.5 .rarw. .rarw. .rarw. .rarw.L-5420 1.5 .rarw. .rarw. .rarw. .rarw.Kaolizer No. 1 2.0 3.0 1.5 2.0 2.0Foaming agentCFC-11 33 29 34 -- --HCFC-123 40 35 41 35 35HCFC-141b 27 24 29 -- --HFC-134b 10 --Isopentane -- 10Physical property of foamDensity (kg/m.sup.3) (free foaming) 25.3 25.2 25.1 25.3 25.3 25.1 25.4 25.2 25.7 26.3 26.4Compressive strength (kg/cm.sup.3) 1.63 1.38 1.39 1.67 1.39 1.37 1.65 1.39 1.32 1.50 1.50Raw temperature dimensional -0.2 -1.5 -0.9 -0.3 -1.7 -1.6 -0.3 -1.7 -1.5 -1.5stability (%, -30.degree. C. .times. 24 hr.)Heat conductivity (kcal/mhr .degree.C.) 0.0159 0.0162 0.0161 0.0160 0.0163 0.0164 0.0160 0.0163 0.0163 0.0163 0.0162__________________________________________________________________________ TABLE 17__________________________________________________________________________ Example 103 104 105__________________________________________________________________________Low material (g)MDI-CR 142 150 151Polyol (9) 100Polyol (10) 100Polyol (11) 100Polyol (12)Polyol (13)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 0.5 0.5 0.5Foaming agentCFC-11 36 37 38HCFC-123 44 45 45HCFC-141b 30 31 31HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 25.4 25.1 25.3 24.9 24.7 24.9 25.3 25.1 25.1Compressive strength (kg/cm.sup.2) 1.82 1.64 1.66 1.83 1.84 1.67 1.80 1.62 1.67Low temperature dimensional -0.1 -0.8 -0.9 -0.3 -1.5 -1.2 -0.2 -0.8 -0.7stability (%, -30.degree. C. .times. 24 hr)Heat conductivity (kcal/mhr .degree.C.) 0.0158 0.0160 0.0159 0.0159 0.0160 0.0159 0.0156 0.0166 0.0157__________________________________________________________________________ Example Low material (g) MDI-CR 149 148 Polyol (9) Polyol (10) Polyol (11) Polyol (12) 100 Polyol (13) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 1.0 1.0 Foaming agent CFC-11 36 37 37 HCFC-123 45 45 HCFC-141b 31 31 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 25.6 25.4 25.7 25.4 25.5 25.5 Compressive strength (kg/cm.sup.2) 1.87 1.62 1.68 1.88 1.63 1.69 Low temperature dimensional -0.1 -0.9 -0.4 -0.1 -0.7 -0.4 stability (%, -30.degree. C. .times. 24 hr) Heat conductivity (kcal/mhr .degree.C.) 0.0157 0.0162 0.0157 0.0160 0.0160 0.0160__________________________________________________________________________ TABLE 18__________________________________________________________________________ Example 108 109 110__________________________________________________________________________Low material (g)MDI-CR 147 119 127Polyol (14) 100Polyol (15) 100Polyol (16) 100Polyol (17)Polyol (18)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 1.0 4.0 4.0Foaming agentCFC-11 37 33 34HCFC-123 45 39 41HCFC-141b 31 27 28HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 25.4 25.1 25.3 24.9 24.6 24.3 25.3 25.4 26.0Compressive strength (kg/cm.sup.2) 1.87 1.62 1.65 1.86 1.69 1.39 1.86 1.62 1.61Low temperature dimensional -0.1 -0.9 -0.3 -0.0 -0.4 -0.3 -0.1 -0.8 -0.5stability (%, -30 .degree.C. .times. 24 hr)Heat conductivity (kcal/mhr .degree.C.) 0.0160 0.0162 0.0161 0.0161 0.0164 0.0161 0.0162 0.0165 0.0162__________________________________________________________________________ Example 111 112__________________________________________________________________________ Low material (g) MDI-CR 135 118 Polyol (14) Polyol (15) Polyol (16) Polyol (17) 100 Polyol (18) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 4.0 2.0 Foaming agent CFC-11 35 33 HCFC-123 42 39 HCFC-141b 29 27 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 25.3 24.3 24.7 25.0 24.7 24.9 Compressive strength (kg/cm.sup.2) 1.87 1.66 1.67 1.68 1.66 1.62 Low temperature dimensional -0.1 -0.8 -0.5 -0.1 -0.4 -0.4 stability (%, -30 .degree.C. .times. 24 hr) Heat conductivity (kcal/mhr .degree.C.) 0.0159 0.0160 0.0160 0.0158 0.0160 0.0160__________________________________________________________________________ TABLE 19__________________________________________________________________________ Example 113 114 115__________________________________________________________________________Low material (g)MDI-CR 115 131 124Polyol (19) 100Polyol (20) 100Polyol (21) 100Polyol (22)Polyol (23)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 2.0 4.0 4.0Foaming agentCFC-11 32 35 34HCFC-123 39 42 40HCFC-141b 27 29 28HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 25.1 24.9 25.1 25.2 24.7 25.3 25.3 25.1 25.3Compressive strength (kg/cm.sup.2) 1.85 1.67 1.66 1.87 1.66 1.67 1.80 1.65 1.66Low temperature dimensional -0.0 -0.4 -0.4 -0.3 -1.3 -1.3 -0.7 -1.2 -1.1stability (%, -30.degree. C. .times. 24 hr)Heat conductivity (kcal/mhr .degree.C.) 0.0159 0.0160 0.0160 0.0160 0.0162 0.0160 0.0166 0.0167 0.0165__________________________________________________________________________ Example 116 117__________________________________________________________________________ Low material (g) MDI-CR 156 162 Polyol (19) Polyol (20) Polyol (21) Polyol (22) 100 Polyol (23) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 1.0 1.0 Foaming agent CFC-11 39 39 HCFC-123 47 47 HCFC-141b 32 33 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 25.0 25.1 25.1 25.2 25.3 25.6 Compressive strength (kg/cm.sup.2) 1.83 1.62 1.65 1.83 1.67 1.66 Low temperature dimensional -0.9 -1.7 -1.8 -0.6 -1.7 -1.7 stability (%, -30.degree. C. .times. 24 hr) Heat conductivity (kcal/mhr .degree.C.) 0.0165 0.0167 0.0165 0.0157 0.0157 0.0157__________________________________________________________________________ TABLE 20__________________________________________________________________________ Example 118 119 120__________________________________________________________________________Low material (g)MDI-CR 164 161 162Polyol (24) 100Polyol (25) 100Polyol (26) 100Polyol (27)Polyol (28)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 1.0 3.0 3.0Foaming agentCFC-11 40 39 39HCFC-123 48 47 47HCFC-141b 33 33 33HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 25.3 25.2 25.3 25.4 25.3 25.4 25.4 25.3 25.3Compressive strength (kg/cm.sup.2) 1.80 1.63 1.67 1.82 1.67 1.65 1.83 1.67 1.68Low temperature dimensional -0.0 -0.6 -0.2 -0.0 -0.8 -0.5 -0.1 -0.2 -0.1stability (%, -30.degree. C. .times. 24 hr)Heat conductivity (kcal/mhr .degree.C.) 0.0157 0.0158 0.0157 0.0156 0.0158 0.0156 0.0160 0.0163 0.0161__________________________________________________________________________ Example 121 122__________________________________________________________________________ Low material (g) MDI-CR 165 139 Polyol (24) Polyol (25) Polyol (26) Polyol (27) 100 Polyol (28) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 3.0 2.0 Foaming agent CFC-11 40 36 HCFC-123 48 43 HCFC-141b 33 30 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 25.3 25.4 25.4 25.7 25.3 25.2 Compressive strength (kg/cm.sup.2) 1.85 1.70 1.72 1.84 1.69 1.65 Low temperature dimensional -0.4 -1.3 -0.1 -1.0 -1.7 -1.6 stability (%, -30.degree. C. .times. 24 hr) Heat conductivity (kcal/mhr .degree.C.) 0.0162 0.0162 0.0162 0.0160 0.0161 0.0162__________________________________________________________________________ TABLE 21__________________________________________________________________________ Example 123 124 125Low material (g)MDI-CR 147 153 142Polyol (24) 100Polyol (25) 100Polyol (26) 100Polyol (27)Polyol (28)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 2.0 2.0 4.5Foaming agentCFC-11 37 38 36HCFC-123 44 45 44HCFC-141b 31 32 30HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 25.4 25.4 25.7 26.0 26.0 25.9 24.9 25.2 25.3Compressive strength (kg/cm.sup.2) 1.82 1.62 1.59 1.82 1.62 1.59 1.83 1.63 1.68Low temperature dimensional -0.7 -1.6 -0.9 -0.1 -0.9 -0.8 -0.1 -0.7 -0.5stability (%, -30.degree. C. .times. 24 hr)Heat conductivity (kcal/mhr .degree.C.) 0.0162 0.0162 0.0163 0.0162 0.0162 0.0163 0.0162 0.0164 0.0163__________________________________________________________________________ Example 126 127__________________________________________________________________________ Low material (g) MDI-CR 149 149 Polyol (24) Polyol (25) Polyol (26) Polyol (27) 100 Polyol (28) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 4.5 4.5 Foaming agent CFC-11 37 37 HCFC-123 45 45 HCFC-141b 31 31 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 25.2 25.3 25.3 25.3 25.3 25.2 Compressive strength (kg/cm.sup.2) 1.83 1.72 1.65 1.84 1.72 1.63 Low temperature dimensional -0.6 -1.2 -1.1 -0.0 -0.3 -0.1 stability (%, -30.degree. C. .times. 24 hr) Heat conductivity (kcal/mhr .degree.C.) 0.0163 0.0164 0.0165 0.0163 0.0164 0.0165__________________________________________________________________________ TABLE 22__________________________________________________________________________ Example 128 129 130Low material (g)MDI-CR 138 141 143Polyol (24) 100Polyol (25) 100Polyol (26) 100Polyol (27)Polyol (28)H.sub.2 O 1.5 .rarw. .rarw.L-5420 1.5 .rarw. .rarw.Kaolizer No. 1 0.5 0.5 0.5Foaming agentCFC-11 36 36 36HCFC-123 43 43 44HCFC-141b 30 30 30HFC-134bPhysical property of foamDensity (kg/m.sup.3) (free foaming) 26.1 25.9 25.3 26.1 25.4 25.4 26.3 25.3 25.4Compressive strength (kg/cm.sup.2) 1.87 1.72 1.65 1.84 1.62 1.65 1.83 1.72 1.65Low temperature dimensional -0.5 -1.7 -1.2 -0.5 -1.4 -1.2 -0.7 -1.2 -1.1stability (%, -30.degree. C. .times. 24 hr)Heat conductivity (kcal/mhr .degree.C.) 0.0159 0.0161 0.0160 0.0160 0.0160 0.0160 0.0162 0.0163 0.0162 Example 131 132__________________________________________________________________________ Low material (g) MDI-CR 143 140 Polyol (24) Polyol (25) Polyol (26) Polyol (27) 100 Polyol (28) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 0.7 0.7 Foaming agent CFC-11 27 36 HCFC-123 44 43 HCFC-141b 30 30 HFC-134b Physical property of foam Density (kg/m.sup.3) (free foaming) 25.7 25.3 25.4 25.3 25.3 25.4 Compressive strength (kg/cm.sup.2) 1.85 1.65 1.67 1.84 1.67 1.63 Low temperature dimensional -0.6 -2.2 -1.6 -0.7 -1.6 -1.3 stability (%, -30.degree. C. .times. 24 hr) Heat conductivity (kcal/mhr .degree.C.) 0.0163 0.0165 0.0163 0.0165 0.167 0.0165__________________________________________________________________________ TABLE 23__________________________________________________________________________ Example 133 134 135 136__________________________________________________________________________Low material (g)MDI-CR 135 144 141 138Polyol (39) 100Polyol (40) 100Polyol (41) 100Polyol (42) 100H.sub.2 O 1.5 .rarw. .rarw. .rarw.L-5420 1.5 .rarw. .rarw. .rarw.Kaolizer No. 1 0.7 0.2 0.2 0.2Foaming agentCFC-11 36 35 36 38HCFC-123 43 42 44 45HCFC-141b 30 29 30 31HFC-134bPhysical property of foamDensity (kg/m.sup.3) 25.4 25.3 25.7 25.4 25.3 25.3 25.7 25.3 25.7 25.6 25.7 25.7(free foaming)Compressive strength (kg/cm.sup.2) 1.82 1.63 1.67 1.83 1.63 1.67 1.85 1.63 1.70 1.84 1.69 1.74Low temperature dimensional -0.1 -0.6 -0.5 -0.1 -0.7 -0.5 -0.1 -0.9 -0.2 -0.2 -0.8 -0.5stability (%, -30.degree. C. .times. 24 hr)Heat conductivity 0.0160 0.0163 0.0162 0.0162 0.0165 0.0163 0.0160 0.0162 0.0161 0.0159 0.0162 0.0161(kcal/mhr .degree.C.)__________________________________________________________________________ TABLE 24__________________________________________________________________________Polyol (A) + Polyol component (B) + Polyol component (C)__________________________________________________________________________ Example 137 138 139 140__________________________________________________________________________Low material (g)MDI-CR 153 156 158 144Polyol (43) 100Polyol (44) 100Polyol (45) 100Polyol (46) 100H.sub.2 O 1.5 .rarw. .rarw. .rarw.L-5420 1.5 .rarw. .rarw. .rarw.Kaolizer No. 1 0.5 0.5 0.8 3.0Foaming agentCFC-11 38 38 38 37HCFC-123 46 46 45 44HCFC-141b 32 32 32 31HFC-134bPhysical property of foamDensity (kg/m.sup.3) 26.2 25.7 25.3 26.1 26.0 25.7 25.2 25.7 25.3 25.6 25.7 25.3(free foaming)Compressive strength (kg/cm.sup.2) 1.86 1.62 1.61 1.87 1.62 1.63 1.84 1.63 1.64 1.83 1.62 1.65Low temperature dimensional -0.1 -1.2 -1.1 -0.2 -1.3 - 1.4 -0.4 -2.1 -2.0 -0.4 -1.8 -1.6stability (%, -30.degree. C. .times. 24 hr)Heat conductivity 0.0159 0.0161 0.0160 0.0160 0.0163 0.0164 0.0162 0.0163 0.0163 0.0163 0.0162 0.0163(kcal/mhr .degree.C.)__________________________________________________________________________ Comparative Example 23 24 25 26__________________________________________________________________________Low material (g)MDI-CR 140 172 140 184Polyol (CE1) 100Polyol (CE2) 100Polyol (CE3) 100Polyol (CE4) 100Polyol (CE5)Polyol (CE6)H.sub.2 O 1.5 .rarw. .rarw. .rarw.L-5420 1.5 .rarw. .rarw. .rarw.Kaolizer No. 1 2.0 1.0 4.0 3.0Foaming agentCFC-11 36 41 36 43HCFC-123 43 49 43 51HCFC-141b 30 34 30 36Physical property of foamDensity (kg/m.sup.3) 25.4 23.2 23.2 25.7 23.7 23.8 25.4 22.9 23.5 26.1 25.7 25.8(free foaming)Compressive strength (kg/cm.sup.2 ) 1.62 1.32 1.35 1.60 1.32 1.37 1.57 1.30 1.31 1.41 1.31 1.31Low temperature dimensional -0.5 -10.1 -9.1 -0.5 -8.9 -7.5 -0.4 -9.1 -6.5 -0.4 -10.2 -8.9stability (%, -30.degree. C. .times. 24 hr)Heat conductivity 0.0171 0.0178 0.0177 0.0170 0.0179 0.0179 0.0172 0.0181 0.0173 0.0173 0.0179 0.0176(kcal/mhr .degree.C.)__________________________________________________________________________ Comparative Example 27 28__________________________________________________________________________ Lowmaterial (g) MDI-CR 129 153 Polyol (CE1) Polyol (CE2) Polyol (CE3) Polyol (CE4) Polyol (CE5) 100 Polyol (CE6) 100 H.sub.2 O .rarw. .rarw. L-5420 .rarw. .rarw. Kaolizer No. 1 0.5 0.5 Foaming agent CFC-11 34 38 HCFC-123 41 46 HCFC-141b 29 32 Physical property of foam Density (Kg/m.sup.3) 25.7 25.0 25.3 25.1 25.4 25.0 (free foamong) Compressive strength (kg/cm.sup.2) 1.47 1.37 1.32 1.52 1.31 1.32 Low temperature dimensional -0.4 -12.1 -7.2 -0.4 -10.9 -8.7 stability (%, -30.degree. C. .times. 24 hr) Heat conductivity 0.0171 0.0178 0.0177 0.0175 0.0183 0.0177 (Kcal/mhr .degree.C.)__________________________________________________________________________ Note: CE: Comparative Example

Preparation of prepolymer

Polyol .alpha.

polyol Obtained by the addition of propylene oxide to glycerol.

Hydroxyl value was 450 mgKOH/g. Viscosity was 480 cp/25 .degree. C. TRC-90A

Crude tolylene diisocyanate produced by Mitsui Toatsu Chemicals, Inc. NCO content was 39.0%.

Preparation procedure for prepolymer mixture

A mixture of 890 g of TRC-90A and 110 g of polyol .alpha. were reacted at 80 .degree. C. for 2 hours and cooled to room temperature. Prepolymer thus obtained was mixed with 1000 g of MDI-CR to obtain a prepolymer mixture having NCO content of 31.0%.

Results using the prepolymer mixture are illustrated in Table 25.

TABLE 25__________________________________________________________________________ Example 141 142 143 144__________________________________________________________________________Low material (g)Mixed prepolymer 152 117 120 142Polyol (1) 100Polyol (3) 100Polyol (6) 100Polyol (9) 100H.sub.2 O 1.5 1.5 1.5 1.5L-5420 1.5 1.5 1.5 1.5Kaolizer No. 1 0.2 0.8 0.2 0.2Foaming agentCFC-11 38 33 33 36HCFC-123 45 39 40 44HCFC-141b 31 25 25 30HFC-134b 2Isopentane 2Physical property of foamDensity (kg/m.sup.3) 24.5 24.8 25.2 24.8 25.3 25.5 25.0 25.1 25.3 25.0 25.1 25.2(free foaming)Compressive strength (kg/cm.sup.2) 1.51 1.32 1.26 1.50 1.32 1.27 1.50 1.30 1.24 1.50 1.30 1.20Low temperature dimensional -0.1 -0.3 -0.8 -0.2 -0.3 -0.5 -0.2 - 0.4 -1.0 -0.2 -0.4 -1.0stability (%, -30.degree. C. .times. 24 hr)Heat conductivity 0.0158 0.0159 0.0161 0.0160 0.0162 0.0164 0.0163 0.0165 0.0167 0.0163 0.0165 0.0167(kcal/mhr .degree.C.)__________________________________________________________________________ Example 145 146 147 148__________________________________________________________________________Low material (g)Mixed prepolymer 150 142 146 157Polyol (16) 100Polyol (22) 100Polyol (34) 100Polyol (43) 100H.sub.2 O 1.5 1.5 1.5 1.5L-5420 1.5 1.5 1.5 1.5Kaolizer No. 1 1.8 0.2 2.2 2.0Foaming agentCFC-11 37 36 36 38HCFC-123 44 44 44 46HCFC-141b 31 30 31 32Physical property of foamDensity (kg/m.sup.3) 25.0 25.3 25.4 24.8 25.0 25.1 25.0 25.0 25.2 24.6 24.7 25.2(free foaming)Compressive strength (kg/cm.sup.2) 1.55 1.38 1.30 1.30 1.15 1.18 1.65 1.40 1.38 1.50 1.25 1.19Low temperature dimensional -0.8 -1.5 -1.8 -0.6 -1.8 -2.0 -0.4 -1.0 -1.5 -0.2 -0.8 -1.0stability (%, -30.degree. C. .times. 24 hr)Heat conductivity 0.0161 0.0165 0.0163 0.0168 0.0170 0.0171 0.0163 0.0165 0.0165 0.0165 0.0168 0.0170(kcal/mhr .degree.C.)__________________________________________________________________________

As seen in these results, the polyols of the invention have suitable reactivity. Consequently, the mixture of foaming ingredients does not cause sagging phenomenon, even when it is sprayed on a vertical face material, and can give good appearance on the surface of spray applied foam. Good adhesion of sprayed foam to the facing material can also be obtained. The rigid foam thus obtained has excellent flame retardance and low heat conductivity, and thus provides composite boards having excellent performance.

The formulation of polyols used in the preparation of rigid polyurethane foam are illustrated in Table 1 to Table 4. However, the formulations are not limited to the above embodiment and it is to be understood that the formulations illustrated in Examples 1 to 148 can also be used for the preparation of polyurethane foam composites.

(1) Preparation of rigid polyurethane foam composite having facing material

According to the above examples, preparation of a rigid polyurethane foam composite having facing material of the invention was carried out.

Polyols obtained in examples and comparative examples illustrated in Table 5, Table 6, Table 7 and Table 9 were used as the raw material of rigid polyurethane foams.

The facing material for use in the invention includes, for example, corrugated paper boards, laminated papers and other paper products, polyethylene, polypropylene, polyvinyl chloride and other synthetic resin plates; and aluminum, steel and other metal plates.

1) Polyurethane foam composite having one facing material (Table 26, 27)

The same formulations as illustrated in Table 26 were sprayed on a facing material under the following conditions to prepare a rigid polyurethane foam having one facing material. Properties of the product obtained are summarized in Table 27.

Atomizer: Model--Fee Head D Gum (a product of Gusmer Co., Ltd.) Output pressure: 50 kg/cm.sup.2 Liquid temperature: 40.degree. C. Facing material: Corrugated paper board TABLE 26______________________________________ Comparative Example Ex. 149 150 151 152 34 35______________________________________Formulation (g)MDR-CR 152 152 142 142 124 141Polyol(1) 100 100(9) 100(22) 100(Comp. Ex. 1) 100(Comp. Ex. 8) 100TCEP 10 10 10 10 10 10H.sub.2 O 0.5 0.5 0.5 0.5 0.5 0.5L-5420 1.5 1.5 1.5 1.5 1.5 1.5Kaolizer No. 1 1.5 1.5 3.0 1.0 1.5 1.5LL-690D 0.1 0.1 0.1 0.1 0.1 0.1CFC-11 33HCFC-123 50 48 45 48HCFC-141b 43______________________________________ Note: TCEP: Flame retardant, Tris(2chloroethyl)phosphate a product of Daihachi Chemical Comp. LL690D: Catalyst, Lead Octoate of 40% by weight dioctylphtharate solution TABLE 27__________________________________________________________________________ Example Comparative Exp. 153 154 155 156 36 37__________________________________________________________________________Reactivity 4.about.5 4.about.5 4.about.5 5 5.about.6 5Tack-free time (sec.)Sag phenomenon (NOTE) none none none none exist existSurface appearance all goodAdhesionFoam density (kg/m.sup.3) 36.5 37.0 37.0 38.0 39.0 39.0Compressive strength (kg/cm.sup.3) 3.33 3.35 3.25 3.25 3.10 2.95Heat conductivity 0.0175 0.0172 0.0176 0.0180 0.0190 0.0188(kcal/m .multidot. hr .multidot. .degree.C.)mCombustibility (2)Combustion time (sec.) 23 24 23 24 35 33Burned distance (mm) 18 17 18 19 20 21__________________________________________________________________________ Note: (1) Sag is a phenomenon where a raw material mixture before curing sags o runs down on a vertical surface when the mixture is sprayed to foam on th surface. (2) Combustibility (Flame retardation): according to ASTM D 1691

2) Preparation of rigid polyurethane foam having a plurality of facing materials (Table 28, 29)

In the test, rigid polyurethane foam composite boards having two facing materials were prepared with a continuous process under the following conditions by using the formulations illustrated in Table 28.

Properties of the product obtained are summarized in Table 29.

Foaming machine: High pressure foam dispensing machine Model-MQ. (a product of Hennecke Machinen Bau) Line Speed: 10 m/min Temperature Material: 30.degree.-40.degree. C. Cure oven: 55.degree. C. Product: 1 m Width.times.40 mm Thickness 35 mm Foam layer Facing material: Laminated paper on the top and bottom TABLE 28______________________________________ Comparative Example Ex. 157 158 159 160 38 39______________________________________Formulation (g)MDR-CR 154 154 149 149 140 158Polyol(5) 100 100(12) 100(27) 100(Comp. Ex. 1) 100(Comp. Ex. 8) 100TCEP 10 10 10 10 10 10H.sub.2 O 1.5 1.5 1.5 1.5 1.5 1.5L-5420 1.5 1.5 1.5 1.5 1.5 1.5Kaolizer No. 1 0.2 0.2 0.3 3.0 1.0 1.0CFC-11 33HCFC-123 46 45 43 46HCFC-141b 43______________________________________ TABLE 29__________________________________________________________________________ Example Comparative Exp. 161 162 163 164 40 41__________________________________________________________________________Formulation 157 158 159 160 38 39(in TABLE 28)Adhesion between face all goodFoam density (kg/m.sup.3) 31.5 32.0 31.8 30.0 31.0 31.5Compressive strength (kg/cm.sup.3) 1.53 1.50 1.60 1.55 1.05 1.00Flexural strength (kg/cm.sup.3) 2.40 2.30 2.35 2.45 1.95 1.85Heat conductivity (kcal/cm.sup.2) 0.0170 0.0172 0.0173 0.0170 0.0185 0.0186CombustibilityCombustion time (sec.) 22 21 21 23 30 31Burned distance (mm) 16 14 15 16 21 20__________________________________________________________________________

As seen in these results, the polyols of the invention have suitable reactivity in addition to the excellent physical properties. Consequently, the mixture of foaming ingredients does not cause sagging phenomenon, even when it is sprayed on a vertical face material, and can give good appearance on the surface of spray applied foam. Good adhesion of sprayed foam to the facing material can also be obtained. The rigid foam thus obtained has excellent flame retardance and low heat conductivity, and thus provides composite boards having excellent performance.

The formulations used in the preparation of rigid polyurethane foam composites are illustrated in Table 1 and 4. However, the formulations are not limited to the above embodiment and it is to be understood that the formulations illustrated in Examples 1 to 148 can also be used for the preparation of polyurethane foam composites.

Claims

1. A polyol (A) comprising polyol component (a) and polyol component (b); said polyol component (a) having a number average molecular weight of from 500 to 1800 and an average functionality of from 4 to 12, having at least one residual epoxy group, and being obtained by the addition of an alkylene oxide to a liquid polymer (g2) resulting from the reaction of an active hydrogen containing compound (g) which is one or more compounds selected from the group consisting of glycols, polyhydric alcohols and polysaccharides having a functionality of from 2 to 8, or an alkylene oxide adduct thereof (g1), with an epoxy resin represented by the formula (I): ##STR6## wherein R.sub.1 is a hydrogen, alkyl having from 1 to 9 carbon atoms, chlorine, bromine, fluorine or a hydroxy, m is an integer of from 1 to 3, R.sub.2 is a glycidyloxy or a glycidylamino, n is an integer of from 0 to 4, X and Y may be the same or different, and are a divalent group selected from the group consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and sulfonyl, or may be a combination of the above-mentioned groups; said polyol component (b) being obtained by the addition of an alkylene oxide to an active hydrogen containing compound (j), wherein compound (j) may be the same or different than active hydrogen containing compound (g).

2. The polyol (A) of claim 1 wherein the alkylene oxide adduct (g1) is a polyol obtained by adding less than 3 moles of the alkylene oxide per equivalent of the active hydrogen in the active hydrogen containing compound (g).

3. The polyol (A) of claim 1 wherein the polymer (g2) is obtained by reacting the active hydrogen containing compound (g) or the alkylene oxide adduct thereof (g1) of from 0.5 to 2.0 moles per equivalent of epoxy group in the epoxy resin represented by the formula (I).

4. The polyol (A) of claim 1 wherein polyol component (a) is obtained by adding from 0.5 to 3 moles of the alkylene oxide per equivalent of the active hydrogen in the polymer (g2).

5. The polyol (A) of claim 1 wherein the polyol component (b) is obtained by adding from 0.5 to 3.0 moles of alkylene oxide per equivalent of the active hydrogen in the active hydrogen containing compound (j).

6. The polyol (A) of claim 1 wherein the mixing ratio of the polyol component (a) to polyol component (b), the ratio (a)/(b), is from 0.1 to 4.0 by weight.

7. The polyol (A) of claim 1 wherein the active hydrogen containing compound (j) are one or more of compound selected from the group consisting of glycols, polyhydric alcohols, polysaccharides and alkanolamines having a functionality of from 2 to 8 represented by the formula (II):

NR.sub.3 R.sub.3 R.sub.4 (II)

wherein R.sub.3 and R.sub.4 may be the same or different, and are individually a hydrogen, hydroxyethyl or a hydroxyisopropyl, excluding the case wherein both R.sub.3 and R.sub.4 are hydrogen atoms.

8. A polyol (D) comprising polyol (A) and phenol resin based polyol component (B) and/or aromatic amine based polyol component (C); said polyol (A) comprising polyol component (a) and polyol component (b); said polyol (a) having a number average molecular weight of from 500 to 1800 and an average functionality of from 4 to 12, having at least one residual epoxy group, and being obtained by the addition of an alkylene oxide to a liquid polymer (g2) resulting from the reaction of an active hydrogen containing compound (g) or an alkylene oxide adduct thereof (g1), with an epoxy resin represented by the formula (I): ##STR7## wherein R.sub.1 is a hydrogen, alkyl having from 1 to 9 carbon atoms, chlorine, bromine, fluorine or a hydroxy, m is an integer of from 1 to 3, R.sub.2 is a glycidyloxy or a glycidylamino, n is an integer of from 0 to 4, and X and Y may be the same or different and are a divalent group selected from the group consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and sulfonyl, or may be a combination of the above-mentioned groups; said polyol component (b) being obtained by the addition of an alkylene oxide to an active hydrogen containing compound (j), wherein compound (j) may be the same or different than active hydrogen containing compound (g).

9. The polyol (D) of claim 8 wherein the phenol resin based polyol component (B) comprises polyol component (a1) and polyol component (b1) or polyol component (c1); said polyol component (a1) having a hydroxyl value of from 145 to 350 mg KOH/g and being obtained by the addition of from 1.0 to 4.5 moles of the alkylene oxide to one equivalent of a hydroxy group in a phenol resin having a number average molecular weight of from 650 to 1400, an average functionality of from 3 to 8, and represented by the formula (III): ##STR8## wherein R.sub.5 is a hydrogen, alkyl having from 1 to 9 carbon atoms, chlorine, bromine, fluorine or hydroxy, is an integer of from 1 to 3, s is an integer of from 1 to 6, V and W are the same or different divalent group selected from the group consisting of an alkylene having from 1 to 10 carbon atoms, xylylene, oxy, thio and sulfonyl, or may be a combination of the above-mentioned groups; said polyol component (b1) having a hydroxyl value of from 240 to 800 mg KOH/g and being obtained by the addition of from 0.5 to 3.0 moles of the alkylene oxide to one equivalent of the active hydrogen in one or more of alkanolamine represented by the formula (II):

NR.sub.3 R.sub.3 R.sub.4 (II)

wherein R.sub.3 and R.sub.4 may be the same or different, and are individually a hydrogen, hydroxyethyl or a hydroxyisopropyl, excluding the case wherein both R.sub.3 and R.sub.4 are hydrogen; said polyol component (c1) having a hydroxyl value of from 130 to 750 mg KOH/g and being obtained by the addition of from 0.5 to 6.5 moles of the alkylene oxide to one equivalent of the hydroxyl group in one or more of the active hydrogen containing compound selected from the group consisting of aliphatic polyhydroxy compounds having an average functionality of from 2 to 8.

10. The polyol (D) of claim 9 wherein the phenol resin is a novolak resin having the formula (III) wherein R.sub.5 is a hydrogen and both V and W are methylene.

11. The polyol (D) of claim 10 wherein the novolak resin has a number average molecular weight of from 650 to 900, average functionality of from 3 to 8, and a softening point of from 75.degree. to 115.degree. C.

12. The polyol (D) of claim 8 wherein the aromatic amine based polyol component (C) comprises polyol component (a2) and polyol component (b1) or polyol component (c1); said polyol component (a2) being obtained by the addition of from 1.0 to 9.0 moles of the alkylene oxide to one equivalent of the active hydrogen in the aromatic amine represented by the formula (IV) or formula (V): ##STR9## wherein E is methylene, xylylene or ethylidene, R is a hydrogen, aliphatic hydrocarbon group having from 1 to 10 carbon atoms or alicyclic hydrocarbon group, and u is an integer of from 0 to 5, ##STR10## wherein R.sub.0 is a hydrogen, chlorine, bromine, fluorine, aliphatic hydrocarbon group having from 1 to 10 carbon atoms or alicylic hydrocarbon group, t is an integer of from 1 to 3, and p is an integer of from 0 to 2; said polyol component (b1) being obtained by the addition of from 0.5 to 3.0 moles of the alkylene oxide to one equivalent of the active hydrogen in the alkanolamine represented by the formula (II):

NR.sub.3 R.sub.3 R.sub.4 (II)

wherein R.sub.3 and R.sub.4 may be the same or different, and are individually a hydrogen, hydroxyethyl or hydroxyisopropyl, excluding the case wherein both R.sub.3 and R.sub.4 are hydrogen; said polyol component (c1) being obtained by the addition of from 0.5 to 6.5 moles of the alkylene oxide to one equivalent of the active hydrogen in an aliphatic polyhydroxy compound.

13. The polyol (D) of claim 8 wherein the ratio [polyol component (B)+polyol component (C)]/polyol (A) is in the range of from 0.1 to 4.0 by weight, and the proportion of polyol component (B) and polyol component (C) in the mixture satisfies the relation, polyol component (B)=100-polyol component (C).

14. The polyol (D) of claim 8 wherein the ratio (a)/(b) in the polyol (A) is from 0.1 to 4.0 by weight, the ratio (a1)/(b1) and (a1)/(c1) in the polyol component (B) are from 0.25 to 4.0 by weight and from 0.1 to 4.0 by weight respectively, and the ratio (a2)/(b1) and (a2)/(c1) in the polyol component (C) are from 0.25 to 4.0 by weight and from 0.1 to 4.0 by weight respectively.

15. A polyurethane resin obtained by reacting a polyol with an organic polyisocyanate comprising using the polyol (A) of claim 1 as said polyol.

16. A polyurethane resin obtained by reacting a polyol with an organic polyisocyanate comprising using the polyol (D) of claim 8 as said polyol.

17. The polyurethane resin of claim 15 or claim 16 wherein a portion or the whole of the organic polyisocyanate comprises a prepolymer of the organic polyisocyanate.

18. The polyurethane resin of claim 15 or claim 16 wherein the equivalent ratio of the isocyanate group in the organic polyisocyanate to the hydroxyl group in the polyol is in the range of from 0.8 to 5.0.

19. A rigid polyurethane foam obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst and cell regulator, said polyol comprising polyol (A) according to claim 1, and said foaming agent being selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons, and mixtures thereof.

20. A rigid polyurethane foam according to claim 19, wherein said resin premix further comprises an auxiliary foaming agent, said auxiliary foaming agent being selected from water, low boiling point compounds, or mixtures thereof.

21. A rigid polyurethane foam obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst and cell regulator, said polyol comprising polyol D according to claim 8, and said foaming agent being selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons and mixtures thereof.

22. A rigid polyurethane foam according to claim 21, wherein said resin premix further comprises an auxiliary foaming agent selected from water, low boiling point compounds, or mixtures thereof.

23. A process comprising preparing a rigid polyurethane foam, said rigid polyurethane foam being obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst and cell regulator, said polyol comprising polyol (A) according to claim 1, and said foaming agent being selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons and mixtures thereof.

24. A process according to claim 23, wherein said resin premix further comprises an auxiliary foaming agent, said auxiliary foaming agent being selected from water, low boiling point compounds, or mixtures thereof.

25. A process comprising preparing a rigid polyurethane foam, said rigid polyurethane foam being obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst and cell regulator, said polyol comprising polyol D according to claim 8, and said foaming agent being selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons, and mixtures thereof.

26. A process according to claim 25, wherein said resin premix further comprises an auxiliary foaming agent selected from water, low boiling point compounds, or mixtures thereof.

27. A process for preparing a rigid polyurethane foam composite comprising forming a rigid polyurethane foam on a face material or in a cavity surrounded by a plurality of face materials, wherein said polyurethane foam is obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst and cell regulator, said polyol comprising polyol (A) according to claim 1, and said foaming agent being selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons and mixtures thereof.

28. A process according to claim 27, wherein said resin premix further comprises an auxiliary foaming agent, said auxiliary foaming agent being selected from water, low boiling point compounds, or mixtures thereof.

29. A process for preparing a rigid polyurethane foam composite comprising forming a rigid polyurethane foam on a face material or in a cavity surrounded by a plurality of face materials, wherein said polyurethane foam is obtained by the reaction of an organic polyisocyanate with a resin premix comprising a polyol, foaming agent, catalyst and cell regulator, said polyol comprising polyol D according to claim 8, and said foaming agent being selected from the group consisting of hydrochlorofluorocarbons, hydrofluorocarbons and mixtures thereof.

30. A process according to claim 27, wherein said resin premix further comprises an auxiliary foaming agent selected from water, low boiling point compounds, or mixtures thereof.

31. The rigid polyurethane foam of claim 19 or claim 21 wherein the hydrochlorofluorocarbon is 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane or 1-chloro-1,1-difluoromethane and the hydrofluorocarbon is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.

32. The rigid polyurethane foam of claim 19 or claim 21 wherein a portion or the whole of the organic polyisocyanate comprises a prepolymer of the organic polyisocyanate.

33. The rigid polyurethane foam of claim 19 or claim 21 wherein the equivalent ratio of the isocyanate group in the organic polyisocyanate to the hydroxyl group in the polyol is in the range of from 0.8 to 5.0.

34. A preparation process of the rigid polyurethane foam of claim 23 or claim 25 wherein the hydrochlorofluorocarbon is 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane or 1-chloro-1,1-difluoromethane and the hydrofluorocarbon is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.

35. The preparation process of the rigid polyurethane foam of claim 23 or claim 25 wherein a portion or the whole of the organic polyisocyanate comprises a prepolymer of the organic polyisocyanate.

36. The preparation process of the rigid polyurethane foam of claim 23 or claim 25 wherein the equivalent ratio of the isocyanate group in the organic polyisocyanate to the hydroxyl group in the polyol is in the range of from 0.8 to 5.0.

37. The preparation process of claim 27 or claim 29 wherein the rigid polyurethane foam is formed in a plurality of face material by spreading, pouring or spraying.

38. The preparation process of claim 27 or claim 29 wherein the rigid polyurethane foam is formed on a face material by spraying.

39. The preparation process of claim 27 or claim 29 wherein the hydrochlorofluorocarbon is 2,2-dichloro-1,1,1-trifluoroethane, 1,1-dichloro-1-fluoroethane, 1-chloro-1,1-difluoroethane or 1-chloro-1,1-difluoromethane and the hydrofluorocarbon is 1,1,1,2-tetrafluoroethane or 1,1-difluoroethane.

40. The preparation process of claim 27 or claim 29 wherein a portion or the whole of the organic polyisocyanate comprises a prepolymer of the organic polyisocyanate.

41. The preparation process of claim 27 or claim 29 wherein the equivalent ratio of the isocyanate group in the organic polyisocyanate to the hydroxyl group in the polyol is in the range of from 0.8 to 5.0.