JP2999796B2 - Urethane resin and use thereof - Google Patents

Description

The present invention relates to a novel polyurethane resin, a foam using the same as a raw material, a method for producing the same, and a method for producing a rigid polyurethane foam composite with a face material.

In the production of the rigid polyurethane foam of the present invention, the hydrochlorofluorocarbons and the novel polyoxyalkylene polyols, which have a very low risk of environmental destruction, have excellent mutual mixing and dispersibility, good workability, and polyoxyalkylene polyol. Polyurethane resins produced from the above and an organic polyisocyanate and, if necessary, a catalyst have an extremely favorable effect because they are resistant to dissolution in the hydrochlorofluorocarbons. That is,
Polyurethane foam as a product is excellent in heat insulating properties, strength, low-temperature dimensional stability, and flame retardancy, and therefore, is extremely useful as a heat insulating structural material such as refrigerators, freezers, and heat insulating panels.

[Conventional technology]

Rigid polyurethane foam has excellent heat insulation properties and low-temperature dimensional stability, so various composites to which it is applied can be used as insulation, structural materials or instruments for refrigerators, freezer warehouses, building walls, ceilings, ships or vehicles, etc. Widely used as a heat insulating or protective cover.

In addition, a method of manufacturing a composite in which a rigid polyurethane foam is formed on one face material and in a space surrounded by a plurality of face materials by a batch method or a continuous method has already been widely performed.

Currently, when producing polyurethane foam, CFC-11 and CFC-12, which are fluorocarbons (hereinafter abbreviated as CFC), are used as a foaming method as a foaming method. It has been taken up as an environmental destructive substance that destroys and increases the greenhouse effect, and its production and use have recently been regulated.
At the same time, as a substitute for CFC-11 and CFC-12, hydrochlorofluorocarbons (hereinafter
HCFC), 2,2-dichloro-1,1,1-trifluoroethane (HCFC-123) and 1,1-dichloro-1-fluoroethane (HCFC-141b) have been attracting attention, These fluorocarbons have CFC-11 dissolving power for polyurethane resin.
Compared with CFC-12 or CFC-12, they have the drawback of greatly reducing the properties of polyurethane foam, such as a decrease in closed cell ratio and foam strength. In particular, the heat insulating effect, which is a characteristic of the rigid polyurethane foam, is significantly reduced because the above-mentioned fluorocarbon dissolves the closed cells of the foam during foaming.

Therefore, the necessity of developing a new polyurethane resin or polyurethane foam that can be used in combination with HCFC has emerged. Among the polyoxyalkylene polyols used as conventional raw materials for producing polyurethane resins, there is an example in which a polyoxyalkylene polyol obtained by adding an alkylene oxide to a novolak resin is used in combination with a polyether polyol and / or a polyester polyol (Japanese Patent Publication No. 46-19764). No. 3797, Japanese Patent Publication No. 47
-19911, JP-A-63-264616, JP-A-1-1-1
No. 35824), all of which only use a novolak resin-based polyol for the purpose of improving the flame retardancy of a polyurethane foam. As in the present invention, a specific combination of a phenolic resin and a polyoxyalkylene polyol having an alkanolamine or an aliphatic polyhydroxy compound as an initiator improves the solubility resistance of the polyurethane resin in HCFC-123 or HCFC-141b. It is not intended to improve the physical properties of the polyurethane foam used for these CFC blowing agents.

[Problems to be solved by the invention]

From the above background, hydrochlorofluorocarbons (HCFCs) are examples of foaming agents with low environmental destruction. However, the strong dissolving power for polyurethane resin causes a decrease in foam physical properties and a decrease in closed cell ratio. It was not easy to obtain a foam having satisfactory properties.

In producing rigid polyurethane foams using HCFCs, e.g., HCFC-123, HCFC-141b above as blowing agents, the prior art has shown that the use of blowing agents from
In the case of switching to C-123 or HCFC-141b, (1) the reactivity is delayed, so that when a non-horizontal surface is discharged, the raw material liquid drips on the discharge surface before the foaming and curing is completed.

(2) Mechanical strength of the obtained foam, such as low-temperature dimensional stability and compressive strength, is significantly reduced.

(3) The thermal conductivity of the foam increases significantly.

Various undesired problems have been confirmed.

Needless to say, polyurethane foams and their composites having such problems naturally cause deterioration in quality.

An object of the present invention is to provide a novel polyurethane which uses HCFC and solves the above-mentioned various problems, and has physical properties equal to or higher than that of a conventional polyurethane foam using chlorofluorocarbons (CFC) as a foaming agent. An object of the present invention is to provide a polyurethane resin and a method for producing a rigid polyurethane foam or a foam using the polyurethane resin or a composite thereof.

[Means for solving the problem]

The present inventors have conducted various studies based on the premise that hydrochlorofluorocarbons are used in order to solve the above-mentioned problems, and as a result, have reached the present invention.

 That is, the present invention is as follows.

[1] Represented by the following general formula (I) and having a number average molecular weight of 650
Phenol resin having an average number of functional groups of 3 to 8 and a hydroxyl value of 14 to 1 mol of alkylene oxide added to 1 mol of hydroxyl group of the phenol resin.
5 to 350 mgKOH / g of polyoxyalkylene polyol (a), per mol of active hydrogen of alkanolamine which is one or a mixture of two or more selected from the group consisting of compounds represented by the following general formula (II) Hydroxyl value obtained by adding 0.5 to 3.0 mol of alkylene oxide is 240 to 800
mgKOH / g polyoxyalkylene polyol (b), aliphatic polyhydroxy which is one or a mixture of two or more selected from the group consisting of glycols having 2 to 8 functional groups, polyhydric alcohols and polysaccharides In the polyoxyalkylene polyol (c) having a hydroxyl value of 130 to 750 mgKOH / g obtained by adding 0.8 to 6.5 moles of alkylene oxide per mole of hydroxyl group of the compound, the weight mixing ratio of (a) and (b) (a ) / (B) is 0.25 to 4.0, or (a) and (c)
Each having a weight ratio (a) / (c) of 0.1 to 4.0, a mixed polyoxyalkylene polyol having a hydroxyl value of 180 to 700 mgKOH / g, an organic polyisocyanate, or, if necessary, a catalyst mixed therewith. Polyurethane resin obtained by reacting.

(In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6.
It is. X is -CR ₁ R _2- , xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Is an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. [2] In preparing a rigid polyurethane foam by mixing a resin stock solution containing a polyoxyalkylene polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries with an organic polyisocyanate, the polyoxyalkylene polyol is used as the polyoxyalkylene polyol. The number average molecular weight represented by the following general formula (I) is
A polyoxyalkylene polyol (a) having a hydroxyl value of 145 to 350 mgKOH / g, obtained by adding a phenol resin having an average functional group number of 3 to 8 to 650 to 1400 and adding 1.0 to 4.5 moles of alkylene oxide per mole of hydroxyl group of the phenol resin. ), Obtained by adding 0.5 to 3.0 moles of alkylene oxide per mole of active hydrogen of alkanolamine which is one or a mixture of two or more kinds selected from the group consisting of compounds represented by the following general formula (II). Hydroxyl number is 240-800
mgKOH / g polyoxyalkylene polyol (b), aliphatic polyhydroxy which is one or a mixture of two or more selected from the group consisting of glycols having 2 to 8 functional groups, polyhydric alcohols and polysaccharides In the polyoxyalkylene polyol (c) having a hydroxyl value of 130 to 750 mgKOH / g obtained by adding 0.8 to 6.5 moles of alkylene oxide per mole of hydroxyl group of the compound, the weight mixing ratio of (a) and (b) (a ) / (B) is 0.25 to 4.0, or (a) and (c)
Using a mixed polyoxyalkylene polyol having a hydroxyl value of 180 to 700 mgKOH / g having a weight mixing ratio (a) / (c) of 0.1 to 4.0 with hydrochlorofluorocarbons or those containing the same A rigid polyurethane foam characterized by using:

(In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6.
It is. X is -CR ₁ R _2- , xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Is an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. [3] When a raw resin solution containing a polyoxyalkylene polyol, a foaming agent, a catalyst, a foam stabilizer, and other auxiliaries is mixed with an organic polyisocyanate to produce a rigid polyurethane foam, the polyoxyalkylene polyol is used as the polyoxyalkylene polyol. The number average molecular weight represented by the following general formula (I) is
A polyoxyalkylene polyol (a) having a hydroxyl value of 145 to 350 mgKOH / g, obtained by adding a phenol resin having an average functional group number of 3 to 8 to 650 to 1400 and adding 1.0 to 4.5 moles of alkylene oxide per mole of hydroxyl group of the phenol resin. ), Obtained by adding 0.5 to 3.0 moles of alkylene oxide per mole of active hydrogen of alkanolamine which is one or a mixture of two or more kinds selected from the group consisting of compounds represented by the following general formula (II). Hydroxyl number is 240-800
mgKOH / g polyoxyalkylene polyol (b), aliphatic polyhydroxy which is one or a mixture of two or more selected from the group consisting of glycols having 2 to 8 functional groups, polyhydric alcohols and polysaccharides In the polyoxyalkylene polyol (c) having a hydroxyl value of 130 to 750 mgKOH / g obtained by adding 0.8 to 6.5 moles of alkylene oxide per mole of hydroxyl group of the compound, the weight mixing ratio of (a) and (b) (a ) / (B) is 0.25 to 4.0, or (a) and (c)
Using a mixed polyoxyalkylene polyol having a hydroxyl value of 180 to 700 mgKOH / g having a weight mixing ratio (a) / (c) of 0.1 to 4.0 with hydrochlorofluorocarbons or those containing the same A method for producing a rigid polyurethane foam, characterized by using:

(In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6.
It is. X is -CR ₁ R _2- , xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Is an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. [4] A resin stock solution containing a polyoxyalkylene polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries is mixed with an organic polyisocyanate, and the mixture is mixed on one sheet or a plurality of sheets. When producing a composite in which a rigid polyurethane foam is formed in the voids surrounded by the polyoxyalkylene polyol, the polyoxyalkylene polyol has a number average molecular weight represented by the following general formula (I) of 650 to 1400 and an average number of functional groups of 3 ~
Polyoxyalkylene polyol (a) having a hydroxyl value of 145 to 350 mgKOH / g obtained by adding 1.0 to 4.5 moles of alkylene oxide per mole of hydroxyl group of the phenol resin, using a phenol resin having a phenolic resin represented by the following general formula (II). Polyol having a hydroxyl value of 240 to 800 mg KOH / g obtained by adding 0.5 to 3.0 mol of alkylene oxide per mol of active hydrogen of alkanolamine, which is one or a mixture of two or more selected from the group consisting of Oxyalkylene polyol (b), glycols having 2 to 8 functional groups,
0.8 to 6.5 alkylene oxides per mole of hydroxyl group of the aliphatic polyhydroxy compound which is one or a mixture of two or more selected from the group consisting of polyhydric alcohols and polysaccharides.
In the polyoxyalkylene polyol (c) having a hydroxyl value of 130 to 750 mgKOH / g obtained by mole addition,
The weight mixing ratio (a) / (b) of (a) and (b) is 0.25 to
4.0, or the weight mixing ratio of (a) and (c) (a) /
(C) 0.1 to 4.0, hydroxyl number 180 to 700 mg KO
A method for producing a rigid polyurethane foam composite, comprising using a mixed polyoxyalkylene polyol of H / g and using a hydrochlorofluorocarbon or a substance containing the same as the blowing agent.

(In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6. X is —CR ₁ R ₂ —, xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Alkyl group, alicyclic hydrocarbon group and aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. [1] Polyurethane Resin The invention relating to this item is as described in the above [I].

Further, the embodiments are described in claims 2 to 5.

Further, as for the resin described in this section, those described in [2] to [4] described below are applied to this section as they are, except for the foaming relation.

The phenolic resin used in the present invention is a compound represented by the following general formula (I), (In the formula (I), R ¹ is selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom consisting of chlorine, bromine and fluorine, a hydroxyl group, an alkyl ether group consisting of methoxy, ethoxy and butoxy. Represents an atom or a group, m
Is 1 to 3, and n is 1 to 6.

X is -CR ₁ R _2- , xylylene, oxy, thiodithio,
A divalent group selected from the group consisting of sulfonyl,
Consists of one or more of these linking groups. Here, R ₁ and R ₂ are a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Those having a number average molecular weight (Mn) of 650 to 1,400 and an average number of functional groups (f) of 3 to 8 are used.

For example, phenols and aldehydes such as phenol, cresol, butylphenol, nonylphenol, chlorophenol, resorcin, hydroquinone, catechol, guaiacol, bisphenol A, bisphenol S, or α, α′-dimethoxyxylene or α, α′-dichloroxylene , Or obtained by reacting sulfur or the like by an ordinary method. Furthermore, (Mn) is 650 to 900 and (f) is 3 to
8. Novolak resins having a softening point of 75 to 115 ° C. are mentioned as preferred compounds.

Examples of the alkylene oxide used in the present invention include ethylene oxide, propylene oxide, and butylene oxide, and these may be used in combination of two or more.

When the number of added alkylene oxides increases, the flon resistance generally tends to deteriorate, but the molecular weight of the phenolic resin increases.
If the number is less than 650, the number of added alkylene oxides is 1
Even in the case of 1 mole per mole, when the addition amount of alkylene oxide to alkanolamine (described later) is at least 0.5 mole, phenol resin (a) to which alkylene oxide is added and alkanolamine (b) to which alkylene oxide is added. When the weight ratio (a) / (b) is changed to 0.25 to 4.0, and when the addition amount of alkylene oxide (described later) to the aliphatic polyhydroxy compound is at least 0.8 mol, the aliphatic polyoxyalkylene compound to which the alkylene oxide is added When the weight ratio (a) / (c) with respect to the hydroxy compound (c) was changed to 0.1 to 4.0, they tended to be dissolved in HCFC when reacted with an organic polyisocyanate to form a polyurethane resin.
When the (Mn) of the phenolic resin exceeds 1400, the viscosity is high even if the mixing ratio is changed, and the mixing and dispersing property in HCFC is poor, and the workability in reacting is poor, or the alkanolamine or fat It takes time to uniformly mix with a polyoxyalkylene polyol or an organic polyisocyanate using an aromatic polyhydroxy compound as an initiator, or even if a compound having a low viscosity is selected as a compounding partner, the polyurethane resin has poor CFC-solubility resistance and is preferable. Absent.

The polyoxyalkylene polyol (a) of the present invention is obtained by adding 1.0 to 4.5 moles of alkylene oxide per mole of phenolic hydroxyl group of a phenol resin. Alkylene oxide is added in an amount of 1.
If the amount is less than 0 mol, that is, if a large amount of phenolic hydroxyl groups remains, it is not preferable because a polyurethane foam has poor foam properties. Also, 4.5
If the alkylene oxide is added in excess of the moles, the viscosity decreases, and HCFC-123 and HCFC-1 used as HCFCs are used.
The mixing and dispersibility in 41b is improved, but the CFC solubility resistance of the polyurethane resin is lost.

When (f) of the phenolic resin is less than 3, a polyurethane resin obtained by mixing with a polyoxyalkylene polyol having an alkanolamine or an aliphatic polyhydroxy compound as an initiator and reacting with a polyisocyanate is used. Tend to worsen,
When (f) exceeds 8, there is a disadvantage that the polyurethane resin obtained by reacting with the organic polyisocyanate becomes brittle.

The alkanolamine used in the present invention includes the following general formula (II): NR ₁ ′ R ₁ ′ R ₂ ′ (II) (wherein R ₁ ′ and R ₂ ′ are hydrogen atoms) , -CH ₂ CH ₂ OH group, -CH ₂ C
One atom or group selected from the group consisting of H (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. ), For example, monoethanolamine,
Examples thereof include diethanolamine, triethanolamine, monoisopropanolamine, diisopropanolamine, and triisopropanolamine.

The polyoxyalkylene polyol (b) of the present invention is obtained by adding 0.5 to 3.0 mol of alkylene oxide per 1 mol of active hydrogen of alkanolamine. If the addition of the alkylene oxide is less than 0.5 mol per mol of active hydrogen of the alkanolamine, the physical properties of the alkanolamine when formed into a foam also deteriorate because the crosslinker properties of the alkanolamine remain. When it exceeds 3.0 moles, the mixing ratio with the polyoxyalkylene polyol (a) (a) /
If (b) exceeds 4.0, the physical properties deteriorate and it cannot be used as a foam.

In the present invention, the mixing ratio (a) / (b) of the polyoxyalkylene polyols (a) and (b) is preferably from 0.25 to 4.0 by weight. Those with a weight ratio exceeding 4.0 are viscous and HCF
The dispersibility in mixing with C-123 and HCFC-141b tends to be poor, and there is a problem in operation when the polyurethane resin is used, which is not preferable. On the other hand, those having a molecular weight of less than 0.25 are not preferable because the foam properties are inferior.

The aliphatic polyhydroxy compound used in the present invention is one or more selected from the group consisting of glycols having 2 to 8 functional groups, polyhydric alcohols, and polysaccharides.
Specifically, ethylene glycols as glycols,
Diethylene glycol, propylene glycol, dipropylene glycol, butanediol, neopentyl glycol, cyclohexane dimethanol, cyclohexanetetramethanol, glycerin as a polyhydric alcohol,
Trimethylolethane, trimethylolpropane, and pentaerythritol, and polysaccharides such as methyl glycoside, sorbitol, mannitol, dulcitol, and sucrose.

The number of alkylene oxides added per mole of hydroxyl group of the aliphatic polyhydroxy compound is preferably 0.8 to 6.5 mol.
When the amount is less than 0.8 mol, the foam tends to become brittle when formed into a urethane foam, and when the amount exceeds 6.5 mol, the resistance to chlorofluorocarbon dissolution of the polyurethane resin made from the material decreases.

The weight mixing ratio (a) / (c) of the polyoxyalkylene polyols (a) and (c) each using a phenol resin and an aliphatic polyhydroxy compound as initiators is 0.1
~ 4.0 is preferred. When the mixing ratio is less than 0.1, there is a tendency that the chlorofluorocarbon solubility is reduced when the polyurethane resin is formed by a reaction in the presence of a catalyst, and when the mixing ratio is more than 4.0, the viscosity is too high and the polyurethane resin is used. Has the disadvantage that the workability of the device is poor.

The catalyst used for obtaining the polyoxyalkylene polyols (a), (b) and (c) in the present invention is an amine compound represented by the following general formula (III) or (IV) as an amine.

NR ₁ ″ R ₁ ″ R ₂ ″ (III) R ₁ ″ R ₂ ″ N (CH ₂ ) n NR ₁ ″ NR ₂ ... (IV) (where R ₁ ″ is a hydrogen atom and has 1 to 1 carbon atoms) An alkyl group of 6,
—CH ₂ CH ₂ OH or —CH ₂ CH (CH ₃ ) OH; R ₂ ″ is a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, —CH ₂ C
It represents an H ₂ OH group or a —CH ₂ CH (CH ₃ ) OH group. N is 1 to 6
It is. However, in (III), the case where both R ₁ ″ and R ₂ ″ are hydrogen atoms is excluded. Examples of the amine compound include dibutylamine, ethylenediamine, tetramethylenediamine, monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, triethylamine, tri-n-propylamine, di-n-propylamine, and n-amine.
Examples thereof include propylamine, n-amylamine, N, N-dimethylethanolamine, isobutylamine, isoamylamine, and methyldiethylamine.

As the alkali hydroxide, lithium hydroxide, sodium hydroxide, potassium hydroxide, magnesium hydroxide,
Examples include calcium hydroxide and barium hydroxide.

Each of the above catalysts can be used alone or in combination of two or more.

As the organic polyisocyanate used in the present invention, conventionally known ones are not particularly limited, and aromatic, aliphatic, alicyclic polyisocyanates and modified products thereof,
Dimer, trimer such as diphenylmethane diisocyanate, crude diphenylmethane diisocyanate, tolylene diisocyanate, crude tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, hydrogenated diphenylmethane Diisocyanate, hydrogenated tolylene diisocyanate, triphenylmethylene triisocyanate,
Tolylene triisocyanate, uretdione, isocyanurate, modified (carbodiimide, etc.) diphenylmethane diisocyanate and the like, and mixtures thereof, and excessive amounts of these organic polyisocyanates and polyols (eg, low molecular weight polyols or polymer polyols)
Isocyanate group-terminated prepolymer (NCO group content: 5 to 3) obtained by reaction with O group / active hydrogen (equivalent ratio) of 2.0 to 5.0
5%).

These organic polyisocyanates are used alone or in combination of two or more. The amount used is such that the equivalent ratio of the isocyanate group (NCO group) to the active hydrogen in the resin solution is 0.8 to 5.
So that it becomes 0.

[2] Polyurethane foam The invention relating to this section is as described in the above [2].

Further, the embodiments are described in claims 7 to 11.

In this section, the polyoxyalkylene polyol, organic polyisocyanate and the like used in the above section [1] and in the following sections [3] and [4] can naturally be applied to this section.

The phenolic resin used in the present invention is a compound represented by the aforementioned general formula (I), having a number average molecular weight (Mn) of 650 to 1400 and a functional group number (f) of 3 to 8. For example, phenols and aldehydes such as phenol, cresol, butylphenol, nonylphenol, chlorophenol, resorcinol, hydroquinone, catechol, guaiacol, bisphenol A and bisphenol S, or α, α′-dimethoxyxylene or α, α′-dichloro It includes those obtained by reacting xylene or sulfur with a known method in the presence of an acidic catalyst.

On the other hand, specific examples of the initiator that can be used by mixing with the phenol resin are shown below.

Aliphatic polyhydroxy compounds include ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, butanediol, neopentyl glycol, cyclohexane dimethanol, cyclohexanetetramethanol, dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane, 1 , 3,6-hexanetriol, pentaerythritol, methyl glycoside, sorbitol, mannitol, sucrose, bisphenol A, hydroxylated 1,2-polybutadiene, hydroxylated 1,4-polybutadiene and the like.

The alkanolamines include monoethanolamine, diethanolamine, triethanolamine,
Monoisopropanolamine, diisopropanolamine, triisopropanolamine and the like can be mentioned.

The preferred range of the hydroxyl value of the polyoxyalkylene polyol used in the present invention obtained by adding an alkylene oxide to the compound having two or more active hydrogens is 180 to 700 mgKOH / g. In addition, polyoxyalkylene polyols having a hydroxyl value adjusted to 240 to 800 and 130 to 750 mg KOH / g, respectively, by separately adding an alkylene oxide to the initiator of the alkanolamines or the aliphatic polyhydroxy compounds shown in the above specific examples, and Formula (I)
A polyoxyalkylene polyol having a hydroxyl value of 145 to 350 mgKOH / g obtained by adding an alkylene oxide to the phenol compound shown in (1) can be used after mixing at a predetermined mixing ratio.

In addition to hydrochlorofluorocarbons (HCFC), chlorofluorocarbons such as trichlorofluoromethane (CFC-11), lower hydrocarbon compounds or low-boiling chlorinated hydrocarbons, or water can be used as the blowing agent. .

Examples of the catalyst which can be used in the present invention include amine compounds (triethylamine, tripropylamine, triisopropanolamine, tributylamine, trioctylamine, hexadecylmethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecyl Morpholine, monoethanolamine, diethanolamine,
Triethanolamine, N-methyldiethanolamine, N, N-dimethylethanolamine, diethylenediamine, N, N, N ', N'-tetramethylethylenediamine,
N, N, N ', N'-tetramethylpropylenediamine, N, N,
N ', N'-tetomethylbutanediamine, N, N, N', N'-tetomethyl-1,3-butanediamine, N, N, N ', N'-tetomethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylamine, N, N-dimethylcyclohexylamine, N, N, N ', N
, N ″ -pentamethyldiethylenetriamine, triethylenediamine, organic acid salts of triethylenediamine, oxyalkylene adducts of amino groups of primary and secondary amines,
Azacyclic compounds such as N, N-dialkylpiperazines,
Various N, N ′, N ″ -trialkylaminoalkylhexahydrotriazines, β-aminocarbonyl catalysts of JP-B-52-43517, β-aminonitrile catalysts of JP-B-53-14279, etc. Tin, tin octylate, tin oleate, tin laurate, dibutyltin diacetate,
Dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.).

These catalysts are used alone or as a mixture.The amount of the catalyst used is 0.0001 to 10.
0 parts by weight.

The foam stabilizer in the present invention is a conventionally known organosilicon-based surfactant, for example, L-50 manufactured by Nippon Unicar Co., Ltd.
1, L-532, L-540, L-544, L-3550, L-5302,
L-5305, L-5320, L-5340, L-5410, L-5420,
L-5421, L-5710, L-5720 and the like, and SH-190, SH-192, SH-193, SH-194, SH-SH, manufactured by Toray Silicone Co., Ltd.
-195, SH-200, SPX-253, etc., and F-114, F-121, F-122, F-220, F-23 manufactured by Shin-Etsu Silicone Co., Ltd.
0, F-258, F-260B, F-317, F-341, F-345, etc., and TFA-4200, TFA-42
02 and so on.

The amount of the foaming agent used is 0.1 to 20 parts by weight based on a total of 100 parts by weight of the compound having active hydrogen and the organic polyisocyanate.
Parts by weight.

Examples of the flame retardant include tris (2-chloroethyl) phosphate, tris (dichloropropyl) phosphate, tris (dibromopropyl) phosphate, CR-505 and CR-507 manufactured by Daihachi Chemical Co., and Ph. Manufactured by Monsanto Chemical Co.
Osgard 2XC-20 and C-22-R (Phosgard is a trademark of Monsanto Chemical Co., Ltd.) and Fyrol 6 manufactured by Stoffer Chemical Co. (Fyrol is a trademark of Stoffer Chemical Co., Ltd.) can be used.

Other known plasticizers, fillers, stabilizers, colorants, and the like in urethane chemistry can be added as necessary.

[3] Manufacturing method of rigid polyurethane foam The invention relating to this item is as described in the above [3].
Further, the embodiments are described in claims 13 to 17.
An applied invention based on the knowledge obtained by the inventions of the above [1] and [2] is [3].

Accordingly, the polyoxyalkylene polyols, organic polyisocyanates and the like used in this section can all be those described in the above [1] and [2] as they are.

The phenolic resin used in the present invention has a number average molecular weight (Mn) of 650 to 1400 and a functional group number (f) of 3 to 8 as described in the preceding section.

Furthermore, as a phenol resin, (Mn) is 650 to 900,
A novolak resin having (f) of 3 to 8 and a softening point of 75 to 115 ° C is a preferred compound.

On the other hand, specific examples of the initiator that can be used by mixing with the phenol resin are also the same as those described in the preceding section.

The preferred range of the hydroxyl value of the polyoxyalkylene polyol obtained by adding an alkylene oxide to these initiators is 180 to 700 mgKOH / g.

The organic polyisocyanate used in the present invention is the same as described in the preceding section.

The blowing agent is also the same as described in the previous section.

In addition, a foam stabilizer, a catalyst, a flame retardant, a plasticizer, a filler, a stabilizer, a colorant, and the like can be added as required. These additives are the same as those described in the previous section.

[4] Method for producing rigid polyurethane foam composite The invention relating to this item is as described in the above [4].
Further, the embodiments are described in claims 19 to 28.
The applied invention based on the knowledge obtained by the above-mentioned inventions [1] to [3] is the item [4].

Therefore, the polyoxyalkylene polyol, organic polyisocyanate, etc. used in this section are [1] to
Everything described in [3] can be applied as it is.

Examples of the upper surface material, the lower surface material and the side material used in the present invention include veneer plywood, aluminum plate, iron plate, corrugated pole, thick letter, laminated paper, cloth, and the above-mentioned paper or cloth, gypsum board, etc. The upper surface material, the lower surface material, and the side surface material may be the same or different.

Further, the composite of the present invention is produced by a continuous method, a semi-continuous method, or a batch method.

In the continuous method, usually a lower surface material supply device and an upper surface material supply device,
It has traverse type head, double conveyor, heating tunnel, cutter and others. Usually, a method is adopted in which after applying the foam raw material liquid to the lower surface material, the upper material is applied before the raw material liquid foams but hardens.

The batch method requires a relatively compact apparatus as compared with the continuous method, and a product having irregularities can be relatively easily produced.

The batch method generally includes a method in which an injection head is inserted between the upper and lower surfaces and the head is moved while the foam raw material liquid is injected, or a method in which the foam raw material liquid is injected by a one-shot method. In any case, the face material is fixed by equipment such as a press in order to suppress the expansion that occurs while the foaming proceeds.

Further, the rigid polyurethane foam of the present invention can be formed inside an outer shell having irregularities such as a refrigerator and a showcase.

In an embodiment of the present invention, a resin solution is prepared by mixing predetermined amounts of a polyoxyalkylene polyol, a catalyst, a blowing agent, a flame retardant, and other auxiliaries.

The resin solution and the organic polyisocyanate are rapidly mixed at a predetermined ratio using a polyurethane foaming machine with a mixing head or the like.

The composite of the present invention is produced by combining the obtained rigid polyurethane foam raw material liquid with a foaming machine that is compatible with the above-described continuous method, batch method, or semi-continuous method.

At this time, the flow rate ratio between the organic polyisocyanate and the resin solution is adjusted so that the equivalent method of the organic polyisocyanate and the active hydrogen in the polyoxyalkylene polyol becomes 0.8 to 5.0.

The rigid polyurethane foam composite with face material obtained by the present invention is useful as a heat insulating material or a structural material for building walls, ceiling panels, warehouses, refrigerators, ships, vehicles, and the like.

〔Example〕

(1) Physical properties of polyurethane resin and polyurethane foam using polyoxyalkylene polyol starting from “alkanolamine” The physical properties of phenolic resin, novolak resin, and other raw materials used in this section are shown below. -1.

The various polyoxyalkylene polyols shown in the following Tables 2 to 4 were reacted at the ratio of mixed polyoxyalkylene polyol / organic polyisocyanate (weight ratio) shown in the same table to produce a polyurethane resin. ,
The CFC absorption was measured.

In addition, the mixing and dispersibility (workability) of CFCs and polyoxyalkylene polyol when preparing a resin premix having the following formulation, and the closed cell ratio of the obtained polyurethane foam were determined.

Resin premix ・ Polyoxyalkylene polyol: 100g ・ Water: 0.5g ・ Silicone foaming agent L-5420: 1.5g (manufactured by Nippon Unicar Co., Ltd.) Kaolyzer No.1: 1.0g (manufactured by Kao Corporation) ・ Foaming Agent (CFC) HCFC or CFC: 40 g Organic polyisocyanate Crude diphenylmethane diisocyanate (MDI-CR200) listed in the table (Mitsui Toatsu Chemicals Co., Ltd.) Both stock solutions are rapidly stirred and mixed, and immediately 200 × 200 × 200mm
And then foamed and cured to form a foam.

Example 1 Number average molecular weight (Mn) 723, average number of functional groups (f) 6.37,
500 g of a novolak resin having a softening point of 95 ° C. (brand # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) was charged into an autoclave 2 and heated and melted at 120 ° C. after purging with nitrogen. 4 g of sodium hydroxide and 4 g of dimethyl ether amine were added and mixed, and 821 g of propylene oxide was gradually charged. After 3 hours, the propylene oxide in the system was removed, neutralized with acetic acid, and filtered under reduced pressure to obtain a hydroxyl value of 198 mgKOH.
/ g of polyoxyalkylene polyol (a-1) 1303 g
I got

Similarly, 500 g of triethanolamine was charged into 2 autoclaves, and 821 g of propylene oxide was added at 120 ° C.
Was gradually charged and reacted for 3 hours. Unreacted propylene oxide is removed from the reaction product to give a hydroxyl value of 71.
8 mgKOH / g polyoxyalkylene polyol (b-1)
1292 g was obtained. Polyoxyalkylene polyol (a-
The number of propylene oxide additions per mole of hydroxyl group of 1) and (b-1) was 3.1 mole and 0.5 mole, respectively.

Polyoxyalkylene polyol (a-1) and (b-1) are mixed in a weight ratio of (a-1) / (b-1) = 0.25.
Mixed, hydroxyl value 615mgKOH / g, viscosity 3600cp / 25
° C polyoxyalkylene polyol (A-1) was obtained.

Example 2 500 g of novolak resin (brand name # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) having (Mn) 723, (f) 6.37 and a softening point of 95 ° C. was charged into an autoclave 2 and heated and melted at 120 ° C. after purging with nitrogen. . 2.3 g of dimethylethanolamine was added and mixed, and 274 g of propylene oxide was gradually charged. After 3 hours, propylene oxide in the system was removed, and a polyoxyalkylene polyol having a hydroxyl value of 339 mgKOH / g (a-
2) 730 g was obtained. The number of propylene oxide additions per mole of the phenolic hydroxyl group in this polyoxyalkylene polyol was 1.0 mole.

Polyoxyalkylene polyol (a-2) and (b-1) synthesized in the same manner as in Example 1 were mixed at a weight mixing ratio of (a-2) / (b-1) = 1.0, and the hydroxyl value was 532 mgKOH / g. Thus, a polyoxyalkylene polyol (A-2) having a viscosity of 19700 cp / 25 ° C. was obtained.

Example 3 500 g of triethanolamine was charged into 2 autoclaves, and charged at 120 ° C. to remove 1752 g of propylene oxide, followed by a reaction for 3 hours. Unreacted propylene oxide was removed from the reaction product to obtain a polyoxyalkylene polyol (b-2) having a hydroxyl value of 253 mgKOH / g. The number of propylene oxide added per mole of hydroxyl group of the polyoxyalkylene polyol (b-2) was 2.9 mol.

The polyoxyalkylene polyols (a-2) and (b-2) synthesized in the same manner as in Example 2 were mixed at a polymerization mixing ratio (a-2) / (b-2) = 2.0, and the hydroxyl value was 308 mgKOH / g. Thus, a polyoxyalkylene polyol (A-3) having a viscosity of 31,500 cp / 25 ° C. was obtained.

Example 4 500 g of novolak resin (brand name # 9000, manufactured by Mitsui Toatsu Chemicals, Inc.) having (Mn) 644, (f) 5.62 and softening point of 93 ° C. was charged into an autoclave of 2, and heated and melted at 120 ° C. after purging with nitrogen. . 3.1 g of dimethylethanolamine was added and mixed, and 547 g of propylene oxide was gradually charged. After 3 hours, the propylene oxide in the system was removed, and a polyoxyalkylene polyol having a hydroxyl value of 250 mgKOH / g (a-
3) 982 g was obtained. Similarly, triethanolamine 50
0 g was charged into 2 autoclaves, and 1348 g of propylene oxide was gradually charged at 120 ° C. and reacted for 3 hours.
Removing unreacted propylene oxide from the reaction product,
1726 g of a polyoxyalkylene polyol (b-3) having a hydroxyl value of 372 mgKOH / g was obtained.

Polyoxyalkylene polyol (a-3), (b-
The number of propylene oxide additions per mole of hydroxyl group in 3) was 1.9 mole and 2.1 mole.

Polyoxyalkylene polyol (a-3) and (b-3) were mixed at a weight ratio of (a-3) / (b-3) = 0.43.
, Hydroxyl value 298mgKOH / g, viscosity 9670cp / 25
° C polyoxyalkylene polyol (A-4) was obtained.

Example 5 500 g of novolak resin (brand name # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) having (Mn) 723, (f) 6.37 and a softening point of 95 ° C. was charged into an autoclave 2 and heated and melted at 120 ° C. after purging with nitrogen. . 4 g of dimethylethanolamine was added and mixed, and 537 g of ethylene oxide was gradually charged. After 3 hours, the ethylene oxide in the system is removed, and the hydroxyl value
204 mg KOH / g of polyoxyalkylene polyol (a-
4) 1010 g was obtained. Similarly, triethanolamine 5
00 g was charged into an autoclave (2), and 268 g of ethylene oxide was gradually charged at 120 ° C., followed by a reaction for 3 hours. Unreacted ethylene oxide was removed from the reaction product to obtain a polyoxyalkylene polyol (b-4) having a hydroxyl value of 661 mgKOH / g. The polyoxyalkylene polyols (a-4) and (b-4) had 2.8 moles and 0.6 moles of ethylene oxide added per mole of hydroxyl group, respectively.

Polyoxyalkylene polyol (a-4) and (b-4) were mixed at a weight mixing ratio of (a-4) / (b-4) = 1.0
, Hydroxyl value 465mgKOH / g, viscosity 13000cp / 25
The polyoxyalkylene polyol (A-5) of ° C was obtained.

Example 6 The polyoxyalkylene polyols (a-1) and (b-1) obtained in Example 1 were mixed at a weight mixing ratio of (a-1) /
(B-1) = 4.0 and a hydroxyl value of 302 mgKOH /
g, a polyoxyalkylene polyol (A-6) having a viscosity of 28000 cp / 25 ° C. was obtained.

Example 7 o-Cresol was reacted with formalin in the presence of a p-toluenesulfonic acid catalyst to obtain (M
n) = 815, (f) 6.71, 500 g of a cresol / novolak type phenol resin having a softening point of 103 ° C. were charged into an autoclave of 2, followed by purging with nitrogen and melting by heating to 120 ° C. 2.3 g of dimethylethanolamine was added and mixed, and 305 g of propylene oxide was gradually charged. After the reaction for 3 hours, propylene oxide in the system was removed, and the hydroxyl value was 295 mgK
OH / g of polyoxyalkylene polyol (a-5)
1 g was obtained. The number of propylene oxide additions per mole of phenolic hydroxyl groups in this polyoxyalkylene polyol was 1.2 moles.

Polyoxyalkylene polyol (a-5) and the polyoxyalkylene polyol (b) obtained in Example 1
-1) was mixed at a weight mixing ratio of (a-5) / (b-1) = 1.0 to obtain a polyoxyalkylene polyol (A-7) having a hydroxyl value of 507 mgKOH / g and a viscosity of 19700 cp / 25 ° C.

Example 8 500 g of novolak resin (brand # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) having a melting point of (Mn) 723, (f) 6.37 and a softening point of 95 ° C. were charged into an autoclave 2 and then heated and melted at 120 ° C. after purging with nitrogen. . 2.3 g of dimethylethanolamine was added and mixed, and 300 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed to obtain 774 g of polyoxyalkylene polyol (a-6) having a hydroxyl value of 320 mgKOH / g.

The number of propylene oxide added per mole of the phenolic hydroxyl group of this polyoxyalkylene polyol was 1.1 mole.

The weight ratio of (b-2) obtained in Example 3 was (a-6) /
(B-2) = 2.0 and a hydroxyl value of 295 mg KOH /
g, a polyoxyalkylene polyol (A-8) having a viscosity of 31,500 cp / 25 ° C. was obtained.

Example 9 Novolak-type phenolic resin (Mn) 723, (f) 6.37, softening point 95 ° C (brand name # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) 50
0 g and 280 g of triethanolamine were charged into an autoclave 3 and purged with nitrogen, followed by heating and melting at 120 ° C. 2.6 g of sodium hydroxide and dimethylethanolamine 2.
6 g was added and mixed, and 1395 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and further filtered under reduced pressure.
2090 g of polyoxyalkylene polyol (A-9) having a hydroxyl value of 291 mgKOH / g and 26400 cp / 25 ° C. was obtained.

The number of propylene oxide additions per mole of each of the phenolic hydroxyl group and active hydrogen of this polyoxyalkylene polyol was 4.5 mol and 0.5 mol, respectively.

Example 10 A mixture of bisphenol A and nonylphenol (weight mixing ratio of bisphenol A / nonylphenol = 1/4) and formalin were reacted in the presence of a p-toluenesulfonic acid catalyst to obtain (Mn) 1032, f)
5.18, 500 g of phenol resin having a softening point of 121 ° C., 2.3 g of dimethylethanolamine and 320 g of propylene oxide,
In the same manner as in Example 10, 744 g of a polyoxyalkylene polyol (a-7) having a hydroxyl value of 182 mgKOH / g was obtained.

The number of propylene oxide additions per mole of the phenolic hydroxyl group of the polyoxyalkylene polyol (a-7) is
1.9 mol.

500 g of triethanolamine was charged into 2 autoclaves, and 706 g of propylene oxide was gradually charged at 120 ° C., followed by a reaction for 3 hours. Unreacted propylene oxide was removed from the reaction product to obtain a polyoxyalkylene polyol (b-5) having a hydroxyl value of 496 mgKOH / g. The number of propylene oxide additions per mole of hydroxyl group of the polyoxyalkylene polyol (b-5) was 1.1 mole.

A polyoxyalkylene polyol (a-7) and (b-5) are mixed at a weight ratio of (a-7) / (b-5) = 0.67, and a polyoxyalkylene having a hydroxyl value of 370 mgKOH / g and a viscosity of 30300 cp / 25 ° C. A polyol (A-10) was obtained.

Example 11 Novolak type phenol resin (Mn) 867, (f) 7.70, softening point 115 ° C (Mitsui Toatsu Chemical Co., Ltd. brand # 1000HS)
Charge 500g into 2 autoclaves and after purging with nitrogen 120
Heated and melted at ℃. 2.6 g of sodium hydroxide and 2.6 g of dimethylethanolamine were added and mixed, and 1231 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and filtered under reduced pressure to obtain 1640 g of polyoxyalkylene polyol (a-8) having a hydroxyl value of 153 mgKOH / g. The number of propylene oxide additions per mole of phenolic hydroxyl groups in this polyoxyalkylene polyol was 4.
4 moles.

Polyoxyalkylene polyol (a-8) and the polyoxyalkylene polyol (b) obtained in Example 3
-2) were mixed at a weight ratio of (a-8) / (b-2) = 1.5 to obtain a polyoxyalkylene polyol (A-11) having a hydroxyl value of 193 mgKOH / g and a viscosity of 18,900 cp / 25 ° C.

Example 12 Novolak-type phenol resin (brand name # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) having (Mn) 723, (f) 6.37, and softening point of 95 ° C. 50
0 g was charged into an autoclave No. 2 and purged with nitrogen, followed by heating and dissolving at 120 ° C. 2.3 g of dimethylethanolamine was added and mixed, and 305 g of propylene oxide was gradually charged. After the reaction for 3 hours, propylene oxide in the system was removed to obtain 781 g of a polyoxyalkylene polyol (a-9) having a hydroxyl value of 316 mgKOH / g. The number of propylene oxide additions per mole of the phenolic hydroxyl group in this polyoxyalkylene polyol was 1.1 mole.

Weight ratio of (a-9) / (b-1) = polyoxyalkylene polyol (a-9) and polyoxyalkylene polyol (b-1) synthesized by the same method as in Example 1.
Mix with 1, hydroxyl value 517mgKOH / g, viscosity 19700cp /
A polyoxyalkylene polyol (A-12) at 25 ° C. was obtained.

Example 13 Novolak-type phenol resin (Mn) 723, (f) 6.37, softening point 95 ° C. (Mitsui Toatsu Chemical Co., Ltd. brand # 2000) 30
7 g and 583 g of triethanolamine were charged into an autoclave 2 and purged with nitrogen and dissolved by heating at 120 ° C. 4.5 g of sodium hydroxide was added and mixed, and 886 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid,
Filtered under reduced pressure, hydroxyl value 450mgKOH / g, viscosity 860cp / 25
1470g of polyoxyalkylene polyol (A-13) at ℃
I got The number of propylene oxide additions per mole of each of the phenolic hydroxyl group and active hydrogen of the polyoxyalkylene polyol was 2.5 mol and 1.2 mol, respectively.

Comparative Example 1 Novolak-type phenol resin (Mn) 723, (f) 6.37, softening point 95 ° C (brand name # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) 50
0 g was charged into an autoclave No. 2 and purged with nitrogen, followed by heating and dissolving at 120 ° C. 5.3 g of dimethylethanolamine was added and mixed, and 1277 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed to obtain 1770 g of polyoxyalkylene polyol (a-10) having a hydroxyl value of 139 mgKOH / g. The number of propylene oxide additions per mol of the phenolic hydroxyl group of this polyoxyalkylene polyol was 5.0 mol.

Polyoxyalkylene polyol (a-10) and (b-2) synthesized in the same manner as in Example 3 were mixed at a weight mixing ratio of (a-10) / (b-2) = 1.0, and the hydroxyl value was 196 mgKOH / g. Thus, a polyoxyalkylene polyol (A-14) having a viscosity of 6300 cp / 25 ° C. was obtained.

Comparative Example 2 Novolak-type phenol resin (brand name # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) having (Mn) 723, (f) 6.37, and softening point of 95 ° C. 50
0 g was charged into an autoclave No. 2 and purged with nitrogen, followed by heating and melting at 120 ° C. 1.9 g of dimethylethanolamine was added and mixed, and 127 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed to obtain 627 g of polyoxyalkylene polyol (a-11) having a hydroxyl value of 390 mgKOH / g. The number of propylene oxide additions per mole of the phenolic hydroxyl group in this polyoxyalkylene polyol was 0.5 mole.

Polyoxyalkylene polyol (a-11) and (b-2) synthesized by the same method as in Example 3 were mixed at a weight mixing ratio of (a-11) / (b-2) = 1.0, and the hydroxyl value was 320 mgKOH / g. Thus, a polyoxyalkylene polyol (A-15) having a viscosity of 22000 cp / 25 ° C. was obtained.

Comparative Example 3 Polyoxyalkylene polyol having a hydroxyl value of 400 mg KOH / g and a viscosity of 10,000 cp / 25 ° C. (Mitsui Toatsu Chemical Co., Ltd.)
The same examination as in the example was conducted for brand name NC-400).

Comparative Example 4 Polyoxyalkylene polyol having a hydroxyl value of 470 mgKOH / g and a viscosity of 13000 cp / 25 ° C. (Mitsui Toatsu Chemical Co., Ltd.)
The same examination as in the example was conducted for brand name NT-470).

Tables 2 to 4 show the essential points of Examples 1 to 13 and Comparative Examples 1 to 4 and the workability and physical properties of the foams in producing the polyurethane foam.

As described above, the polyurethane resin composed of a mixed polyoxyalkylene polyol of a phenolic resin-based polyoxyalkylene polyol and an alkanolamine-based polyoxyalkylene polyol has good solubility resistance to hydrochlorofluorocarbon, and has a hydrophobizing agent as a foaming agent. It has been found that rigid polyurethane foams using chlorofluorocarbons also have physical properties comparable to those of conventional foams using chlorofluorocarbons.

(2) Physical Properties of Polyurethane Resin and Polyurethane Foam Using Polyoxyalkylene Polyol Initiated by "Aliphatic Polyhydroxy Compound" The phenol resin, novolak resin and other physical properties of the raw materials used in this section are shown in Table 1 above. Is the same as

The various polyoxyalkylene polyols shown in the following Table-5 were reacted at the ratio of mixed polyoxyalkylene polyol / organic polyisocyanate (weight ratio) shown in the same table to produce a polyurethane resin, and the absorption of CFC therein. The rate was measured.

Further, the mixing and dispersibility (workability) of chlorofluorocarbon and polyoxyalkylene polyol when preparing a resin premix having the following formulation, and the closed cell rate of the obtained polyurethane foam were determined.

Resin premix ・ Polyoxyalkylene polyol: 100g ・ Water: 0.5g ・ Silicone foam stabilizer L-5420: 1.5g (manufactured by Nippon Unicar Co., Ltd.) ・ Kaolyzer No.1: 1.0g (manufactured by Kao Corporation) ・Blowing agent (Freon): 40 g HCFC or CFC Organic polyisocyanate Crude diphenylmethane diisocyanate (MDI-CR 200) Listed in the table (Mitsui Toatsu Chemicals, Inc.) The foam was injected into a 200 mm vertical panel and foamed and cured to form a foam.

Example 14 500 g of glycerin and 3 g of potassium hydroxide were charged into a 2 autoclave, and propylene oxide 8 was added at 120 ° C.
After gradually charging 32 g, the mixture was reacted for 3 hours. Unreacted propylene oxide was removed from the reaction product, neutralized with phosphoric acid, further filtered and dried, and the hydroxyl value was 730 mg KOH.
/ g of polyoxyalkylene polyol (b-1) 1251 g
I got The number of propylene oxide added per mole of hydroxyl group in (b-1) was 0.8 mol.

The same polyoxyalkylene polyol (a-1) as obtained in Example 1 and the above (b-1) were mixed by weight (a-
1) / (b-1) = 1 and a hydroxyl value of 460 mgK
A polyoxyalkylene polyol (B-1) having an OH / g and a viscosity of 6300 cp / 25 ° C. was obtained.

Example 15 Mixing ratio (a-5) of the polyoxyalkylene polyols (a-5) and (b-1) obtained in Example 7 and Example 14
/ (B-1) = 4 and a hydroxyl value of 390 mgKOH /
g, a polyoxyalkylene polyol (B-2) having a viscosity of 12700 cp / 25 ° C. was obtained.

Example 16 Trimethylol propane 500 g and sodium hydroxide 2 g
Was charged into an autoclave No. 5, and 4230 g of propylene oxide was gradually charged at 120 ° C., followed by a reaction for 3 hours.
Removing unreacted propylene oxide from the reaction product,
Neutralized with phosphoric acid, further dried by filtration and dried to obtain a polyoxyalkylene polyol having a hydroxyl value of 141 mgKOH / g (b-
2) 4528 g was obtained. The number of propylene oxide added per mole of hydroxyl group in (b-2) was 6.2 mol.

The polyoxyalkylene polyol obtained in Example 8 (a
-6) and (b-2) by weight mixing ratio (a-6) / (b-
2) Mix at 1.5, hydroxyl value 245mgKOH / g, viscosity 4
900 cp / 25 ° C polyoxyalkylene polyol (B-
3) was obtained.

Example 17 Novolak-type phenolic resin (Mn) 723, (f) 6.37, softening point 95 ° C (brand # 2000, manufactured by Mitsui Toatsu Chemicals, Inc.) 25
0 g and 500 g of glycerin were charged into an autoclave 2 and purged with nitrogen and heated and melted at 120 ° C. 5.2 g of sodium hydroxide and 5.2 g of dimethylethanolamine were added and mixed, and 1965 g of propylene oxide was gradually charged. After reacting for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and further filtered under reduced pressure to obtain 1790 g of a polyoxyalkylene polyol (B-4) having a hydroxyl value of 195 mgKOH / g and a viscosity of 5300 cp / 25 ° C. Was. The number of propylene oxide additions per mole of each of the phenolic hydroxyl groups and glycerin hydroxyl groups of this polyoxyalkylene polyol was 4.5 mol and 1.5 mol, respectively.

Example 18 Glycerin 110 g, sucrose 390 g and sodium hydroxide
2 g was charged into 2 autoclaves, 2420 g of propylene oxide was gradually charged at 120 ° C., and after reacting for 3 hours, unreacted propylene oxide was removed from the reaction product, neutralized with phosphoric acid, further filtered and dried. And a hydroxyl number of 25
1 mgKOH / g polyoxyalkylene polyol (b-3)
2813 g was obtained. Polyoxyalkylene polyol (b-
The number of propylene oxide added per mole of hydroxyl group in 3) was 3.1 mole. The polyoxyalkylene polyol (a-7) obtained in Example 10 and the above (b-3) were mixed at a weight mixing ratio of (a-7) / (b-3) = 0.33, and the hydroxyl value was 235 mgKOH / g and the viscosity was A polyoxyalkylene polyol (B-5) at 2800 cp / 25 ° C. was obtained.

Example 19 500 g of glycerin and 3 g of potassium hydroxide were charged into an autoclave of 5 and 2383 g of propylene oxide was gradually charged at 120 ° C., and reacted for 3 hours. The unreacted propylene oxide was removed from the reaction product, neutralized with phosphoric acid, filtered and dried to obtain 2760 g of a polyoxyalkylene polyol (b-4) having a hydroxyl value of 327 mgKOH / g. The number of propylene oxide added per mole of hydroxyl group of the polyoxyalkylene polyol (b-4) was 2.4 mol.

Furthermore, polyoxyalkylene polyol (b-4)
(Mn) 867, (f) 7.7
0 After charging 500 g of novolak type phenol resin (brand name # 1000HS manufactured by Mitsui Toatsu Chemicals Co., Ltd.) with a softening point of 115 ° C, after nitrogen replacement
It was heated and melted at 120 ° C. 5.2 g of sodium hydroxide and 5.2 g of dimethylethanolamine were added and mixed, and 760 g of propylene oxide was gradually charged. After the reaction for 3 hours, propylene oxide in the system was removed, neutralized with acetic acid, and further filtered under reduced pressure to obtain a hydroxyl value of 267 mg KOH.
/ g, 3980 g of polyoxyalkylene polyol (B-6) having a viscosity of 3100 cp / 25 ° C. was obtained. The number of propylene oxide additions per mol of the phenolic hydroxyl group of the polyoxyalkylene polyol (B-6) was 2.8 mol.

Example 20 Glycerin 250 g, sucrose 250 g and sodium hydroxide
3 g was charged into 2 autoclaves, and 3530 g of propylene oxide was gradually charged at 120 ° C., followed by a reaction for 3 hours.
Removing unreacted propylene oxide from the reaction product,
3860 g of a polyoxyalkylene polyol (b-5) having a hydroxyl value of 207 mgKOH / g was obtained. The number of propylene oxide additions per mol of hydroxyl group of the polyoxyalkylene polyol (b-5) was 4.1 mol.

Further, the polyoxyalkylene polyol (a-3) obtained in Example 4 and the above (b-5) were mixed at a weight mixing ratio (a-
3) / (b-5) = 3 and a hydroxyl value of 240 mgK
A polyoxyalkylene polyol (B-7) having an OH / g and a viscosity of 9750 cp / 25 ° C. was obtained.

Table 5 shows the main points of Examples 14 to 20, the CFC absorption of the polyurethane resin, the workability in producing the polyurethane foam, and the physical properties of the foam.

As described above, the polyurethane resin composed of a mixed polyoxyalkylene polyol of a phenolic resin-based polyoxyalkylene polyol and an aliphatic polyhydroxy compound-based polyoxyalkylene polyol has good solubility resistance to hydrochlorofluorocarbon, and foaming. It has been found that rigid polyurethane foams using hydrochlorofluorocarbons as agents have physical properties comparable to foams using chlorofluorocarbons of conventional formulations.

(3) Production of rigid polyurethane foam As described above, "phenol resin + alkanolamine"
As "phenol resin + aliphatic polyhydroxy compound" -based various polyoxyalkylene polyols and foaming agents,
A basic study was conducted on a polyurethane foam using a combination of hydrochlorofluorocarbons.

Next, based on the results of the above-mentioned studies, a more specific study was conducted on a rigid polyurethane foam and its production.

The physical properties of the polyoxyalkylene polyol used are shown in Tables 6 and 7.

The other raw materials used are as follows.

・ MDI-CR: Crude diphenyl methane diisocyanate manufactured by Mitsui Toatsu Chemicals, Inc. NCO%: 31.0 ・ L-5421: Nippon Unicar Co., Ltd., foam stabilizer Organosilicon-based surfactant ・ TMHDA: Active material Chemical Co., Ltd., catalyst Tetramethylhexamethylenediamine Trademark: MINICO-TMHD ・ LL-690D: Sankyokisei Co., Ltd., catalyst 40% by weight solution of lead octylate in dioctyl phthalate ・ TCEP: Daihachi Chemical Co., Ltd. ), Flame retardant tris (2-chloroethyl) phosphate ・ CFC-11: trichlorofluoromethane chlorofluorocarbons, blowing agent ・ HCFC-123: 2,2-dichloro-1,1,1-trifluoroethane hydrochlorofluorocarbons , Blowing agent ・ HCFC-141b: 1,1-dichloro-1-fluoroethane Hydrochlorofluorocarbons, Blowing agent ・ H ₂ O: Water Blowing agent Examples 21 to 27, Comparative Examples 5 to 9 Table 6 and Table 6 To 7 100 g of the polyoxyalkylene polyol (C-1 to C-10) was mixed with a foaming agent, a foam stabilizer, and a catalyst according to the formulations shown in Tables 8 and 9 to prepare a resin stock solution. The amount of organic polyisocyanate (MDI-CR) shown in Tables 8 and 9
Was added, and the mixture was rapidly mixed for 8 seconds with a stirrer having a rotation speed of 5000 rpm, and immediately mixed with the internal dimensions 200 × 200 × 200 mm and 380 ×
Injected into a vertical panel with a volume of 380 x 35 mm, foamed freely,
After leaving for one day, 80 × 80 from 200 × 200 × 200mm foam
A sample of × 30 mm was cut out, and the compressive strength was cut out according to the method of JIS-A-9514, and a sample of 200 × 200 × 25 mm was cut out of a 380 × 380 × 35 mm foam, and the sample was cut out of JIS-A-1.
The thermal conductivity was measured according to the method of 412.

In addition, in order to evaluate the reactivity, a resin stock solution and an organic polyisocyanate (MDI-CR) were previously prepared at 20 ° C., allowed to freely foam under the same conditions as above, and the cream time / gel time / tack free time of the reaction solution was determined. Observation was performed, and the number of seconds was obtained in the order described above.

The experimental results were as shown in Table-8 and Table-9.

As can be seen from Tables 8 and 9, when the blowing agent in the conventional formulation is replaced with hydrochlorofluorocarbons, the reactivity becomes slow and the physical properties of the obtained foam deteriorate, but the polyoxyalkylene polyol of the present invention is used. With the use of hydrochlorofluorocarbons,
A foam having excellent physical properties was obtained.

(4) Production of Rigid Polyurethane Foam Composite Board with Face Material Based on the above experiment, production of the rigid polyurethane foam composite board with face material of the present invention was attempted.

1) Production of rigid polyurethane foam composite board having one face material The raw materials of polyoxyalkylene polyol used in the experiment of this section and their hydroxyl values are shown in Table 10 and Table 10
11 streets.

First, the physical properties of the foam part of the composite board of the present invention were evaluated.

Examples 28 to 43, Comparative Examples 10 to 19 Various polyoxyalkylene polyol compositions (D-1 to D-14 and B-4, A-
6, C-4) A foaming agent, a foam stabilizer and a catalyst were mixed with 100 g of 100 g to prepare a stock resin solution, and the amount of organic polyisocyanate shown in the same table was added thereto. (MDI-CR) and a stirrer with a rotation speed of 5000 rpm.
Mix rapidly for 8 seconds and immediately mix this inside 200 × 200 × 200mm
And the same 380 × 380 × 35mm volume of the vertical panel, poured freely, allowed to stand for 1 day, cut out a 80 × 80 × 30mm sample from the 200 × 200 × 200mm foam, JIS-A-9
Cut out the compressive strength according to the method of 514, and cut out a 200 × 200 × 25mm sample from a 380 × 380 × 35mm foam,
The thermal conductivity was measured according to the method of JIS-A-1412.

In addition, in order to evaluate the reactivity, a resin stock solution and an organic polyisocyanate (MDI-CR) were previously prepared at 20 ° C., allowed to freely foam under the same conditions as above, and the cream time / gel time / tack free time of the reaction solution was determined. Observation was performed, and the number of seconds was obtained in the order described above.

 The experimental results were as shown in Table-12.

Next, the blended formulations of Examples 28 and 32 and Comparative Examples 10 and 12 were sprayed and discharged on one surface under the following conditions to produce a rigid polyurethane foam composite plate with a surface material. Table 13 shows the physical properties of the product.

Foaming machine: Model-FF head D gun manufactured by Gasmer Co., Ltd. Discharge pressure: 50 kg / cm ² Liquid temperature: 40 ° C Surface material: cardboard paper Other physical property test methods were performed according to the methods described in Table-8.

2) Production of rigid polyurethane foam composite board having a plurality of face materials The raw materials of polyoxyalkylene polyol used in the experiments in this section and their hydroxyl values are shown in Table 10 and Table 10.
11 streets.

For the various polyoxyalkylene polyols shown in Table 10 and Table 11, according to the formulations shown in Table 14 and Table 15, auxiliary agents such as a foaming agent, a foam stabilizer, and a catalyst were mixed to form a resin stock solution. Then, an organic polyisocyanate (MDI-CR) in an amount shown in the same table was added thereto, and the compressive strength, flammability, thermal conductivity and other physical properties were measured by the same operation as in the preceding section.

 The measurement results were as shown in Table-14 and Table-15.

Next, a rigid polyurethane foam composite board with a two-sided material was produced by a continuous method under the following conditions for the compounding formulations of Examples 36 and 39 and Comparative Examples 15 and 19. Table 16 shows the physical properties of the product.

Model name: High-pressure foaming machine with mixing head manufactured by Henneke (MQ type) Line speed: 10m / min Temperature: Raw material 30-40 ° C Curing oven 55 ° C Product: 1m wide x 40mm thick Foam layer 35mm Surface material: Laminated paper Top surface Used for materials and bottom materials As can be seen from the above experimental results, when the phenolic resin-based polyoxyalkylene polyol of the present invention is used, the foam is sprayed onto a non-horizontal portion because of the appropriate reactivity in addition to the excellent physical properties of the foam described above. Even before the foaming and hardening, there was no dripping phenomenon in which the raw material liquid drips, the adhesion to the face material was good, and the properties of the spray discharge surface were also good.
In addition, a composite plate with a surface material having excellent flame retardancy and low thermal conductivity was obtained.

The raw material liquids used in this section are illustrated in Tables 12 and 14, but without being limited to these raw material liquids,
It is needless to say that all the raw material liquids shown in Examples 1 to 27 can be used from the point of the present invention.

〔The invention's effect〕

When a hydrochlorofluorocarbon is used as a foaming agent, when a specific polyoxyalkylene polyol obtained by adding a phenol resin as an initiator and an alkanolamine or an aliphatic polyhydroxy compound as an initiator is used, Compared with the conventional method using fluorocarbons, a rigid polyurethane foam is obtained which is not inferior in various physical properties such as workability, closed cell agent, reactivity, compressive strength, low temperature dimensional stability, thermal conductivity, flame retardancy, etc. Was.

Furthermore, in the production of the rigid polyurethane foam composite with the face material, in addition to the above excellent physical properties, no liquid dripping phenomenon was observed, and the adhesion to the face material was extremely good.

In other words, it was found that even if chlorofluorocarbons, which are considered to have high pollution, were not used, a product equivalent to or higher than the conventional product could be obtained by the present invention, and the product was industrially extremely useful.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 75:08 (31) Claimed priority number Japanese Patent Application No. 1-150362 (32) Priority date June 15, 2001 (1989. 6.15) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-150363 (32) Priority date June 15, 2001 (1989.6.15) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-165319 (32) Priority date June 29, 2001 (1989. 6.29) (33) Priority claim country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-211284 (32) Priority date August 18, 2001 (August 18, 1989) (33) Priority claim country Japan (JP) (31) Priority claim No. Japanese Patent Application No. 1-211285 (32) Priority Date August 18, 2001 (August 18, 1989) (33) Country of priority claim Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-221487 (32) The other day December 13, 2001 (Dec. 13, 1989) (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application No. 1-321488 (32) Priority date December 13, 2001 Date (1989.12.13) (33) Country of priority claim Japan (JP) (72) Inventor Seiji Ezaki 1-4 Shiomidai, Isogo-ku, Yokohama, Kanagawa Prefecture (72) Inventor Toshio Nozawa, Kasama, Sakae-ku, Yokohama, Kanagawa 1190-cho (72) Inventor Haruhiko Kawakami 4-19 Morigo-cho, Atsuta-ku, Nagoya-shi, Aichi (56) References JP-A-63-264616 (JP, A) JP-A-1-135824 (JP, A) 60-166315 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C08G 18/48-18/50 C08J 9/14

Claims (17)

(57) [Claims] 1. A phenol resin represented by the following general formula (I) having a number average molecular weight of 650 to 1400 and an average number of functional groups of 3 to 8; Alkanol which is one or a mixture of two or more polyoxyalkylene polyols (a) having a hydroxyl value of 145 to 350 mgKOH / g and a compound represented by the following general formula (II) to which 4.5 mol has been added. The hydroxyl value obtained by adding 0.5 to 3.0 moles of alkylene oxide per mole of active hydrogen of the amine is 240 to 8
00 mg KOH / g polyoxyalkylene polyol (b),
Glycols having 2 to 8 functional groups, polyhydric alcohols,
A hydroxyl value of 130 to 750 mgKOH / g obtained by adding 0.8 to 6.5 moles of alkylene oxide per mole of hydroxyl group of an aliphatic polyhydroxy compound, which is one or a mixture of two or more kinds selected from the group consisting of polysaccharides; In the polyoxyalkylene polyol (c), the weight mixing ratio (a) / (b) of (a) and (b) is 0.25 to 4.0, or the weight mixing ratio (a) / (c) of (a) / (c) (C) 0.1 to 4.0, each of the mixed polyoxyalkylene polyols having a hydroxyl value of 180 to 700 mgKOH / g, an organic polyisocyanate, or a polyurethane resin obtained by mixing and reacting a catalyst with these, if necessary. (In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6.
It is. X is -CR ₁ R _2- , xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Is an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. ) 2. The phenol resin according to claim 1, wherein R ¹ is a hydrogen atom, m is 1, and both X and Y are —CH ₂ — groups. The polyurethane resin according to claim 1. 3. The novolak resin has an average molecular weight of 650 to 900,
The polyurethane resin according to claim 2, wherein the average number of functional groups is 3 to 8, and the softening point is 75 to 115C. 4. A method in which a part or all of an organic polyisocyanate is reacted with an organic polyisocyanate and an active hydrogen-containing compound at an isocyanate group / active hydrogen (equivalent ratio) of 2.0 to 5.0 to obtain an NCO group at the molecular terminal. The polyurethane resin according to claim 1, which is a prepolymer having the following formula: 5. An equivalent ratio of an isocyanate group of an organic polyisocyanate to an active hydrogen group of an active hydrogen-containing compound is 0.8.
The polyurethane resin according to claim 1, which has a molecular weight of from 5.0 to 5.0. 6. A rigid polyurethane foam is produced by mixing a stock resin solution containing a polyoxyalkylene polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries with an organic polyisocyanate. A phenol resin having a number average molecular weight of 650 to 1400 and an average number of functional groups of 3 to 8 represented by the following general formula (I) was used, and 1.0 to 4.5 mol of alkylene oxide was added per 1 mol of hydroxyl group of the phenol resin. Active hydrogen of alkanolamine, which is a polyoxyalkylene polyol (a) having a hydroxyl value of 145 to 350 mgKOH / g and one or a mixture of two or more compounds selected from the group consisting of compounds represented by the following general formula (II) The hydroxyl value obtained by adding 0.5 to 3.0 moles of alkylene oxide per mole is 24.
0 to 800 mgKOH / g of a polyoxyalkylene polyol (b), an aliphatic which is one or a mixture of two or more selected from the group consisting of glycols having 2 to 8 functional groups, polyhydric alcohols and polysaccharides In the polyoxyalkylene polyol (c) having a hydroxyl value of 130 to 750 mgKOH / g obtained by adding 0.8 to 6.5 moles of alkylene oxide per mole of hydroxyl group of the polyhydroxy compound, (a) and (b)
(A) / (b) is 0.25 to 4.0, or the weight mixing ratio (a) / (c) of (a) and (c) is 0.1 to 4.0.
Using a mixed polyoxyalkylene polyol having a hydroxyl value of 180 to 700 mgKOH / g, which is 4.0, as the blowing agent,
A rigid polyurethane foam using a hydrochlorofluorocarbon or a material containing the same. (In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6.
It is. X is -CR ₁ R _2- , xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Is an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. ) 7. The phenolic resin according to claim 6, wherein R ¹ is a hydrogen atom, m is 1, and both X and Y are —CH ₂ — groups. The rigid polyurethane foam according to claim (6). 8. A novolak resin having an average molecular weight of 650 to 900,
The rigid polyurethane foam according to claim 7, having an average number of functional groups of 3 to 8 and a softening point of 75 to 115 ° C. 9. The method according to claim 9, wherein the hydrochlorofluorocarbon is 2,2.
2-dichloro-1,1,1-trifluoroethane or 1,1-
The rigid polyurethane foam according to claim 6, which is dichloro-1-fluoroethane. 10. An NCO group at the molecular end obtained by reacting an organic polyisocyanate with a part or all of an organic polyisocyanate and an active hydrogen-containing compound at an isocyanate group / active hydrogen (equivalent ratio) of 2.0 to 5.0. The rigid polyurethane foam according to claim 6, which is a prepolymer having: 11. An equivalent ratio of an isocyanate group of an organic polyisocyanate to an active hydrogen group of an active hydrogen-containing compound is 0.1.
The polyurethane foam according to claim 6, wherein the number is from 8 to 5.0. 12. A rigid polyurethane foam is produced by mixing a stock resin solution containing a polyoxyalkylene polyol, a foaming agent, a catalyst, a foam stabilizer and other auxiliaries with an organic polyisocyanate. A phenol resin having a number average molecular weight of 650 to 1400 and an average number of functional groups of 3 to 8 represented by the following general formula (I) was used, and 1.0 to 4.5 mol of alkylene oxide was added per 1 mol of hydroxyl group of the phenol resin. Active hydrogen of alkanolamine, which is a polyoxyalkylene polyol (a) having a hydroxyl value of 145 to 350 mgKOH / g and one or a mixture of two or more compounds selected from the group consisting of compounds represented by the following general formula (II) The hydroxyl value obtained by adding 0.5 to 3.0 moles of alkylene oxide per mole is 24.
Aliphatic which is one or a mixture of two or more selected from the group consisting of polyoxyalkylene polyol (b) having 0 to 800 mgKOH / g, glycols having 2 to 8 functional groups, polyhydric alcohols and polysaccharides In the polyoxyalkylene polyol (c) having a hydroxyl value of 130 to 750 mgKOH / g obtained by adding 0.8 to 6.5 moles of alkylene oxide per mole of hydroxyl group of the polyhydroxy compound, (a) and (b)
(A) / (b) is 0.25 to 4.0, or (a) / (c) is 0.1 to 4.0.
Using a mixed polyoxyalkylene polyol having a hydroxyl value of 180 to 700 mgKOH / g, which is 4.0, as the blowing agent,
A method for producing a rigid polyurethane foam, comprising using a hydrochlorofluorocarbon or a substance containing the same. (In the formula (I), R ¹ represents a hydrogen atom, an alkyl group having 1 to 9 carbon atoms, a halogen atom composed of chlorine, bromine or fluorine, a hydroxyl group, an alkyl ether group composed of methoxy, ethoxy, butoxy. M is 1 And n is 1 to 6.
It is. X is -CR ₁ R _2- , xylylene, oxy, thio,
It represents a divalent group selected from the group consisting of dithio and sulfonyl, and Y is one or more of these groups. Here, R ₁ and R ₂ are a hydrogen atom, and have 1 to 6 carbon atoms.
Is an alkyl group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. ) NR ₁ ′ R ₁ ′ R ₂ ′ (II) (In the formula (II), R ₁ ′ and R ₂ ′ are a hydrogen atom, a —CH ₂ CH ₂ OH group,
And represents one atom or group selected from the group consisting of —CH ₂ CH (CH ₃ ) OH groups. However, cases where both R ₁ ′ and R ₂ ′ are hydrogen atoms are excluded. ) 13. The phenol resin according to claim 12, wherein R ¹ is a hydrogen atom, m
Is a novolak resin wherein X and Y are both —CH ₂ — groups. 14. A novolak resin having an average molecular weight of 650 to 90.
The method for producing a rigid polyurethane foam according to claim 13, wherein 0, the average number of functional groups is 3 to 8, and the softening point is 75 to 115 ° C. 15. The hydrochlorofluorocarbons,
2,2-dichloro-1,1,1-trifluoroethane or 1,1
The process for producing a rigid polyurethane foam according to claim 12, which is -dichloro-1-fluoroethane. 16. An NCO group at the molecular end obtained by reacting an organic polyisocyanate with a part or all of an organic polyisocyanate and an active hydrogen-containing compound at an isocyanate group / active hydrogen (equivalent ratio) of 2.0 to 5.0. The method for producing a rigid polyurethane foam according to claim 12, which is a prepolymer having the following formula: 17. An organic polyisocyanate having an equivalent ratio of an isocyanate group to an active hydrogen group of an active hydrogen-containing compound of 0.3.
The method for producing a polyurethane foam according to claim 12, which is 8 to 5.0.