JPH10279653A - Production of rigid polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a rigid polyurethane foam of which the polyol component is excellent in storage stability and compatibility with an org. polyisocyanate component even when a hydrocarbon compd. is used as the blowing agent and which has excellent foam properties by using polyphenylmethane polyisocyanate contg. a specified amt. of dinuclear compds. and having a specified viscosity as the org. polyisocyanate component. SOLUTION: Polyphenylmethane polyisocyanate contg. 0.1-30 wt.% dinuclear isomers other than 4,4'-diphenylmethane diisocyanate and having a viscosity of 200-500 mPa.s (at 25 deg.C) is used as the org. polyisocyanate component. This polyisocyanate may be used jointly with tolylene diisocyanate. A partially urethanized product of such an isocyanate compd. may also be used. Pref. hydrocarbon compds. usable as the blowing agent are n-pentane, isopentane, cyclopentane, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing a rigid polyurethane foam, and more particularly to a method for improving a foaming agent, which is useful as a heat insulating or heat insulating structural material for refrigerators, freezers, heat insulating panels, ships or vehicles or houses. And a method for producing a rigid polyurethane foam.

[0002]

2. Description of the Related Art A rigid polyurethane foam has a closed cell structure, and contains chlorofluorocarbon gas, carbon dioxide gas and the like in cells. This foam has excellent heat insulation performance, low-temperature dimensional stability, workability, etc., and is therefore widely used as a heat insulating material for refrigerators, freezers, building materials and the like, or as a lightweight structural material.

[0003]

[0007] Chlorofluorocarbons have been used as a foaming agent for rigid polyurethane foams, but regulations are being made as substances causing environmental problems such as destruction of the ozone layer and global warming. Among them, R-11 (trichlorofluoromethane) is also included.
Therefore, development of a technique using a foaming agent that does not destroy the ozone layer is being studied.

In order to solve the above problems, for example, Japanese Patent Application Laid-Open No. 2-91132 discloses that R-11 and a hydrocarbon compound (ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-pentane, Hexane,
By using in combination with isohexane, n-heptane, isoheptane, cyclopentane, cyclohexane, cycloheptane or the like, or using a hydrocarbon compound alone, it is possible to obtain a rigid polyurethane foam having excellent filling properties, dimensional stability, compressive strength, etc. Has been disclosed. Further, JP-A-3-152
No. 160 discloses that a rigid polyurethane foam having a low thermal conductivity can be obtained by using cyclopentane, cyclohexane or the like. However, hydrocarbon compounds have a disadvantage that they are difficult to dissolve in polyols used for producing ordinary rigid polyurethane foams. Therefore, the storage stability as a polyol component is inferior, the types of polyols that can be used are limited, and a study on a combination with a polyisocyanate component is required. There is also a demand for further improvements in various properties of rigid polyurethane foams such as filling properties, dimensional stability at low temperature, wet heat and high temperature, compressive strength, thermal conductivity and the like.

[0005]

In the production of rigid polyurethane foams, the present inventors have found that the storage stability of the polyol component is good and the compatibility with the polyisocyanate component is good even when a hydrocarbon compound is used as a foaming agent. As a result of intensive studies and investigations on the composition of a good foam, the present invention has been reached.

That is, the present invention relates to an organic polyisocyanate,
In the method for producing a rigid polyurethane foam obtained by reacting a polyol, a catalyst, a foam stabilizer and a foaming agent, the organic polyisocyanate (a) having a viscosity of 20
A polyphenylmethane polyisocyanate having a temperature of 0 to 500 mPa · s / 25 ° C. is used, and the isocyanate contains 0.1 to 30% by weight of isomers other than 4,4′-diphenylmethane diisocyanate consisting of binuclear substances. Using a hydrocarbon compound as a foaming agent.

According to the present invention, there is provided a process for producing a rigid polyurethane foam obtained by reacting an organic polyisocyanate, a polyol, a catalyst, a foam stabilizer and a foaming agent.
(B) a polyphenylmethane polyisocyanate at 500 mPa · s / 25 ° C. containing 0.1 to 30% by weight of an isomer other than binuclear 4,4′-diphenylmethane diisocyanate; A) A method for producing a rigid polyurethane foam, which comprises using tolylene diisocyanate and a hydrocarbon compound as the foaming agent.

[0008] The present invention provides that the above (a) polyphenylmethane polyisocyanate is a partially urethane compound;
A method for producing a rigid polyurethane foam, characterized in that:

The present invention provides a method for producing a rigid polyurethane foam, wherein the (a) polyphenylmethane polyisocyanate and / or (b) tolylene diisocyanate is a partially urethane compound.

The present invention is a process for producing a rigid polyurethane foam, which comprises adding a foam stabilizer as necessary to the organic polyisocyanate (a) and / or (b).

In the present invention, when (a) and (b) are used in combination as the organic polyisocyanate, it is preferred that (a) / (b) = 70/30 to 99/1 be used in a weight ratio. This is a method for producing a rigid polyurethane foam.

According to the present invention, as the polyol, a polyether polyol having a number average molecular weight of 400 to 6000 and an average number of functional groups of 2 to 6 and / or a number average molecular weight of 400 to 6000 is used.
6000, a method for producing a rigid polyurethane foam, comprising using a polyester polyol having 2 to 3 functional groups.

[0013] The present invention is a method for producing a rigid polyurethane foam, characterized by foaming at a temperature of each component of 10 to 60 ° C in the production of the rigid polyurethane foam.

By using the component for a rigid polyurethane foam according to the present invention, the foam has excellent foaming properties, and the resulting foam has excellent dimensional stability, heat insulating properties, light weight and sound absorbing properties, and changes over time of the foam. It has excellent performance such as no.

[0015]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The organic polyisocyanate used in the present invention includes (a) a viscosity of 200 to 500 mPa.
S / 25 ° C. polyphenylmethane polyisocyanate (hereinafter abbreviated as polymeric MDI). Or
A combination of (a) polymeric MDI and (b) tolylene diisocyanate (hereinafter abbreviated as TDI). (A) The viscosity of the polymeric MDI is preferably from 250 to 450 m
Pa · s / 25 ° C.

A foam stabilizer, a catalyst, a flame retardant and the like can be added to (a) the polymeric MDI of the present invention, or (a) the polymeric MDI and (b) the TDI, if necessary. In the present invention, when (a) polymeric MDI and (b) TDI are used in combination, the weight ratio of (a) /
(B) = 70/30 to 99/1. Further, as the organic polyisocyanate, the above-mentioned (a) Polymeric M
An NCO group-terminated partial urethane obtained by reacting DI with an active hydrogen group-containing compound in an excess of an isocyanate group can be used. The NCO group content is 26.0
To 31.5% by weight, preferably 28.0 to 31.0% by weight.

The (a) polymeric MDI of the present invention can be obtained by phosgenating polyphenylmethane polyamine obtained by a condensation reaction between aniline and formalin. Therefore, the composition of the diphenylmethane-based polyisocyanate is basically determined by the raw material composition and reaction conditions at the time of condensation. The polyisocyanate of the present invention refers to a reaction solution after phosgenation or a bottoms obtained by removing a solvent from the reaction solution or distilling and separating out a part of MDI. May be used. (A) Polymeric MDI is composed of a polynuclear body and a binuclear body, and the polynuclear body has three or more benzene nuclei,
A binuclear has two benzene nuclei. (A) Polynuclear, binuclear, isomers, etc. of polymeric MDI are determined from a calibration curve based on the area percentage of each peak obtained by gel permeation chromatography or gas chromatography.

The organic polyisocyanate (a) used in the present invention has a viscosity of 200 to 500 mPa · s / 25.
° C polymeric MDI consists of polynuclear and binuclear,
The binucleate contains isomers other than 4,4'-MDI in an amount of 0.1 to 0.1%.
70% by weight, preferably 0.3 to 70% by weight.
Preferably, it is composed of a polynuclear body and a binuclear body, and the weight mixing ratio of the binuclear body and the trinuclear body in the polynuclear body is 1: 3 to 3: 1, and the binuclear body contains 4,4'- 0.1 to 7 isomers other than MDI
0% by weight, and the number of functional groups is 2.3 or more. More preferably, the MDI comprises a polynuclear and a binuclear, the polynuclear comprises 15 to 85% by weight, the binuclear comprises 85 to 15% by weight, preferably the polynuclear comprises 20 to 80% by weight, The core is 80 to 20% by weight. Particularly preferably, the weight mixing ratio of the binuclear and the trinuclear in the polynuclear is 1: 3 to 3: 1,
In the binuclear body, isomers other than 4,4'-MDI are 1.0 to 1.0%.
The content is 60% by weight, and the number of functional groups is 2.3 or more, preferably 2.3 to 3.1.

As the organic polyisocyanate (b) TDI used in the present invention, 2,4-TDI,
A single isomer such as 6-TDI or an arbitrary mixture thereof is used. Preferred TDI is 2,4-TDI / 2,6
-A TDI body having an 80/20 weight ratio, or NDI obtained by reacting TDI with a polyol in excess of NCO group
It is a CO group terminal partial urethane compound. The NCO group content is 20 to 40% by weight, preferably 25.0 to 35.0.
% By weight.

The compound having an active hydrogen group for obtaining (a) a partially urethane compound of polymeric MDI or (b) a partially urethane compound of TDI has a number average molecular weight of 3
And polyether polyols and polyester polyols having a number average molecular weight of from 62 to 300 and a molecular weight of from 62 to less than 300. As the polyether polyol, for example, ethylene glycol, propanediol,
Butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, neopentyl glycol, 3-methyl-
1,5-pentanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugar alcohols such as sucrose, glucose, fructose, bisphenol A, ethylenediamine, propylenediamine, diethylenetriamine, toluenediamine, metaphenylenediamine, As an initiator, one or more compounds having two or more active hydrogen groups, such as diphenylmethanediamine, xylylenediamine, etc., ethylene oxide, propylene oxide,
Examples include those produced by subjecting one or more monomers such as butylene oxide, amylene oxide, glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, and phenyl glycidyl ether to addition polymerization by a known method. As the polyol, a polyester polyol having a number average molecular weight of 300 to 3000 is, for example, a compound having two or more active hydrogen groups and adipic acid, malonic acid, succinic acid, tartaric acid, pimelic acid, sebacic acid, oxalic acid. And orthophthalic acid, isophthalic acid, terephthalic acid, azelaic acid, trimellitic acid, and the like, and polyols obtained by a known method. Further, examples of the polyol include compounds having two or more active hydrogen groups having a number average molecular weight of 62 to less than 300.

In addition to those in which a part of these NCO groups are modified to urethane / urea, those to which biuret, allophanate, carbodiimide, oxazolidone, amide, imide or the like may be modified.

In (a) and (b) used as the organic polyisocyanate of the present invention, other polyisocyanates can be used in combination. For example, phenylene diisocyanate, 1,3-xylylene diisocyanate, 1,4
-Xylylene diisocyanate, 1,4-naphthylene diisocyanate, 1,5-naphthylene diisocyanate, 4,4'-diphenyl ether diisocyanate,
2-nitrodiphenyl-4,4'-diisocyanate,
2,2'-diphenylpropane-4,4'-diisocyanate, 3,3'-dimethyldiphenylmethane-4,
Aromatic polyisocyanates such as 4'-diisocyanate and 4,4'-diphenylpropane diisocyanate;
Examples include aliphatic diisocyanates such as isophorone diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanates such as hydrogenated TDI and hydrogenated MDI. These can be used alone or as a mixture of two or more.

Foam stabilizers which can be added to the organic polyisocyanates of the present invention include, for example, polyglycol ethers containing the required number of alkylene oxides such as propylene oxide, butylene oxide, preferably ethylene oxide, and at least It is obtained by condensing with an organic compound containing one reactive hydrogen atom. Non-ionic surfactants such as alcohols, phenols, thiols, primary or secondary amines, carboxylic acids or sulfonic acids, or amides thereof, are organic compounds containing at least one reactive hydrogen atom. And a surfactant which is a polyalkylene oxide derivative of a phenolic compound having one or more alkyl substituents. Furthermore, preferred foam stabilizers in the present invention include Pluronic surfactants, which are generally such as butylene oxide, amylene oxide, phenylethylene oxide, cyclohexene oxide, propylene oxide, or mixtures thereof. A 1,2-alkylene oxide or a substituted alkylene oxide is polymerized in the presence of an alkali catalyst to produce a corresponding water-insoluble polyalkylene glycol, which is condensed with the required number of moles of ethylene oxide under the same conditions. The resulting nonionic surfactant.
Furthermore, alcohols obtained by reducing aldehydes generated by a catalytic reaction between polyolefins such as tripropylene, tetrapropylene, pentapropylene, ditributylene, triisobutylene, tetrabutylene, propyleneisobutylene, and tributene with carbon monoxide and hydrogen are used. And nonionic surfactants obtained by reacting a necessary number of moles of ethylene oxide. In addition, there are silicone surfactants, some of which have an active hydrogen group and some of which do not.
Preferred are those containing no active hydrogen groups. For example, Nippon Unicar's L-5340, SZ-1642,
Gold Schmidt B-8450, Toray Dow SF
-2964 and SF-2936F. The amount of the surfactant used is 0.001 to 2 parts by weight based on 100 parts by weight of the organic polyisocyanate.

The catalyst which can be added to (a) the polymeric MDI of the present invention as needed includes, for example, 2,4,6-tris (dimethylaminomethyl) phenol which is also effective as a trimerization catalyst. N, N ', N "
Tris (dimethylaminopropyl) hexahydro-triazine, a mixture of potassium octylate and diethylene glycol, a mixture of tertiary amine, potassium octylate and diethylene glycol, potassium phenolate, phenolates such as sodium methoxide, alcoholates, 2,
4-bis (dimemylaminomethyl) phenol, 2,6
-Di-t-butyl-4-dimethylaminotrimethylsilanephenol, triethylamine diazabicycloundecene, lead naphthenate, lead octate, dibutyltin dilaurate, triethylamine, tripropylamine, triethylenediamine, dimethylethanolamine, tetramethylhexa Methylene diamine and the like can be mentioned. The amount of the catalyst used depends on the activity of the catalyst, but may be 0.001 to 20% by weight based on the organic polyisocyanate. In the present invention, a polyisocyanate component is formed using the above-mentioned organic polyisocyanate, foam stabilizer, catalyst if necessary, and other additives.

The polyol used in the present invention includes:
A polymer polyol having a number average molecular weight of 300 to 7000,
Low molecular polyols having a number average molecular weight of 62 to less than 300; As the polyester polyol as a high molecular polyol having a number average molecular weight of 300 to 7000, for example, ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, decamethylene glycol, One or more compounds having at least two or more hydroxyl groups, such as neopentyl glycol, 3-methyl-1,5-pentanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, bisphenol A; Adipic acid,
Malonic, succinic, tartaric, pimelic, sebacic,
Oxalic acid, orthophthalic acid, isophthalic acid, terephthalic acid, azelaic acid, trimellitic acid, glutaconic acid, α
At least two or more carboxyls such as hydromuconic acid, β-hydromuconic acid, α-butyl-α-ethylglutaric acid, α, β-diethylsuccinic acid, hemimelitic acid, 1,4-cyclohexanedicarboxylic acid, etc. A polyol obtained by using one or two or more compounds having a group and producing the compound by a known method is exemplified. Further, a polyol obtained by ring-opening polymerization of a lactone (for example, ε-caprolactone) may be mentioned. Further, there may be mentioned, for example, those obtained by adding a product obtained by adding ethylene oxide to nonylphenol as an additive for improving the compatibility with other polyols to a polyester polyol and a recovered polyester obtained by decomposing a polyester molded product. . Preferred polyester polyols are aromatic polyester polyols having a number average molecular weight of 410 to 5000, a number of functional groups of 2 to 3, and a hydroxyl value of 1.
It is 50 to 500 mgKOH / g (hereinafter, the unit of the hydroxyl value is omitted).

Examples of the polyether polyol as a high molecular polyol having a number average molecular weight of 400 to 6000 include ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, Decamethylene glycol, neopentyl glycol, 3-methyl-1,5-
Pentanediol, glycerin, trimethylolpropane, pentaerythritol, sorbitol, sugar alcohols such as sucrose, glucose, fructose, bisphenol A, ethylenediamine, propylenediamine, diethylenetriamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylyl Active hydrogen such as diamine
One or more compounds having one or more compounds as initiators, one or more monomers such as ethylene oxide, propylene oxide, butylene oxide, amylene oxide, glycidyl ether, methyl glycidyl ether, t-butyl glycidyl ether, and phenyl glycidyl ether Can be produced by addition polymerization using a known method. Preferred polyether polyols are toluenediamine-based polyether polyols, toluenediamine / shucrose-based polyether polyols and the like, having a number average molecular weight of 410 to 5000, an average functional group number of 2 to 6,
The hydroxyl value is 150 to 550. Further, the flame-retardant polyol containing phosphorus has a number average molecular weight of 410 to 500.
A polyol having 0, a functional group number of 2 to 6, and a hydroxyl value of 150 to 550 is also preferable.

Examples of the low molecular polyol having a number average molecular weight of 62 to less than 300 include glycol, triol, polyether polyol, polyester polyol and the like. For example, glycols and triols used when producing the above-mentioned polyether polyols, polyester polyols and the like are used. As a polyether polyol,
Ethylene glycol, propanediol, butanediol, diethylene glycol, dipropylene glycol,
Active hydrogen such as glycols such as tripropylene glycol and glycerin, polyhydric alcohols such as trimethylolpropane, ethylenediamine, propylenediamine, diethylenetriamine, toluenediamine, metaphenylenediamine, diphenylmethanediamine, xylylenediamine, etc. Examples thereof include compounds having two or more compounds alone or a mixture of two or more compounds, or compounds obtained by an addition polymerization reaction of these compounds with an alkylene oxide. The above-mentioned high-molecular polyol and low-molecular polyol can be used alone or as a mixture of two or more.

As the catalyst, foam stabilizer and foaming agent used in the present invention, for example, as the catalyst and foam stabilizer, those mentioned above which can be used for the polyisocyanate component can be used. Examples of the flame retardant used as necessary in the present invention include triethyl phosphate, trischloroethyl phosphate, trischloropropyl phosphate, tricresyl phosphate, and chlorinated paraffin. The amount of the flame retardant used may be 0.001 to 20% by weight based on 100 parts by weight of the polyol.

The hydrocarbon compound as a foaming agent used in the present invention includes, for example, aliphatic, alicyclic, aromatic and the like.
They can be used alone or as a mixture of two or more. For example, ethane, propane, n-butane, isobutane, n-pentane, isopentane, neopentane, n-hexane,
Isohexane, n-heptane, isoheptane, dimethylethylmethane, 2-methylpentane, 2,3-dimethylbutane, pentene-1,2-methylbutene, 3-methylbutene, hexene-1, cyclopentane, cyclohexane, cycloheptane, benzene No. Preferred blowing agents are n-pentane, isopentane, cyclopentane and the like.

The foam stabilizer used in the polyisocyanate component of the present invention improves the stability of the liquid and is stable without generating crystallinity, precipitates and the like even in a cold region of -20 ° C. or lower. Further, the compatibility of the entire system is improved, the overall composition is balanced, the reactivity is improved, and the physical properties such as dimensional stability, flowability, and thermal conductivity of the obtained foam are improved. In addition, the catalyst has the effect of improving reactivity, promoting urethane formation and foaming at the same time as the formation of a part of a nitrate, thereby improving physical properties and shortening the working time.

Other additives used in the present invention include, for example, fillers, plasticizers, viscosity modifiers, coloring agents, stabilizers and the like.

The process for producing a rigid polyurethane foam of the present invention comprises the steps of: preparing an NCO group and a polyol from (A) a polyisocyanate component and (B) a polyol component (polyol, catalyst, foam stabilizer, foaming agent and other additives). The equivalent ratio of the active hydrogen groups in the component is NCO group / active hydrogen group = 0.8 to
It is used in the range of 1.5, preferably 0.9 to 1.3.
The polyisocyanate component and the polyol component are
The foam can be obtained by keeping the temperature at 60 ° C. and using a low-pressure or high-pressure foaming machine generally used in urethane foam production equipment. Further, the polyisocyanate component and the polyol component are kept at 10 to 50 ° C.
It can be foamed using a method of stirring and mixing at 0 rpm for 2 to 10 seconds and immediately pouring it into a molding die, or a low-pressure or high-pressure foaming machine generally used in urethane foam production equipment. In this case, if the mold or the free-foaming container is heated to 40 ° C. or higher, the foaming time can be reduced.

The polyol component thus obtained is excellent in storage stability, and the obtained rigid polyurethane foam is particularly excellent in dimensional stability, thermal conductivity, etc., and has heat insulating properties and lightweight structural materials. Since it has performance, sound absorption and the like, it can be applied to fields such as building materials, household goods, leisure goods, and the like, for example, refrigerators, freezers, cooler boxes, vending machines, showcases, and the like.

[0034]

The rigid polyurethane foam of the present invention is
Low temperature for both polyisocyanate component and polyol component,
It has excellent long-term storage stability at high temperature, good compatibility between various components, and therefore, foaming proceeds smoothly, and a foam having particularly excellent dimensional stability, flowability, thermal conductivity, and the like can be obtained.

[0035]

EXAMPLES The present invention will be described below with reference to examples.
The present invention is not limited by these examples. "Parts" and "%" in the examples are "parts by weight" and "% by weight", respectively, unless otherwise specified.

(Adjustment of Polyisocyanate Components A to F)
Polymeric MDI, TD containing specific viscosity and isomer
A polyisocyanate component was prepared using I and a foam stabilizer.
Table 1 shows the formulations and properties of the polyisocyanate components A to F.

[0037]

[Table 1]

[Notes to Table 1] Isocyanate (1): Polymeric MDI having a viscosity of 300 mPa · s / 25 ° C. (39.0% of binuclear, isomer other than 4,4′-MDI in binuclear 0. 8%, binuclear / trinuclear = 1.50 weight ratio) NCO content 31.0% Isocyanate (2): Polymeric MDI having a viscosity of 400 mPa · s / 25 ° C. (binuclear 35.0%, binuclear 70.0% of isomers other than 4,4'-MDI in the body, binuclear / trinuclear = 1.00 weight ratio) NCO content 30.0%, isocyanate (3): NCO group terminal partial urethane (Product obtained by reacting 100 parts of polymeric MDI of isocyanate (1) with 1.5 parts of 3-methyl-1,5-pentanediol) NCO content: 29.4% Isocyanate (4): TDI (Coronate T- 80, 2,4- / 2,6-isomer ratio 0/20, manufactured by Nippon Polyurethane Industry) SF-2936F: Silicone foam stabilizer, manufactured by Toray Dow SZ-1642: Same as above, manufactured by Nippon Unicar SZ-1649: Same as above, manufactured by Nippon Unicar B-8451: Same as above, manufactured by Gold Schmidt Storage stability Properties: ◎ mark good

(Adjustment of Polyisocyanate Components GL)
Polymeric MDI, TD containing specific viscosity and isomer
I, a polyisocyanate component was prepared using an NCO group-terminated prepolymer and, if necessary, a surfactant and the like. Table 2 shows the formulations and properties of the polyisocyanate components GL.

[0040]

[Table 2]

[Note in Table 2] Isocyanate (5): NCO group terminal partial urethane (a product obtained by reacting 100 parts of coronate T-80 with 35 parts of polyethylene glycol (hydroxyl value: 280) at 60 ° C.) Content 30.0%

(Adjustment of Polyisocyanate Components MP)
A polyisocyanate component was prepared using a polymeric MDI, TDI, NCO-terminated prepolymer having a specific viscosity, and, if necessary, a foam stabilizer. Polyisocyanate component M to N
Table 3 shows the formulation and properties of

[0043]

[Table 3]

[Note in Table 3] Isocyanate (6): Polymeric MDI having a viscosity of 150 mPa · s / 25 ° C. (47.0% binuclear, isomer 7 other than 4,4′-MDI in the binuclear body) 0.0%, binuclear / trinuclear = 1.88 weight ratio) NCO content 32.0% Isocyanate (7): Polymeric MDI having a viscosity of 700 mPa · s / 25 ° C., (binuclear 30.0%, 0.1% of isomers other than 4,4'-MDI in the nucleus, binucleate / trinucleus = 0.67 weight ratio) NCO content 29.3% Storage stability: 印 mark good, △ mark slight There is a precipitate, × mark There is a precipitate

[Adjustment of Polyol Components 1-2] A polyol component was prepared using a polyol, a foam stabilizer, a catalyst, a blowing agent (cyclopentane), and water. Table 4 shows the formulation and properties.

[0046]

[Table 4]

[Notes in Table 4] Polyol (1): Tolylenediamine-based polyether polyol, hydroxyl value = 425 Polyol (2): Tolylenediamine and sucrose-based polyether polyol, hydroxyl value = 432 polyol ( 3): phosphorus-containing flame-retardant polyol, hydroxyl value = 450 polyol (4): aromatic polyester polyol,
Hydroxyl value = 350, number of functional groups = 2 Silicone (1): Silicone foam stabilizer, manufactured by Shin-Etsu Silicone Silicone (2): Silicone foam stabilizer, manufactured by Nippon Unicar Catalyst (1): Pentamethyldiethylenetriamine Catalyst (2): Tetramethylpropylenediamine Catalyst (3): 33% diethylene glycol solution of triethylenediamine Zeonsolve HP: Cyclopentane, manufactured by Zeon Japan

Examples 1 to 6 Production of rigid polyurethane foam The isocyanate component and the polyol component shown in Table 5 were converted to N
Using an equivalent ratio of CO group / active hydrogen group of 1.15, each was adjusted to 20 ° C. ± 1 ° C., weighed in a 2.0-liter polyethylene beaker, and stirred for 2 to 5 at a rotation speed of 5000 rpm with a stirring mixer. Stir and mix for 40 seconds beforehand
In a 250 x 250 x 250 mm aluminum container kept warm, a polyethylene bag was set and free foaming was performed to test the foamability. Table 5 shows the results. Similarly, the foam stock solution stirred and mixed was kept at 40 ° C. 500
A foam obtained by injecting it into a vertical aluminum mold of × 500 × 60 mm was used for a physical property test. Table 5 shows the performance of the obtained foam. Further, a foam stock solution similarly stirred and mixed is poured into an inverted L-shaped mold [thickness × width × length = 30 × 300 × (500 + 500) mm] kept at 40 ° C. to obtain flowability and filling property. And so on. Table 5 shows the results.

[0049]

[Table 5]

[Notes in Table 5] Test method Flowability: The form was taken out of the mold and determined by determining the weight and volume occupied by the form. Filling property: The form was taken out of the mold and judged. ：: excellent, ：: normal, Δ: slightly inferior, ×: inferior Dimensional stability: in accordance with JIS K6767. Thermal conductivity: A thermal conductivity measuring device manufactured by Anacon was used.

Examples 7 to 12 Production of Rigid Polyurethane Foam A rigid polyurethane foam was produced in the same manner as in Example 1 using the isocyanate component and the polyol component shown in Table 6. A physical property test was performed in the same manner as in Example 1. Table 6 shows the results.

[0052]

[Table 6]

Comparative Examples 1 to 3 Production of Rigid Polyurethane Foam Rigid polyurethane foam was produced in the same manner as in Example 1 using the polyisocyanate component and the polyol component shown in Table 7. A physical property test was performed in the same manner as in Example 1. Table 7 shows the results.

[0054]

[Table 7]

Claims (4)

[Claims] An organic polyisocyanate, a polyol,
A method for producing a rigid polyurethane foam obtained by reacting a catalyst, a foam stabilizer and a foaming agent, wherein the organic polyisocyanate has (a) a viscosity of 2
A polyphenylmethane polyisocyanate having a temperature of from 00 to 500 mPa · s / 25 ° C., wherein the isocyanate contains 0.1 to 30% by weight of isomers other than 4,4′-diphenylmethane diisocyanate consisting of binuclear substances; Using a hydrocarbon compound as a foaming agent. 2. An organic polyisocyanate, a polyol,
A method for producing a rigid polyurethane foam obtained by reacting a catalyst, a foam stabilizer and a foaming agent, wherein the organic polyisocyanate has (a) a viscosity of 2
Polyisocyanate having a polyphenylmethane polyisocyanate temperature of from 500 to 500 mPa · s / 25 ° C. and containing 0.1 to 30% by weight of an isomer other than binuclear 4,4′-diphenylmethane diisocyanate; (B) A method for producing a rigid polyurethane foam, comprising using tolylene diisocyanate and using a hydrocarbon compound as the blowing agent. 3. A method for producing a rigid polyurethane foam, wherein (a) the polyphenylmethane polyisocyanate according to claim 1 is a partially urethane compound. 4. A method for producing a rigid polyurethane foam, wherein the (a) polyphenylmethane polyisocyanate and / or (b) tolylene diisocyanate according to claim 2 is a partially urethane compound.