JP2017179320A - Polyol composition for hard polyurethane foam, and manufacturing method of hard polyurethane foam using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition excellent in storage stability even when using only water as a foaming agent, a hard polyurethane foam excellent in dimensional stability of a foam even with low density and a manufacturing method therefor.SOLUTION: There is provided a polyol composition for hard polyurethane foam using organic polyisocyanate as a polyisocyanate component for obtaining a hard polyurethane foam, and using combination of polyether polyol consisting of polyalkylene oxide having equivalent molecular weights of 100 to 200 and 900 to 2200 as a polyol component and water of a specific amount as a foaming agent. There is provided a manufacturing method of a hard polyurethane foam using the composition.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition for rigid polyurethane foam and a method for producing a rigid polyurethane foam using the same.

  Conventionally, rigid polyurethane foam has been used as a heat insulating material for building materials and home appliances. As foaming agents for rigid polyurethane foams, chlorofluorocarbons have been mainly used. However, the use of chlorofluorocarbons has a problem of adverse effects on the environment due to destruction of the ozone layer. And for polyurethane foam, water has become a useful blowing agent. However, changing the foaming agent from chlorofluorocarbon to water alone has an extremely large effect on foam properties.For example, the compatibility between various raw materials decreases, the cell viscosity increases due to an increase in liquid viscosity, and the flow properties decrease. Examples include densification, deterioration of heat insulation performance, especially dimensional stability performance at room temperature and high temperature, increase in brittleness due to resin skeleton, etc., and decrease in adhesive strength with face materials made of wood, plastic, metal, etc. . As described above, there are many disadvantages in obtaining rigid polyurethane foam using water alone as a foaming agent, but as a method for improving the physical properties of conventional water-foamed rigid foam, generally an isomer is mixed with a polyisocyanate component. There are known methods (for example, see Patent Document 1), improvement of reaction catalyst (see Patent Document 2), examination of modification of polyol, and the like.

  In addition, as a technique for improving dimensional stability, there is a technique of communicating bubbles, and as a communication technique, a method using brominated polyol, amino polyol or the like as a polyol component (see Patent Document 3), in-mold A method for applying external pressure (see Patent Document 4) has been known. Further, for example, a method comprising 30 to 60% by weight of a polyoxyalkylene polyol having a functional group number of 2 to 3.5, a hydroxyl value of 28 to 90 mgKOH / g and a polyoxyethylene unit content of 5% by weight or less (patent document) 5) was known. However, in this method, it is necessary to use 30% by weight or more of the long-chain polyether polyol, and there is a fear that the physical properties such as mechanical strength may be significantly lowered due to the reduced crosslink density of the rigid polyurethane foam.

  As another method, there is a method using a so-called bubble communicating agent. For example, a method using a saturated monocarboxylic acid metal salt such as calcium stearate, magnesium stearate, strontium stearate, calcium myristate (see Patent Document 6), a method using continuous silicon (see Patent Document 7), and the like. .

  However, these bubble communicating agents have poor compatibility with commonly used polyols, and there is a concern that the storage stability of the polyol mixture may be deteriorated. In addition, in order to obtain a sufficient communication effect, it is necessary to increase the amount of addition. In this case, the cell collapses and it is difficult to obtain a fine cell structure.

JP-A-4-30093 JP-A-4-298519 JP-A-8-20624 Japanese Patent Laid-Open No. 8-59879 JP-A-6-25375 JP 61-153480 A JP 2008-239933 A

  The present invention has been made in view of the above-mentioned background art, and the object thereof is to provide a polyol composition that is excellent in storage stability even when only water is used as a foaming agent, and in a foam even at low density. The object is to provide a method for producing a rigid polyurethane foam having excellent dimensional stability.

  As a result of diligent research and investigations to solve such problems in conventional water foaming, the present inventors have used an organic polyisocyanate as the polyisocyanate component and a combination of a polyol having a specific molecular weight as the polyol component. As a result, it was found that even when water is used as a blowing agent, a rigid polyurethane foam having excellent foam physical properties can be obtained even with low density and excellent storage stability of the polyol composition, and the present invention has been completed. It was.

  That is, the present invention includes the following embodiments.

[1] A composition comprising a low molecular weight polyol (A), a long molecular weight polyol (B), trischloropropyl phosphate (C), and water (D),
The low molecular weight polyol (A) is one or a combination of two or more polyether polyols, which are polymers of alkylene oxide, with an equivalent molecular weight of 100 to 200, and the long molecular weight polyol (B) is equivalent molecular weight = It is one or a combination of two or more polyether polyols that are 900-2200 alkylene oxide polymers, and 40 to 70% by weight of low molecular weight polyol (A) in the composition, long molecular weight Containing 3 to 20% by weight of polyol (B), 10 to 30% by weight of trischloropropyl phosphate (C), and 5 to 12% by weight of water (D);
A polyol composition for rigid polyurethane foams.

[2] In the polyol composition for rigid polyurethane foam, the low molecular weight polyol (A) is 50 to 60% by weight, the long molecular weight polyol (B) is 15 to 18% by weight, and the trischloropropyl phosphate (C) is 12 to 16%. Containing 8% to 10% by weight of water (D),
The polyol composition for rigid polyurethane foam according to the above [1], wherein

[3] The polyol composition for rigid polyurethane foam according to [1] or [2] above further contains an aliphatic alcohol (E),
The aliphatic alcohol (E) is a primary monoalcohol having 6 to 14 carbon atoms and 2 to 10% by weight in the composition;
A polyol composition for rigid polyurethane foams.

[4] The polyol composition for rigid polyurethane foam according to the above [3] comprises a low molecular weight polyol (A), a long molecular weight polyol (B), an aliphatic alcohol (E), trischloropropyl phosphate (C), and water. Containing (D),
The low molecular weight polyol (A) is one or a combination of two or more polyether polyols, which is a polymer of alkylene oxide with an equivalent molecular weight of 120 to 200,
The long molecular weight polyol (B) is a polyether polyol which is a polymer of alkylene oxide having an equivalent molecular weight of 2000 to 2200,
The aliphatic alcohol (E) is a primary monoalcohol having 6 to 14 carbon atoms, and 50 to 70% by weight of the low molecular weight polyol (A) and 3 of the long molecular weight polyol (B) in the composition. -8% by weight, aliphatic alcohol (E) 5-10% by weight, trischloropropyl phosphate (C) 10-30% by weight, and water (D) 5-12% by weight Polyol composition for rigid polyurethane foam.

  [5] The polyol composition for rigid polyurethane foam according to any one of the above [1] to [4], wherein the content of the ethylene oxide unit in the long molecular weight polyol (B) is 3 to 20% by weight. .

  [6] A rigid polyurethane foam which is a reaction foamed product of the polyol composition for rigid polyurethane foam according to any one of [1] to [5] above and an organic polyisocyanate.

  [7] A metal siding material having a foam density of 25 kg / m3 to 30 kg / m3, comprising the rigid polyurethane foam according to [6].

  [8] A roof material having a foam density of 25 kg / m3 to 30 kg / m3, comprising the rigid polyurethane foam according to [6].

  [9] A method for producing a rigid polyurethane foam, comprising reacting the polyol composition for rigid polyurethane foam according to any one of [1] to [5] above with an organic polyisocyanate in the presence of a catalyst.

  [10] The polyol composition for rigid polyurethane foam according to any one of [1] to [5] above and an organic polyisocyanate, in the presence of a catalyst, an active hydrogen group in the polyol composition for rigid polyurethane foam, A method for producing a rigid polyurethane foam, comprising reacting the organic polyisocyanate component with an NCO group equivalent ratio of 60 to 130.

  The polyol composition for rigid polyurethane foam of the present invention is excellent in storage stability of a polyol composition using only water as a foaming agent. Further, by using it in a method for producing a rigid polyurethane foam, it is possible to obtain an open-celled rigid polyurethane foam that is excellent in dimensional stability even at a low density.

  The polyol composition for rigid polyurethane foam of the present invention contains a low molecular weight polyol (A), a long molecular weight polyol (B), trischloropropyl phosphate (C), and water (D), and the low molecular weight polyol (A) is 1 or a combination of two or more polyether polyols, which is a polymer of alkylene oxide with an equivalent molecular weight of 100 to 200, and the long molecular weight polyol (B) is the weight of an alkylene oxide with an equivalent molecular weight of 900 to 2200. A polyether polyol which is a coalescence, and the composition contains a low molecular weight polyol (A) of 40 to 70% by weight, a long molecular weight polyol (B) of 3 to 20% by weight, and trischloropropyl phosphate (C). It is characterized by containing 10 to 30% by weight and 5 to 12% by weight of water (D).

  Although it does not specifically limit as a low molecular weight polyol (A) used for the polyol composition for rigid polyurethane foams of this invention, For example, sucrose, sorbitol, ethylenediamine, tolylenediamine, pentaerythritol, glycerol is started. By addition polymerization of 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 by known methods. The polyether polyol obtained is mentioned.

  Content of a low molecular weight polyol (A) is 40 to 70 weight% in the polyol composition for rigid polyurethane foams, and 40 to 50 weight% is preferable. If it is less than 40% by weight, the compatibility of the polyol mixture is insufficient, phase separation and turbidity of the polyol mixture occur, and if it exceeds 70% by weight, the communication is insufficient and the foam shrinks.

  The equivalent molecular weight of the low molecular weight polyol (A) is 100 to 200. If it is less than 100, the compatibility of the polyol mixture is insufficient, phase separation and turbidity of the polyol mixture occur, and if it exceeds 200, foam communication is insufficient and the foam shrinks.

  The long molecular weight polyol (B) used in the polyol composition for rigid polyurethane foam of the present invention is not particularly limited, and examples thereof include ethylene glycol, propylene glycol, butanediol, diethylene glycol, dipropylene glycol and the like as initiators. Obtained by addition polymerization of 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 by a known method. And polyether polyols.

  The content of the long molecular weight polyol (B) is 3 to 20% by weight in the polyol composition for rigid polyurethane foam, and preferably 15 to 18% by weight. If the amount is less than 3% by weight, the communication is insufficient and causes shrinkage of the foam. If the amount exceeds 20% by weight, the compatibility of the polyol mixture is insufficient and phase separation and turbidity of the polyol mixture occur.

  The equivalent molecular weight of the long molecular weight polyol (B) is 900-2200. If it is less than 900, the foam is not sufficiently communicated to cause shrinkage of the foam. If it exceeds 2200, the polyol mixture is not sufficiently compatible, and phase separation and turbidity of the polyol mixture occur.

  A polyether polyol containing an ethylene oxide unit can also be suitably used. The content of the ethylene oxide unit in the polyether polyol is preferably 3 to 20% by weight, more preferably 6 to 15% by weight.

  The trischloropropyl phosphate (C) used in the polyol composition for rigid polyurethane foam of the present invention mainly provides a function as a flame retardant that imparts flame retardancy to the foam. Examples of flame retardants other than trischloropropyl phosphate include tris (chloroethyl) phosphate, tris (dichloropropyl) phosphate, tetrakis (2-chloroethyl) ethylene diphosphate, 2,2-bis (chloromethyl) -1,3- Propane bis (chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, tris (tribromoneopentyl) phosphate, 2,2-bis (chloromethyl) trimethylenebis (bis (2-chloroethyl) phosphate), poly Oxyalkylenebisdichloroalkyl phosphate, halogen-containing phosphate phosphonate oligomer ester, trimethyl phosphate, triphenyl phosphate, tricresyl phosphate, cresyl diphenyl phosphate , Tri-2-ethylhexyl phosphate, tributyl phosphate, trixylenyl phosphate, triethyl phosphate, trioctyl phosphate, dimethyl methyl phosphate, diethyl phenyl phosphate, dimethyl phenyl phosphate, resorcinol diphenyl phosphate, ethyl phosphite, Diethyl phosphite, ethyl ethylene phosphate oligomer, aromatic phosphoric acid oligomer ester (resorcinol bisdiphenyl phosphate, resorcinol bisdixylenyl phosphate, bisphenol A bisdiphenyl phosphate, etc.), so-called phosphorus-containing polyol having a hydroxyl group in the phosphoric acid compound Etc., halogen-based phosphate esters or non-halogen-based phosphate esters and oligomers thereof.

  These flame retardants can be used alone or in combination of two or more as long as the performance is not adversely affected.

  The content of trischloropropyl phosphate (C) is 10 to 30% by weight in the polyol composition for rigid polyurethane foam, and more preferably 12 to 16% by weight. If it is less than 10% by weight, a foam having self-extinguishing properties cannot be obtained. When it is more than 30% by weight, the foam strength is lowered and shrinkage is caused.

  Water (D) as a blowing agent used in the present invention can be used without particular limitation as long as it does not contain a component that affects the reaction. City water, ion-exchanged water or distilled water can be preferably used. The content of water (D) is 5 to 12% by weight, and more preferably 8 to 10% by weight. When it is less than 5% by weight, the foaming ratio of the foam is insufficient, and a high-density foam is obtained. When it exceeds 12% by weight, the foaming ratio of the foam increases and the foam strength decreases.

  An aliphatic alcohol (E) can be used in combination with the polyol composition for rigid polyurethane foam of the present invention. The aliphatic alcohol (E) is preferably a primary monoalcohol having 6 to 14 carbon atoms, such as hexanol, octanol, nonanol, decanol, undecyl alcohol, lauryl alcohol, tridecyl alcohol, tetradecyl alcohol and the like. It is done.

  When using together aliphatic alcohol (E), 2 to 10 weight% is preferable and 3 to 8 weight% is more preferable. If it is less than 2% by weight, the polyol mixture is insufficiently compatible, and there is a risk of phase separation and turbidity of the polyol mixture. If it is more than 10% by weight, the foam strength may be lowered.

  The polyol composition for rigid polyurethane foam of the present invention may further contain a catalyst, a foam stabilizer, and other additives.

  The catalyst is not particularly limited, but for example, tertiary amines such as tetramethylethylenediamine, dimethylethanolamine, triethylenediamine, tetramethylpropanediamine, tetramethylhexamethylenediamine, dimethylcyclohexylamine, pentamethyldiethylenetriamine, Organic tin compounds such as stannous octoate and dibutyltin dilaurate are listed. Further, imidazoles such as trimethylimidazole, 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-methylimidazole and the like can be mentioned. Can be used as a mixture.

  The foam stabilizer can be used without any particular restriction on the usual foam stabilizer for rigid polyurethane foam. Examples thereof include polyoxyalkylene-based foaming agents such as polyoxyalkylene alkyl ether and polyoxyalkylene alkylamino ether, and organosilicon foam stabilizers such as organopolysiloxane and siloxaneoxyalkylene copolymer.

  As other additives, plasticizers, flame retardants, colorants and the like used for ordinary rigid polyurethane foams can be suitably used.

  A rigid polyurethane foam is obtained by reacting the polyol composition for rigid polyurethane foam of the present invention with an organic polyisocyanate in the presence of a catalyst.

  The organic polyisocyanate is not particularly limited, but polyphenylmethane polyisocyanate (hereinafter abbreviated as “polymeric MDI”) is preferable. The NCO content of the polymeric MDI is 28.0 to 33.0% by weight, preferably 28.5 to 32.8% by weight, the viscosity at 25 ° C. is 110 to 200 mPa · s, and the number of functional groups is 2.1 or more. , Preferably 2.2 to 3.1. Polymeric MDI is obtained by phosgenating polyphenylmethane polyamine obtained by condensation reaction of aniline and formalin. Therefore, the composition of polymeric MDI is basically determined by the raw material composition and reaction conditions during condensation.

  Specifically, the organic polyisocyanate is preferably a reaction solution after phosgenation, or removal of the solvent from the reaction solution, or a bottom solution obtained by distilling and separating a part of the polymeric MDI, such as reaction conditions and separation conditions. It may be a mixture of several different types. The polymeric MDI preferably used in the present invention comprises a binuclear body having two benzene rings and a polynuclear body having three or more benzene rings.

  Further, as the organic polyisocyanate used in the present invention, polymeric MDI and other polyisocyanates can be used in combination. Other polyisocyanates include, 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-4,4′-diisocyanate, 4,4′-diphenylpropane Aromatic polyisocyanates such as diisocyanates, aliphatic diisocyanates such as isophorone diisocyanate, tetramethylene diisocyanate and hexamethylene diisocyanate, alicyclic diisions such as hydrogenated TDI and hydrogenated MDI There is a cyanate and the like. These can be used alone or as a mixture of two or more.

  In the method for producing a rigid polyurethane foam of the present invention, an equivalent ratio of active hydrogen groups in the polyol composition for rigid polyurethane foam of the present invention to NCO groups in the organic polyisocyanate component (hereinafter referred to as “NCO index”). The reaction is preferably carried out at 60 to 130. More preferably, it is the range of 80-110. If the NCO index is less than the lower limit, the foam strength may decrease and shrinkage may occur. If the NCO index is higher than the upper limit, the foam becomes brittle, and sufficient adhesive strength with the face material may not be obtained.

Here, the NCO index is expressed by the following equation.
NCO index = (NCO group / active hydrogen group) × 100

  The rigid polyurethane foam thus obtained is excellent in dimensional stability and has a lightweight structural material, performance as a heat insulating material, sound absorption, etc., so that it is mainly used in the field of building materials, for example, rooftops. It can be used as a metal siding material for heat insulation. A rigid polyurethane foam having a density of 25 kg / m3 to 30 kg / m3 as a structure can be suitably used as a roofing material.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto.

[Free-foam foaming conditions]
The organic polyisocyanate and the polyol mixture were each adjusted to a temperature of 20 ° C., mixed with stirring (6000 rpm), and a rigid polyurethane foam was obtained by free foaming. The free density was measured by cutting a sample into a size of 20 cm × 20 cm × 12 cm after 10 minutes from foaming. As the foam container, square aluminum BOX having a mold temperature of 20 ° C. and a size of 25 cm × 25 cm × 25 cm was used.

[20mm thick mold foaming conditions]
The organic polyisocyanate and the polyol mixture were each adjusted to a temperature of 20 ° C. and mixed with stirring (6000 rpm) to obtain a rigid polyurethane foam having a thickness of 20 mm. As the foam container, a mold of 25 cm × 50 cm × 2 cm thickness, which was adjusted to a mold temperature of 50 ° C., was used, and the demolding time was 2 minutes.

[Physical property measurement conditions]
The physical properties were measured by the following methods.

The foam density is measured according to JIS A 9511, and the unit is kg / m 3.
Wet heat dimensional stability is measured by ASTM D 2126 and is carried out at 70 ° C. for 48 hours in an atmosphere with a relative humidity of 95%, the unit is%.
High temperature dimensional stability is measured by ASTM D 2126 and is maintained at 80 ° C. for 48 hours, in units of%.
Low temperature dimensional stability is measured by ASTM D 2126 and is maintained at −30 ° C. for 48 hours, in units of%.
The compressive strength is measured according to JIS A 9511, the crosshead speed is 2 mm / min, and the unit is kPa.
The closed cell ratio is measured by ASTM D 2856, and the unit is%.
The oxygen index was measured according to JIS K 7201.
As for dimensional stability, a sample having a volume change rate within ± 2% was evaluated as ◯.
An oxygen index of 21.0 or higher was regarded as having self-extinguishing properties (◯).
The storage stability was evaluated as ◯ when the sample was allowed to stand at storage temperatures of 20 ° C. and 5 ° C. for 90 days, respectively, and not turbid or separated.
The appearance of the foam was visually evaluated, and the cells were fine and uniform.

<Examples 1 to 11>
The polyol, additive, catalyst, foaming agent and the like shown in Table 1 were used as a polyol composition for a rigid polyurethane foam, and a rigid polyurethane foam was produced using Polymeric MDI (MR-200 manufactured by Tosoh Corporation). Further, the components shown in Table 1 were adjusted to a temperature of 20 ° C., mixed with stirring (6000 rpm), and a rigid polyurethane foam was obtained by free foaming.

  Mold foam with a thickness of 20 mm is made into a polyol composition for rigid polyurethane foam using the polyols, additives, catalysts, foaming agents, etc. shown in Table 1, and rigid polyurethane using polymeric MDI (MR-200 manufactured by Tosoh Corporation). A foam was produced. The results are shown in Table 2.

[Explanation of Table 1]
f: Average number of functional groups OHV: Hydroxyl value (mgKOH / g)
Mn: Number average molecular weight Low molecular weight polyol (A):
(A) -1: polyether polyol (shoe-closed system), average functional group number 4.3, hydroxyl value 440, number average molecular weight 550
(A) -2: polyether polyol (shoe-closed system), average functional group number 4.3, hydroxyl value 310, number average molecular weight 780
(A) -3: Polyether polyol (glycerin type), average number of functional groups 3, hydroxyl value 245, number average molecular weight 690
(A) -4: polyether polyol (ethylenediamine), average functional group number 4, hydroxyl value 750, number average molecular weight 300
(A) -5: polyether polyol (glycerin), average functional group number 3, hydroxyl value 1120, number average molecular weight 150
(A) -6: polyether polyol (glycerin type), average functional group number 3, hydroxyl value 540, number average molecular weight 311
Long molecular weight polyol (B):
(B) -1: polyether polyol (propylene glycol type), average functional group number 2, hydroxyl value 28, number average molecular weight 4000
(B) -2: polyether polyol (propylene glycol type), average functional group number 2, hydroxyl value 27, number average molecular weight 4200
(B) -3: polyether polyol (propylene glycol type), average functional group number 2, hydroxyl value 26, number average molecular weight 4400
(B) -4: Polyether polyol (glycerin type), average functional group number 3, hydroxyl value 56, number average molecular weight 3000
(B) -5: Polyether polyol (glycerin type), average functional group number 3, hydroxyl value 62, number average molecular weight 2700, ethylene oxide unit content 10% by weight
Octanol: Also known as 2-ethylhexanol TCPP: Trischloropropyl phosphate Made by Tosoh Corporation

<Comparative Examples 1-5>
Using the polyol, additive, catalyst, foaming agent and the like shown in Table 3 as the polyol component, the same operations as in Examples 1 to 11 were performed to obtain a rigid polyurethane foam. The results are shown in Table 4.

[Explanation of Table 3]
f: Average number of functional groups OHV: Hydroxylation (mgKOH / g)
Mn: Number average molecular weight Long molecular weight polyol (B):
(B) -6: Polyether polyol (propylene glycol type), average functional group number 2, hydroxyl value 66, number average molecular weight 1700

  In the polyol mixtures used in Examples 1 to 11, phase separation and turbidity were not observed in a storage stability test at storage temperatures of 20 ° C. and 5 ° C.

  The rigid polyurethane foams obtained in Examples 1 to 11 are excellent in dimensional stability under wet heat conditions, high temperature conditions, and low temperature conditions, have good foam physical properties, and can be used as a roofing material.

  Comparative Example 1 was performed under the same conditions as Example 1 except that long molecular weight polyol (B) -1 was changed to (B) -6. The foam was inferior in dimensional stability and was not practical due to shrinkage.

Comparative Example 2
The same conditions as in Example 4 were followed except that the long molecular weight polyol (B) -1 was changed to (B) -6. The foam was inferior in dimensional stability and was not practical due to shrinkage.

Comparative Example 3
The process was performed under the same conditions as in Example 6 except that the long molecular weight polyol (B) -2 was changed to (B) -6. The foam was inferior in dimensional stability and was not practical due to shrinkage.

Comparative Example 4
It carried out on the same conditions as Example 9 except having reduced the addition amount of long molecular weight polyol (B) -4. The foam was inferior in dimensional stability and was not practical due to shrinkage.

Comparative Example 5
It carried out on the same conditions as Example 1 except having changed the ratio of low molecular polyol (A) -4 and (A) -5. This polyol mixture was not practical because phase separation and turbidity occurred in a storage stability test at storage temperatures of 20 ° C. and 5 ° C.

Claims (10)

A composition comprising a low molecular weight polyol (A), a long molecular weight polyol (B), trischloropropyl phosphate (C), and water (D),
The low molecular weight polyol (A) is an equivalent molecular weight of 100 to 200, a polyether polyol that is a polymer of alkylene oxide, or a combination of two or more kinds,
The long molecular weight polyol (B) is one or a combination of two or more polyether polyols, which are polymers of alkylene oxide, with an equivalent molecular weight of 900 to 2200, and a low molecular weight polyol ( A) 40 to 70% by weight, long molecular weight polyol (B) 3 to 20% by weight, trischloropropyl phosphate (C) 10 to 30% by weight, and water (D) 5 to 12% by weight. ,
A polyol composition for rigid polyurethane foams. In the polyol composition for rigid polyurethane foam, the low molecular weight polyol (A) is 50 to 60% by weight, the long molecular weight polyol (B) is 15 to 18% by weight, the trischloropropyl phosphate (C) is 12 to 16% by weight, And 8 to 10% by weight of water (D),
The polyol composition for rigid polyurethane foam according to claim 1. The polyol composition for rigid polyurethane foam according to claim 1 or 2, further containing an aliphatic alcohol (E),
The aliphatic alcohol (E) is a primary monoalcohol having 6 to 14 carbon atoms and 2 to 10% by weight in the composition;
A polyol composition for rigid polyurethane foams. The polyol composition for rigid polyurethane foam according to claim 3, comprising a low molecular weight polyol (A), a long molecular weight polyol (B), an aliphatic alcohol (E), trischloropropyl phosphate (C), and water (D). Contains,
The low molecular weight polyol (A) is one or a combination of two or more polyether polyols, which is a polymer of alkylene oxide with an equivalent molecular weight of 120 to 200,
The long molecular weight polyol (B) is a polyether polyol which is a polymer of alkylene oxide having an equivalent molecular weight of 2000 to 2200,
The aliphatic alcohol (E) is a primary monoalcohol having 6 to 14 carbon atoms, and 50 to 70% by weight of the low molecular weight polyol (A) and 3 of the long molecular weight polyol (B) in the composition. -8% by weight, aliphatic alcohol (E) 5-10% by weight, trischloropropyl phosphate (C) 10-30% by weight, and water (D) 5-12% by weight Polyol composition for rigid polyurethane foam.   The polyol composition for rigid polyurethane foam according to any one of claims 1 to 4, wherein the content of the ethylene oxide unit of the long molecular weight polyol (B) is 3 to 20% by weight.   The rigid polyurethane foam which is a reaction foam of the polyol composition for rigid polyurethane foams in any one of Claims 1 thru | or 5, and organic polyisocyanate.   A metal siding material having a foam density of 25 kg / m3 to 30 kg / m3, comprising the rigid polyurethane foam according to claim 6.   A roofing material comprising a rigid polyurethane foam according to claim 6 and having a foam density of 25 kg / m3 to 30 kg / m3.   A method for producing a rigid polyurethane foam, comprising reacting the polyol composition for a rigid polyurethane foam according to any one of claims 1 to 5 with an organic polyisocyanate in the presence of a catalyst.   An active hydrogen group in the polyol composition for rigid polyurethane foam and the organic polyisocyanate component in the presence of a catalyst in the polyol composition for rigid polyurethane foam according to any one of claims 1 to 5 and the organic polyisocyanate. A process for producing a rigid polyurethane foam, characterized in that the reaction is carried out with an equivalent ratio of NCO groups of 60 to 130.