JP2007186551A - Polyol composition for rigid polyurethane foam and method for producing rigid polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition capable of forming a rigid polyurethane foam having low density and especially effectively prevented shrinkage by using water as a foaming agent and provide a method for producing a rigid polyurethane foam by using the polyol composition. <P>SOLUTION: The polyol composition contains water as a foaming agent, a polyol compound composed mainly of an amine polyol having a tertiary amino group and a foam stabilizer component containing (a) a cyclic dialkylpolysiloxane having 4-5 Si-O bonds, (b) a silicone polymer comprising a cohydrolytic condensation product of Si(OR<SP>2</SP>)<SB>4</SB>and at least one kind of compound selected from (R<SP>1</SP>)Si(OR<SP>2</SP>)<SB>3</SB>, (R<SP>1</SP>)<SB>2</SB>Si(OR<SP>2</SP>)<SB>2</SB>and (R<SP>1</SP>)<SB>3</SB>Si(OR<SP>2</SP>), and (c) at least one kind of copolymerized silicone compound comprising a graft copolymer of polydimethylsiloxane and polyoxyalkylene glycol. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyol composition for rigid polyurethane foam using water as a foaming agent, and a method for producing a rigid polyurethane foam using the polyol composition.

  Rigid polyurethane foam is a well-known material as a heat insulating material, a lightweight structural material, and the like. Such a rigid polyurethane foam is formed by mixing a polyol composition containing a polyol compound and a foaming agent as essential components and a polyisocyanate component, and foaming and curing. In the past, chlorofluorocarbon compounds such as CFC-11 were used as foaming agents, but CFC compounds were prohibited because they caused destruction of the ozone layer, and were switched to HCFC-141b. Although switching to an HFC compound having a coefficient of zero has been performed, the HFC compound has a problem that it has a large GWP (global warming potential) and is currently expensive.

  Although a technique using pentane such as n-pentane, iso-pentane, cyclopentane or the like as a low-cost blowing agent instead of halogenated hydrocarbon compounds such as HFC compounds is known, pentanes are highly flammable. In order to produce a polyol composition or rigid polyurethane foam using these as a foaming agent, there is a problem that a large amount of cost is required for equipment for fire prevention.

  There is no problem in the working environment or the global environment, and water is known as a low-cost foaming agent, and rigid polyurethane foam using water as a foaming agent without using other foaming agents is known. The low-density water-foamed rigid polyurethane foam has a problem of large dimensional change. As a technique for solving such a problem, a technique using a specific silicon compound is known (Patent Documents 1, 2, etc.).

Japanese Patent No. 2722952 JP 2004-315580 A

  However, according to the techniques described in Patent Documents 1 and 2, a rigid polyurethane foam in which shrinkage is suppressed can be obtained, but shrinkage still occurs, and further improvement is demanded.

  The present invention relates to a polyol composition capable of forming a rigid polyurethane foam having water as a foaming agent and having a low density and particularly effectively prevented from shrinkage, and a method for producing a rigid polyurethane foam using the polyol composition Is intended to provide.

The present invention is a polyol composition comprising a polyol compound, a foaming agent and a foam stabilizer, mixed with and reacted with a polyisocyanate component to form a rigid polyurethane foam,
The blowing agent is water;
The polyol compound is mainly composed of an amine polyol having a tertiary amino group,
The foam stabilizer component includes (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) _2. , (R ¹ ) ₃ Si (OR ² ) and a silicon polymer (R ¹ having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of Si (OR ² ) and Si (OR ² ) ₄ An alkyl group or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, R ¹ and R ² may be the same or different), and (c) polydimethylsiloxane and polyoxyalkylene glycol It contains at least one copolymer silicon compound which is a graft copolymer of the above.

  Rigid polyurethane foam produced using a polyol composition having such a composition is a hard polyurethane foam that has a low density and is particularly effectively prevented from shrinking compared to the foams of Patent Documents 1 and 2. Polyurethane foam.

The density of the free polyurethane foam of the rigid polyurethane foam of the present invention (foam foamed with a cylindrical mold having an open top) is preferably 15 to 35 kg / m ³ .

A high-density foam having a density of free foaming foam of more than 35 kg / m ³ has limited use, while having good dimensional stability without using the present invention. A foam having a density of free foaming foam of less than 15 kg / m ³ It is difficult to prevent the occurrence of shrinkage.

  In the above polyol composition for rigid polyurethane foam, when the total amount is 100 parts by weight, the polyol compound contains an aromatic diamine having a hydroxyl value of 300 to 500 mgKOH / g as an initiator (aromatic amine). (Polyol) It is preferable to contain 30 to 5 parts by weight of a polyol (aliphatic amine polyol) having an initiator of 70 to 95 parts by weight and an aliphatic diamine having a hydroxyl value of 400 to 600 mgKOH / g.

  By using the polyol composition having such a structure, a rigid polyurethane foam having a low density and excellent strength, particularly bending strength can be produced.

  In the above polyol composition for rigid polyurethane foam, it is preferable that the catalyst has an imidazole catalyst as a main component.

  By using the polyol composition having such a configuration, it is possible to produce a rigid polyurethane foam having excellent adhesive strength with the face material when laminated with the face material.

The method for producing a rigid polyurethane foam of the present invention is a method for producing a rigid polyurethane foam by mixing and reacting a polyol composition containing a polyol compound, a foaming agent and a foam stabilizer and a polyisocyanate component,
The blowing agent is water;
The polyol compound is mainly composed of an amine polyol having a tertiary amino group,
The foam stabilizer component includes (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) _2. , (R ¹ ) ₃ Si (OR ² ) and a silicon polymer (R ¹ having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of Si (OR ² ) and Si (OR ² ) ₄ An alkyl group or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, R ¹ and R ² may be the same or different), and (c) polydimethylsiloxane and polyoxyalkylene glycol It contains at least one copolymer silicon compound which is a graft copolymer of the above.

  According to the manufacturing method of such a configuration, it is possible to manufacture a rigid polyurethane foam that uses water as a foaming agent, has a low density, and is particularly effectively prevented from shrinking, as compared with the foams of Patent Documents 1 and 2. .

  In the method for producing a rigid polyurethane foam, when the polyol compound is 100 parts by weight in total, the polyol compound contains an aromatic diamine having a hydroxyl value of 300 to 500 mgKOH / g as an initiator (aromatic amine polyol). ) It is preferable to contain 30 to 5 parts by weight of a polyol (aliphatic amine polyol) having an initiator of 70 to 95 parts by weight and an aliphatic diamine having a hydroxyl value of 400 to 600 mgKOH / g.

  According to the manufacturing method of such a configuration, it is possible to manufacture a rigid polyurethane foam that uses water as a foaming agent, has a low density and effectively prevents shrinkage, and has excellent foam strength, particularly bending strength. .

  In the above-mentioned method for producing a rigid polyurethane foam, it is preferable that the catalyst has an imidazole catalyst as a main component.

  According to this configuration manufacturing method, it is possible to manufacture a rigid polyurethane foam excellent in adhesive strength with the face material when laminated with the face material.

  In the method for producing a rigid polyurethane foam, the foam stabilizer component is produced by previously mixing three components of (a) a cyclic dialkylpolysiloxane, (b) a silicon polymer, and (c) a copolymerized silicon compound. And then mixed with other polyol composition constituents.

  With such a configuration, the storage stability of the polyol composition is improved, and a rigid polyurethane foam having a stable quality can be produced. In particular, it is preferable that (a) the cyclic dialkylpolysiloxane and (b) the silicon polymer are first mixed and dissolved, and then (c) the mixed silicon compound is mixed with the copolymerized silicon compound because a mixed solution can be produced in a short time.

  The polyol composition of the present invention is mainly composed of an amine polyol having a tertiary amino group, and more preferably a polyol compound (aromatic compound) containing an aromatic diamine having a hydroxyl value of 300 to 500 mgKOH / g as an initiator. Group (polyol amine polyol) and a polyol (aliphatic amine polyol) having an aliphatic diamine having a hydroxyl value of 400 to 600 mgKOH / g as an initiator.

  The aromatic amine polyol is a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, preferably only propylene oxide, or about a tetrafunctional functional group obtained by ring-opening addition of propylene oxide and ethylene oxide using an aromatic diamine as an initiator. It is a polyol compound having a tertiary amino group. As aromatic diamine which is an initiator, well-known aromatic diamine can be used without limitation. Specific examples include 2,4-toluenediamine, 2,6-toluenediamine, diethyltoluenediamine, 4,4'-diaminodiphenylmethane, p-phenylenediamine, o-phenylenediamine, naphthalenediamine and the like. Of these, the use of toluenediamine (2,4-toluenediamine, 2,6-toluenediamine or a mixture thereof) is particularly preferred in that the obtained rigid polyurethane foam has excellent properties such as heat insulation and strength.

  Aliphatic amine polyols are cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, preferably only propylene oxide, or about a tetrafunctional functional group obtained by ring-opening addition of propylene oxide and ethylene oxide using an aliphatic diamine as an initiator. It is a polyol compound having a tertiary amino group. Examples of the aliphatic diamine that is an initiator include ethylene diamine, propylene diamine, 1,4-butylene diamine, and hexamethylene diamine.

  In the present invention, in addition to the above-described polyol compound, other polyether compounds such as hydroquinone, bisphenol A, and xylylene glycol are used as initiators as long as the characteristics of the present invention are not impaired. An aliphatic polyfunctional alcohol such as polyol, sucrose, sorbitol, pentaerythritol, trimethylolpropane, glycerin, etc. and a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, preferably only propylene oxide, or propylene oxide and ethylene oxide An aliphatic polyether polyol subjected to ring-opening addition, a trifunctional polyol compound using triethanolamine as an initiator, or the like may be added. The addition amount of these polyol compounds is preferably less than 10% by weight in the total amount of the polyol compounds, that is, the amine polyol is preferably 90% by weight or more.

  In the above-mentioned polyol compound, when propylene oxide and ethylene oxide are used as the cyclic ether used for the synthesis of the polyol compound, the amount of ethylene oxide used is preferably 5 to 40% in the cyclic ether. More preferably, it is -20%.

  You may use a crosslinking agent as a component which comprises the polyol composition for rigid polyurethane foams of this invention. As the crosslinking agent, low molecular weight polyhydric alcohols used in the technical field of polyurethane can be used. Specifically, trimethylolpropane, glycerin, pentaerythritol, triethanolamine and the like are exemplified.

In the present invention, the (b) silicon polymer used as the foam stabilizer component is (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) ₂ , (R ¹ ) ₃ Si (OR ² ). ) And at least one selected from the group consisting of Si (OR ² ) ₄ and co-hydrolyzing and condensing using water and a catalyst to form a polysiloxane bond. R ¹ and R ² may be the same or different and are preferably a methyl group or an ethyl group. Further, (a) cyclic dialkylpolysiloxane can also be produced by a known method, and is preferably cyclic dimethylsiloxane.

  (C) A copolymer silicon compound is a compound used as a foam stabilizer in the technical field of polyurethane foam. In the present invention, among these known foam stabilizers, those having an Si content of 10 to 40% by weight, that is, the content of copolymerized polyoxyalkylene glycol is small and generally low in activity. It is preferable to use a foam stabilizer (low activity foam stabilizer). When the Si content is low, the activity is high, and when the Si content is high, the compatibility with the polyol composition is lowered. Specific examples of the low activity foam stabilizer having a Si content of 10 to 40% by weight include S-824-02 (Si = 25 wt%; Toray Dow Corning Silicon), SF-2945, SF-2935, SZ-. 1605, BY-10-540, SH-193 (Si = 30 wt%; Toray Dow Corning Silicon), SZ-1704 (Si = 25 wt%; Toray Dow Corning Silicon), F501 (Si = 25 wt%; Shin-Etsu Chemical) The foam stabilizer can be used. Two or more kinds of foam stabilizers (copolymerized silicon compounds) having polyoxyalkylene glycol may be used, and (a) a cyclic dialkylpolysiloxane may be contained.

  In addition to the above components (a) to (c), a medium to high activity foam stabilizer having a Si content of 10% by weight or less may be added to the foam stabilizer component of the present invention. However, the addition amount of the moderately active or highly active foam stabilizer is preferably less than 10% by weight in the foam stabilizer component.

  As the silicon compounds (a), (b), and (c), commercially available products can be used. Specifically, as a composition containing (a) and (b), F701 (Shin-Etsu Chemical Co., Ltd.) is used. Illustrated and suitable for use. As described above, (a) a cyclic dialkylpolysiloxane, (b) a silicon polymer, and (c) a foam stabilizer that is a copolymerized silicon compound are mixed in advance and used as a foam stabilizer composition in the production of a polyol composition. It is preferable to do.

  The mixing ratio of (a) cyclic dialkylpolysiloxane and (b) silicon polymer is preferably 1/9 to 8/2 in weight ratio. The mixing ratio of (a) cyclic dialkylpolysiloxane and (b) silicon polymer to (c) copolymerized silicon compound is (a) + (b) / (c) = 1. It is preferably 0.0 / 0.5 to 1.0 / 1.5.

  With such a configuration, the closed cell ratio can be adjusted to a range of 70 to 85%, and as a result, the shrinkage is effectively suppressed, and a rigid polyurethane foam excellent in bending strength can be obtained.

  The polyisocyanate compound that forms a rigid polyurethane foam by mixing and reacting with the polyol composition is easy to handle, fast in reaction, excellent in the physical properties of the resulting rigid polyurethane foam, and low in cost. For this reason, liquid MDI is used. As liquid MDI, Crude MDI (c-MDI) (Sumijoule 44V-10, Sumijoule 44V-20, etc. (manufactured by Sumika Bayer Urethane Co., Ltd.), Millionate MR-200 (Nippon Polyurethane Industry)), uretonimine-containing MDI (Millionate) MTL (manufactured by Nippon Polyurethane Industry) or the like is used. In addition to liquid MDI, other polyisocyanate compounds may be used in combination. As the polyisocyanate compound used in combination, a polyisocyanate compound known in the technical field of polyurethane can be used without limitation.

  In the production of the rigid polyurethane foam of the present invention, the equivalent ratio (NCO index) of isocyanate groups to active hydrogen groups is 1.0 to 1.7, more preferably 1.0 to 1.3.

  In the production of the rigid polyurethane foam of the present invention, in addition to the above components, catalysts, flame retardants, colorants, antioxidants and the like well known to those skilled in the art can be used.

  As the catalyst, a known tertiary amine catalyst or imidazole catalyst can be used. Specific examples of the imidazole catalyst include 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole and the like. Further, as the tertiary amine catalyst, specifically, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine (kaolyzer No. 1), N , N, N ′, N ′, N ″ -N-alkylpolyalkylenepolyamines such as pentamethyldiethylenetriamine (Kaolinizer No. 3), diazabicycloundecene (DBU), N, N-dimethylcyclohexylamine (polycat) -8), tertiary amines such as triethylenediamine and N-methylmorpholine can be exemplified.

  It is also preferable to use a catalyst that forms an isocyanurate bond that contributes to an improvement in flame retardancy in the structure of the polyurethane molecule. For example, potassium acetate, potassium octylate, a quaternary ammonium salt catalyst (disclosed in JP-A-9-104734) is used. It can be illustrated. Some of the above-mentioned tertiary amine catalysts also promote the isocyanurate ring formation reaction. A catalyst that promotes the formation of isocyanurate bonds and a catalyst that promotes the formation of urethane bonds may be used in combination.

  In the present invention, addition of a flame retardant is also a preferred embodiment, and examples of suitable flame retardants include metal compounds such as halogen-containing compounds, organic phosphate esters, and aluminum hydroxide.

  However, excessive addition of a powdery flame retardant such as aluminum hydroxide may cause problems such as an effect on the foaming behavior of the foam, and the amount added is limited to a range that does not cause such problems.

  Organophosphates are suitable additives because they also have an action as a plasticizer and thus have an effect of improving the brittleness of rigid polyurethane foam. It also has the effect of reducing the viscosity of the polyol composition. Examples of the organic phosphate esters include halogenated alkyl esters of phosphoric acid, alkyl phosphate esters, aryl phosphate esters, phosphonate esters, and the like. Specifically, tris (β-chloroethyl) phosphate (CLP, Daihachi Chemical), Tris (β-chloropropyl) phosphate (TMCPP, Daihachi Chemical), Tributoxyethyl phosphate (TBXP, Daihachi Chemical), Tributyl phosphate, Triethyl phosphate, Cresyl phenyl phosphate, Dimethyl methylphosphonate Etc., and one or more of these can be used. The addition amount of the organic phosphates is 40 parts by weight or less, preferably 5 to 40 parts by weight, based on 100 parts by weight of the total polyol compound. If this range is exceeded, problems such as insufficient plasticization and flame retardant effects and deterioration of the mechanical properties of the foam may occur.

  As a method for producing the rigid polyurethane foam of the present invention, a known method for producing a sandwich panel such as an injection molding method or a continuous production method can be used, but a continuous production method is preferred.

(Polyol composition)
A polyol composition was prepared with the composition described in the upper part of Table 1. The contents and characteristics of the raw materials used are as follows.
a) Polyol 1
A polyol compound obtained by ring-opening addition of propylene oxide and ethylene oxide to toluenediamine;
Hydroxyl value = 400 mgKOH / g
b) Polyol 2
A polyol compound obtained by adding propylene oxide to ethylenediamine;
Hydroxyl value = 505 mgKOH / g
c) Polyol 3
A polyol polyol compound obtained by ring-opening addition of propylene oxide to an initiator containing sucrose;
Hydroxyl value = 450 mgKOH / g
d) Polyol 4
A polyol compound obtained by adding propylene oxide to triethanolamine;
Hydroxyl value = 345 mgKOH / g
e) Polyol 5
Polyol compound in which propylene oxide is added to pentaerythritol;
Hydroxyl value = 450 mgKOH / g
f) Catalyst A: Kalyzer No. 300 (Kao)
B: Kaulizer No. 1 (Kao-No.1) (Kao)
g) Foam stabilizer component A: (a) 1: 1 (weight ratio) mixture of cyclic dialkylpolysiloxane and (b) silicon polymer F701 (Shin-Etsu Chemical Co., Ltd.) and (c) polydimethylsiloxane and polyoxyalkylene glycol F701: F501 = 1.0: 1.0 in a weight ratio with F501 (Shin-Etsu Chemical Co., Ltd.), which is a copolymerized silicon compound as a copolymer, B: (c) Copolymerized silicon compound (low activity foam stabilizer) ) SH-193 (Si content = 30 wt%, polyoxyalkylene glycol = polyoxyethylene glycol, Toray Dow Corning Silicon)
C: Highly active silicone foam stabilizer B-8465 (Gold Schmidt)
h) Polyisocyanate component: Millionate MR-200 (crude MDI: Nippon Polyurethane Industry).

(Experimental example)
A rigid polyurethane foam was prepared by a conventional method with the formulation described in the upper part of Table 1. The polyol composition was prepared by first stirring and mixing water and the components excluding the foam stabilizer component, then adding the foam stabilizer component and mixing thoroughly, and finally adding and mixing water. The foam stabilizer component was mixed in advance and used. The isocyanate index (NCO / OH equivalent ratio) in the mixing of the polyol composition and the polyisocyanate component was 1.0. The evaluation described below was performed, and the results are shown in the lower part of Table 1.

(Evaluation)
1) Liquid fluidity The temperature of a mold having a width of 400 mm and a thickness of 20 mm was adjusted to 50 ° C., and a foamed stock solution composition in which a polyol composition and a polyisocyanate component were mixed was poured along one side at the end of the mold. The length and weight that spread from the injection position until the foaming stock composition was foam-cured was measured, and the elongation of the foam per unit weight was calculated by (length) ÷ (weight). The evaluation results were as follows: the foam elongation was 330 mm / 100 g or more, ◯, less than 330 mm / 100 g, 300 mm / 100 g or more, Δ, and less than 300 mm / 100 g, x.

2) Foam density (kg / m ³ )
A foam sample of 100 mm x 100 mm and thickness 100 mm from the core layer obtained by free foaming using an upper open mold of 200 mm x 200 mm, depth 200 mm, and removing the skin layer from the obtained rigid polyurethane foam (free foamed foam) Was cut out and weighed to calculate the density.

3) Dimensional stability The foam sample used for the above-mentioned measurement of the foam density was allowed to stand for 48 hours under high temperature and high humidity conditions (temperature 70 ° C., relative humidity 95%), and the dimensional change rate in the vertical direction of foaming was measured.

4) Bending strength A sample having a length of 120 mm, a width of 50 mm, and a thickness of 10 mm is cut out from the core portion of the above-mentioned free foaming foam with the foaming vertical direction as the length direction,
Support point spacing 100mm
Indenter diameter 10mm
Crosshead speed 10mm / min
Measurement temperature 23 ℃
The bending strength was measured under the following conditions.

5) face material adhesive length 800 mm, width 400 mm, using a mold depth 50 mm, density covered with kraft paper on the lower surface is prepared rigid polyurethane foam panels face with material so as to be 50 kg / ^{m 3} did. A peel test was performed on the produced rigid polyurethane foam panel by the method shown in FIG. 1 to determine the adhesive strength. In the measurement, a notch having a width of 5 cm was put in the face material, the face material was evaluated by pulling in the W direction and obtaining a peeling load. As a result, the adhesive strength of 1.2 kgf or more is ◯, less than 1.2 kgf is 1.0 kgf or more (practically usable but slightly low adhesive strength) is △, less than 1.0 kgf (practical) That are problematic for general use) are shown as x.

  The evaluation results are shown in the lower part of Table 1. As shown in this result, the rigid polyurethane foams of Experimental Examples 1 to 5 using the amine polyol and the foam stabilizer component of the present invention did not substantially undergo dimensional change. The rigid polyurethane foam of Experimental Example 9 outside this range developed shrinkage. Further, the rigid polyurethane foams of Experimental Examples 1 and 2 in which the composition of the amine polyol is a preferred ratio of the aromatic amine polyol and the aliphatic amine polyol had high bending strength, but Experimental Examples 6 to 8 having different polyol compounds were used. The rigid polyurethane foam had a low bending strength. The rigid polyurethane foam of Experimental Example 3 using a tertiary amine catalyst instead of the imidazole catalyst was slightly inferior in adhesion to the face material.

The figure which showed the measuring method of the adhesive strength of paper surface material and rigid polyurethane foam

Claims (9)

A polyol composition comprising a polyol compound, a foaming agent and a foam stabilizer, and mixed and reacted with a polyisocyanate component to form a rigid polyurethane foam,
The blowing agent is water;
The polyol compound is mainly composed of an amine polyol having a tertiary amino group,
The foam stabilizer component includes (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) _2. , (R ¹ ) ₃ Si (OR ² ) and a silicon polymer (R ¹ having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of Si (OR ² ) and Si (OR ² ) ₄ An alkyl group or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, R ¹ and R ² may be the same or different), and (c) polydimethylsiloxane and polyoxyalkylene glycol A polyol composition for rigid polyurethane foam, comprising at least one copolymerized silicon compound which is a graft copolymer of   When the total amount of the polyol compound is 100 parts by weight, 70 to 95 parts by weight of a polyol compound (aromatic amine polyol) containing an aromatic diamine having a hydroxyl value of 300 to 500 mgKOH / g as an initiator, and a hydroxyl value of 400 The polyol composition for rigid polyurethane foam according to claim 1, comprising 30 to 5 parts by weight of a polyol (aliphatic amine polyol) having an initiator of ˜600 mg KOH / g of an aliphatic diamine.   The polyol composition for rigid polyurethane foam according to claim 1 or 2, wherein the (c) copolymerized silicon compound has a Si content of 10 to 40% by weight.   The polyol composition for rigid polyurethane foam according to any one of claims 1 to 3, wherein the catalyst contains an imidazole catalyst as a main component. A method for producing a rigid polyurethane foam comprising mixing and reacting a polyol composition containing a polyol compound, a foaming agent and a foam stabilizer and a polyisocyanate component to form a rigid polyurethane foam,
The blowing agent is water;
The polyol compound is mainly composed of an amine polyol having a tertiary amino group,
The foam stabilizer component includes (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) ₂ Si (OR ² ) _2. , (R ¹ ) ₃ Si (OR ² ) and a silicon polymer (R ¹ having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of Si (OR ² ) and Si (OR ² ) ₄ An alkyl group or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, R ¹ and R ² may be the same or different), and (c) polydimethylsiloxane and polyoxyalkylene glycol A method for producing a rigid polyurethane foam, comprising at least one copolymerized silicon compound that is a graft copolymer of   When the total amount of the polyol compound is 100 parts by weight, 70 to 95 parts by weight of a polyol compound (aromatic amine polyol) containing an aromatic diamine having a hydroxyl value of 300 to 500 mgKOH / g as an initiator, and a hydroxyl value of 400 The method for producing a rigid polyurethane foam according to claim 5, comprising 30 to 5 parts by weight of a polyol (aliphatic amine polyol) having an initiator of ˜600 mg KOH / g of an aliphatic diamine.   The method for producing a rigid polyurethane foam according to claim 5 or 6, wherein the (c) copolymerized silicon compound has a Si content of 10 to 40% by weight.   The method for producing a rigid polyurethane foam according to any one of claims 5 to 7, wherein the catalyst contains an imidazole catalyst as a main component.   The foam stabilizer component is prepared by previously mixing (a) a cyclic dialkylpolysiloxane, (b) a silicon polymer, and (c) a copolymerized silicon compound, and mixing with other polyol composition components. A method for producing a rigid polyurethane foam according to any one of claims 5 to 8.

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