JP2006137810A - 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 which contains water as a foaming agent and gives rigid polyurethane foam having a low density, effectively preventing shrinkage, and not forming cracks, and to provide a method for producing a rigid polyurethane foam. <P>SOLUTION: This polyol composition contains water as a foaming agent, 30 to 50 pts.wt. of an aliphatic polyetherpolyol containing sucrose as an initiator, 20 to 40 pts.wt. of an aliphatic aminepolyol, and 10 to 30 pts.wt. of pentaerythritolpolyol as polyols, and three of (a) a cyclic dialkylpolysiloxane, (b) a silicone polymer of cohydrolysis condensate of at least one compound selected from the group consisting of (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>) with Si(OR<SP>2</SP>)<SB>4</SB>, and (c) a graft copolymer of polydimethylsiloxane with a polyoxyalkylene glycol, as a foam stabilizer. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a polyol composition for a rigid polyurethane foam having foamed water 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 they were prohibited because CFC compounds caused destruction of the ozone layer, and 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 addition, there is a problem that a large amount of cost is required for the equipment for fire prevention.

There is no problem in both the work environment and the global environment, and water is known as a low-cost foaming agent. Hard polyurethane foams using water as a foaming agent are known, but low-density water-foaming rigid polyurethane Foam has the problem of large dimensional changes. As a technique for solving such a problem, a technique using a specific silicone compound is known (Patent Document 1).
Japanese Patent No. 2722952

  However, according to the technique described in Patent Document 1, it is possible to obtain a rigid polyurethane foam in which shrinkage is suppressed, but there is still room for improvement with respect to a rigid polyurethane foam for applications requiring high dimensional accuracy. In addition, the adhesiveness to the face material is not sufficient, and improvement is required.

  The present invention uses a polyol composition for rigid polyurethane foam, which uses water as a foaming agent, has a low density and effectively prevents shrinkage, and has excellent adhesive strength with a face material, and the polyol composition. An object of the present invention is to provide a method for producing a rigid polyurethane foam.

The present invention is a polyol composition for a rigid polyurethane foam for forming a rigid polyurethane foam by mixing and reacting with a polyisocyanate component, comprising a polyol compound, a foaming agent and a foam stabilizer.
The blowing agent is water;
When the total amount of the polyol compound is 100 parts by weight, an aliphatic polyether polyol having an average number of functional groups of 5 to 8 and a hydroxyl value of 350 to 550 mgKOH / g as an initiator, 30 to 50 parts by weight, average 20 to 40 parts by weight of a polyol compound (aliphatic amine polyol) containing an aliphatic diamine having 3 to 4 functional groups and a hydroxyl value of 400 to 600 mgKOH / g as an initiator, and an average functional group number of 3 to 4 and a hydroxyl value of 350 to 550 mgKOH 10 to 30 parts by weight of a polyol (PE polyol) having an initiator of / g pentaerythritol,
The foam stabilizer 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 , A silicone polymer (R ¹ is an alkyl having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ Group or 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.), (C) Graft of polydimethylsiloxane and polyoxyalkylene glycol It contains three types of copolymer silicone compounds which are copolymers.

  A rigid polyurethane foam using a polyol composition having such a composition is a rigid polyurethane foam that uses water as a foaming agent, has a low density, effectively prevents shrinkage, and has excellent adhesive strength with a face material. .

  The reason why foam shrinkage is prevented by the above composition is not clear, but polyurethane foam is formed by using a specific composition polyol and cyclic dialkylpolysiloxane (a) and silicone polymer (b). It is presumed that fine pores are formed and shrinkage due to pressure drop due to the diffusion of carbon dioxide in the bubbles is prevented without impairing the heat insulation.

  The addition of PE polyol is considered to be particularly effective for shrinkage resistance and adhesion to a face material. When the amount of PE polyol added is less than 10 parts by weight, the shrinkage resistance and the adhesiveness to the face material are not sufficient, and when it exceeds 30 parts by weight, the adhesiveness to the face material decreases. The addition amount of water as a foaming agent is preferably 2 to 10 parts by weight, and more preferably 4 to 7 parts by weight with respect to 100 parts by weight of the total polyol compound.

  The above-mentioned polyol composition for rigid polyurethane foam preferably further contains 5 to 20 parts by weight of a polyether polyol (glycerin polyol) having a hydroxyl value of 40 to 70 mg KOH / g as a initiator.

  The rigid polyurethane foam using the polyol composition having such a composition is particularly excellent in adhesion to the face material. The content of glycerin polyol having a hydroxyl value of 40 to 70 mgKOH / g greatly affects the adhesion between the rigid polyurethane foam and the face material. When the content is less than 5 parts by weight, the adhesive strength with the face material is lowered. If it exceeds 20 parts by weight, the shrinkage resistance is lowered.

The density of the rigid polyurethane foam of the present invention is preferably 15 to 35 kg / m ³ .

A high density foam having a density exceeding 35 kg / m ³ has limited applications, but shrinkage is not a problem. A foam having a density of less than 15 kg / m ³ has a low strength and is difficult to manufacture.

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;
When the total amount of the polyol compound is 100 parts by weight, an aliphatic polyether polyol having an average number of functional groups of 5 to 8 and a hydroxyl value of 350 to 550 mgKOH / g as an initiator, 30 to 50 parts by weight, average 20 to 40 parts by weight of a polyol compound (aliphatic amine polyol) containing an aliphatic diamine having 3 to 4 functional groups and a hydroxyl value of 400 to 600 mgKOH / g as an initiator, an average number of functional groups of 4 to 5, and a hydroxyl value of 350 to 550 mgKOH 10 to 30 parts by weight of a polyol (PE polyol) having an initiator of / g pentaerythritol,
The foam stabilizer 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 , A silicone polymer (R ¹ is an alkyl having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ Group or 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.), (C) Graft of polydimethylsiloxane and polyoxyalkylene glycol It contains three types of copolymer silicone compounds which are copolymers.

  By the manufacturing method having such a configuration, it is possible to manufacture a rigid polyurethane foam that uses water as a foaming agent, has a low density, effectively prevents shrinkage, and has excellent adhesive strength with a face material.

  In the manufacturing method of the above-mentioned rigid polyurethane foam, it is preferable that the polyol composition further contains 5 to 20 parts by weight of a polyether polyol (glycerin polyol) having a hydroxyl value of 40 to 70 mg KOH / g as an initiator.

  By the production method using the polyol composition having such a composition, it is possible to produce a rigid polyurethane foam panel having particularly excellent adhesion to the face material.

  In the method for producing a rigid polyurethane foam, the foam stabilizer is prepared by previously mixing three components of (a) a cyclic dialkylpolysiloxane, (b) a silicone polymer, and (c) a copolymerized silicone compound. It is preferable to mix with the other polyol composition constituents except, and finally add and mix the water of the blowing agent.

  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 silicone polymer are first mixed and dissolved, and then mixed with the (c) copolymerized silicone compound because a mixed solution can be produced in a short time.

  In the polyol composition of the present invention, an aliphatic polyether polyol containing sucrose having an average number of functional groups of 5 to 8 and a hydroxyl value of 350 to 550 mgKOH / g as an initiator, an average number of functional groups of 3 to 4, and a hydroxyl value of 400 to A polyol compound (aliphatic amine polyol) containing 600 mg KOH / g aliphatic diamine as an initiator, and a polyol (PE polyol) initiated with pentaerythritol having an average functional group number of 3 to 4 and a hydroxyl value of 350 to 550 mg KOH / g Is used. Preferably, a polyether polyol (glycerin polyol) further containing glycerin as an initiator is used.

  Aliphatic polyether polyols are sucrose only, or a mixture of sucrose and other aliphatic polyfunctional alcohols as initiators and cyclic ether compounds such as ethylene oxide, propylene oxide, butylene oxide, preferably only propylene oxide, or propylene A polyol compound obtained by ring-opening addition of oxide and ethylene oxide.

  PE polyol, one of the aliphatic polyether polyols, is a cyclic ether compound such as ethylene oxide, propylene oxide, butylene oxide, preferably only propylene oxide, or propylene oxide and ethylene oxide, with pentaerythritol as an initiator. It is an added polyol compound. Further, glycerin polyol which is one kind of aliphatic polyether polyol is obtained by ring-opening addition of cyclic ether compounds such as ethylene oxide, propylene oxide and butylene oxide, preferably propylene oxide or propylene oxide and ethylene oxide, using glycerin as an initiator. It is a polyol compound. PE polyol has a functional group number of 4 when pentaerythritol is used as an initiator. However, when pentaerythritol is dissolved in water, ethylene glycol or the like and a cyclic ether compound is subjected to ring-opening addition, a polyol compound having an average functional group number of 3 to 4 It becomes. Since glycerin is liquid at normal temperature and usually used alone as an initiator, the number of functional groups of glycerin polyol is 3.

  Examples of the aliphatic amine polyol include alkylene diamine polyols and alkanol amine polyols. These polyol compounds are polyfunctional polyol compounds having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using alkylene diamine or alkanol amine as an initiator. As the alkylene diamine, known compounds can be used without limitation. Specifically, use of alkylene diamine having 2 to 8 carbon atoms such as ethylene diamine, propylene diamine, butylene diamine, hexamethylene diamine, and neopentyl diamine is preferable. Among these, the use of alkylenediamine having a small number of carbon atoms is more preferable, and the use of a polyol compound having ethylenediamine or propylenediamine as an initiator is particularly preferable. In the alkylene diamine-based polyol, the alkylene diamine as the initiator may be used alone or in combination of two or more. Examples of the alkanolamine include monoethanolamine, diethanolamine, and triethanolamine. The number of functional groups of the polyol compound using alkylene diamine as the initiator is 4, and the number of functional groups of the polyol compound using alkanolamine as the initiator is 3.

  In the above-mentioned aliphatic polyether polyol, aliphatic amine polyol, and PE 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 5 in the cyclic ether. It is preferable that it is -40%, and it is more preferable that it is 5-20%.

  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) silicone 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) The copolymer silicone 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. Specifically, SH-193 (Si = 30 wt%; Toray Dow Corning Silicon), S-824-02 (Si = 25 wt%; Nihon Unicar), SZ-1704 (Si = 25 wt%; Nihon Unicar), F501 ( A foam stabilizer such as Si = 25 wt%; Shin-Etsu Chemical Co., Ltd.) can be used. Two or more kinds of foam stabilizers (copolymerized silicone compounds) having polyoxyalkylene glycol may be used, or (a) a cyclic dialkylpolysiloxane may be contained.

  As the silicone compounds (a), (b), and (c), commercially available products can be used. Specifically, F701 (Shin-Etsu Chemical Co., Ltd.) is used as a composition containing (a) and (b). Illustrated and suitable for use. As described above, (a) a cyclic dialkylpolysiloxane, (b) a silicone polymer and (c) a copolymerized silicone 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) silicone polymer is preferably 1/9 to 8/2 in weight ratio. The mixing ratio of (a) cyclic dialkylpolysiloxane and (b) silicone polymer to (c) copolymer silicone compound is (a) + (b) / (c) = 1 by weight ratio. / 9 to 8/2 is preferable.

  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 1.1 to 1.5.

  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.

  Examples of the catalyst include N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylhexamethylenediamine (Kaorizer No. 1), N, N, N ′, N ′, N-alkylpolyalkylenepolyamines such as N ″ -pentamethyldiethylenetriamine (Kaorizer No. 3), diazabicycloundecene (DBU), N, N-dimethylcyclohexylamine (Polycat-8), triethylenediamine, N— It is preferable to use tertiary amines such as methylmorpholine.

  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, organophosphates, antimony trioxide, and aluminum hydroxide. .

  However, when an excessive amount of powdery flame retardant such as antimony trioxide is added excessively, there may be a problem that the foaming behavior of the foam is affected.

  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 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.

(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 A
A polyol polyol compound obtained by ring-opening addition of propylene oxide to an initiator containing sucrose;
Hydroxyl value = 450 mgKOH / g, Viscosity = 6000 mPa · sec (25 ° C.)
b) Polyol B
A polyol compound obtained by ring-opening addition of propylene oxide to ethylenediamine;
Hydroxyl value = 500 mgKOH / g, Viscosity = 6250 mPa · sec (25 ° C.)
c) Polyol C
A polyol compound obtained by adding propylene oxide to pentaerythryl;
Hydroxyl value = 450 mgKOH / g, Viscosity = 2500 mPa · sec (25 ° C.)
d) Polyol D
A polyol compound obtained by adding propylene oxide to glycerin;
Hydroxyl value = 56 mgKOH / g, Viscosity = 715 mPa · sec (25 ° C.)
e) Polyol E
A polyol compound in which propylene oxide and ethylene oxide are added using toluenediamine as an initiator;
Hydroxyl value = 410 mgKOH / g, Viscosity = 6000 mPa · sec (25 ° C.)
f) TMCPP: Phosphorus flame retardant (plasticizer) (Daihachi Chemical Industry)
g) Catalyst kaolinizer No. 1 (Kao-No. 1), Kaorizer No. 1 3 (Kao.-No.3) (Kao)
h) Foam stabilizer composition (a) 1: 1 (weight ratio) mixture of cyclic dialkylpolysiloxane and (b) silicone polymer F701 (Shin-Etsu Chemical Co., Ltd.), polydimethylsiloxane and polyoxyalkylene glycol copolymer F701: F501 = 1: 1 mixture by weight ratio with F501 (Shin-Etsu Chemical Co., Ltd.) containing a certain copolymerized silicone compound, and (c) copolymerized silicone compound: SH-193 (Si content = 30 wt%, polyoxy Alkylene glycol = polyoxyethylene glycol, Toray Dow Corning Silicon) was mixed at F701 + F501: SH-193 = 3: 2 (weight ratio) and used as a foam stabilizer composition.
i) Polyisocyanate component: Sumidur 44V-20 (Suika Bayer Urethane).

(Examples and comparative examples)
Rigid polyurethane foams were prepared by conventional methods with the formulations shown in the upper part of Table 1 for Examples and Table 2 for Comparative Examples. The polyol composition is prepared by first stirring and mixing the components excluding water and the foam stabilizer composition, then adding the foam stabilizer composition and mixing thoroughly, and finally adding and mixing the foam stabilizer composition. Prepared. The isocyanate index (NCO / OH equivalent ratio) in the mixing of the polyol composition and the polyisocyanate component was 1.33. The evaluation described below was performed, and the results are shown in the lower part of Table 1 for the examples and in Table 2 for the comparative examples.

(Evaluation)
1) Foam density (kg / m ³ )
A foam sample of 100 mm × 100 mm and thickness 100 mm was cut out from the core layer excluding the skin layer from the rigid polyurethane foam obtained by free foaming using a mold of 200 mm × 200 mm, depth 200 mm, and weighed. Density was calculated.

2) Shrink resistance [a] Dimensional stability of the core of the free foaming foam: The foam sample used for the above-mentioned measurement of the foam density is left for 48 hours in a high temperature and high humidity condition (temperature 70 ° C., relative humidity 95%), The dimensional change rate in the vertical direction of foaming was measured.
[B] Dimensional stability of mold foam core: A rigid polyurethane foam panel was prepared using a mold having a length of 800 mm, a width of 400 mm, and a depth of 50 mm so that the density was 33 kg / m ³ . From this rigid polyurethane foam panel, a measurement sample of 100 × 100 mm and a thickness of 25 mm was cut out, 9 pieces in total, 3 from the center and 3 from each end, and left under the same conditions as in [A] above. The dimensional change rate in the direction was measured to determine the maximum value.

3) Face material adhesiveness Use a mold with a length of 800 mm, width of 400 mm, and depth of 50 mm, and lay kraft paper on the bottom surface to produce a hard polyurethane foam panel with face material so that the density is 33 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 with 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.

4) Storage stability of polyol composition The polyol composition is allowed to stand for 1 month in a sealed state at a temperature of 40 ° C. to produce a free-foam foam, and the dimensional change rate of the core (above 2) [A]) Measurements were made.

上記の結果より本願発明の範囲内においては、フォームのコア部の寸法変化率にて表される耐収縮性、面材との接着性、ポリオール組成物のいずれについても良好であった。これに対してシュークロースを開始剤成分として含むポリオールＡの配合割合が多すぎるもの、エチレンジアミンを開始剤とするポリオールＢの配合割合が多すぎるものは、いずれも面材との接着性が十分ではなく、ポリオールＡの配合割合が少なすぎるもの、ポリオールＢの配合割合が少なすぎるもの、ペンタエリスリトールを開始剤とするポリオールＣを配合しないものは、いずれも耐収縮性、面材との接着性、ポリオール組成物の安定性の全てにおいて満足すべきものではなかった。

From the above results, within the scope of the present invention, the shrinkage resistance expressed by the dimensional change rate of the core portion of the foam, the adhesion to the face material, and the polyol composition were all good. On the other hand, those having too much blending ratio of polyol A containing sucrose as an initiator component and those having too much blending ratio of polyol B having ethylenediamine as an initiator are not sufficiently adhesive to the face material. None, the blending ratio of the polyol A is too small, the blending ratio of the polyol B is too small, and the polyol C that uses pentaerythritol as an initiator is not shrinkage resistance, adhesion to the face material, Not all of the stability of the polyol composition was satisfactory.

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

Claims (7)

A polyol composition comprising a polyol compound, a foaming agent and a foam stabilizer, and mixed with and reacted with a polyisocyanate component to form a rigid polyurethane foam,
The blowing agent is water;
When the total amount of the polyol compound is 100 parts by weight, an aliphatic polyether polyol having an average number of functional groups of 5 to 8 and a hydroxyl value of 350 to 550 mgKOH / g as an initiator, 30 to 50 parts by weight, average 20 to 40 parts by weight of a polyol compound (aliphatic amine polyol) containing an aliphatic diamine having 3 to 4 functional groups and a hydroxyl value of 400 to 600 mgKOH / g as an initiator, and an average functional group number of 3 to 4 and a hydroxyl value of 350 to 550 mgKOH 10 to 30 parts by weight of a polyol (PE polyol) having an initiator of / g pentaerythritol,
The foam stabilizer 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 , A silicone polymer (R ¹ is an alkyl having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ Group or 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.), (C) Graft of polydimethylsiloxane and polyoxyalkylene glycol A polyol composition for rigid polyurethane foam, comprising three kinds of copolymer silicone compounds which are copolymers.   The polyol composition for rigid polyurethane foam according to claim 1, further comprising 5 to 20 parts by weight of a polyether polyol (glycerin polyol) having a hydroxyl value of 40 to 70 mgKOH / g as an initiator.   The polyol composition for rigid polyurethane foam according to claim 1 or 2, wherein the (c) copolymerized silicone compound has a Si content of 10 to 40% by weight. 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;
When the total amount of the polyol compound is 100 parts by weight, an aliphatic polyether polyol having an average number of functional groups of 5 to 8 and a hydroxyl value of 350 to 550 mgKOH / g as an initiator, 30 to 50 parts by weight, average 20 to 40 parts by weight of a polyol compound (aliphatic amine polyol) containing an aliphatic diamine having 3 to 4 functional groups and a hydroxyl value of 400 to 600 mgKOH / g as an initiator, and an average functional group number of 3 to 4 and a hydroxyl value of 350 to 550 mgKOH 10 to 30 parts by weight of a polyol (PE polyol) having an initiator of / g pentaerythritol,
The foam stabilizer 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 , A silicone polymer (R ¹ is an alkyl having 1 or 2 carbon atoms) which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ Group or 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.), (C) Graft of polydimethylsiloxane and polyoxyalkylene glycol A method for producing a rigid polyurethane foam, comprising three kinds of copolymerized silicone compounds which are copolymers.   The method for producing a rigid polyurethane foam according to claim 4, further comprising 5 to 20 parts by weight of a polyether polyol (glycerin polyol) having a hydroxyl value of 40 to 70 mg KOH / g as an initiator.   The foam stabilizer is characterized in that three components of (a) cyclic dialkylpolysiloxane, (b) silicone polymer, and (c) copolymerized silicone compound are mixed in advance and mixed with other components of the polyol composition. The manufacturing method of the rigid polyurethane foam of Claim 4 or 5. The method for producing a rigid polyurethane foam according to any one of claims 4 to 6, wherein the (c) copolymer silicone compound has a Si content of 10 to 40% by weight.

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