JP4978986B2 - Polyol composition for foamed rigid polyurethane foam and method for producing foamed rigid polyurethane foam - Google Patents

Description

  The present invention relates to a polyol composition for foamed 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 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 great expense is required for the equipment for preventing fire.

  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 (Patent Document 1) that limits the cream time of the rigid polyurethane foam foam concentrate solution and the closed cell ratio of the obtained rigid polyurethane foam is known.

  Patent Document 2 discloses a rigid urethane foam that uses water and an HFC compound in combination as a foaming agent.

Japanese Patent Laid-Open No. 2001-40054 JP 2004-51693 A

  However, the technique described in Patent Document 1 uses a polyether polyol compound starting from piperazine or aminoalkylpiperazine as a raw material, and is not sufficiently flame retardant. In order to improve flame retardancy, the use of aromatic ester-based polyols is conceivable. However, when a known ester polyol of ethylene glycol or diethylene glycol and terephthalic acid or orthophthalic acid is used, hydrolysis occurs due to the presence of water as a blowing agent, Since the generated acid forms a salt with the catalyst amine, the reactivity is lowered, and it becomes difficult to produce a rigid polyurethane foam by a spray method as the polyol composition is stored.

  In addition, as described above, the technique disclosed in Patent Document 2 is expensive, and it is difficult to adjust the reactivity mildly compared to the conventional formulation using HCFC-141b. However, in a refrigerated warehouse that requires a thick blow of rigid polyurethane foam by the spray method, there is a problem that workability is poor, such as being unable to blow smoothly.

  In view of the above-mentioned problems of the known technology, the present invention is capable of forming a rigid polyurethane foam having low density and excellent flame retardancy using water as a foaming agent, and also having excellent storage stability. It is an object of the present invention to provide a polyol composition and a method for producing a rigid polyurethane foam using the polyol composition.

The polyol composition for foamed rigid polyurethane foam of the present invention is a polyol composition comprising a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst, mixed with a polyisocyanate component and reacted to form a rigid polyurethane foam. There,
The polyol compound is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid comprises terephthalic acid and orthophthalic acid.

  The polyol composition having the above-described configuration is capable of forming a rigid polyurethane foam having a low density and excellent flame retardancy using water as a foaming agent, and having excellent storage stability.

  When the average molecular weight of polyoxyethylene glycol constituting the ester polyol (by end group quantification method) is less than 150, hydrolysis resistance is lowered and the storage stability of the polyol composition becomes insufficient. The flame retardancy of the resulting rigid polyurethane foam is reduced. When the aromatic dicarboxylic acid constituting the ester polyol is only terephthalic acid, the hydrolysis resistance of the ester polyol is not sufficient, and when only the orthophthalic acid is used, the flame retardancy is not sufficient.

  In the polyol composition for foamed rigid polyurethane foam, the molar ratio of terephthalic acid / orthophthalic acid of the aromatic dicarboxylic acid is preferably 5/95 to 95/5.

  The polyol composition having such a structure has practical storage stability to the extent that a rigid polyurethane foam can be produced even after market distribution, just after production, and a rigid polyurethane foam excellent in flame retardancy. Can be manufactured. When the molar ratio of terephthalic acid / orthophthalic acid exceeds 95/5 and the ratio of terephthalic acid is large, the storage stability of the polyol composition decreases, and is less than 5/95, when the ratio of orthophthalic acid is large. The flame resistance of the resulting rigid polyurethane foam may be reduced. The molar ratio of terephthalic acid / orthophthalic acid is more preferably 40/60 to 60/40, since both the storage stability of the polyol composition and the combustion resistance of the resulting rigid polyurethane foam can be satisfied.

  The polyol composition for foamed rigid polyurethane foam described above preferably further includes a polyether polyol represented by a chemical formula (Chemical Formula 3) having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4.

  In the general formula (Chemical Formula 3), R is an alkyl group having 1 to 4 carbon atoms, X is an organic group containing at least one of oxyethylene group and oxypropylene group, Y is an ethylene group or propylene group, m is 0 or 1, q is 1 or 2, m + g = 2, and the average value of n is 1 to 4.

  By using the above polyol compound in combination, a rigid polyurethane foam excellent in flame retardancy can be produced.

  When using a polyol compound having a chemical structure represented by the above general formula (Chemical Formula 3), the ratio of ester polyol / (Chemical Formula 3) polyol is preferably 95/5 to 5/95 by weight, It is more preferably 95/5 to 45/55, and further preferably 90/10 to 50/50.

In the polyol composition for foamed rigid polyurethane foam, the foam stabilizer is (a) a cyclic dialkylpolysiloxane containing 4 to 5 Si—O bonds, (b) (R ¹ ) Si (OR ² ) ₃ , (R ¹ ) A silicone polymer that is a cohydrolysis condensate of at least one selected from the group consisting of ₂ Si (OR ² ) ₂ and (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ R ¹ is an alkyl group having 1 or 2 carbon atoms or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different. It is preferable to include.

  The rigid polyurethane foam using the polyol composition having such a composition uses water as a foaming agent, has a low density and effectively prevents shrinkage, and has excellent adhesive strength with a face material and a base material to be sprayed. Rigid polyurethane foam.

  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 very fine pores are formed, and shrinkage due to pressure drop due to diffusion of carbon dioxide in the bubbles is prevented without impairing the heat insulation.

Another aspect of the present invention is a method for producing a rigid polyurethane foam, wherein a polyol composition containing a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst is mixed with a polyisocyanate component and reacted to form a rigid polyurethane foam. And
The polyol compound is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid comprises terephthalic acid and orthophthalic acid.

  By the production method having the above-described configuration, a rigid polyurethane foam having low density and excellent flame retardancy can be produced using water as a foaming agent.

  In the production method of the foamed rigid polyurethane foam, the molar ratio of terephthalic acid / orthophthalic acid of the aromatic dicarboxylic acid is preferably 5/95 to 95/5, and preferably 40/60 to 60/40. More preferred.

  With such a configuration, a rigid polyurethane foam having practically excellent flame retardancy can be produced. When the molar ratio of terephthalic acid / orthophthalic acid exceeds 95/5, the storage stability of the polyol composition is lowered and the produced rigid polyurethane foam tends to shrink, and when it is less than 5/95, it is manufactured. The fire resistance of the hard polyurethane foam may decrease.

  In the manufacturing method of said foaming rigid polyurethane foam, it further contains 35-70 weight part of polyether polyols shown by the said Chemical formula (Chemical formula 3) whose hydroxyl value is 250-550 mgKOH / g and functional group number is 2-4. preferable.

  By the above production method, a rigid polyurethane foam excellent in flame retardancy can be produced.

Also in the above-described method for manufacturing a foamed rigid polyurethane foam, wherein the foam stabilizer, (a) cyclic dialkyl polysiloxane Si-O bond the containing ^{4-5, (b) (R 1)} Si (OR 2) 3, Silicone weight which is a cohydrolysis condensate of at least one selected from the group consisting of (R ¹ ) ₂ Si (OR ² ) ₂ and (R ¹ ) ₃ Si (OR ² ) and Si (OR ² ) ₄ 2 of a combination (R ¹ is an alkyl group having 1 or 2 carbon atoms or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different). Preferably it contains seeds.

  According to the manufacturing method of the above configuration, water is used as a foaming agent, and a rigid polyurethane foam that is low in density and effectively prevented from shrinking and has excellent adhesive strength with a face material or a base material to be sprayed is manufactured. can do.

The present invention relates to a polyol composition for foamed rigid polyurethane foam for mixing with a polyisocyanate component by a spray device and reacting to form a rigid polyurethane foam.
The polyol composition has practical storage stability to the extent that it can produce a rigid polyurethane foam by spraying, just after production, even after market distribution, and has excellent flame retardancy. Polyurethane foam can be produced. Moreover, since a polyisocyanate component and a polyol composition can be mixed and sprayed / foamed using a spray device, a heat insulating layer excellent in flame retardancy can be easily formed on an object.

  The present invention relates to a method for producing a foamed rigid polyurethane foam using a spray device. By using a spray device, the polyisocyanate component and the polyol composition can be mixed and foamed, and a rigid polyurethane foam excellent in flame retardancy can be produced.

  As a foaming method of the rigid polyurethane foam, a foaming method known in the technical field of polyurethane can be used without limitation. For example, a continuous production method, a discontinuous production method, a spray method, an injection method, or the like can be used. In particular, the spray method is a method in which a two-component undiluted solution is mixed and sprayed onto a construction object with a spray device, and when reaching the object, it is foamed and cured, and is an effective method because construction is easy. In addition, the continuous production method is a method in which a mixed stock solution is flowed on the lower surface material on the continuous conveyor, and the upper surface material is supplied and continuously foamed, and a sandwich panel can be produced by cutting to a predetermined length. it can.

  The polyol composition of the present invention contains a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst. The viscosity of the polyol composition of the present invention is preferably 1000 mPa · s (20 ° C.) or less, and preferably 800 mPa · s (20 ° C.) or less, from the viewpoint of easily producing a rigid polyurethane foam by a spray method. More preferred. In the case of the continuous production method, the viscosity can be increased as compared with the spray method, so that it is preferably 1500 mPa · s (20 ° C.) or less, more preferably 1000 mPa · s (20 ° C.) or less. preferable.

  As described above, the polyol compound is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid, the polyoxyethylene glycol has an average molecular weight of 150 to 500, and the aromatic dicarboxylic acid is terephthalic acid and orthophthalic acid. It is characterized by the following. The polyoxyethylene glycol having an average molecular weight of 150 to 500 may contain diethylene glycol or triethylene glycol. Such an ester polyol can be produced by the same production method as an ester polyol composed of an aromatic dicarboxylic acid and ethylene glycol or diethylene glycol which are generally used conventionally. The bifunctional polyoxyethylene glycol constituting the ester polyol can also be produced by a conventional method, and a commercially available product may be used alone or in combination with two or more urethanes having more preferable characteristics. It is also a preferred aspect to form a foam. For example, as polyoxyethylene glycol having an average molecular weight of 150 to 500, a commercially available product that falls within this range may be used alone, or two or more kinds may be used in combination and the average molecular weight may fall within the above range.

  In addition to the ester polyol compound as described above, the polyol composition of the present invention further includes a polyether polyol represented by a chemical formula (chemical formula 3) having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4. It is preferable.

  The polyol compound represented by the above chemical formula (Chemical Formula 3) used in the present invention is a polyol compound called Mannich polyol, and obtained by a Mannich reaction of phenol and / or an alkyl-substituted derivative thereof, formaldehyde and alkanolamine. An active hydrogen compound or an active hydrogen compound obtained by subjecting this compound to ring-opening addition polymerization of at least one of ethylene oxide and propylene oxide.

  The polyol composition of the present invention may further contain at least one polyol compound having a hydroxyl value of 200 to 500 mgKOH / g selected from aliphatic amine polyols and aromatic amine polyols.

  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.

  The aromatic amine-based polyol is a polyfunctional polyether polyol compound having a terminal hydroxyl group obtained by ring-opening addition of at least one of ethylene oxide and propylene oxide using an aromatic diamine as an initiator. As the initiator, known aromatic diamines 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. The aliphatic amine-based polyol is preferably used for spray foam, and the aromatic amine-based polyol is preferably used for foam by a continuous production method.

  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.

  Moreover, in addition to a) and (b) used as a foam stabilizer component in the present invention, (c) a copolymer silicone compound which is a graft copolymer of polydimethylsiloxane and polyoxyalkylene glycol may be included. The copolymerized 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), etc. A foaming agent 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.

  Commercially available products can be used as the silicone compounds (a) and (b), and specifically, compositions containing (a) and (b) are suitable for use. As described above, it is preferable that (a) a cyclic dialkylpolysiloxane and (b) a foam stabilizer which is a silicone polymer are mixed in advance and used as a foam stabilizer composition in the production of a polyol composition.

  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), prepolymer-modified crude MDI and the like are 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, 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), 1-isobutyl-2-methylimidazole, 1-methylimidazole, 1,2-dimethylimidazole, etc., diazabicycloundecene ( DBU), tertiary amines such as N, N-dimethylcyclohexylamine (Polycat-8), triethylenediamine, N-methylmorpholine, bis (2-dimethyl-aminoethyl) ether (NIAX-A-1), Dimethylmethanolamine, dimethylethanolamine, 2- [methyl [2- (dimethylamine B) ethyl] amino] ethanol (TMAEEA), 2- [2- (dimethylamino) ethoxy] ethanol (DMAEE), 1,3-bis (dimethylamino) -2-propanol (TMHPDA), 4-methylpiperazine-1 -Ethanol, 3,3 '-[3- (dimethylamino) propylimino] bis (2-propanol) (Thancat-DPA), 2-morpholinoethanol, 1- [bis [3- (dimethylamino) propyl] amino] Ethan-2-ol (Polycat 16), 1- [bis [3- (dimethylamino) propyl] amino] propan-2-ol (Polycat 17), 1- (2-hydroxypropyl) -imidazoline (Dabco WT It is preferable to use reactive amines such as) etc. In addition, when a catalyst is used in combination, the blending ratio (weight ratio) is As long as the use in the art of urethane, it is not particularly limited.

  It is also preferable to use a catalyst that forms an isocyanurate bond that contributes to improvement in flame retardancy in the structure of the polyurethane molecule. For example, potassium acetate, potassium octylate, and a quaternary ammonium salt catalyst (disclosed in JP-A-9-104734) are 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. Commercially available Dabco-TMR, Dabco-TMR-2 (air products) and the like can also be used as the quaternary ammonium salt catalyst.

  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. .

  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.

  In the method for producing a rigid polyurethane foam, the isocyanate group / active hydrogen group equivalent ratio (NCO index) in the mixing of the polyol composition and the polyisocyanate component is 1.0 to 4.0, more preferably 1.3. It is -3.5, More preferably, it is 1.3-2.0. More preferably, the NCO index is 1.3 or more, and the catalyst contains a trimerization catalyst.

With such a configuration, it is possible to produce a rigid polyurethane foam in which many isocyanurate bonds are formed in the resin constituting the rigid polyurethane foam and the flame retardancy is further improved. The density of the rigid polyurethane foam produced according to the present invention is preferably 20 g / m ^{3 to} 50 kg / m ³ .

(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
Esters polyol (Hitachi Chemical Co., Ltd.) made from triethylene glycol and trifunctional glycol terephthalic acid / orthophthalic acid = 1/1 (50/50) aromatic carboxylic acid, polyfunctional ethyleneoxy (PEG) with an average molecular weight of 290 polymer);
Hydroxyl value = 150 mgKOH / g, viscosity = 2500 mPa · sec (25 ° C.)
b) Polyol B
Mannich polyol compound (Daiichi Kogyo Seiyaku Co., Ltd.);
Hydroxyl value = 315 mgKOH / g, viscosity = 1300 mPa · sec (25 ° C.)
c) Polyol C
A polyether polyol compound (Asahi Glass) using ethylenediamine as an initiator;
Hydroxyl value = 500 mgKOH / g, Viscosity = 6000 mPa · sec (25 ° C.)
d) Polyol D
Ester polyol (Hitachi Kasei Polymer) produced from orthophthalic acid and polyoxyethylene glycol (PEG) 400 by a conventional method;
Hydroxyl value = 110 mgKOH / g, viscosity = 900 mPa · sec (25 ° C.)
e) Polyol E
Ester polyol (Hitachi Kasei Polymer) produced from terephthalic acid and bifunctional polyoxyethylene glycol (PEG) having an average molecular weight of 400 by a conventional method;
Hydroxyl value = 150 mgKOH / g, viscosity = 3000 mPa · sec (25 ° C.)
f) Polyol F
Ester polyol (Hitachi Kasei Polymer) prepared from terephthalic acid / orthophthalic acid = 1/1 aromatic carboxylic acid and diethylene glycol by a conventional method;
Hydroxyl value = 150 mgKOH / g, Viscosity = 1500 mPa · sec (25 ° C.)
g) Polyol G
Polyether polyol compound (Mitsui Chemicals) using toluenediamine as an initiator;
Hydroxyl value = 400 mgKOH / g, Viscosity = 6500 mPa · sec (25 ° C.)
h) TMCPP: Phosphorus flame retardant (plasticizer) (Daihachi Chemical Industry)
i) Catalyst Tetramethylhexamethylenediamine (Kaorizer No. 1) (Kao)
Foaming catalyst (Kaorizer No. 3) (Kao)
Quaternary ammonium salt catalyst (Dabco-TMR) (Air Products)
j) Foam stabilizer composition (a) a mixture of cyclic dialkylpolysiloxane and (b) silicone polymer (weight ratio (a) :( b) = 1: 1), (c) polydimethylsiloxane and polyoxyalkylene A mixture having a weight ratio of ((a) + (b)) :( c) = 1: 1 to the copolymerized silicone compound which is a copolymer of glycol was used as the foam stabilizer composition.
k) Polyisocyanate component: Sumidur 44V-20 (Suika Bayer Urethane).

(Examples 1-4, Comparative Examples 1-3)
In Examples 1 to 4 and Comparative Examples 1 to 3, polyol compositions were prepared by blending the polyol compounds described in the upper part of Table 2. In the formulation other than the polyol compound, the total amount of the polyol compound was 100 parts by weight, the flame retardant TMCPP (Daihachi Chemical Industry) was 30 parts by weight, and Kaolinizer No. 1, kaolinizer no. 3 and Dabco-TMR (weight ratio: No. 1: No. 3: Dabco-TMR = 1: 1: 2) in total 10 parts by weight, 5 parts by weight of blowing agent water, and the foam stabilizer composition 4 Part by weight. The polyol composition was prepared by first stirring and mixing the components excluding the foam stabilizer composition and water, and then adding and mixing the foam stabilizer composition. In the production of the rigid polyurethane foam, the polyol composition and the polyisocyanate component were mixed with a laboratory stirrer so that the NCO index was 1.33.

(Example 5)
In Example 5, the total amount of the polyol compound was 100 parts by weight, the flame retardant TMCPP (Daihachi Chemical Industry) was 30 parts by weight, and the catalyst Kaolinizer No. 1, kaolinizer no. 3 and Dabco-TMR (weight ratio: No. 1: No. 3: Dabco-TMR = 1: 1: 2) in total 2 parts by weight, 6 parts by weight of blowing agent water, and the above foam stabilizer composition 2 Part by weight. The polyol composition was prepared by first stirring and mixing the components excluding the foam stabilizer composition and water, and then adding and mixing the foam stabilizer composition. In the production of rigid polyurethane foam, the polyol composition and the polyisocyanate component were mixed with a laboratory stirrer so that the NCO index was 1.5.

  The polyol A used in Examples 1 to 5 was prepared from a combination of polyoxyethylene glycol (PEG) having an average molecular weight of 200 and 400.

  The evaluation described below was performed, and the results are shown in the lower part of Table 1. The viscosity (mPa · s) of the polyol composition was measured at 20 ° C. using a B-type viscometer.

(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. The density (kg / m ³ ) was calculated.

2) Combustion resistance
(A) The foamed rigid polyurethane foam by the spray method was evaluated according to JIS A 1321. As for the evaluation results, the classification was flame retardant third grade, and those that conformed to the determination of the surface test were evaluated as ◯, and those that did not conform were evaluated as ×.
(B) For the foamed rigid polyurethane foam by the continuous production method, a sample of (99 ± 1) mm × (99 ± 1) mm is cut out and conforms to ISO-5660 for 5 minutes at a radiant heat intensity of 50 kW / m ² . The maximum heat generation rate (heating rate) when heated and the total heat generation were measured. This measurement method is a test method defined as corresponding to the standard according to the corn calorimeter method at the Building Comprehensive Testing Laboratory, which is a public institution prescribed in Article 108-2 of the Building Standard Law Enforcement Ordinance. The case where the test was endured for 20 minutes was evaluated as passing the incombustible standard.

3) Storage stability of the polyol composition A sample having the same shape as the sample used for the measurement of the foam density by producing a free-foam foam by leaving the polyol composition in a sealed state for 1 month at a temperature of 40 ° C. Was left for 48 hours under high temperature and high humidity conditions (temperature 70 ° C., relative humidity 95%), and the dimensional change rate (%) of the core in the vertical direction of foaming was measured. When a polyol composition with poor storage stability is used, the dimensional change rate increases. Those with a dimensional change rate of 10% or less were marked with ◯, and those with a dimensional change rate exceeding 10%.

  From the results shown in Table 1, the polyol composition of the present invention was excellent in storage stability, and the rigid polyurethane foam produced using the polyol composition was excellent in flame retardancy. In contrast, even when the same ester polyol is used, combustion resistance is not sufficient when only orthophthalic acid is used, and storage stability is not sufficient when only terephthalic acid is used. It was. In addition, the storage stability was not good when the conventional ester polyol using diethylene glycol was used.

Claims (8)

A polyol composition comprising a polyol compound, water as a blowing agent, a foam stabilizer and a catalyst, mixed with a polyisocyanate component and reacted to form a rigid polyurethane foam,
The polyol compound is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid comprises terephthalic acid and orthophthalic acid,
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 Or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different.) Polyol composition.   The polyol composition for foamed rigid polyurethane foam according to claim 1, wherein the aromatic dicarboxylic acid has a terephthalic acid / orthophthalic acid molar ratio of 5/95 to 95/5. The polyol composition for foamed rigid polyurethane foam according to claim 1 or 2, further comprising a Mannich polyol having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4. A method for producing a rigid polyurethane foam comprising mixing a polyol composition containing a polyol compound, water as a foaming agent, a foam stabilizer and a catalyst and a polyisocyanate component, and reacting them to form a rigid polyurethane foam,
The polyol compound is an ester polyol of polyoxyethylene glycol and aromatic dicarboxylic acid,
The polyoxyethylene glycol has an average molecular weight of 150 to 500,
The aromatic dicarboxylic acid comprises terephthalic acid and orthophthalic acid,
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 Or a phenyl group, R ² is an alkyl group having 1 or 2 carbon atoms, and R ¹ and R ² may be the same or different.) Manufacturing method.   The method for producing a rigid foamed polyurethane foam according to claim 4, wherein the aromatic dicarboxylic acid has a terephthalic acid / orthophthalic acid molar ratio of 5/95 to 95/5. The method for producing a foamed rigid polyurethane foam according to claim 4 or 5, further comprising Mannich polyol having a hydroxyl value of 250 to 550 mgKOH / g and a functional group number of 2 to 4.   The polyol composition for foamed rigid polyurethane foam according to any one of claims 1 to 3, which is mixed with a polyisocyanate component by a spray device and reacted to form a foamed rigid polyurethane foam.   The manufacturing method of the foaming rigid polyurethane foam in any one of Claims 4-6 using a spray apparatus.