JPH1053665A - Isocyanurate-modified rigid polyurethane foam and method for producing the same - Google Patents

Abstract

(57) [Abstract] (Modified) [Problem] In the field of spraying where hard polyurethane foam is sprayed directly on the construction site of an apartment house or office building, etc. on the wall or ceiling, outside air is required for construction at low temperatures in winter. However, there is a problem that the thickness of the foam shrinks or decreases immediately after spraying because the reaction is difficult to proceed because heat is easily taken away. SOLUTION: When the polyhydroxy compound is 100% by weight, it contains 5% to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less and 5 to 100% by weight of an aromatic hydroxy compound. things and,
By using a polyester polyol obtained by esterifying phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid which is a polybasic acid component and a polybasic acid obtained by mixing these or a derivative thereof, by 5% by weight or more,
An isocyanurate-modified rigid polyurethane foam and a method for producing the same are preferably employed, particularly without shrinkage during airless spray foaming.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an isocyanurate-modified rigid polyurethane foam mainly used for applications such as a heat insulating material and a method for producing the same.

[0002]

2. Description of the Related Art Ordinary rigid polyurethane foams are widely used as heat insulating materials for houses, refrigerators, etc. because of their good heat insulating properties and self-adhesiveness. This rigid polyurethane foam is generally produced by mixing and stirring a polyhydroxy compound and a polyisocyanate with a catalyst, a foaming agent, a foam stabilizer and other auxiliaries, and reacting them in the presence of bubbles.

[0003] However, ordinary rigid polyurethane foams have a characteristic that once ignited, the flame is easily propagated, and particularly a fire during construction at a construction site has been reported. Therefore, recently, isocyanurate-modified rigid polyurethane foams having high flame-retardant performance have been increasingly used.

This isocyanurate-modified rigid polyurethane foam is a special rigid polyurethane foam having a basic skeleton of a urethane bond obtained from a polyhydroxy compound and a polyisocyanate compound and an isocyanurate bond obtained by trimerizing an isocyanate group of the polyisocyanate compound. It is characterized by its high flame-retardant performance, and has been used in the past, but has recently received particular attention from the viewpoint of disaster prevention.

[0005]

The flame-retardant performance of isocyanurate-modified rigid polyurethane foams generally uses a polyester polyol obtained by esterifying phthalic acid as a polybasic acid component as a hydroxy compound, or isocyanate obtained from a polyisocyanate. Exhibited by nullate binding. However, the latter has a problem that the foam undergoes shrinkage immediately after foaming, depending on environmental conditions, because the reaction progresses particularly slowly and the foam strength is not easily developed. Especially in the field of spraying where hard polyurethane foam is sprayed directly on the walls and ceilings of construction sites such as apartment houses and office buildings, when the work is performed at low temperatures in the winter season, the reaction is difficult to proceed because the outside air is easily deprived of heat. Immediately after that, there was a problem that the thickness of the foam was reduced.

[0006] Such a tendency is found in trichloromonofluoromethane (hereinafter referred to as R-11) which has been conventionally used as a foaming agent for rigid urethane foams. Freon R-141b (dichloromonofluoroethane) is more prominent because it has a high boiling point and is hardly foamed due to its high solubility in polyhydroxy compounds.

The present invention has been made in view of the above circumstances, and provides a stable isocyanurate-modified rigid polyurethane foam which does not easily shrink immediately after foaming even under a low ambient temperature during foaming, and a method for producing the same. The purpose is to provide.

[0008]

The isocyanurate-modified rigid polyurethane foam of the present invention (hereinafter simply referred to as rigid polyurethane foam) comprises a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst and other auxiliaries. An isocyanurate-modified rigid polyurethane foam comprising a polyisocyanate compound, wherein when the total polyhydroxy compound is 100% by weight, an amino alcohol (alkamine) compound having a molecular weight of 200 or less is contained therein in an amount of 5% by weight or more.
It is characterized by containing 30% by weight.

The rigid polyurethane foam according to claim 2 of the present invention is an isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst, other auxiliaries and a polyisocyanate compound. Assuming that the polyhydroxy compound is 100% by weight, it contains 5% to 30% by weight of an amino alcohol (alkamine) compound having a molecular weight of 200 or less, and terephthalic acid, isophthalic acid or trimellitic acid, and a mixture thereof. A polybasic acid or a polyester polyol obtained by esterifying a derivative thereof is contained in an amount of 20% by weight or more.

The rigid polyurethane foam according to claim 3 of the present invention is an isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst, other auxiliaries and a polyisocyanate compound. When the polyhydroxy compound is 100% by weight, the polyhydroxy compound contains 5 to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less and 5 to 100% by weight of an aromatic hydroxy compound. The basic acid components phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid and polybasic acids obtained by mixing these,
Alternatively, a polyester polyol obtained by esterifying these derivatives is contained in an amount of 5% by weight or more.

The rigid polyurethane foam according to claim 4 of the present invention is characterized in that a fluorine compound having an ozone destruction coefficient of 0 is used as a foaming agent.

A rigid polyurethane foam according to a fifth aspect of the present invention is characterized in that the isocyanate-modified rigid polyurethane foam described in each of the above items is used for airless spray foaming.

[0013] The method for producing a rigid polyurethane foam according to claim 6 of the present invention comprises reacting a polyhydroxy compound and a polyisocyanate compound in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, In producing an isocyanurate-modified rigid polyurethane foam, when an aminoalcohol (alkamine) compound having a molecular weight of 200 or less is 100% by weight of the total polyhydroxy compound, it is contained and blended in the range of 5% by weight to 30% by weight. It is characterized by doing.

[0014] The method for producing a rigid polyurethane foam according to claim 7 of the present invention comprises reacting a polyhydroxy compound with a polyisocyanate compound in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries, to obtain isocyanurate. In producing a modified rigid polyurethane foam, a molecular weight of 20
When 0 or less amino alcohol (alkamine) compound is 100% by weight of the total polyhydroxy compound, it is blended in the range of 5% by weight to 30% by weight, and terephthalic acid, isophthalic acid, or trimellitic acid, and the like. Or a polyester polyol obtained by subjecting a polybasic acid or a derivative thereof to an esterification reaction is mixed in an amount of 20% by weight or more.

The method for producing a rigid polyurethane foam according to claim 8 of the present invention is an isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst, other auxiliaries and a polyisocyanate compound. The total polyhydroxy compound being 100% by weight, containing 5% to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less and containing 5 to 100% by weight of an aromatic hydroxy compound. And at least 5% by weight of a polyester polyol obtained by esterifying a polybasic acid component such as phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid and a polybasic acid obtained by mixing them, or a derivative thereof. Features.

A method for producing a rigid polyurethane foam according to a ninth aspect of the present invention is characterized in that a fluorine compound having an ozone destruction coefficient of 0 is used as a foaming agent.

The method for producing a rigid polyurethane foam according to claim 10 of the present invention is characterized in that the method is for airless spray foaming.

[0018]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The details of the present invention will be described below.
Examples of the amino alcohol (alkamine) compound used in the present invention include, for example, ethanolamines such as monoethanolamine, diethanolamine and triethanolamine, and compounds obtained by ring-opening addition polymerization of ethylene oxide and propylene oxide with these, and the like. They can be used alone or in combination of two or more.

The amino alcohol (alkamine) compound is used in an amount of 5% by weight to 30% by weight, preferably 10% by weight to 25% by weight, based on 100% by weight of the total polyhydroxy compound. is there.
If the amount used is less than 5% by weight, the effect of suppressing the shrinkage of the foam immediately after foaming is insufficient, and if it exceeds 30% by weight, the reaction becomes too fast and the foaming becomes unstable, resulting in flame retardancy of the foam. It is not recommended because the performance also tends to decrease extremely.

The polyester polyol used in the present invention may be terephthalic acid, isophthalic acid, trimellitic acid or a mixture thereof, or a derivative thereof as a polybasic acid component, such as ethylene glycol or propylene glycol. Polyester polyol (= polyester polyol A) obtained by esterification with a hydroxy compound, or phthalic acid, isophthalic acid, terephthalic acid or trimellitic acid, or a mixture thereof, or bisphenol A as a polybasic acid component Benzene ring-containing hydroxy compounds such as phenol, bisphenol S and phenol, or derivatives thereof, and those obtained by ring-opening addition polymerization of an alkylene oxide to a hydroxyl group in an amount of 1 to several mols in the total hydroxy compound component, from 5 to 10 Wt% polyester polyols obtained by esterification using (polyester polyol B)
It is. Other polyhydroxy compounds include polyether polyols obtained by ring-opening addition polymerization of glycerin, sucrose, ethylenediamine, tolylenediamine and the like with an alkylene oxide such as ethylene oxide and propylene oxide.

Each of these can be used alone or in combination of two or more. When the flame retardancy of the foam is taken into consideration, the polyester polyol A contains 100% by weight of the total polyhydroxy compound. To 2
It is desirable to use 0% by weight or more, more preferably 50% by weight or more. If less than 20% by weight, the effect is not so much recognized. Further, in consideration of the handling properties such as viscosity and the flame-retardant effect of the polyester polyol B, the aromatic hydroxy compound is used in the range of 20 to 80% by weight of all the hydroxy compound components to be esterified. Is more preferred.

The blowing agent used in the present invention is R-141.
(b) HCFCs and a fluorine compound having an ozone depletion potential of 0 are used. This fluorine compound is, for example, HFC-245fa, 236ea, H
FE-347 (liquid above 0 ° C), HFC-13
4a (gas at normal temperature) and the like.

The amount of the foaming agent to be used is arbitrarily determined according to its type and the density of the intended foam.
b or hydrofluorocarbons (HFCs) such as R-245fa, 245ca, 236ea and the like, whose ozone destruction coefficient is “0”, usually 10 to 80% by weight based on 100% by weight of the total polyhydroxy compound; Particularly, 20 to 70% by weight is desirable. Hydrocarbon (HC) such as water and cyclopentane if necessary
And one or more foaming agents of hydrochlorocarbons such as methylene chloride. In this case, the amount of the foaming agent to be used in combination is the total polyhydroxy compound 10
Although 0 to 80% by weight can be arbitrarily selected with respect to 0% by weight, R-22 and R-13 having an ozone destruction coefficient of 0 can be selected.
4a and other low-boiling hydrochlorofluorocarbons (H
When using CFC) or HFC together, the total volume of the system stock solution (mixed solution + polyisocyanate)
A very small amount of 0.1 to 10% by volume (Vol%) may be used. In this case, R-141b or R-245fa is used in advance.
A simple method such as charging the mixture into a stock mixture in the form of a mixed Freon mixed with the above, or directly adding the third component to the component stock solution can be used.

The polyisocyanate compound used in the present invention includes aromatic isocyanates such as diphenylmethane diisocyanate and tolylene diisocyanate; alicyclic isocyanates such as isophorone diisocyanate; and aliphatic isocyanates such as hexamethylene diisocyanate. Isocyanates and their crude products can be used.

When the isocyanurate-modified rigid polyurethane foam is used, the polyisocyanate index relative to the total amount of the polyhydroxy compound and other compounds having active hydrogen such as water is preferably in the range of 130 to 350. In particular, in the case of the in-situ foaming spray method, if this index is too high, unreacted isocyanate groups will remain depending on the construction atmosphere temperature, and the foam will be more likely to shrink, or the flame retardant performance will be reduced. Therefore, about 130 to 200 is preferable.

The catalyst used in the present invention includes:
Mainly compounds used for isocyanurate modification such as trisdiaminopropylhexahydrotriazine, potassium acetate, potassium octylate, and amine compounds such as triethylenediamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, and dibutyltin dilaurate And those used in ordinary polyurethane foams, such as organometallic compounds such as stannas octoate.

Further, the auxiliary agent used in the present invention includes optional components other than those described above, for example, a flame retardant, a filler and the like.
It can be used within the range not hindering the object of the present invention.

[0028]

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

Examples 1 to 9 Each of the foams of Examples 1 to 9 and Comparative Examples 1 to 3 was produced by the following method. According to the blending recipe shown in Table 1, first, a blending liquid of the component A was prepared, and a blending liquid A and a polyisocyanate were prepared.
Next, Gasmer Model FF1600 (manufactured by Gasmer) as an airless mixing type high pressure spray foaming machine system
And the mixed solution A and the polyisocyanate are pumped from the main pump, and the low boiling point blowing agent is pumped as the third component from the subunit pump.
20mm, 5mm thick calcium silicate plate, 0-5
Spray foaming was performed at room temperature of ℃. The temperature of the liquid mixture in the foaming machine was set at 40 ° C, and the air pressure of the air pump was set at 5 k.
g / cm ² . The rigid polyurethane foam was laminated and sprayed two or three times to have a total thickness of 15 to 20 mm. The results are shown in Examples 1 to 9 in Table 1.

Examples 1 to 3 contain 10 to 25 parts by weight of an amino alcohol having a molecular weight of 200 or less and a large amount of an isophthalic acid / terephthalic acid-based polyester polyol as a main component. When the isophthalic acid / terephthalic acid-based polyester polyol was used in a small amount or was not used, Examples 8 to 9 were carried out in the case where a phenol-modified polyester polyol based on phthalic acid was used. . Example 7 shows an example in which a foaming agent having an ozone destruction coefficient of 0 is used in combination.

[Comparative Examples 1 to 3] The molecular weight of the present invention is 20.
Table 1 shows the results when no amino alcohol (alkamine) compound having a molecular weight of 0 or less was used (Comparative Examples 1 and 2) or when 40 parts by weight of an amino alcohol compound having a molecular weight of 200 or less was used (Comparative Example 3). A rigid polyurethane foam was obtained in the same manner as in the example according to the compounding recipe. The results are shown in Comparative Examples 1 to 3.

[0032]

[Table 1]

The following formulation was used in Table 1. Polyol A: Polyether polyol “GR-07” (manufactured by Takeda Pharmaceutical Co., Ltd.) (ethylenediamine-based polyol: average molecular weight: 290 to 300) Polyol B: Manufactured by Toho Rika Kogyo Co., Ltd., based on isophthalic acid / terephthalic acid Polyester polyol Polyol C: phthalic acid-based polyester polyol "PL-2001" manufactured by Toho Rika Kogyo Co., Ltd. Polyol D: phthalic acid-based phenol 80% modified polyester polyol manufactured by Toho Rika Kogyo Co., Ltd. Polyol E: Toho Rika Kogyo Co., Ltd., phthalic acid based phenol 5% modified polyester polyol Flame retardant: Stoffer Japan Co., Ltd., Tris monochloropropyl phosphate "Phirol PCF" Foam stabilizer: Nippon Unicar Co., Ltd. Made, silicone foam stabilizer -5420 "foaming agent 1: Daikin Industries Co. Ltd., dichloro monofluoro ethane" Daifuron 141b "blowing agent 2: Mitsui Fluorochemicals Co., Ltd., 1,1,
1,2-Tetrafluoroethane “HFC-134a” Catalyst A: DO of lead octylate, manufactured by Nippon Chemical Industry Co., Ltd.
P solution (lead concentration 17%) Catalyst B: Kao Corporation, Tetramethylhexamethylenediamine “Kaolyzer NO.1” Catalyst C: Nippon Chemical Industry Co., Ltd., potassium 2-ethylhexylate “B-15G” Polyisocyanate: Sumitomo Bayer Urethane Co., Ltd., crude diphenylmethane diisocyanate diethanolamine: Nippon Shokubai Chemical Co., Ltd. Triethanolamine: Nippon Shokubai Chemical Co., Ltd.

The evaluation method of each form shown in Table 1 was performed as follows. (1) Spray atomization width (cm) The urethane foam stock solution was spray-foamed from a spray nozzle directly below about 1 m above the ground, and the atomization width of the obtained foam was measured. (2) Shrinkage in the thickness direction The shrinkage in the thickness direction is determined by spraying the calcium silicate plate to obtain a foam in the thickness direction immediately after the foam is obtained,
The dimensional change rate of the thickness in the thickness direction after 2 hours from the application was measured. (3) The test method and evaluation of flame retardancy are based on JIS-A132
1, a urethane foam having a foam thickness of 15 to 20 mm applied to a calcium silicate plate was placed in a 22 × 2 matrix.
The slice was sliced into 2 cm and subjected to a surface test (heating time: 6 minutes) to measure the smoke emission coefficient (C _A ).

[0035]

As described above, the present invention, that is, as described in detail above, reacts a polyhydroxy compound with a polyisocyanate compound in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries. In producing an isocyanurate-modified rigid polyurethane foam, when an amino alcohol (alkamine) compound having a molecular weight of 200 or less is 100% by weight of all polyhydroxy compounds, it is used in a range of 5% by weight to 30% by weight therein. In addition, in addition to the above, terephthalic acid, isophthalic acid, or trimellitic acid, and a polybasic acid obtained by mixing them, or a polyester polyol obtained by subjecting a derivative thereof to an esterification reaction is 20% by weight or more, preferably 50% by weight or more. % By weight or more, or phthalic acid, isophthalic acid,
Or trimellitic acid and a polybasic acid obtained by mixing them, or a derivative thereof and an aromatic hydroxy compound in 5 to 5
5% by weight or more of a polyester polyol obtained by esterifying a polyester polyol containing 100% by weight thereof is used therein. By using an isocyanurate-modified rigid polyurethane foam and a method for producing the same, the ambient temperature during foaming is reduced. Even in a low temperature range of 0 to 5 ° C., an isocyanurate-modified rigid polyurethane foam with little shrinkage immediately after foaming and excellent flame retardancy was obtained. In particular, as shown in Table 1, when only claim 1 is used, that is, when a specific amino alcohol is used in a specific amount, the shrinkage rate is reduced, but does not contribute to flame retardancy. However, claim 2, that is, when a specific amino alcohol is used and a polyol obtained by esterifying terephthalic acid or isophthalic acid, trimellitic acid, a mixture thereof, or the like is used together in a specific amount, and claim 3, that is, when a specific amino alcohol is used. When alcohol, and a specific amount of phthalic acid, isophthalic acid, trimellitic acid, a mixture thereof and a polyol obtained by esterifying an aromatic compound are simultaneously used,
It can be seen that there is no shrinkage and the flame retardancy (C _A value) is also improved more than expected.

──────────────────────────────────────────────────続 き Continuation of the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical display location C08G 101: 00) C08L 75:04

Claims (10)

[Claims] 1. An isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst, other auxiliaries and a polyisocyanate compound, wherein the total polyhydroxy compound is 100% by weight. An isocyanurate-modified rigid polyurethane foam containing 5% to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less. 2. An isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst and other auxiliaries and a polyisocyanate compound, wherein the total polyhydroxy compound is 100% by weight. It contains 5% by weight to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less, and is obtained by esterifying terephthalic acid, isophthalic acid, or trimellitic acid, and a polybasic acid obtained by mixing them, or a derivative thereof. An isocyanurate-modified rigid polyurethane foam containing at least 20% by weight of a polyester polyol. 3. An isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst and other auxiliaries and a polyisocyanate compound, wherein the total polyhydroxy compound is 100% by weight. A compound containing 5 to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less and 5 to 100% by weight of an aromatic hydroxy compound;
A polybasic acid component, phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid, and a polybasic acid obtained by mixing these, or a polyester polyol obtained by esterifying the derivative thereof with 5% by weight or more. Isocyanurate-modified rigid polyurethane foam. 4. The isocyanurate-modified rigid polyurethane foam according to claim 1, wherein a fluorine compound having an ozone destruction coefficient of 0 is used as a foaming agent. 5. The isocyanurate-modified rigid polyurethane foam according to any one of claims 1 to 4, wherein the isocyanurate-modified rigid polyurethane foam is for airless spray foaming. 6. A method for producing an isocyanurate-modified rigid polyurethane foam by reacting a polyhydroxy compound and a polyisocyanate compound in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries. A method for producing an isocyanurate-modified rigid polyurethane foam, characterized in that an amino alcohol compound is added in a range of 5% by weight to 30% by weight based on 100% by weight of a total polyhydroxy compound. 7. A method for producing an isocyanurate-modified rigid polyurethane foam by reacting a polyhydroxy compound and a polyisocyanate compound in the presence of a foaming agent, a catalyst, a foam stabilizer and other auxiliaries. Amino alcohol compound was replaced with all polyhydroxy compound 1
00% by weight, 5% to 30% by weight
And terephthalic acid, isophthalic acid,
A process for producing an isocyanurate-modified rigid polyurethane foam, comprising 20% by weight or more of trimellitic acid, a polybasic acid obtained by mixing them, or a polyester polyol obtained by subjecting a derivative thereof to an esterification reaction. 8. An isocyanurate-modified rigid polyurethane foam comprising a polyhydroxy compound, a foaming agent, a foam stabilizer, a catalyst, other auxiliaries and a polyisocyanate compound, wherein the total polyhydroxy compound is 100% by weight. A compound containing 5 to 30% by weight of an amino alcohol compound having a molecular weight of 200 or less and 5 to 100% by weight of an aromatic hydroxy compound;
A polybasic acid component such as phthalic acid, isophthalic acid, terephthalic acid, or trimellitic acid, and a polybasic acid obtained by mixing them, or a polyester polyol obtained by esterifying a derivative thereof with 5% by weight or more. For producing an isocyanurate-modified rigid polyurethane foam. 9. The method for producing an isocyanurate-modified rigid polyurethane foam according to claim 6, wherein a fluorine compound having an ozone destruction coefficient of 0 is used as a foaming agent. 10. The method for producing an isocyanurate-modified rigid polyurethane foam according to any one of claims 6 to 9, wherein the method for producing the isocyanurate-modified rigid polyurethane foam is for airless spray foaming.