JP2007177172A - Polyester polyol, composition for isocyanurate-modified polyurethane foam using the same, and isocyanurate-modified polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyester polyol which reduces the amount of a foaming agent when used as a raw material of an isocyanurate-modified polyurethane foam, enhances storage stability of a composition for the isocyanurate-modified polyurethane foam, and further, improves the brittleness of a resulting isocyanurate-modified polyurethane foam; and a composition for an isocyanurate-modified polyurethane foam. <P>SOLUTION: The polyester polyol exhibiting a large effect of reducing the amount of a foaming agent can be obtained by using a 4-6C aliphatic polycarboxylic acid and/or a 6-12C aromatic polycarboxylic acid as a carboxylic acid component which is a raw material for producing the polyester polyol and also using a polyhydric alcohol with three or more functional groups having a secondary hydroxy group at least as a part of an alcohol component. The polyester polyol is used for the composition of the isocyanurate-modified polyurethane foam as a part of a polyol component. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyester polyol that can be suitably used as a polyol composition in the production of polyurethane, in particular, isocyanurate-modified polyurethane foam, and isocyanurate-modified urethane foam using such a polyol composition as a part of the polyol component. The present invention relates to a composition for use and an isocyanurate-modified polyurethane foam. Specifically, when used as a raw material for isocyanurate-modified polyurethane foams, the amount of foaming agent is reduced, and when it is used as a part of a polyol component in a composition for isocyanurate-modified polyurethane foams, its storage stability is increased. Furthermore, the present invention relates to a polyester polyol that improves physical properties such as brittleness of the obtained isocyanurate-modified polyurethane foam, an isocyanurate-modified polyurethane foam composition having the improved physical properties, and an isocyanurate-modified polyurethane foam.

  Since polyurethane foam has excellent heat insulating properties, it is widely used for refrigerators, refrigerators, freezer rooms, freezers, heat insulating materials for general buildings, and the like. A polyurethane foam is generally a mixture of a polyisocyanate component liquid (hereinafter abbreviated as A liquid), a polyether polyol and / or polyester polyol, a foaming agent, and a catalyst or a foam stabilizer as necessary. (Abbreviated as “B liquid”), the liquid A and the liquid B are mixed, and foamed and cured in a short time.

  One of the most important properties required for polyurethane foam is flame retardancy. In order to enhance the flame retardancy of polyurethane foam, flame retardants such as halogen-containing phosphate esters are blended, phthalic polyester polyols are blended as part of the polyol component, and the isocyanate index is increased. In general, the flame retardancy is improved by modifying the polyurethane foam with isocyanurate.

  As the blowing agent, a low-boiling nonpolar organic solvent is generally used. Specifically, in addition to the HCFC-based blowing agent, HC-based blowing agents such as pentane and cyclopentane are used. In addition, depending on the use and production conditions of polyurethane foam, there are practical problems with HC foaming agents having a low flash point and explosive properties, and HCFC foaming agents are frequently used.

  On the other hand, since the destruction of the ozone layer has become a problem, CFC foaming agents that have been widely used until now, especially HCFC foaming agents with a small ozone destruction coefficient, especially HCFC-141b, are replaced by CFC-11e. in use. However, this HCFC-141b also has an ozone depletion coefficient that is not zero, and its use has been restricted since the end of 2003. As an alternative, HFC-based foaming agents, particularly HFC-245fa and HFC-365mfc are used, HC foaming agents are also promising foaming agents.

  A common problem when using these foaming agents that are expected to be used now and in the future is that these foaming agents are global warming substances. It is taken up as an environmental problem. Furthermore, most of these blowing agents are very expensive, and it is highly desirable to reduce the amount of use from the viewpoint of environmental protection and economically.

  Although these foaming agents are not used at all, the technology of complete water foaming using carbon dioxide gas generated by the reaction of water and the polyisocyanate component as the foaming agent has been considerably advanced, but conventional HCFC foaming agents and HFC foaming agents Compared with foaming prescriptions using resin, the reactivity and foaming efficiency are reduced (densification), the brittleness of the surface of the molded body is deteriorated, the strength of the resulting foam is lowered, the dimensional stability is lowered, In addition, the gas in the cell is all carbon dioxide, so that the heat insulating property is low, and it is difficult to use in fields where heat insulating performance is required. In order to cope with such problems, it is useful to some extent to increase the density of polyurethane foam, but it is still not satisfactory when considering industrialization and commercialization.

  On the other hand, in the prescription using the HCFC foaming agent, the HFC foaming agent, and the HC foaming agent, a prescription in which a lot of water is blended from the viewpoint of environmental consideration and cost reduction (see Patent Document 1) has been studied. However, the increase of the urea group produced by the reaction between water and the polyisocyanate component increases the brittleness of the polyurethane foam and may cause a decrease in adhesive strength.

  In particular, as a common problem when water is used as a foaming agent or a part thereof, there is a problem that the polyester polyol in the compounded liquid is hydrolyzed and cannot normally foam. General airless spray compounded liquids are blended with polyester polyols to obtain highly flame retardant polyurethane foam, but must be stored for a period of 1 to 2 months from the time of compounding until actual use. In other words, the initial reactivity is lost in a short period due to hydrolysis of the polyester polyol, making it difficult to produce polyurethane foam. Although a method of suppressing the hydrolysis of polyester polyol by using an imidazole compound as a catalyst and increasing its storage stability (see Patent Document 2) has also been proposed, it is still possible to completely prevent the hydrolysis of polyester polyol. It is impossible and has not solved the problem.

  As a method for effectively reducing the amount of HCFC-based blowing agent, HFC-based blowing agent, HC-based blowing agent, etc., a method using a polyether polyol having a specific structure comprising an alkylene oxide adduct of toluenediamine (see Patent Document 3) And a method using a polyether polyol having a specific structure made of an alkylene oxide adduct of N-aminoethylpiperazine (see Patent Document 4). According to this method, a side reaction occurs in which carbon dioxide gas is generated from the polyether polyol by some mechanism at the time of foaming, and the by-produced carbon dioxide gas acts as a foaming agent at the same time, so that an HCFC foaming agent and an HFC foaming agent are produced. It is possible to reduce the amount of HC foaming agent used.

  However, the process for producing such toluenediamine-based polyether polyol and N-aminoethylpiperazine-based polyether polyol is the same as that for general polyether polyol, and it is a non-catalytic ethylene to toluenediamine or N-aminoethylpiperazine. After the addition of oxide, it is a multi-step process in which propylene oxide is added in the presence of alkali, the salt formed by neutralizing the alkali is filtered off, dehydration is performed, and a stabilizer is added. The cost is very high compared to general polyester polyols. In addition to the high viscosity of the product itself, it is not good for blending, and the effect of reducing the foaming agent is not so great. Increasing the amount added reduces other physical properties such as flame retardancy, adhesiveness, brittleness and dimensional stability. It is not completely satisfactory when considering an effect commensurate with the cost such as causing it.

On the other hand, polyester polyols having a specific number of functional groups obtained by esterifying an aliphatic polyvalent carboxylic acid such as adipic acid and an aliphatic polyhydric alcohol such as diethylene glycol, glycerin, and trimethylolpropane are known. For example, a method for producing a polyester polyol having a functional group number of about 2.0 to 4.0 using an aliphatic polyhydric carboxylic acid, an aliphatic polyhydric alcohol containing 3 or more, and a composition for rigid urethane foam using the same, Rigid urethane foam has been proposed. (See Patent Document 5) These increase the strength and dimensional stability of the resulting polyurethane foam by increasing the number of functional groups of the polyester polyol. However, nothing is mentioned about the fact that the amount of foaming agent used can be reduced by using such polyester polyol, and such effects are not recognized at all in Examples and Comparative Examples. As described above, in the urethane foam manufacturing technology described in the publicly known literatures, polyester polyols and polyurethane foam compositions that have a significant effect of reducing the foaming agent and find industrial advantages are known. It is not done.
JP 2003-277461 A JP 2004-59900 A 7-108939 JP-A-7-97429 Japanese Patent No. 3651038

  Therefore, the object of the present invention is (1) stronger cohesive force between molecules than polyether polyol, does not cause deterioration of physical properties such as flame retardancy and adhesiveness, and further exhibits a great effect of reducing foaming agent. To provide a polyester polyol that can be used, (2) to provide a polyurethane foam composition having excellent storage stability using the polyester polyol, and (3) to suppress hydrolysis of the polyester polyol, and to provide storage stability thereof. An object of the present invention is to provide a polyurethane foam having excellent physical properties by enhancing the properties.

  As a result of diligent studies to achieve these objectives, it has been found that the use of a polyester polyol having a specific production method and specific structural characteristics as a raw material can reduce the amount of foaming agent used in the production of polyurethane foam. Got. That is, an aliphatic polycarboxylic acid having 4 to 6 carbon atoms and / or an aromatic polyvalent carboxylic acid having 8 to 12 carbon atoms is used as the carboxylic acid component which is a raw material for producing the polyester polyol, and at least one of the alcohol components is used. By using a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group as a part, a polyester polyol having a large effect of reducing the foaming agent can be obtained, and the polyester polyol can be used as part of a polyol component to form a polyurethane foam. As a result, it was found that the storage stability of the resulting polyurethane foam can be improved, and physical properties such as brittleness and adhesiveness of the resulting polyurethane foam can be improved, thereby completing the present invention.

In order to confirm the effect of the present invention, the gas composition in the cell of the urethane foam was examined, and the polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group such as glycerin of the present invention was used as a raw material. More carbon dioxide gas than expected was detected from the isocyanurate-modified rigid urethane foam foamed with a polyester polyol and having an isocyanate index of 130 or more.
Rigid urethane foam is a closed cell, and gas replacement with the outside air hardly occurs in a short period of time. For this reason, since the gas composition in the cell immediately after foaming became equal to the foaming agent composition, it was suggested that carbon dioxide gas was generated during foaming. Even when water is not actively added to the foaming raw material, it is inevitable that carbon dioxide gas is generated because some water (about 100 ppm) exists, but the actually detected carbon dioxide gas is derived from such water. It was far beyond the theoretical amount. From this, it was speculated that from the polyester polyol in the present invention, water was generated by some mechanism during foaming, and this water further reacted with isocyanate to generate carbon dioxide gas.

  On the other hand, carbon dioxide gas was hardly detected from the polyurethane foam foamed under the condition that the isocyanate index was less than 130. Further, even if the isocyanurate-modified polyurethane foam is foamed under a condition where the isocyanate index is 130 or more, it contains a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group such as glycerin of the present invention. When a polyester polyol using a polyhydric alcohol containing a polyhydric alcohol having 3 or more functional groups having no secondary hydroxyl group such as trimethylolpropane instead of the polyester polyol using the alcohol as a raw material, carbon dioxide gas Almost no detection. From this, in the presence of an excess polyisocyanate component, the secondary hydroxyl group of the polyester polyol undergoes a desorption reaction faster than the formation of a urethane bond by reaction with the polyisocyanate component, and the desorbed water contains excess polyisocyanate. It was estimated that carbon dioxide gas was generated by reacting with the isocyanate component. That is, it can be said that it is important for the polyester polyol to have a secondary hydroxyl group and to have an isocyanate index of 130 or more in which an excess polyisocyanate component is present in order to exhibit the effects of the present invention.

  Furthermore, in formulas using HCFC foaming agents, HFC foaming agents, and HC foaming agents, it is common to add a small amount of water for the purpose of considering physical properties and reducing foaming agent costs. When the polyester polyol is blended, as described above, the storage stability of the blended liquid is lowered due to hydrolysis. However, since it is considered that a small amount of water is by-produced during foaming from the polyester polyol of the present invention, it is not necessary to positively add water to the foaming raw material. As a result, hydrolysis of the polyester polyol is suppressed, and the storage stability of the blended liquid is improved. In addition, the polyester polyol obtained by the present invention is incorporated into the polyurethane molecule as one component of polyurethane, as in the case of polyester polyols conventionally used for general purposes, so that the physical properties of the polyurethane foam are not impaired. The above characteristics can be exhibited.

That is, this invention has the summary characterized by the following.
(1) A polyester polyol obtained by an esterification reaction of a carboxylic acid component and an alcohol component. When used as a polyol component at the time of urethane foam production, 1 to 10 parts by weight of the polyester polyol is removed. A polyester polyol having a detachable hydroxyl group corresponding to water separation.
(2) The carboxylic acid component is an aliphatic polycarboxylic acid having 4 to 6 carbon atoms, and the alcohol component is a polyhydric alcohol containing a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group. The polyester polyol according to (1), which is characterized.
(3) The carboxylic acid component is an aliphatic polycarboxylic acid having 4 to 6 carbon atoms and an aromatic polyvalent carboxylic acid having 8 to 12 carbon atoms, and the alcohol component has 3 or more functional groups having at least one secondary hydroxyl group. The polyester polyol according to (1), which is a polyhydric alcohol containing a polyhydric alcohol.
(4) The polyester polyol according to (2) or (3), wherein the polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group is glycerin.
(5) The polyester polyol according to (2) or (3), wherein the aliphatic polycarboxylic acid having 4 to 6 carbon atoms is succinic acid or adipic acid.
(6) In an isocyanurate-modified polyurethane foam composition comprising (a) polyisocyanate, (b) polyol, (c) foaming agent, (d) catalyst, (e) surfactant and (f) other auxiliary agent, A composition for an isocyanurate-modified polyurethane foam, wherein the polyester polyol according to any one of (1) to (5) is used in an amount of 1 to 40% by weight of the (b) polyol component.
(7) The isocyanurate-modified polyurethane foam composition as described in (6), wherein the isocyanate index is 130 or more.
(8) The composition for isocyanurate-modified polyurethane foam according to (6), wherein (c) the foaming agent is a foaming agent having an ozone depletion coefficient of 0.8 or less.
(9) (c) The foaming agent is one or more foaming agents selected from the group consisting of HCFC foaming agents, HFC foaming agents, and HC foaming agents. A composition for isocyanurate-modified polyurethane foam.
(10) An isocyanurate-modified polyurethane foam obtained by foam-curing the composition for isocyanurate-modified urethane foam according to any one of (6) to (9).

  According to the present invention, when used as a raw material for an isocyanurate-modified polyurethane foam, the amount of blowing agent used is reduced, and when used as a part of a polyol component in a composition for isocyanurate-modified polyurethane foam, its storage stability Polyester polyol that improves properties and further improves physical properties such as brittleness of the resulting isocyanurate-modified polyurethane foam, isocyanurate-modified polyurethane foam composition and isocyanurate-modified polyurethane foam having the improved properties can do.

  Hereinafter, the present invention will be described in detail. The polyester polyol in the present invention is preferably a polyester polyol used for a polyurethane, particularly an isocyanurate-modified polyurethane foam, and is a polyester polyol obtained from a polyvalent carboxylic acid component and a polyhydric alcohol component.

  In the present invention, examples of the carboxylic acid component that is a raw material of the polyester polyol include aliphatic polycarboxylic acids having 4 to 6 carbon atoms and aromatic polycarboxylic acids having 8 to 12 carbon atoms. Examples of the aliphatic polycarboxylic acid having 4 to 6 carbon atoms include succinic acid, adipic acid, glutaric acid, fumaric acid, maleic acid, malic acid, and the like. Phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid and the like. These carboxylic acid components may be used alone or as a mixture, but when only aromatic polyvalent carboxylic acid is used, the viscosity tends to be too high. Preferred is an aliphatic polyvalent carboxylic acid alone or a combination of an aliphatic polyvalent carboxylic acid having 4 to 6 carbon atoms and an aromatic polyvalent carboxylic acid having 8 to 12 carbon atoms.

  Among these carboxylic acid components, it is preferable to use succinic acid or adipic acid as the aliphatic polyvalent carboxylic acid. The preferred amount of succinic acid or adipic acid is 30 mol% or more, preferably 50 mol% or more, more preferably 70 mol% or more of the total carboxylic acid component, and the total amount of the carboxylic acid component may be succinic acid or adipic acid. When the amount of succinic acid or adipic acid used is less than 30 mol% of the total carboxylic acid component, the effect of improving the brittleness of the isocyanurate-modified polyurethane foam is small. Moreover, the viscosity of the obtained polyester polyol is increased, workability is deteriorated, and compatibility with the foaming agent may be deteriorated. The succinic acid or adipic acid of the present invention includes succinic anhydride or adipic anhydride, and instead of succinic acid or adipic acid, the number of carbons such as methanol, ethanol, 2-ethylhexanol, etc. Those esterified with 1 to 8 monoalcohols such as dimethyl succinic acid or dimethyl adipic acid may be used. The amount used in these cases is calculated as mol% converted to succinic acid. A crude product such as a mixture of adipic acid, glutaric acid and succinic acid obtained in the production process of succinic acid or adipic acid may be used as long as the effects of the present invention are not impaired.

  When the total amount of the carboxylic acid component is not succinic acid or adipic acid, an aliphatic dicarboxylic acid other than succinic acid or adipic acid, or an aliphatic tricarboxylic acid can be used. Suitable aliphatic carboxylic acid components include glutaric acid, fumaric acid, maleic acid, malic acid and acid anhydrides thereof. As carboxylic acids other than these aliphatic polycarboxylic acids, aromatic polycarboxylic acids having 8 to 12 carbon atoms such as phthalic acid, terephthalic acid, isophthalic acid, trimellitic acid may be used. Of these carboxylic acid components other than succinic acid, phthalic acid, terephthalic acid, fumaric acid, and maleic acid are particularly preferable. These carboxylic acids may be esterified with a monohydric alcohol having 1 to 8 carbon atoms such as methanol, ethanol, 2-ethylhexanol, etc., such as dimethyl terephthalic acid.

  In the present invention, it is essential to use a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group as a part of the alcohol component which is a raw material of the polyester polyol. Examples of the polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group include glycerin, erythritol, sorbitol, sucrose, diglycerin, and triglycerin. Of these, glycerin is particularly preferred. The amount of polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group is 30 mol% or more of the total alcohol component, preferably 40 mol% or more, more preferably 50 mol% or more, and the total amount of the alcohol component. May be a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group. When the amount of polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group is less than 30 mol% of the total alcohol components, the effect of reducing the amount of foaming agent used is small.

  When the total amount of the alcohol component is not glycerin or a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group, other polyhydric alcohols can be used in combination. Usually, other alcohols used in combination include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,2-butanediol, 1,3-butanediol, 1 , 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, diols such as cyclohexanediol and cyclohexanedimethanol, and triols such as trimethylolpropane, polyethylene glycol, Long chain polyether polyols such as polypropylene glycol, polyoxyethylene / oxypropylene copolymer glycol, and polytetramethylene ether glycol may be used. . Of these alcohol components other than glycerin, diethylene glycol and triethylene glycol are particularly preferable.

  As a hydroxyl value of the polyester polyol in this invention, it is the range of 200-600 mgKOH / g, Preferably it is the range of 300-500 mgKOH / g. When the hydroxyl value is less than 200, the viscosity increases and handling becomes difficult. On the other hand, if it is larger than 600, the physical properties of the isocyanurate-modified polyurethane foam are lowered, and the amount of the polyisocyanate component is increased, which is disadvantageous in terms of cost.

  The number of functional groups of the polyester polyol in the present invention is usually in the range of 2.5 to 6.0. Preferably it is the range of 3.0-5.0. If the number of functional groups is less than 2.5, the effect of reducing the amount of foaming agent used is reduced, and the physical properties of the isocyanurate-modified polyurethane foam are deteriorated. On the other hand, if it is greater than 6.0, the viscosity will increase and handling will be difficult, and the effect of reducing the amount of foaming agent used will reach its peak.

  Moreover, monovalent alcohols, such as methanol, ethanol, isopropanol, and 2-ethylhexanol, can also be used as a method for reducing the viscosity of the polyester polyol. However, when these monohydric alcohols are used, it is important that the hydroxyl value and the number of functional groups are not deviated from the above ranges. Furthermore, since it may be distilled out of the reaction system in the synthesis of the polyester polyol, the yield may be deteriorated, and the strength and heat resistance of the polyurethane may be adversely affected.

  In the esterification reaction in the present invention, an esterification catalyst is usually used. In general, an acid catalyst is often used as the catalyst. Examples of the Lewis acid include orthotitanate esters such as tetraisopropyl titanate and tetra-n-butyl titanate, tin compounds such as diethyl tin oxide and dibutyl tin oxide, and metal compounds such as zinc oxide. In addition to the Lewis acid, a Bronsted acid such as p-toluenesulfonic acid may be used.

  On the other hand, the obtained polyester polyol is urethanated with the polyisocyanate component to become polyurethane. At this time, it is desirable that the catalyst used for the synthesis of the polyester polyol does not affect the reaction behavior of the urethanization reaction. . Therefore, among the above esterification catalysts, orthotitanate is preferable, and the amount used is usually 1.0% by weight or less, preferably 0, based on the total amount of the carboxylic acid component and alcohol component used as raw materials. .2% by weight or less, usually 0.01% by weight or more, preferably 0.03% by weight or more. Depending on the use of the polyurethane, the reaction may be carried out without using these esterification catalysts, or it may be removed by purification after the reaction.

  The reaction temperature is usually 150 ° C. or higher, preferably 180 ° C. or higher, and is usually 250 ° C. or lower, preferably 230 ° C. or lower. For example, the reaction is easy to control if the reaction is started at 150 ° C. and the temperature is gradually raised to 230 ° C. as the reaction proceeds. On the other hand, the reaction pressure may be normal pressure, but it may be gradually reduced with the progress of the reaction in order to remove by-product water out of the system and complete the reaction quickly. However, if the degree of vacuum during the reaction is insufficient, the degree of completion of the esterification reaction is lowered, and a polyester polyol having a high acid value is produced. On the other hand, if the pressure is excessively reduced during the reaction, not only the alcohol component is distilled out of the system and the yield is deteriorated, but also a high molecular weight polyester polyol is formed, and the viscosity of the obtained polyester polyol is remarkably increased. There may be a tendency to reduce the compatibility with the blowing agent. Accordingly, the appropriate ultimate reaction pressure varies depending on the reaction temperature. For example, when the reaction temperature is 200 ° C., the pressure is usually 2 kPa or more, preferably 5 kPa or more, and usually 50 kPa or less, preferably 30 kPa. Although it is the following, depending on the viscosity and hydroxyl value of the target polyester polyol, the type of alcohol used, and the amount used, the reaction may be carried out under conditions other than the above pressure range. Further, instead of reducing the pressure, a small amount of an organic solvent such as toluene or xylene may be used in combination, and water produced as a by-product may be removed azeotropically outside the system.

  In the case of polyester polyol, the end point of the reaction is usually determined by the amount of unreacted carboxyl groups of the polyvalent carboxylic acid used. On the other hand, in the use of polyurethane, the presence of an acid is often unfavorable, such as reducing the reactivity, with respect to a urethanization reaction with a polyisocyanate component. Therefore, the polyester polyol is preferably as low as possible in the amount of unreacted carboxylic acid, that is, the acid value. In the use of the isocyanurate-modified polyurethane foam, the acid value is usually 5 mgKOH / g or less, preferably 3 mgKOH / g or less, more preferably 1 mgKOH / g or less. Further, under more severe urethanization reaction conditions, 0.5 mgKOH / g or less may be desired.

  In addition, in order to keep the average number of functional groups of the ester compound at a constant target value and / or to keep the average molecular weight constant, the alcohol component that is in an equilibrium state with the transesterification reaction during the esterification reaction is removed from the reaction system as much as possible. It is important not to distill off. If the alcohol component is distilled too much, the average number of functional groups of the ester compound will differ from the original product design, the average molecular weight will increase, and the resulting polyester polyol viscosity will increase significantly. It is not preferable. Therefore, the amount of the alcohol component distilled out of the system during the esterification reaction is usually 5% or less, preferably 3% or less, more preferably 1% or less, based on the total alcohol components. However, the alcohol component may be distilled out beyond the above range depending on the target viscosity and hydroxyl value of the polyester polyol and the amount of the alcohol component used. The desirable number average molecular weight of the polyester polyol of the present invention is generally in the range of 200 to 2000, more preferably in the range of 300 to 1000, depending on the intended use.

  At the start of the reaction, it is preferable to replace the space of the reaction vessel with nitrogen in order to prevent coloring of the produced polyester polyol, and to remove the dissolved oxygen in the reaction solution. Moreover, after completion | finish of reaction, you may adjust the physical property and performance of polyester polyol by distilling an unreacted free alcohol component out of the system on suitable pressure-reduced conditions.

  The reaction mode of the polyester polyol in the present invention can be applied in ordinary batch equipment or continuous equipment, but the reaction time is long and the viscosity of the resulting polyester polyol is considerably higher than the alcohol component used as a raw material. A batch reaction is preferred because it increases.

  The polyester polyol obtained according to the present invention is preferably a polyurethane obtained by reacting a polyol and a polyisocyanate component, particularly an isocyanurate-modified polyurethane foam, and a foaming agent having an ozone depletion coefficient of 0.8 or less, In particular, the amount of foaming agents such as HFC foaming agents such as HFC-245fa and HFC-365mfc, and HC foaming agents such as pentane and cyclopentane is reduced, and the brittleness of the resulting isocyanurate-modified polyurethane foam is reduced. It is useful as a polyester polyol that improves physical properties.

The composition for isocyanurate-modified polyurethane foam in the present invention includes (a) polyisocyanate, (b) polyol, (c) foaming agent, (d) catalyst, (e) surfactant and (f) other auxiliary agent. The above-described polyester polyol is used as a component of the polyol (b). Practically, the isocyanurate-modified polyurethane foam is composed of (a) a liquid A composed of a polyisocyanate component, (b) a polyol composed of a polyether polyol and / or a polyester polyol, (c) a foaming agent, and (d) a catalyst. , (E) a foam stabilizer, and, if necessary, (f) a liquid B composed of other auxiliary agents, is produced by a method of mixing, foaming and curing in a short time.

  (A) The polyisocyanate component is not particularly limited as long as it is an organic compound having two or more isocyanate groups in one molecule. Examples thereof include aliphatic, alicyclic, and aromatic polyisocyanates, or modified products thereof. Specifically, examples of the aliphatic and alicyclic polyisocyanates include hexamethylene diisocyanate and isophorone diisocyanate. Examples of the aromatic polyisocyanate include tolylene diisocyanate, diphenylmethane diisocyanate, and polyphenylene polymethylene polyisocyanate. Further, these carbodiimide-modified products and prepolymers are also included.

  A preferred polyisocyanate component (a) in the present invention is an aromatic polyisocyanate or a modified product thereof, particularly preferably diphenylmethane diisocyanate, polyphenylene polymethylene polyisocyanate, tolylene diisocyanate, and a modified product thereof. However, they may be mixed and used. As the polyphenylene polymethylene polyisocyanate, those having an isocyanate group content of usually 29 to 32% by weight and a viscosity of usually 250 mPa · s (25 ° C.) or less are used. Among these modified products, the carbodiimide modified product is a product in which a carbodiimide bond is introduced using a known phosphorus catalyst or the like. The prepolymer is obtained by reacting the above polyisocyanate with a polyol, leaving an isocyanate group at the terminal. As the polyol used at that time, the polyol used in the production of polyurethane can be usually used.

  Practically, as liquid A, in addition to these polyisocyanates, additives and auxiliaries may be mixed with the polyisocyanate component and used depending on the application. For example, for the purpose of improving the miscibility with the B liquid, a foam stabilizer used in the B liquid may be used in combination as a compatibilizing agent. In that case, a nonionic surfactant is usually preferred, and a silicone surfactant is particularly often used. Moreover, a flame retardant may be used together for the purpose of improving flame retardancy and adjusting viscosity. In applications of isocyanurate-modified polyurethane foams, chloroalkyl phosphates such as tris (beta chloroethyl) phosphate and tris (beta chloropropyl) phosphate are commonly used. Additives and auxiliaries other than those described above are not particularly limited, and are used for the purpose of improving physical properties and operability in ordinary resins, and should not significantly adversely affect the urethanization reaction. Anything can be used.

  As the (b) polyol component, polyether polyols and polyester polyols having a hydroxyl value of usually 50 to 800 and a functional group number of usually 2.0 to 8.0 can be used. A mixture of two or more types may be used. Examples of polyether polyols include ethylene oxide, propylene oxide, 1,2-butylene oxide and tetrahydrofuran alone or in combination, alkylene oxide polymer, tri- or higher functional polyhydric alcohols such as sucrose, sorbitol, and glycerin. Examples include adducts of the above alkylene oxides, aliphatic amines, and adducts of aromatic amines and the above alkylene oxides. As the polyester polyol, aromatic or aliphatic di- or tricarboxylic acid such as phthalic acid, terephthalic acid, adipic acid, succinic acid and trimellitic acid, and ethylene glycol, diethylene glycol, propylene glycol, dipropylene as the carboxylic acid component. Glycol, 1,4-butanediol, and the like, and glycerin, trimethylolpropane, and other 2- or 3-valent alcohols, obtained by esterification reaction alone or mixed, usually have a hydroxyl value of 100 to 500 and the number of functional groups. Usually, a polyester polyol of about 1.5 to 3.0 is mentioned.

  In the present invention, it is essential to use the above-described polyester polyol of the present invention in combination with these polyether polyols and polyester polyols. The amount used is generally in the range of 1 to 40% by weight, preferably in the range of 3 to 30% by weight, and more preferably in the range of 5 to 20% by weight in all polyol components. When the amount used is less than 1% by weight, there is almost no effect of reducing the amount of foaming agent used. On the other hand, even if it is larger than 40% by weight, the effect of reducing the use amount of the foaming agent is expressed, but it may adversely affect the physical properties such as flame retardancy and dimensional stability of the isocyanurate-modified polyurethane foam. Considering the physical properties of the isocyanurate-modified polyurethane foam, it is preferable to use it within a range that does not cause a problem in practice.

  In addition, compounds having two or more active hydrogens in one molecule such as alcohols such as ethylene glycol, diethylene glycol, propylene glycol, and glycerin, and alkanolamines such as diethanolamine and triethanolamine can be used in combination.

  As the foaming agent (c) used in the isocyanurate-modified polyurethane foam of the present invention, a foaming agent having an ozone depletion coefficient of usually 0.8 or less, for example, HFC-245fa, HFC-365mfc, etc. in addition to HCFC-141b Future blowing agents such as HFC blowing agents, HC blowing agents such as pentane and cyclopentane can be suitably used. These foaming agents may be used alone or in combination. You may use water together as needed, and it is good also considering the whole quantity of a foaming agent as water.

  (D) As a catalyst, the well-known catalyst used for manufacture of a normal isocyanurate modified polyurethane foam can be used. For example, in addition to amine catalysts such as triethylamine and N, N-dimethylhexylamine, potassium catalysts such as potassium octylate, tin catalysts such as dibutyltin dilaurate and tin octylate, and lead catalysts such as lead octylate Examples thereof include metal catalysts.

  (E) As the surfactant, for example, a nonionic, anionic or cationic surfactant can be used as a foam stabilizer, but a nonionic surfactant is preferable, and a silicone surfactant is particularly often used. .

  (F) As other auxiliaries, various compounds can be used as additives and auxiliaries depending on applications. For example, a flame retardant is mentioned as a typical additive. In applications of isocyanurate-modified polyurethane foams, chloroalkyl phosphates such as tris (beta chloroethyl) phosphate and tris (beta chloropropyl) phosphate are commonly used. Additives and auxiliaries other than those described above are not particularly limited, and are used for the purpose of improving physical properties and operability in ordinary resins, and significantly adversely affect the present invention and the urethanization reaction. It can be used as long as it is not.

  The production method of the isocyanurate-modified polyurethane foam in the present invention comprises (a) polyisocyanate, (b) polyol, (c) foaming agent, (d) catalyst, (e) surfactant and (f) other auxiliary agent. The composition is foam-cured. Practically, (a) the polyisocyanate component is liquid A, (b) the polyol component is liquid B, (c) a foaming agent, (d) a catalyst, (e ) Surfactant and (f) Other auxiliary agents are mixed in advance in the liquid A and / or liquid B in advance, and the two liquids are mixed using an apparatus described later, and then foamed and cured. In addition, it is more preferable to mix a foaming agent, a catalyst, and a foam stabilizer in B liquid.

  The isocyanurate-modified polyurethane foam obtained by the present invention has urethane bonds, urea bonds, and isocyanurate bonds. The isocyanurate bond is generated by trimerizing an isocyanate group with a catalyst, and can improve mechanical strength and heat resistance.

  In the present invention, the preferred isocyanate index (number of moles of all isocyanate groups / number of moles of all active hydrogen groups × 100) is 130 or more, usually 130 to 700, preferably 150 to 600, more preferably 170 to 500. is there. When the isocyanate index is less than 130, the effects of the present invention cannot be obtained, and the obtained foam may not have sufficient strength, and is likely to shrink. When it exceeds 700, the resulting foam is brittle. Increases, and the adhesive strength tends to decrease.

  In producing the isocyanurate-modified urethane foam, any apparatus can be used as long as the liquid A and the liquid B can be uniformly mixed. For example, small mixers, low pressure or high pressure foaming machines for injection foaming, low pressure or high pressure foaming machines for slab foaming, low pressure or high pressure foaming machines for continuous lines, used in the production of general urethane foam. A spray foaming machine for spraying construction can be used. In producing the isocyanurate-modified urethane foam, the liquid temperatures of the liquid A and the liquid B are preferably adjusted to 20 to 60 ° C.

EXAMPLES Specific examples of the present invention will be described below in more detail with reference to examples. However, the present invention is not limited to these examples unless it exceeds the gist. Unless otherwise specified, “parts” and “%” in the examples mean “parts by weight” and “% by weight”, respectively.
[Synthesis of polyester polyol]
The polyester polyol was synthesized and evaluated by the following method, and the evaluation results are shown in Table-1. (Examples 1-6 and Comparative Examples 1-4)
"Example 1"

A glass reactor equipped with a stirrer, reflux condenser, thermometer, pressure gauge, heating device, etc. and having a volume of 2 liters was charged with 437 g of succinic acid, 389 g of triethylene glycol, and 307 g of glycerin. After replacing with nitrogen gas, heating of the reactor internals was started. When the reactor internal temperature reached 150 ° C., 0.3 g of tetraisopropyl titanate as a catalyst was added to the reactor to start the reaction. Thereafter, the internal temperature was raised to 210 ° C. over 3 hours, and this temperature was maintained until the end of the reaction. On the other hand, the pressure in the reactor was maintained at 88.0 kPa from the time when the internal temperature reached 150 ° C. until the internal temperature reached 210 ° C. Thereafter, the pressure was gradually reduced over 3 hours to 5.3 kPa, and this pressure was maintained until the reaction was completed. It was visually observed that the reaction mixture became a homogeneous solution as the reaction proceeded. During the progress of the reaction, a part of the reaction mixture was extracted from the reactor, and the acid value of the extracted sample was measured as an index for confirming the progress of the reaction. The reaction was terminated when the acid value became 1.0 or less and the reaction mixture became a uniform solution. After completion of the reaction, the heating was stopped and the system was cooled to around 100 ° C., the reaction product was extracted, and the acid value, hydroxyl value, and viscosity of the extracted sample were measured. Moreover, the solubility of the foaming agent (HFC-245fa, water) with respect to the obtained polyester polyol was measured. The polyester polyol obtained here was designated as “Polyol-1”.
"Example 2"

The reaction was conducted in the same manner as in the raw material of Example 1, except that succinic acid was not used, 490 g of adipic acid, 353 g of triethylene glycol, and 278 g of glycerin were used. The polyester polyol obtained here was designated as “Polyol-2”.
"Example 3"

The reaction was conducted in the same manner as in the raw material of Example 1, except that succinic acid was not used, 237 g of adipic acid, 240 g of phthalic anhydride, 341 g of triethylene glycol, and 269 g of glycerin were used. The polyester polyol obtained here was designated as “Polyol-3”.
Example 4

The reaction was carried out in the same procedure except that the raw material of Example 1 was changed to 474 g of succinic acid, 301 g of triethylene glycol, and 370 g of glycerin. The polyester polyol obtained here was designated as “Polyol-4”.
"Example 5"

The reaction was carried out in the same manner as in the raw material of Example 1, except that succinic acid was not used and 527 g of adipic acid, 271 g of triethylene glycol, and 332 g of glycerin were used. The polyester polyol obtained here was designated as “Polyol-5”.
"Example 6"

The reaction was performed in the same manner as in the raw material of Example 1, except that succinic acid was not used and 557 g of adipic acid, 177 g of triethylene glycol, and 403 g of glycerin were used. The polyester polyol obtained here was designated as “Polyol-6”.
“Comparative Example 1”

The reaction was conducted in the same procedure except that the raw material of Example 1 was changed to 412 g of succinic acid, 640 g of triethylene glycol, and 74 g of glycerin. The polyester polyol obtained here was designated as “Polyol-7”.
"Comparative Example 2"

The reaction was conducted in the same manner as in the raw material of Example 1, except that succinic acid was not used, 396 g of phthalic anhydride, 474 g of triethylene glycol, and 177 g of glycerin were used. The polyester polyol obtained here was designated as “Polyol-8”.
“Comparative Example 3”

The reaction was conducted in the same manner as in the raw material of Example 1, except that glycerin was not used, 383 g of succinic acid, 341 g of triethylene glycol, and 392 g of trimethylolpropane were used. The polyester polyol obtained here was designated as “Polyol-9”.
“Comparative Example 4”

  The reaction was conducted in the same manner as in the raw material of Example 1, except that glycerin was not used, 349 g of succinic acid, 528 g of triethylene glycol, and 229 g of pentaerythritol were used. The polyester polyol obtained here was designated as “Polyol-10”.

The obtained polyester polyol was evaluated by the following method, and the results are shown in "Table-1" and "Table-2".
<Evaluation method>
(1) Acid value It measured based on JISK1557 ₁₉₇₀ .
(2) Hydroxyl value Measured according to JIS K1557 ₁₉₇₀ .
(3) Viscosity Using a rotational viscometer (B-type viscometer) in accordance with JIS K1557 ₁₉₇₀ , the viscosity was measured at 25 ° C.
(4) Number of functional groups Calculated from the charged molar ratio of the raw materials.
(5) Average molecular weight It calculated from the hydroxyl value of the polyester polyol.
(6) Solubility of foaming agent (HFC-245fa, water) in polyester polyol Take 30-50 g of polyester polyol in a 200 ml beaker and use a 30φ three-way receding blade in an open system at room temperature and atmospheric pressure, 400 rpm The solubility obtained by gradually adding the blowing agent while stirring and measuring the maximum addition amount capable of forming a transparent uniform phase within 30 seconds with the naked eye was used as an indicator of the compatibility between the polyester polyol and the blowing agent.

［プレミックス液の調製］
「表−３」〜「表−７」に示す原料、配合でイソシアヌレート変性ポリウレタンフォーム用ポリオールプレミックス、「プレミックス−１〜２０」を調製した。（実施例７〜１７及び比較例５〜１３） さらに、「表−８」に示す原料、配合でポリウレタンフォーム用ポリオールプレミックス、「プレミックス−２１、２２」を調製した。（比較例１４、１５）なお、以下の表中（ｐｂｗ）は重量部を意味する。

[Premix solution preparation]
Polyol premixes for isocyanurate-modified polyurethane foams, “Premix-1 to 20”, were prepared using the raw materials and blends shown in “Table-3” to “Table-7”. (Examples 7 to 17 and Comparative Examples 5 to 13) Furthermore, a polyol premix for polyurethane foam, “Premix-21 and 22”, was prepared using the raw materials and blends shown in “Table-8”. (Comparative Examples 14 and 15) In the table below, (pbw) means parts by weight.

In the blending examples of “Table-3” to “Table-8”, the following materials were used.
Polyol-1 to 10: The above-described polyester polyol Polyol-11: “MAXIMOL RFK-556” Terephthalic acid-based polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
Polyol-12: “MAXIMOL SDK-145” Succinic polyester polyol (manufactured by Kawasaki Kasei Kogyo Co., Ltd.)
Polyol-13: “GR-04” ethylenediamine-based polyether polyol (manufactured by Mitsui Takeda Chemical Co., Ltd.)
Foaming agent: HFC-245fa (manufactured by Central Glass Co., Ltd.)
Water: ion-exchanged water Catalyst-1: "KAO riser No1" Amine-based catalyst (manufactured by Kao Corporation)
Catalyst-2: “DABCO K-15” Fatty acid potassium-based catalyst (produced by Air Products Japan Co., Ltd.)
Foam stabilizer: “SZ-1717” Silicone foam stabilizer (Toray Dow Corning Silicone Co., Ltd.)
Flame retardant: Tris (beta chloropropyl) phosphate Phosphorus flame retardant (Daihachi Chemical Co., Ltd.)

[Production of isocyanurate-modified polyurethane foam and polyurethane foam]
Production and evaluation of isocyanurate-modified polyurethane foams (Examples 18 to 28, Comparative Examples 16 to 24) and polyurethane foams (Comparative Examples 24 to 26) were performed by the methods shown below. The evaluation results are shown in “Table-9” to “Table-14”.

<Manufacturing method>
After mixing A liquid (polyisocyanate liquid) and B liquid (premix) as described in "Table-3"-"Table-8", it poured into the injection | pouring box and made free foaming, and manufactured the urethane foam. The following polyisocyanate liquid was used.
Polyisocyanate liquid: “Millionate MR-200” Polymeric MDI (manufactured by Nippon Polyurethane Industry Co., Ltd.)

<Foaming conditions>
<Isocyanurate-modified polyurethane foam>
Isocyanate index: 170
Room temperature: 24 ℃ ± 1 ℃
Liquid temperature: 15 ° C ± 1 ° C
Stirring: 3000 rpm × 5 to 10 seconds Injection box: Wooden 200 mm × 200 mm × 200 mm Upper open <Polyurethane foam>
Isocyanate index: 110
Room temperature: 24 ℃ ± 1 ℃
Liquid temperature: 15 ° C ± 1 ° C
Stirring: 3000 rpm × 10 seconds Injection box: Wooden 200 mm × 200 mm × 200 mm Upper opening Opening time: 1 hour

The obtained isocyanurate-modified polyurethane foam and the polyurethane foam were evaluated by the following methods, and the results are shown in "Table-9" to "Table-14".
<Evaluation method>
(1) Reactivity Cream time: After mixing A liquid and B liquid, the time until foaming height reached 1% was measured.
Gel time: After mixing the liquid A and the liquid B, the time until the thread was started to be pulled with a stylus was measured.
Rise time: After mixing A liquid and B liquid, the time until the foaming height reached 95% was measured.
(2) it was measured in accordance with the core density JIS A9511 _2003.
(3) Brittleness Urethane foam was evaluated by qualitative observation of the surface and bottom.
◎ There is almost no brittleness.
○ There is some brittleness.
△ brittle

［プレミックス液の保存安定性試験］
以下に示す方法で、プレミックス液の保存安定性の評価を行った。
「表−３」、「表−７」に示した原料、配合でイソシアヌレート変性ポリウレタンフォーム用ポリオールプレミックス、「プレミックスー２」、「プレミックスー１８〜２０」を調整後、４０℃の恒温槽で４週間保存したものでそれぞれイソシアヌレート変性ポリウレタンフォームを製造して反応性を評価した。評価結果を「表−１５」に示す。（実施例２９、３０及び比較例２７、２８）

[Storage stability test of premix solution]
The storage stability of the premix solution was evaluated by the method shown below.
After adjusting the polyol premix for isocyanurate-modified polyurethane foam, “Premix-2” and “Premix-18-20” with the raw materials and blends shown in “Table-3” and “Table-7”, 4 in a constant temperature bath at 40 ° C. Reactivities were evaluated by producing isocyanurate-modified polyurethane foams that were stored for a week. The evaluation results are shown in “Table-15”. (Examples 29 and 30 and Comparative Examples 27 and 28)

From “Table-1” to “Table-15”, the following is mainly apparent.
(1) Comparative results of Examples 18 to 22 and Comparative Examples 16 to 18 As the aliphatic polycarboxylic acid having 4 to 6 carbon atoms of the present invention, a polyfunctional group having 3 or more functional groups having at least one secondary hydroxyl group. In the case of Examples 18 to 22 in which polyol-1 using glycerin as the monohydric alcohol was blended, the core density of the isocyanurate-modified polyurethane foam was greatly reduced as compared with the cases of Comparative Examples 16 to 18 in which the blend was not blended. There is also an improvement. When the amount is increased, the effect is further increased.

(2) Comparative results of Examples 19, 23 to 27 and Comparisons 16 and 19 to 22 The aliphatic polycarboxylic acid having 4 to 6 carbon atoms and / or the aromatic polyvalent carboxylic acid having 6 to 12 carbon atoms of the present invention. Succinic acid, adipic acid, and phthalic anhydride are used, and polyols 2 to 6 having 3.5 to 4.5 functional groups using glycerin as a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group are blended In Examples 19 and 23 to 27, Comparative Example 21 and 22 in which polyols 9 and 10 having 3.5 functional groups using trimethylolpropane or pentaerythritol instead of glycerin were used instead of Comparative Example 16 and glycerin. As compared with the case of, the core density of the isocyanurate-modified polyurethane foam is greatly reduced, and the brittleness is also improved. On the other hand, even in Comparative Examples 19 and 20 in which polyols 7 and 8 having a functional group number of 2.5 to 2.8 were blended, although a decrease in brittleness was observed in Comparative Example 20 using an aromatic polyvalent carboxylic acid. As in Example 19 and the like, an effect of lowering the core density of the isocyanurate-modified polyurethane foam was observed. In particular, in Comparative Example 19 using an aliphatic polyvalent carboxylic acid, improvement in brittleness was observed as the core density decreased as in Example 19 and the like.

(3) Comparative results of Examples 19 and 28 and Comparative Examples 23 and 24 As the aliphatic polycarboxylic acid having 4 to 6 carbon atoms of the present invention, a polyfunctional group having 3 or more functional groups having at least one secondary hydroxyl group. In the case of Example 19 in which polyol-1 using glycerin as a monohydric alcohol was blended, 20 parts of foaming agent and 1.5 parts of water and Example 28 in which 30 parts of foaming agent were not used with water In the case of Comparative Example 24 in which 30 parts of the foaming agent and 1.5 parts of water were not blended, and in the case of Comparative Example 23 in which 40 parts of the foaming agent were not used, and isocyanurate-modified polyurethane The core density of the foam is almost the same. Therefore, when 20 parts of polyol-1 is blended, there is an effect equivalent to blending 10 parts as foaming agent and 1-1.5 parts as water. That is, there is a reduction effect of about 25 to 35% of the foaming agent.

(4) Comparative Examples 25 and 26
Comparative Example 25 in which polyol 1 using glycerin as a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group as succinic acid as aliphatic polyhydric carboxylic acid having 4 to 6 carbon atoms of the present invention was used. In any of Comparative Examples 26 that were not blended, the core density of the polyurethane foam was almost the same. From this, the effect of the present invention can hardly be obtained in a polyurethane foam having an isocyanate index of 130 or less.

(5) Comparative results of Examples 19, 28 to 30 and Comparative Examples 23, 24, 27, and 28 The present invention has at least one succinic acid and secondary hydroxyl group as the aliphatic polycarboxylic acid having 4 to 6 carbon atoms. In the case of Examples 19 and 30 in which polyol-1 using glycerin was used as a polyhydric alcohol having 3 or more functional groups and water was used, and Comparative Examples 24 and 28 in which water was used without adding polyol-1 When compared, both cause hydrolysis during the storage period and the reactivity is reduced. On the other hand, in the case of Examples 28 and 29 in which polyol 1 was blended and no water was used, and in Comparative Examples 23 and 27 in which polyol 1 was not blended and water was not used, both were during the storage period. No decrease in reactivity due to hydrolysis is observed. From this, when producing an isocyanurate-modified polyurethane foam having an equivalent core density, the storage stability is good and the blowing agent can be reduced by blending the polyol-1 of the present invention of Examples 28 and 29. This is a case where water is not used.

  According to the present invention, when used as a raw material for an isocyanurate-modified polyurethane foam, the amount of foaming agent is reduced, and when used as a part of a polyol component in a composition for isocyanurate-modified polyurethane foam, Polyester polyol for improving storage stability and further improving physical properties such as brittleness of the obtained isocyanurate-modified polyurethane foam, isocyanurate-modified polyurethane foam composition having the improved physical properties, and isocyanurate-modified polyurethane Forms can be provided.

Claims (10)

  A polyester polyol obtained by an esterification reaction of a carboxylic acid component and an alcohol component, which corresponds to 1 to 10 parts by weight of desorbed water with respect to 100 parts by weight of the polyester polyol when used as a polyol component during the production of urethane foam. A polyester polyol having a detachable hydroxyl group.   The carboxylic acid component is an aliphatic polycarboxylic acid having 4 to 6 carbon atoms, and the alcohol component is a polyhydric alcohol containing a polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group. The polyester polyol according to claim 1.  The carboxylic acid component is an aliphatic polyvalent carboxylic acid having 4 to 6 carbon atoms and an aromatic polyvalent carboxylic acid having 8 to 12 carbon atoms, and the alcohol component is a polyvalent having 3 or more functional groups having at least one secondary hydroxyl group. The polyester polyol according to claim 1, wherein the polyester polyol is an alcohol-containing polyhydric alcohol.   The polyester polyol according to claim 2 or 3, wherein the polyhydric alcohol having 3 or more functional groups having at least one secondary hydroxyl group is glycerin.   The polyester polyol according to claim 2 or 3, wherein the aliphatic polycarboxylic acid having 4 to 6 carbon atoms is succinic acid or adipic acid.   In the composition for isocyanurate-modified polyurethane foam comprising (a) polyisocyanate, (b) polyol, (c) foaming agent, (d) catalyst, (e) surfactant and (f) other auxiliary agent. A composition for an isocyanurate-modified polyurethane foam, wherein the polyester polyol according to any one of 1 to 5 is used in an amount of 1 to 40% by weight of the (b) polyol component.   The composition for isocyanurate-modified polyurethane foam according to claim 6, wherein the isocyanate index is 130 or more.   (C) The composition for isocyanurate-modified polyurethane foam according to claim 6, wherein the foaming agent is a foaming agent having an ozone depletion coefficient of 0.8 or less.   (C) The isocyanurate modification according to claim 6, wherein the foaming agent is at least one foaming agent selected from the group consisting of HCFC foaming agents, HFC foaming agents and HC foaming agents. A composition for polyurethane foam. An isocyanurate-modified polyurethane foam obtained by foam-curing the composition for isocyanurate-modified urethane foam according to any one of claims 6 to 9.