JP2009275072A - Polyol composition, method for producing the same and method for producing polyurethane resin using the polyol composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition which contains a relatively small amount of aldehyde compounds as impurities and in which the conditions of hydroxy groups are adequately adjusted, to provide a method for producing the same and to provide a method for producing a polyurethane resin using the polyol composition. <P>SOLUTION: The polyol composition is obtained by addition-polymerizing a 2-4C alkylene oxide to the product of esterification reaction of a polycarboxylic acid having three or more carboxy groups within a molecule with a hydroxycarboxylic acid having one or two carboxy groups within a molecule. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyol composition, a method for producing the same, and a method for producing a polyurethane resin using the polyol composition.

  The polyol composition is used in various industrial fields, for example, as a raw material for polyurethane resins such as polyurethane foam and polyurethane elastomer.

  Conventionally, various types of polyol compositions are known. For example, a polyol composition such as a polyether polyol obtained by addition polymerization of an alkylene oxide to an active hydrogen compound such as a polyhydric alcohol is known as a raw material for a polyurethane foam or the like. In such a polyol composition, an alkylene oxide is used to increase the molecular weight in order to impart desired physical properties (such as rebound resilience) to the resulting polyurethane resin.

  However, such a conventional polyol composition can contain a relatively large amount of an aldehyde compound produced by a side reaction of addition polymerization of alkylene oxide, such as acetaldehyde. That is, the polyether polyol is obtained by addition polymerization of a relatively large amount of alkylene oxide with respect to the amount of the active hydrogen compound that is a reaction starting material. Therefore, a polyol composition containing such a polyether polyol is used. Is likely to retain a relatively large amount of aldehyde compounds as impurities generated as described above. Even after the polyol composition has reacted with the polyisocyanate compound, the aldehyde compound can be gradually released into the air and adversely affect human health. There is a demand for a product having as little content of an aldehyde compound produced by the synthesis of polyether polyol as possible.

  On the other hand, by using an active hydrogen compound having a higher molecular weight than the polyhydric alcohol as described above, for example, vegetable oil, the molecular weight of the active hydrogen compound is increased, and the amount of alkylene oxide to be subjected to addition polymerization is increased. A polyol composition has been proposed in which the amount of aldehyde compound produced is reduced by relatively reducing the amount (Patent Document 1). According to such a polyol composition, the amount of alkylene oxide used can be reduced by the amount of vegetable oil and fat, and a polyurethane resin with less aldehyde compound can be obtained instead of the obtained physical properties.

  Also proposed is a polyol composition containing a polyol obtained by condensing 6 to 28 mol of hydroxycarboxylic acid with respect to 1 mol of polyhydric alcohol as a reaction starting material (Patent Document 2).

  The polyol composition as described in Patent Document 2 is such a polyol composition because a plurality of hydroxycarboxylic acids are condensed, the molecular chain length is appropriately extended, and the molecular weight is appropriately increased. According to at least the increase in the molecular weight, the number of moles of alkylene oxide to be addition-polymerized can be further reduced, and the aldehyde compounds as described above can be further reduced.

  However, in the polyol composition as described in Patent Document 2, the hydroxycarboxylic acid used is not necessarily a single compound but may contain impurities such as side reaction products. That is, in this polyol composition, the hydroxyl group of the hydroxycarboxylic acid contained usually takes various forms. For example, even if it is a primary hydroxyl group or a secondary hydroxyl group, Since the site in the acid is different, it is not necessarily the same in terms of reactivity with a polyisocyanate compound or the like. Therefore, for such a polyol composition, an addition polymerization of alkylene oxide is usually further carried out so that the reactivity of the polyol composition with a polyisocyanate compound or the like is desired, and a hydroxyl group can be taken. The aspect has been adjusted. However, in the polyol composition thus obtained, the reaction rate at which the alkylene oxide is addition-polymerized with respect to the hydroxyl group derived from hydroxycarboxylic acid is relatively low, so that the mode in which primary, secondary, etc. hydroxyl groups can be taken is sufficient. It is hard to say that it has been adjusted.

JP 2005-320437 A JP 2006-002145 A

  In view of the above-described problems and demands, the present invention has an object to provide a polyol composition in which the amount of an aldehyde compound as an impurity is relatively small and the aspect of the hydroxyl group can be sufficiently adjusted, and a method for producing the same. To do. It is another object of the present invention to provide a method for producing a polyurethane resin using such a polyol composition.

  In order to solve the above problems, a polyol composition according to the present invention comprises a polycarboxylic acid having three or more carboxyl groups in the molecule, and a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule. And an esterification reaction product obtained by addition polymerization of an alkylene oxide having 2 to 4 carbon atoms.

  According to the polyol composition having the above structure, a polycarboxylic acid having 3 or more carboxyl groups in the molecule and a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule are esterified. Thus, an esterification reaction product as an intermediate raw material is obtained. Here, by condensing a hydroxyl group of a hydroxycarboxylic acid having a relatively high molecular weight to a carboxyl group of the polycarboxylic acid by an esterification reaction, the molecular weight of the esterification reaction product becomes relatively large, and a polyol composition having a desired molecular weight. Can be a thing. Accordingly, the amount of alkylene oxide to be subjected to addition polymerization can be reduced according to the increase in the molecular weight of the condensed hydroxycarboxylic acid, and side reactions accompanying the addition polymerization of alkylene oxide can be reduced.

  Moreover, according to the said structure, the said esterification reaction material turns into the said polyol composition by addition polymerization of the said C2-C4 alkylene oxide. Here, in the esterification reaction product, which is an intermediate raw material, since the carboxyl group is excellent in reactivity with the alkylene oxide, the alkylene oxide is more reliably compared with the case where the alkylene oxide is addition-polymerized to the hydroxyl group. Addition polymerization of oxide proceeds. Therefore, the mode of the hydroxyl group that can be generated as a result of the addition polymerization is determined depending on the alkylene oxide to be used. Therefore, the aspect taken by the hydroxyl group is sufficiently adjusted.

Moreover, it is preferable that the polyol composition which concerns on this invention reacts 1-30 mol of said hydroxycarboxylic acids with respect to 1 mol of said polycarboxylic acids.
By reacting 1 to 30 moles of the hydroxycarboxylic acid with respect to 1 mole of the polycarboxylic acid, the polyurethane resin such as a flexible polyurethane foam has better rebound resilience and the like despite the low aldehyde content. There is an advantage that the physical properties can be imparted.

  In the polyol composition according to the present invention, the hydroxycarboxylic acid preferably has 5 to 30 carbon atoms. When the hydroxycarboxylic acid has 5 to 30 carbon atoms, there is an advantage that the rebound resilience of the molded polyurethane resin is kept higher despite the low aldehyde content.

  The polyol composition according to the present invention is preferably for a polyurethane resin raw material. By using the polyurethane resin raw material, it is possible to obtain a polyurethane resin having suitable elasticity and hardness in spite of low aldehyde content. Particularly, in the flexible polyurethane foam, it is possible to obtain good rebound resilience. There is.

  In the method for producing a polyol composition according to the present invention, a polycarboxylic acid having 3 or more carboxyl groups in a molecule is esterified with a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule. Thus, an esterification reaction product is obtained, and an alkylene oxide having 2 to 4 carbon atoms is subjected to addition polymerization to the esterification reaction product.

  The method for producing a polyurethane resin according to the present invention comprises reacting the polyol composition with a polyisocyanate compound. In the polyol composition, a hydroxyl group that can be generated as a result of addition polymerization of alkylene oxide is adjusted to a desired mode. Therefore, the method for producing a polyurethane resin according to the present invention makes it easy to control the reaction between the polyol composition and the polyisocyanate compound, and makes the physical properties of the polyurethane resin and the like desirable.

  The polyol composition of the present invention has an effect that the amount of the aldehyde compound as an impurity is relatively small and the aspect of the hydroxyl group can be sufficiently adjusted.

  Hereinafter, embodiments of the polyol composition of the present invention will be described.

The polyol composition of this embodiment is an esterification reaction product of a polycarboxylic acid having 3 or more carboxyl groups in the molecule and a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule. And an addition polymerization of an alkylene oxide having 2 to 4 carbon atoms.
That is, in the polyol composition of the present embodiment, the polycarboxylic acid is esterified with the hydroxycarboxylic acid to obtain an esterification reaction product, and an alkylene oxide having 2 to 4 carbon atoms is added to the esterification reaction product. Let me.

  In the polyol composition of this embodiment, first, a polycarboxylic acid having 3 or more carboxyl groups in the molecule and a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule are esterified. The reaction becomes an esterification reaction product as an intermediate raw material. The molecular weight of the esterification reaction product is increased by condensing the hydroxyl group of the hydroxycarboxylic acid to the carboxyl group of the polycarboxylic acid by an esterification reaction. Therefore, according to the increase in the molecular weight of the condensed hydroxycarboxylic acid, the amount of alkylene oxide to be addition-polymerized can be reduced, and the content of the aldehyde compound is reduced.

  Moreover, in the polyol composition of this embodiment, the said C2-C4 alkylene oxide is addition-polymerized by the said esterification reaction material. Since alkylene oxide is addition-polymerized to the carboxyl group of the esterification reaction product, which is an intermediate material, the addition polymerization of alkylene oxide proceeds more reliably than when alkylene oxide is addition-polymerized to a hydroxyl group. To do. Accordingly, the hydroxyl group that can be generated as a result of the addition polymerization is in a desired mode such as a primary hydroxyl group or a secondary hydroxyl group.

In the polyol composition of the present embodiment, the hydroxycarboxylic acid is preferably reacted in an amount of 1 to 30 mol, more preferably in the range of 5 to 25 mol, with respect to 1 mol of the polycarboxylic acid. It is more preferable that 12 moles are reacted.
By reacting 1 to 30 mol of the hydroxycarboxylic acid with respect to 1 mol of the polycarboxylic acid, there is an advantage that the amount of the aldehyde compound that can be contained in the polyol composition is further reduced. In addition, a polyurethane resin having suitable elasticity and hardness can be obtained, and particularly in a flexible polyurethane foam, there is an advantage that good rebound resilience can be obtained.

  In the polyol composition of this embodiment, it is preferable that 1 mol or more of the alkylene oxide having 2 to 4 carbon atoms is used with respect to 1 mol of the carboxyl group contained in the polycarboxylic acid. By using 1 mol or more, there exists an advantage that a carboxyl group is hard to remain in the obtained polyol, and the abnormal reaction in a urethanization reaction at the time of making it react with a polyisocyanate compound becomes difficult to occur. Moreover, it is preferable that 25 mol or less is used with respect to 1 mol of carboxyl groups contained in the polycarboxylic acid, more preferably 15 mol or less is used, and more preferably 10 mol or less is used. Preferably, 5 mol or less is used most preferably. By using 25 mol or less, there exists an advantage that the quantity of the aldehyde compound which can be contained in a polyol composition can be decreased more.

  Examples of the polycarboxylic acids include polycarboxylic acids having three carboxyl groups in the molecule such as citric acid, trimesic acid, propanetricarboxylic acid, trimellitic acid, pyromellitic acid, biphthalic acid, cyclopentanetetracarboxylic acid, and biphenyl. Polycarboxylic acid having four carboxyl groups in the molecule such as tetracarboxylic acid, polycarboxylic acid having five carboxyl groups in the molecule such as benzenepentacarboxylic acid, and six carboxyl groups in the molecule such as benzenehexacarboxylic acid Esterification with a polycarboxylic acid having at least two carboxyl groups in the molecule, a polycarboxylic acid obtained by a condensation reaction of the compound having at least two carboxyl groups in the molecule and a polyamine compound, and a compound having at least two carboxyl groups in the molecule Polycarbonate obtained by reaction Bonn acid, and the like acid anhydrides thereof.

  Among these polycarboxylic acids, polycarboxylic acids having 3 to 6 carboxyl groups in the molecule are preferable in that they are easily available and can impart suitable hardness and mechanical strength to the polyurethane resin. A polycarboxylic acid having 3 to 4 carboxyl groups is more preferable. Of these, a polycarboxylic acid having three carboxyl groups in the molecule is preferable because it is more easily available.

  Of these polycarboxylic acids, natural-derived raw materials or compounds synthesized using these are preferable in terms of substituting fossil-derived resources such as petroleum. Citric acid which is a raw material is preferable. Furthermore, from the viewpoint of carbon neutral that carbon dioxide discharged into the atmosphere and absorbed carbon dioxide can be the same, a plant-derived raw material or a compound synthesized using the same is more preferable.

  Examples of the hydroxycarboxylic acid include hydroxymonocarboxylic acid having one carboxyl group in the molecule and hydroxydicarboxylic acid having two carboxyl groups in the molecule. As said hydroxycarboxylic acid, the said hydroxymonocarboxylic acid is preferable at the point that it is easy to control the average hydroxyl group number of a polyol composition. In addition, the hydroxy monocarboxylic acid preferably has one hydroxyl group in the molecule from the viewpoint that it is easy to control the average number of hydroxyl groups of the polyol composition.

The hydroxycarboxylic acid preferably has 5 to 30 carbon atoms, and more preferably has 10 to 22 carbon atoms. When the number of carbon atoms is 5 to 30, an elastic low-hardness polyurethane resin is obtained, and particularly in a flexible polyurethane foam, there is an advantage that good rebound resilience can be obtained. The carbon number of the hydroxycarboxylic acid means the number of carbons in the hydroxycarboxylic acid molecule, and when a plurality of hydroxycarboxylic acids are mixed, it means the average number of carbons in the mixture.
More specifically, the hydroxycarboxylic acid has 5 to 30 carbon atoms in that it is easy to control the average number of hydroxyl groups in the polyol composition and a low-hardness polyurethane resin having elasticity can be obtained. Certain hydroxy monocarboxylic acids are preferred. Moreover, the hydroxy monocarboxylic acid which has one hydroxyl group in a molecule | numerator and is C5-C30 is preferable at the point that it is easy to control an average hydroxyl group number.

  Examples of the hydroxy monocarboxylic acid include aliphatic hydroxy monocarboxylic acid, aromatic hydroxy monocarboxylic acid, and alkyl ester of unsaturated carboxylic acid having no hydroxyl group, formic acid method, hydroxyformylation, Examples thereof include hydroxylated carboxylic acid obtained by hydroxylation by removal of an alkyl ester by a known method such as ring opening of an epoxy group.

  Examples of the aliphatic hydroxy monocarboxylic acid include glycolic acid, lactic acid, ricinoleic acid, glyceric acid, tartaric acid, leucine acid, mevalonic acid, pantoic acid, cerebric acid, quinic acid, shikimic acid, and the like. Especially, as said aliphatic hydroxymonocarboxylic acid, glycolic acid, ricinoleic acid, etc. are preferable.

  When using the said ricinoleic acid, the mixture containing this ricinoleic acid includes a castor oil fatty acid mixture obtained by hydrolyzing castor oil. The castor oil fatty acid mixture may contain not only ricinoleic acid but also a hydroxycarboxylic acid other than ricinoleic acid, a fatty acid having no hydroxyl group, and the like. It is preferable in that it is relatively easy to obtain.

  Even in the case of using the castor oil fatty acid mixture, the polyol composition of the present embodiment is such that the hydroxyl group of the hydroxycarboxylic acid other than ricinoleic acid and ricinoleic acid in the castor oil fatty acid mixture is the polycarboxylic acid. Since it esterifies to a carboxyl group, the fatty acid having no hydroxyl group that can be present in the castor oil fatty acid mixture hardly contributes to the esterification reaction. Therefore, although a mixture containing a fatty acid having no hydroxyl group is used, a fatty acid having no hydroxyl group is hardly introduced into the molecule in the resulting polyol composition. Thus, the polyol composition of this embodiment has an advantage that a polyol composition in which the aspect of the hydroxyl group is adjusted is easily obtained.

  Examples of the aromatic hydroxy monocarboxylic acid include monohydroxybenzoic acid derivatives such as salicylic acid, creosote acid, vanillic acid, and silling acid, dihydroxybenzoic acid derivatives such as pyrocatechuic acid, resorcylic acid, protocatechuic acid, gentisic acid, and orthoric acid, Trihydroxybenzoic acid derivatives such as gallic acid, phenylacetic acid derivatives such as mandelic acid, benzylic acid, atrolactic acid, cinnamic acid such as mellitoic acid, furoretic acid, coumaric acid, umberic acid, caffeic acid, ferulic acid, sinapinic acid Examples thereof include hydrocinnamic acid derivatives and hydrogenated derivatives thereof.

  Examples of the hydroxylated carboxylic acid include monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid and nervonic acid, and diunsaturated acids such as linoleic acid. Saturated fatty acids, triunsaturated fatty acids such as α-linolenic acid and eleostearic acid, tetraunsaturated fatty acids such as stearidonic acid and arachidonic acid, pentaunsaturated fatty acids such as eicosapentaenoic acid and succinic acid, and hexaunsaturated acids such as docosahexaenoic acid The thing which hydroxylated double bond parts, such as a saturated fatty acid, is mentioned. Among these, as the hydroxylated carboxylic acid, a hydroxycarboxylic acid obtained from a monounsaturated fatty acid is preferable because it can selectively obtain a hydroxycarboxylic acid having one hydroxyl group in the molecule. In this respect, monohydroxy stearic acid obtained from oleic acid is more preferable.

  Examples of the hydroxydicarboxylic acid include malic acid, tartronic acid, citramalic acid, and the like.

  One of the hydroxycarboxylic acids can be used alone. Or 2 or more types may be used together.

  As the esterification reaction product, a polycarboxylic acid having three carboxyl groups in the molecule and the hydroxy monocarboxylic acid can be easily obtained and can impart a suitable hardness and mechanical strength to the polyurethane resin. An esterification reaction product with an acid is preferred.

  As the esterification reaction product, specifically, citric acid or 1,2,4,5-benzenetetracarboxylic acid as a polycarboxylic acid having 3 or more carboxyl groups in the molecule, a hydroxyl group and one Alternatively, an esterification reaction product obtained by reacting monohydroxy stearic acid, glycolic acid, or castor oil fatty acid as a hydroxycarboxylic acid having two carboxyl groups may be mentioned. More specifically, an esterification reaction product of citric acid and monohydroxystearic acid, an esterification reaction product of citric acid and glycolic acid, an esterification reaction product of citric acid and castor oil fatty acid, 1, 2, 4 , 5-benzenetetracarboxylic acid and monohydroxystearic acid esterification reaction product.

  In the esterification reaction, a monocarboxylic acid having no hydroxyl group may be used. Examples of such compounds include the above-mentioned unsaturated monocarboxylic acids having no hydroxyl group, such as crotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, and nervonic acid. Can be mentioned.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, butylene oxide, glycidol, and mixtures thereof. Among these, ethylene oxide, propylene oxide, and a mixture thereof are preferable in that they are excellent in compatibility with other polyols and other additives described later.
Usually, the hydroxyl group produced by addition polymerization of ethylene oxide is a primary hydroxyl group, and the hydroxyl group produced by addition polymerization of propylene oxide is a secondary hydroxyl group. Therefore, when using a mixture of ethylene oxide and propylene oxide, these two types of alkylenes are used. By changing the mixing ratio of oxides, the ratio of primary hydroxyl groups to secondary hydroxyl groups in the polyol composition can be adjusted as appropriate.

  The polyol composition formed by addition polymerization of the alkylene oxide having 2 to 4 carbon atoms may be, for example, one obtained by addition polymerization of either ethylene oxide or propylene oxide. For example, ethylene oxide and propylene oxide are separated from each other. It may be one obtained by addition polymerization, or may be one obtained by addition polymerization of an oxide compound obtained by mixing ethylene oxide and propylene oxide.

  The polyol composition of the present embodiment is preferably used as a polyurethane resin raw material, and more preferably used as a polyurethane foam raw material. By being used as a polyurethane resin raw material, there is an advantage that a low-hardness polyurethane resin having elasticity can be obtained. Further, it is particularly preferably used as a raw material for flexible polyurethane foam, and there is an advantage that good rebound resilience can be obtained by using it as a raw material for flexible polyurethane foam.

  The average hydroxyl value of the polyol composition of the present embodiment is preferably in the range of 15 to 800 mgKOH / g, and more preferably 20 to 600 mgKOH / g. By being within the above range, there is an advantage that suitable hardness and mechanical strength can be imparted to the polyurethane resin. In addition, the said average hydroxyl value can be calculated | required by the method described in the Example.

  When the polyol composition of this embodiment is used for a flexible polyurethane foam, the average hydroxyl value is preferably in the range of 15 to 180 mgKOH / g, more preferably 20 to 150 mgKOH / g. By setting it within the above range, a flexible polyurethane foam having suitable hardness or impact resilience can be obtained.

  In addition, although the polyol composition of this embodiment has a polyol compound as a main component, it may contain a side reaction product or the like generated in association with the esterification reaction or alkylene oxide addition polymerization. For example, when the mixture containing the polycarboxylic acid and the mixture containing the hydroxycarboxylic acid are used in the esterification reaction, impurities contained in the mixture are included in the polyol composition of the present embodiment. Can be.

  Next, an embodiment of a method for producing a polyol composition will be described.

  In the method for producing a polyol composition of the present embodiment, a polycarboxylic acid having 3 or more carboxyl groups in a molecule is esterified with a hydroxyl group and a hydroxycarboxylic acid having 1 or 2 carboxyl groups in the molecule. Thus, an esterification reaction product is obtained, and an alkylene oxide having 2 to 4 carbon atoms is subjected to addition polymerization to the esterification reaction product.

  The said polycarboxylic acid, the said hydroxycarboxylic acid, the said esterification reaction material, and the said alkylene oxide can use the thing similar to what was described in embodiment of the above-mentioned polyol composition.

In the method for producing a polyol composition of the present embodiment, hydroxycarboxylic acid is condensed with a carboxyl group of the polycarboxylic acid by an esterification reaction. Even when a castor oil fatty acid containing a relatively large amount of carboxylic acid other than hydroxycarboxylic acid (for example, nonhydroxycarboxylic acid having no hydroxyl group) is used as the hydroxycarboxylic acid, the nonhydroxycarboxylic acid is In general, the non-hydroxycarboxylic acid is difficult to be introduced as a main component of the polyol composition because it does not react with the polycarboxylic acid. Therefore, even when the castor oil fatty acid is used, the hydroxyl group of the hydroxycarboxylic acid contained in the castor oil fatty acid reacts with the polycarboxylic acid, so that the hydroxycarboxylic acid is selected as the main component of the polyol composition. Easy to introduce.
That is, the method for producing a polyol composition of the present embodiment can produce a desired polyol composition relatively easily even when a hydroxycarboxylic acid having a relatively low purity is used. The desired polyol composition means a polyol composition in which the amount of the aldehyde compound as an impurity is relatively small and the aspect of the hydroxyl group is sufficiently adjusted as described above.

  The esterification reaction between the polycarboxylic acid and the hydroxycarboxylic acid can be performed under normal pressure or under vacuum conditions, and can be performed by employing a conventionally known esterification technique performed using a catalyst. Among them, typical examples include a method of performing an esterification reaction under normal pressure, a method of performing an esterification reaction under vacuum, an esterification reaction in the presence of an inert solvent such as toluene, and then a condensed water. And a method of azeotropically removing the solvent and the solvent and removing them from the reaction system.

  Examples of the esterification reaction catalyst include conventionally known catalysts such as organic acids such as methanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid and xylenesulfonic acid, and inorganic such as sulfuric acid and phosphoric acid. Acids, organic acid salts such as potassium acetate and potassium octylate, metal chlorides such as lithium chloride and potassium chloride, metal oxides such as magnesium oxide and aluminum oxide, metal hydroxides such as sodium hydroxide and potassium hydroxide, Examples thereof include metal alcoholate compounds such as sodium methylate, sodium ethylate, aluminum triisopropoxide, isopropyl titanate and butyl titanate, metal phenolate compounds such as sodium phenolate, and sulfonic acid type ion exchange resins.

  The addition polymerization reaction of alkylene oxide to the esterification reaction product can be carried out according to a conventionally known method.

  Next, an embodiment of a method for producing a polyurethane resin using the polyol composition will be described.

  The method for producing a polyurethane resin according to this embodiment is a reaction between the polyol composition and a polyisocyanate compound. In addition, reaction with the said polyol composition and the said polyisocyanate compound advances, when the hydroxyl group of the said polyol composition and the isocyanate group of the said polyisocyanate compound react mainly.

  In the method for producing a polyurethane resin according to this embodiment, since the hydroxyl group of the polyol composition is adjusted to a desired mode, the properties of the polyurethane resin are likely to be desired. Therefore, desired physical properties can be imparted to the polyurethane resin.

  The polyisocyanate compound is a compound having a plurality of isocyanate groups in the molecule. Examples of the polyisocyanate compounds include toluene diisocyanate (TDI), diphenyl diisocyanate, polymethylene diisocyanate, diphenylmethane diisocyanate (MDI), polymethylene polyphenyl polyisocyanate, naphthalene diisocyanate, xylylene diisocyanate, and triphenylmethane triisocyanate. Mention may be made of isocyanate compounds. In addition, as a modified product of the polyisocyanate compound, a prepolymer modified product, a dimerized modified product, a trimerized modified product, a urea modified product, or a carbodiimide modified product modified with a polyhydric alcohol such as polyether polyol or trimethylolpropane. It may be used. Two or more of these polyisocyanate compounds can be used in combination. Of these, TDI and MDI alone and their combined use are preferred in that the resulting polyurethane resin has good moldability. When producing a flexible polyurethane foam, it is more preferable to use a polymethylene polyphenyl polyisocyanate modified with a polyether polyol in that a polyurethane resin having good moldability and impact resilience can be obtained. Note that at least one polyisocyanate compound may be used.

  The polyol composition can be mixed with other polyol compounds to become a polyol component. In this case, in the method for producing a polyurethane resin of the present embodiment, the polyol component containing the polyol composition is reacted with the polyisocyanate compound.

  The blending ratio of the polyisocyanate compound and the polyol component is a ratio of the total number of isocyanate groups of the polyisocyanate compound and the total number of hydroxyl groups of the polyol component (NCO) in consideration of the moldability of the polyurethane resin. / OH ratio) is preferably 0.8 or more, and more preferably 1.5 or less. In particular, when it is used for a flexible polyurethane foam, it is more preferably 0.9 or more and 1.2 or less in that good rebound resilience can be imparted.

  Although it does not specifically limit as said other polyol compound, It is a polyol which can become a raw material of a polyurethane resin, and what is normally obtained by addition polymerization of an alkylene oxide is mentioned. The ratio of the polyol composition in the polyol component is that the ratio of the other polyol compound obtained by addition polymerization of the alkylene oxide is reduced, and the aldehyde compound contained in the obtained polyurethane resin can be reduced. 10 weight% or more is preferable and 15 weight% or more is more preferable.

  The other polyol compound preferably has an average hydroxyl number of 2.0 or more and an average hydroxyl value of 20 mgKOH / g or more.

  When the average number of hydroxyl groups of the other polyol compound is 2.0 or more, there is an advantage that the polyurethane resin has sufficient mechanical strength. When the other polyol compound is used as a raw material for a flexible polyurethane foam, the average number of hydroxyl groups of the other polyol compound is 6.0 or less, thereby obtaining a low-hardness polyurethane resin having elasticity, In particular, a flexible polyurethane foam has an advantage that good resilience can be obtained.

  The average hydroxyl value of the other polyol compound is preferably 20 to 800 mgKOH / g or more. When the average hydroxyl value is 20 to 800 mgKOH / g or more, there is an advantage that a polyurethane resin having sufficient mechanical strength can be produced. In particular, when used for a flexible polyurethane foam, the average hydroxyl value of the other polyol compound is preferably 20 to 90 mgKOH / g.

  When a plurality of other polyol compounds are used, the mixture preferably has an average hydroxyl number of 2.0 or more and an average hydroxyl value of 20 mgKOH / g or more. That is, in all the individual polyol compounds, not only when the average number of hydroxyl groups is 2.0 or more and the average hydroxyl value is 20 mgKOH / g or more, but each individual polyol compound has an average number of hydroxyl groups of 2.0 or more. Even if the average hydroxyl value is within the range of 20 mgKOH / g or more or outside the range, the mixture as a whole is preferable even if the average hydroxyl number is 2.0 or more and the average hydroxyl value is 20 mgKOH / g or more. Is within.

  Examples of the other polyol compounds include polyester polyols, polycarbonate polyols, polyether polyols, polymer polyols, copolyols thereof, and any two or more mixtures thereof. Of these, polyether polyols, polymer polyols, or mixtures thereof are preferable in that they are excellent in hydrolysis resistance and the like.

  Examples of the polyester polyol include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid, naphthalenedicarboxylic acid, triphthalic acid, and the like. One or more of polycarboxylic acids such as merit acid, acid esters thereof, or acid anhydrides thereof, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1, 3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1, 9-nonanediol, diethylene glycol, dipropi Glycols, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adducts of bisphenol A, low molecular alcohols such as trimethylolpropane, glycerin and pentaerythritol, low molecular weights such as hexamethylenediamine, xylylenediamine and isophoronediamine Examples thereof include polyester polyols and polyester amide polyols obtained by a dehydration condensation reaction with one or more low molecular amino alcohols such as amines, monoethanolamine, and diethanolamine. Examples thereof include lactone polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using low molecular alcohols, low molecular amino alcohols, and the like as initiators.

  Examples of the polycarbonate polyol include a dehydrochlorination reaction of low molecular alcohols and phosgene used for the synthesis of the polyester polyol described above, or the low molecular alcohols and diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, and the like. What is obtained by transesterification reaction is mentioned.

  Examples of the polyether polyol include low-molecular alcohols, low-molecular amines, low-molecular amino alcohols, and phenols that are used for the synthesis of the above-described polyester polyols, ethylene oxide, propylene oxide, butylene oxide, and the like. And polyoxyethylene polyols, polyoxypropylene polyols, polytetramethylene ether polyols, polyoxyethylene polyoxypropylene polyols, and the like obtained by ring-opening polymerization of alkylene oxide, tetrahydrofuran, and the like. Furthermore, the polyester ether polyol which uses the above-mentioned polyester polyol and polycarbonate polyol as an initiator is mentioned. Preferably, what added the alkylene oxide by ring-opening polymerization is mentioned. When these are used, a polyurethane foam having good reactivity and good moldability can be obtained. The alkylene oxide may be added in any form such as random addition or block addition.

  The polymer polyol includes a method of polymerizing an ethylenically unsaturated monomer in a polyether polyol, a method of mixing separately produced polymer fine particles into a polyether polyol, a macromonomer having an ethylenically unsaturated group, and an ethylenically unsaturated monomer. Can be prepared, for example, by polymerizing in a polyether polyol. Examples of the ethylenically unsaturated monomer include monomers such as styrene and acrylonitrile, and mixtures thereof. Of these, those obtained by polymerizing ethylenically unsaturated monomers in polyether polyol are preferred, and those obtained by polymerizing ethylenically unsaturated monomers in polyoxypropylene triol are more preferred. When the content of the polymer fine particles exceeds 50% by weight, the viscosity of the polymer polyol becomes high and workability may be deteriorated during molding.

  In the method for producing the polyurethane resin of the present embodiment, general methods such as a slab method, a one-shot method, a semi-prepolymer method, and a prepolymer method can be employed. By adopting this method, polyurethane foam such as rigid polyurethane foam and flexible polyurethane foam, polyurethane elastomer and the like can be produced.

  In the method for producing a polyurethane resin of the present embodiment, a catalyst, a foaming agent, a foam stabilizer, a crosslinking agent and the like can be further used.

Examples of the catalyst include tertiary amines, diazabicycloalkenes, salts thereof, and organometallic compounds that are generally used in the production of polyurethane resins. Examples of the tertiary amine include N, N-dimethylethanolamine, triethylenediamine, triethylamine, tri-n-butylamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethyl. Examples include hexamethylenediamine and 1,2-dimethylimidazole.
Examples of the organometallic compound include metal salts of metals such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, and iron with organic acids such as octenoic acid and naphthenic acid, dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin. Examples thereof include metal chelate compounds such as diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, acetylacetone aluminum, acetylacetone cobalt, acetylacetone iron, acetylacetone copper, and acetylacetone zinc.
Any of these may be used alone or in admixture of two or more. In the production of polyurethane foam, it is preferable to use a tertiary amine. The amount added can be adjusted as appropriate.

  As the foaming agent, water, hydrogen atom-containing hydrocarbons, methylene chloride, low boiling point hydrocarbons, and liquefied carbon dioxide can be used alone or in combination. Examples of the hydrogen atom-containing halogenated hydrocarbon include HFCs (hydrofluorocarbons) such as HFC-134a, HFC-152a, HFC356mff, HFC236ea, HFC-245ca, and HFC365-mfc. Examples of the low boiling point hydrocarbon include hydrocarbons having a normal boiling point of −5 to 70 ° C., such as butane, pentane, cyclopentane, and mixtures thereof. As the foaming agent, water is particularly preferably used.

  Examples of the foam stabilizer include those usually used in the production of polyurethane resins, such as polyalkylsiloxane-polyoxyalkylene block copolymers. Any of these may be used alone or in admixture of two or more. The foam stabilizer is used in an amount of 5.0 parts by weight or less, preferably 3.0 parts by weight or less based on 100 parts by weight of the polyol component. If it is used in excess of 5 parts by weight, the moldability deteriorates.

As the cross-linking agent, low molecular active hydrogen compounds having a molecular weight of less than 500, such as low molecular alcohols, low molecular amines and low molecular amino alcohols used for the synthesis of the above-described polyester polyols, are preferably used.
Any of the crosslinking agents can be used alone or in admixture of two or more. When the crosslinking agent is used in the preparation of a flexible polyurethane foam, it is preferably used in an amount of 10 parts by weight or less, preferably 5 parts by weight or less based on 100 parts by weight of the polyol component. When the amount exceeds 5 parts by weight, the compression set of the polyurethane foam may be deteriorated.

  In the method for producing a polyurethane resin of the present embodiment, desired additives can be used in addition to the catalyst, the foaming agent, the foam stabilizer, and the crosslinking agent described above. Examples of the additives include fillers such as potassium carbonate and barium sulfate; surfactants such as polyurethane foam stabilizers; antioxidants such as antioxidants and ultraviolet absorbers; flame retardants, colorants, antifungal agents, Examples of the conventional additives include deodorants, foam breakers, dispersants, discoloration inhibitors, plasticizers, solvents, film-forming aids, dispersants, and fragrances.

  Hereinafter, the present invention will be described in more detail with reference to examples.

  First, it shows below about the compound used for manufacture of a polyol composition.

<(A) Polycarboxylic acid having 3 or more carboxyl groups in the molecule>
(A1) Citric acid anhydride (Nacalai Tesque, Inc., trade name: citric acid anhydride)
(A2) 1,2,4,5-benzenetetracarboxylic acid (pyromellitic acid manufactured by Wako Pure Chemical Industries, Ltd.)

<(B) Hydroxycarboxylic acid having 1 or 2 carboxyl groups and hydroxyl groups in the molecule>
(B1) Monohydroxystearic acid The manufacturing method of monohydroxystearic acid is shown below.
High purity oleic acid (manufactured by NOF Corporation, trade name: EXTRA OLEIN ™ 99) 1000 g (3.5 mol), 2000 mL formic acid (Nacalai Tesque) in a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser Co., Ltd., trade name: formic acid) 10 mL of a 70% aqueous solution of perchloric acid (1% by weight based on oleic acid) is heated to reflux in a nitrogen atmosphere for 5-15 minutes, after which excess formic acid is decompressed. in that removal gave crude Holm oxystearic acid 1100 g (iodine value 13.5gI ₂ / 100g, saponification value 298mgKOH / g, an acid value 170 mg KOH / g) and.
This crude formoxystearic acid was boiled for 15 minutes with 100% excess (2 equivalents) of 6N NaOH and then poured into excess 6N HCl with stirring. After the oil layer (upper layer) was cured, the aqueous phase was removed, and the oil layer (solid layer) was added to hot water while stirring and dissolved again. The solid product and allowed to air dry, to yield crude mono-hydroxystearic acid 1050 g (iodine value 15.0gI ₂ / 100g, acid value 184mgKOH / g, an average hydroxyl value 184) and.
Further, 740 g of monohydroxystearic acid (yield 65%, iodine value ₂ gI 2/100 g, acid value 187 mgKOH / g, average hydroxyl value 195 mgKOH / g) was obtained by recrystallization from petroleum naphtha and hexane.
The iodine value was measured according to JIS K3331, the saponification value was measured according to JIS K0070, and the acid value was measured according to JIS K0070. In addition, the average hydroxyl value was measured by the method shown later.
(B2) Glycolic acid (Nacalai Tesque, trade name: glycolic acid)
(B3) Castor oil fatty acid (made by Ito Oil Co., Ltd., trade name “CO-FA” containing ricinoleic acid)

<(C) C2-C4 alkylene oxide>
(C1) Ethylene oxide (C2) Propylene oxide

  Polyol compositions 1 to 11 were produced using the above polycarboxylic acid, hydroxycarboxylic acid, and alkylene oxide.

(Polyol composition 1)
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 57.6 g (0.3 mol) of citric acid and 487 g (1.8 mol) of monohydroxytesalinic acid at a temperature of 160 ° C. Then, the reaction was carried out for 8 hours while removing by-product water from the reaction system. Subsequently, the reaction solution was transferred to an autoclave, and 3.4 g of a 48% potassium hydroxide aqueous solution (0.3 parts by weight as KOH with respect to 100 parts by weight of the reaction solution) was added to maintain the temperature at 130 ° C. and the pressure at 0.2 MPa. Then, 38.4 g (0.9 mol) of ethylene oxide was introduced, and a ripening reaction was further carried out for 1 hour to produce polyol composition 1 (average hydroxyl value 83 mgKOH / g).

(Polyol composition 2-9)
“(A) Type and amount of polycarboxylic acid having 3 or more carboxyl groups in molecule” and “(B) Hydroxycarboxylic acid having 1 or 2 carboxyl groups and hydroxyl group in molecule” The method similar to that of the polyol composition 1 except that the type, amount used and the type, amount used and addition form of “(C) C2-C4 alkylene oxide” were changed as shown in Table 1. The polyol compositions 2 to 9 were produced. In the production of the polyol composition 6, while maintaining the temperature at 130 ° C. and the pressure of 0.2 MPa, the maturation reaction is performed for 1 hour after introducing propylene oxide, and then the temperature is maintained at 130 ° C. and the pressure of 0.2 MPa. Aging reaction was carried out for 1 hour after introducing ethylene oxide. In the production of the polyol composition 7, a mixture of monohydroxytesalinic acid and glycolic acid was used as “hydroxycarboxylic acid having one or two carboxyl groups and hydroxyl groups in the molecule”.

(Polyol composition 10)
An autoclave was charged with 384.0 g (2.0 mol) of citric acid and 4.0 g of a 48% potassium hydroxide aqueous solution and maintained at a temperature of 130 ° C. and a pressure of 0.2 MPa, and 256.0 g (6.0 mol) of ethylene oxide. Then, a polyol composition 10 (average hydroxyl value 482 mgKOH / g) was produced by further aging reaction for 1 hour.

(Polyol composition 11)
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 115.2 g (0.6 mol) of citric acid and 487 g (1.8 mol) of monohydroxytesalinic acid at a temperature of 160 ° C. Then, the polyol composition 11 (average hydroxyl value 168 mgKOH / g) was produced by performing the reaction for 8 hours while removing by-product water from the reaction system.

(Polyol composition 12)
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 27.6 g (0.3 mol) of glycerin and 487 g (1.8 mol) of monohydroxytesalinic acid at a temperature of 160 ° C. The polyol composition 12 (average hydroxyl value 87 mgKOH / g) was produced by carrying out the reaction for 8 hours while removing by-product water from the reaction system.

(Polyol composition 13)
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 27.6 g (0.3 mol) of glycerin and 487 g (1.8 mol) of monohydroxystearic acid at a temperature of 160 ° C. The reaction was carried out for 8 hours while removing by-product water from the reaction system.
Subsequently, the reaction solution was transferred to an autoclave and 3.2 g of a 48% potassium hydroxide aqueous solution (0.3 parts by weight with respect to 100 parts by weight of the reaction solution as KOH) was added to maintain a temperature of 130 ° C. and a pressure of 0.2 MPa. Then, 38.4 g (0.9 mol) of ethylene oxide was introduced, and a aging reaction was further performed for 1 hour to obtain a polyol composition 13 (average hydroxyl value: 89 mgKOH / g).

(Polyol composition 14)
A polyol composition 14 (average hydroxyl value 64 mgKOH / g) was obtained in the same manner as the polyol composition 13 except that the monohydroxystearic acid was changed to 730 g (2.7 mol).

<Content of aldehyde compound>
The content of the aldehyde compound contained in the polyol composition was measured by liquid chromatography (measuring instrument “HP-1050” manufactured by Hured Packart Co., Ltd.) by the following method.
First, a calibration curve was prepared using standard samples of formaldehyde and acetaldehyde. Then, it measured on the following conditions using the synthesized polyol composition, measured each aldehyde amount from the said calibration curve, and made the total amount the aldehyde content.
<Measurement conditions for liquid chromatography>
Column: Inerssil ODS-2 (4.6 mmφ × 150 mm, particle diameter 5 μm)
Eluent: Acetonitrile / Buffer (45/55 (volume ratio)),
(Buffer: 0.025 mol / L sodium dihydrogen phosphate aqueous solution adjusted to pH 4.0 with 1 mol / L phosphoric acid)
Flow rate: 1.0 mL / min.
Detection wavelength: UV355nm
Injection volume: 10 μL
Detection limit: 0.1 ppm

<Average hydroxyl value>
The average hydroxyl value of the manufactured polyol composition was measured according to JIS K1557.

  Table 1 shows the composition ratio in the production of each polyol composition, the content of the aldehyde compound in each polyol composition, and the measurement results of the average hydroxyl value.

  As can be recognized from Table 1, it can be said that the content of the aldehyde compound of the polyol composition of the present invention is relatively small. It can be said that the content of an aldehyde compound in a general polyether polyol is about 3 ppm, and the content of an aldehyde compound in a polyol composition obtained by adding an alkylene oxide to castor oil is about 2 ppm.

<Ratio of primary hydroxyl group of polyol composition>
The ratio of the primary hydroxyl group occupied in all the terminal hydroxyl groups of the polyol compositions 1, 2, 5, 13, and 14 was measured by the following method by 1H-NMR method.
Specifically, trifluoroacetic anhydride was added to the CDCl ₃ solution of each polyol composition to esterify the terminal hydroxyl group, and then 1H-NMR was measured.
More specifically, a methylene hydrogen atom (that is, a primary hydroxyl group: a peak near δ = 5.2 ppm) and a methine hydrogen atom (that is, 1) bonded to a carbon atom esterified with trifluoroacetic acid. The peak integrated value of primary hydroxyl group: peak near δ = 4.3 ppm) was measured, and the ratio of primary hydroxyl group was calculated from the following formula.
Primary hydroxyl group ratio (mol%) = [R / (R + 2S)] × 100
R = Integral value of methylene hydrogen atom peak S = Integral value of methine hydrogen atom peak

  Table 2 shows the composition ratio of the raw materials of each polyol composition and the ratio of primary hydroxyl groups of each polyol composition.

  As can be recognized from Table 2, in the polyol composition of the present invention, the aspect of the hydroxyl group is sufficiently adjusted. That is, when ethylene oxide is used as the alkylene oxide, most of the hydroxyl groups can be primary hydroxyl groups. When propylene oxide is used, most of the hydroxyl groups can be secondary hydroxyl groups. On the other hand, when a polycarboxylic acid having 3 or more carboxyl groups in the molecule is not used, it cannot be said that the hydroxyl group is sufficiently adjusted.

  Then, the polyurethane foam was manufactured using each said polyol composition. In addition to the polyol composition, the following raw materials were used. Table 3 shows the blending amounts of these raw materials.

<Other polyols>
(D-1)
Polyether polyol obtained by addition polymerization of propylene oxide to glycerin and block addition polymerization of ethylene oxide at the terminal (average number of hydroxyl groups 3, average hydroxyl value 34 mgKOH / g, trade name “DKS Propyran 353” (Daiichi Kogyo Seiyaku Co., Ltd.) ))
(D-2)
Polymer polyol in which propylene oxide is added to glycerin and styrene monomer is further polymerized (average number of hydroxyl groups 3, average hydroxyl value 28 mgKOH / g, trade name “Hiflex ND825C” (Daiichi Kogyo Seiyaku Co., Ltd.))
<Catalyst 1>
N, N-dimethylethanolamine Product name: Propamine A (Daiichi Kogyo Seiyaku Co., Ltd.)
<Catalyst 2>
33% DPG solution of triethylenediamine Product name: TOYOCAT TEDA L33 (manufactured by Tosoh Corporation)
<Foam stabilizer>
Silicone foam stabilizer Product name: SZ-1313 (manufactured by Toray Dow Corning Co., Ltd.)
<Foaming agent>
Water <Polyisocyanate compound>
Isocyanate group-terminated urethane prepolymer obtained by reacting polymethylene polyphenyl polyisocyanate with polyoxyethylene polyoxypropylene polyol (free NCO = 29.0%, trade name “DK System B-73E” (Daiichi Kogyo Seiyaku) )

  A polyol composition 1-14, other polyols, water as a foaming agent, a catalyst, and a foam stabilizer were mixed so that the weight ratio shown in Table 3 was obtained, thereby producing a premix. The temperature of the obtained premix was adjusted to 22 ° C., and the polyisocyanate compound similarly adjusted to a temperature of 22 ° C. was further mixed so that the weight ratio shown in Table 2 was obtained (hand mixing) to obtain a polyol-isocyanate mixture. It was. Using this mixture, a polyurethane foam was produced, and physical properties of the polyurethane foam were evaluated.

<Evaluation of reactivity>
The polyol-isocyanate mixture was poured into a polycup and the reactivity (cream time, gel time, rise time) was measured. The cream time was the time when foaming started, the gel time was the time when stringing was finished, and the rise time was the time when foaming was finished.

<Evaluation of foam properties>
The polyol-isocyanate mixture was placed in a 30 × 30 × 10 cm mold adjusted to 55 ° C., and mold foaming was performed. After 15 minutes, the mold was removed, and the moldability (evaluated by using as an index the presence or absence of collapses, the presence or absence of surface skin peeling, and the presence or absence of voids) was evaluated.
Thereafter, the core density (based on JIS K-6400), hardness, impact resilience, and permanent strain of the obtained polyurethane foam were measured based on JIS K-6400.

In Table 3, as can be seen from the comparison between Examples 1 to 11 and Comparative Examples 1 to 5, the polyurethane foam using the polyol composition of each Example can obtain good physical properties.
Polyurethane foam (Comparative Example 1) using the polyol composition 10 synthesized without using a hydroxy acid having one or two carboxyl groups has poor moldability and permanent set, and the hardness becomes very high. Recognize.
When the polyol composition 11 synthesized without using an alkylene oxide having 2 to 4 carbon atoms (Comparative Example 2) is used, the reactivity is very slow, and collapsing occurs before it becomes a normal foam shape. However, a polyurethane foam could not be obtained.
A polyurethane foam using a polyol composition 12 in which a glycerin having three hydroxyl groups is used instead of a polycarboxylic acid having three or more carboxyl groups and no alkylene oxide having 2 to 4 carbon atoms is used (Comparative Example 3) ) Is poor in moldability and permanent set, and has low rebound resilience.
Polyurethane foams (Comparative Examples 4 and 5) using polyol compositions 13 and 14 synthesized using glycerin instead of polycarboxylic acid having 3 or more carboxyl groups have poor permanent distortion and low rebound resilience. I understand.

  The polyol composition of the present invention can be suitably used as a raw material for molded polyurethane resin products such as polyurethane foam. Moreover, the polyurethane resin obtained by the manufacturing method of the polyurethane resin of this invention can be used suitably as a polyurethane foam etc., for example. More specifically, it is suitable for applications in which polyurethane foam is usually used, for example, furniture, automobile seats, headrests and the like.

Claims (6)

  An esterification reaction product of a polycarboxylic acid having three or more carboxyl groups in the molecule and a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule is an alkylene oxide having 2 to 4 carbon atoms. A polyol composition obtained by addition polymerization of.   The polyol composition according to claim 1, wherein 1 to 30 moles of the hydroxycarboxylic acid are reacted with 1 mole of the polycarboxylic acid.   The polyol composition according to claim 1 or 2, wherein the hydroxycarboxylic acid has 5 to 30 carbon atoms.   The polyol composition according to any one of claims 1 to 3, which is used for a polyurethane resin raw material.   A polycarboxylic acid having three or more carboxyl groups in the molecule is esterified with a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule to form an esterification reaction product, and the esterification reaction A method for producing a polyol composition, comprising subjecting a product to addition polymerization of an alkylene oxide having 2 to 4 carbon atoms.   A method for producing a polyurethane resin, comprising reacting the polyol composition according to any one of claims 1 to 4 with a polyisocyanate compound.