JP5269562B2 - POLYOL COMPOSITION, PROCESS FOR PRODUCING THE SAME, AND PROCESS FOR PRODUCING POLYURETHANE RESIN USING THE POLYOL COMPOSITION - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition lower in viscosity than those of conventional ones and good in workability, to provide a method for producing the same, and to provide a method for producing a polyurethane resin using such a polyol composition. <P>SOLUTION: The polyol composition is produced by the addition polymerization of a 2-4C alkylene oxide to a reaction product which is obtained by condensed dehydrogenation among a polycarboxylic acid having in the molecule three or more carboxy groups, a hydroxycarboxylic acid having in the molecule a hydroxy group and one or two carboxy groups and an active hydrogen compound having in the molecule at least two active hydrogen atoms. <P>COPYRIGHT: (C)2010,JPO&amp;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 polyester polyol composition obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol is used as a polyurethane resin such as a polyurethane foam. Known as a raw material.

  Since such a polyol composition contains a polyester compound in which a polyvalent carboxylic acid and a polyhydric alcohol are esterified, it is considered that the ester bond existing in the polyester compound molecule enhances the cohesive force acting between the molecules. Therefore, the viscosity tends to be relatively high, which may be undesirable in terms of workability such as handling. Furthermore, since a reaction liquid for producing a polyurethane resin obtained by mixing such a polyol composition with a polyisocyanate compound or the like can also have a high viscosity, it can be undesirable from the viewpoint of workability such as workability.

  On the other hand, a polyester obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol in a state in which one or more of a specific fatty acid, oil or fatty acid compound is included so as to obtain a low viscosity polyol composition. A polyol composition has been proposed (Patent Document 1).

  However, as disclosed in Patent Document 1, the polyester polyol composition obtained by reacting a polyvalent carboxylic acid and a polyhydric alcohol in a state in which one or more of a specific fatty acid, fat or fatty acid compound is contained still has a satisfactory viscosity. There is a problem that it is not as low as possible and is not necessarily superior in terms of workability. Specifically, for example, in the production of polyurethane resins, in order to improve workability, the viscosity can be lowered by further adding a viscosity reducing agent that can adversely affect the properties of the polyurethane resin and organic solvents such as chlorofluorocarbons. There is a problem of requiring an operation to be performed. Therefore, there is a demand for a polyol composition that is sufficiently low in viscosity and excellent in workability without adding a viscosity reducing agent or an organic solvent.

JP-A-10-330470

  In view of the above problems and demands, an object of the present invention is to provide a polyol composition having a lower viscosity than conventional ones and excellent in workability, and a method for producing the same. 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. When, in the reaction product of an active hydrogen compound comprising by dehydration condensation reaction having at least two active hydrogen in the molecule, a polyol composition ing by addition polymerization of alkylene oxide having 2 to 4 carbon atoms,
The polycarboxylic acid is citric acid or pyromellitic acid;
The hydroxycarboxylic acid is monohydroxystearic acid, glycolic acid, or ricinoleic acid;
The active hydrogen compound is ethylene glycol, an aliphatic monoether polyol compound having one ether group in the molecule and a number average molecular weight of 50 to 1000, a polyester polyol compound having a number average molecular weight of 50 to 1000, and a number average molecular weight. It is a 50 to 1000 polyether polyol compound or an amino group-containing polyol compound having a number average molecular weight of 50 to 1000 .

According to the polyol composition which consists of the said structure, each carboxyl group of the said polycarboxylic acid, the hydroxyl group of the said hydroxycarboxylic acid, or the active hydrogen of the said active hydrogen compound can carry out a dehydration condensation reaction.
Further, the carboxyl group of the hydroxycarboxylic acid and the hydroxyl group of the hydroxycarboxylic acid or the active hydrogen of the active hydrogen compound may undergo a dehydration condensation reaction.
Furthermore, an unreacted hydroxyl group in the hydroxycarboxylic acid after dehydration condensation of the carboxyl group and the carboxyl group of the hydroxycarboxylic acid or the carboxyl group of the polycarboxylic acid can be subjected to a dehydration condensation reaction.
In addition, the unreacted carboxyl group in the hydroxycarboxylic acid after the dehydration condensation of the hydroxyl group and the hydroxyl group of the hydroxycarboxylic acid or the active hydrogen of the active hydrogen compound can be subjected to a dehydration condensation reaction.
In addition, the carboxyl group of the intermediate compound of various embodiments and the hydroxyl group of the intermediate compound of various embodiments or the active hydrogen of the intermediate compound can undergo a dehydration condensation reaction.
By such a dehydration condensation reaction, various intermediate reactants are generated, and various alkylene compounds can be generated by addition polymerization of the alkylene oxide to the intermediate reactant. Accordingly, the polyol composition may contain various polyol compounds.

  That is, the polyol composition contains various compounds that not only have different molecular weights but also greatly different molecular structures. Therefore, although the principle of action is not clearly clarified, the polyol composition is a compound having a similar molecular weight or molecular structure due to the greatly different molecular weight or molecular structure of the contained polyol compound. Compared with a polyol composition, it is extremely difficult to be in a state where the polyol compound is regularly arranged, and a cohesive force that can act between molecules of the polyol compound even though a polyol compound having an ester bond can be included. Can be weak.

The polyol composition according to the present invention is preferably reacted by using 1 to 30 moles of the hydroxycarboxylic acid per 1 mole of the polycarboxylic acid.
By reacting 1 to 30 mol of the hydroxycarboxylic acid with respect to 1 mol of the polycarboxylic acid, a polyurethane resin having suitable elasticity and hardness can be obtained. There is an advantage that rebound resilience can be obtained.
Moreover, there exists an advantage that the said polyol composition can become a thing with a lower viscosity by reacting by using 1-30 mol of said hydroxycarboxylic acids with respect to 1 mol of said polycarboxylic acids.

  The polyol composition according to the present invention is preferably for a polyurethane resin raw material. If used as a polyurethane resin raw material, the viscosity of the reaction solution during production of the polyurethane resin can be relatively low, so that there is an advantage that workability such as workability can be improved. 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.

The method for producing a polyol composition according to the present invention comprises a polycarboxylic acid having three or more carboxyl groups in a molecule, a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule, an active hydrogen compound having at least two active hydrogen reaction product obtained by dehydration condensation reaction, a process for the preparation of a polyol composition Ru by addition polymerization of alkylene oxide having 2 to 4 carbon atoms, the
The polycarboxylic acid is citric acid or pyromellitic acid;
The hydroxycarboxylic acid is monohydroxystearic acid, glycolic acid, or ricinoleic acid;
The active hydrogen compound is ethylene glycol, an aliphatic monoether polyol compound having one ether group in the molecule and a number average molecular weight of 50 to 1000, a polyester polyol compound having a number average molecular weight of 50 to 1000, and a number average molecular weight. It is a 50 to 1000 polyether polyol compound or an amino group-containing polyol compound having a number average molecular weight of 50 to 1000 .

  The method for producing a polyurethane resin according to the present invention comprises reacting the polyol composition with a polyisocyanate compound. Since the polyol composition can have a lower viscosity than the conventional one, the method for producing a polyurethane resin according to the present invention has a relatively low viscosity of the reaction liquid obtained by mixing the polyol composition and the polyisocyanate compound, Workability such as workability can be improved. Moreover, the manufacturing method of the polyurethane resin which concerns on this invention tends to make the physical property etc. of the polyurethane resin obtained desired.

  The principle of action of the polyol composition of the present invention is not clearly elucidated, but it is a compound having a similar molecular weight and molecular structure due to the greatly different molecular weight and molecular structure of the contained polyol compound. Compared with a polyol composition, it is extremely difficult to be in a state where the polyol compound is regularly arranged, and a cohesive force that can act between molecules of the polyol compound even though a polyol compound having an ester bond can be included. Can be weak. Therefore, the polyol composition of the present invention has an effect that the viscosity is lower than that of the conventional one, the workability is excellent, and the handling is easy.

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

  The polyol composition of this embodiment comprises a polycarboxylic acid having 3 or more carboxyl groups in the molecule, a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule, and at least 2 in the molecule. A product obtained by subjecting an active hydrogen compound having one active hydrogen to a dehydration condensation reaction, an alkylene oxide having 2 to 4 carbon atoms is subjected to addition polymerization.

In the polyol composition of the present embodiment, each carboxyl group of the polycarboxylic acid and the hydroxyl group of the hydroxycarboxylic acid or the active hydrogen of the active hydrogen compound can undergo a dehydration condensation reaction in the reaction during production.
Further, the carboxyl group of the hydroxycarboxylic acid and the hydroxyl group of the hydroxycarboxylic acid or the active hydrogen of the active hydrogen compound may undergo a dehydration condensation reaction.
Furthermore, an unreacted hydroxyl group in the hydroxycarboxylic acid after dehydration condensation of the carboxyl group and the carboxyl group of the hydroxycarboxylic acid or the carboxyl group of the polycarboxylic acid can be subjected to a dehydration condensation reaction.
In addition, the unreacted carboxyl group in the hydroxycarboxylic acid after the dehydration condensation of the hydroxyl group and the hydroxyl group of the hydroxycarboxylic acid or the active hydrogen of the active hydrogen compound can be subjected to a dehydration condensation reaction.
In addition, the carboxyl group of the intermediate compound of various embodiments and the hydroxyl group or active hydrogen of the intermediate compound of various embodiments can undergo dehydration condensation reaction.
By such dehydration condensation reaction, various intermediate reactants are generated, and by addition polymerization of the alkylene oxide to the intermediate reactant, various polyol compounds can be generated. Accordingly, the polyol composition may contain various polyol compounds.

  That is, the polyol composition of the present embodiment contains various compounds that not only have different molecular weights but also greatly different molecular structures. Therefore, although the principle of action is not clearly clarified, the polyol composition is a compound having a similar molecular weight or molecular structure due to the greatly different molecular weight or molecular structure of the contained polyol compound. Compared with a polyol composition, it is extremely difficult to be in a state where the polyol compound is regularly arranged, and a cohesive force that can act between molecules of the polyol compound even though a polyol compound having an ester bond can be included. Can be weak. Therefore, the polyol composition of the present embodiment has a lower viscosity than the conventional one, and can be excellent in workability and easy to handle.

The polyol composition of this embodiment is preferably formed by reacting 1 to 30 moles of the hydroxycarboxylic acid with respect to 1 mole of the polycarboxylic acid, and reacted by using 5 to 24 moles. Is more preferable, and it is more preferable that 6 to 21 moles are used and reacted. Moreover, it is still more preferable that 6-12 mol is used and reacted, and it is most preferable that 6-9 mol is used and reacted.
By reacting 1 to 30 mol of the hydroxycarboxylic acid with respect to 1 mol of the polycarboxylic acid, a polyurethane resin having suitable elasticity and hardness can be obtained. There is an advantage that rebound resilience can be obtained.
Moreover, there exists an advantage that the said polyol composition can become a thing with a lower viscosity by reacting by using the said hydroxycarboxylic acid 30 mol or less with respect to 1 mol of said polycarboxylic acids. Furthermore, the hydroxycarboxylic acid is more preferably used in an amount of 24 mol or less, more preferably 21 mol or less, still more preferably 12 mol or less, and most preferably 9 mol or less with respect to 1 mol of the polycarboxylic acid.
Moreover, the molecular weight of the compound contained in the polyol composition of the present embodiment is increased by reacting by using 1 mol or more of the hydroxycarboxylic acid with respect to 1 mol of the polycarboxylic acid, There is an advantage that the average hydroxyl value of the polyol composition can be smaller.

  The polyol composition of the present embodiment is preferably obtained by reacting 1 mol or more of the active hydrogen compound with respect to 1 mol of the carboxyl group contained in the polycarboxylic acid. By using 1 mol or more and making it react, there exists an advantage that an abnormal reaction in a urethanization reaction at the time of making it react with a polyisocyanate compound does not occur easily that a carboxyl group does not remain in the obtained polyol composition. The active hydrogen compound is preferably used in an amount of 5 mol or less, more preferably 3 mol or less, and more preferably 1 mol of the carboxyl group contained in the polycarboxylic acid. . By using 5 mol or less and reacting, there is an advantage that a polyurethane resin having suitable elasticity and hardness can be obtained.

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 4 carboxyl groups in the molecule such as tetracarboxylic acid, polycarboxylic acid having 5 carboxyl groups in the molecule such as benzenepentacarboxylic acid, 6 in the molecule such as benzenehexacarboxylic acid A polycarboxylic acid having a carboxyl group, a polycarboxylic acid obtained by a condensation reaction of a compound having at least two carboxyl groups in the molecule and a polyamine compound, a compound having at least two carboxyl groups in the molecule, and Polycarbonate obtained by esterification reaction of Bonn acids, and include such acid anhydrides, among others, Ru using citric acid or pyromellitic acid.

  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 is used as a raw material. 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.

  The hydroxycarboxylic acid has a hydroxyl group and one or two carboxyl groups in the molecule.

  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. Moreover, as said hydroxy monocarboxylic acid, what has one hydroxyl group in a molecule | numerator is preferable at the point that it is easy to control the average hydroxyl group number of a 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 specifically means the average number of carbon atoms per molecule of the hydroxycarboxylic acid. More specifically, when a plurality of hydroxycarboxylic acids are mixed, it means the average number of carbon atoms of the hydroxycarboxylic acid, that is, the average number of carbon atoms per molecule of the mixed hydroxycarboxylic acid.

  More specifically, as the hydroxycarboxylic acid, it is easy to control the average number of hydroxyl groups of the polyol composition, and a low hardness polyurethane resin having elasticity can be obtained. Hydroxy monocarboxylic acid having 5 to 30 carbon atoms is preferred.

  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. Of these, glycolic acid and ricinoleic acid are used as the aliphatic hydroxymonocarboxylic acid.

  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. An esterification reaction can be performed on a carboxyl group.

  Examples of the aromatic hydroxy monocarboxylic acid include monohydroxybenzoic acid derivatives such as salicylic acid, creosote acid, vanillic acid, and syringic 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 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, the hydroxylated carboxylic acid is preferably a hydroxycarboxylic acid obtained from a monounsaturated fatty acid in that a hydroxycarboxylic acid having one hydroxyl group in the molecule can be selectively obtained . Get the viewpoint that it is easy, using the mono-hydroxy stearic acid obtained from oleic acid.

  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.

  Examples of the polyol composition include a polyol composition obtained by reacting a monocarboxylic acid having no hydroxyl group in addition to the polycarboxylic acid, the hydroxycarboxylic acid, and the active hydrogen compound. Examples of the monocarboxylic acid include clotonic acid, myristoleic acid, palmitoleic acid, oleic acid, elaidic acid, vaccenic acid, gadoleic acid, erucic acid, nervonic acid, and the like. Examples include acids.

  The active hydrogen compound is a compound having at least two active hydrogens in the molecule. The active hydrogen compound is a compound having in its molecule hydrogen of a hydroxyl group, hydrogen of a primary amino group or secondary amino group, or hydrogen of a thiol group as active hydrogen. In addition, the kind of active hydrogen in a molecule | numerator may be 1 type, and 2 or more types may be sufficient as it.

The active hydrogen compound has a number average molecular weight of 50 to 1,000 . By number average molecular weight of 50 to 1000, may be suitable elasticity, Ru obtain a polyurethane resin having a hardness.

  The number average molecular weight is represented by the molecular weight when the molecular structure is known, and is represented by the average value calculated from the mixing ratio when the molecular structure is known. . In addition, the number average molecular weight is measured by high performance liquid chromatography as described below in the case where those having different molecular weights are mixed with a molecular weight distribution, such as polyoxyalkylene glycols such as polyethylene glycol and polypropylene glycol. It is defined by the number average molecular weight.

Here, the measuring method of a number average molecular weight is shown. First, a standard material of polyethylene glycol was measured by high performance liquid chromatography (product name: HP-1050, manufactured by Hewlett-Packard Company) to prepare a calibration curve. Subsequently, each polyol composition was measured under the same conditions, and based on the detected retention time and peak area, each molecular weight and its ratio were determined from a calibration curve, and the number average molecular weight was calculated. The measurement conditions are as follows.
Column: 4.6 mmΦ × 150 mm
(Product name: Inertsil Hewlett Packard)
Eluent: Mixed solvent of water / acetonitrile = 45/55 (weight ratio) Pump flow rate: 1.0 mL / min.
-Column temperature: 40 ° C
-Detector: ELSD drift tube-Detector temperature: 140 ° C

  Specifically, as the active hydrogen compound, a polyol compound having a plurality of hydroxyl groups in the molecule, an amine compound having a primary amino group or a secondary amino group in the molecule, a thiol compound having a thiol group in the molecule, etc. Is mentioned. These active hydrogen compounds can be mixed and used.

  Specific examples of the polyol compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexane glycol, glycerin, trimethylolpropane, pentaerythritol, sorbitol and other aliphatic polyol compounds, diethylene glycol, Aliphatic monoether polyol compounds having one ether group in the molecule such as dipropylene glycol, alicyclic polyol compounds such as α-methylglycoside and sucrose, aromatic polyol compounds such as bisphenol A and bisphenol F, etc. It is done.

  Specific examples of the polyol compound include amino group-containing polyol compounds such as diethanolamine, triethanolamine, and diisopropanolamine.

  Furthermore, examples of the polyol compound include polyester polyol compounds, polyether polyol compounds, polyether polyester polyol compounds, and the like. Moreover, what combined these can be employ | adopted.

  Specific examples of the polyester polyol compound include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid. , One or more of polycarboxylic acids such as naphthalenedicarboxylic acid and trimellitic acid, acid esters thereof, or acid anhydrides thereof, and 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 , Dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular alcohol compounds such as trimethylolpropane, glycerin, pentaerythritol, hexamethylenediamine, xylylenediamine, isophoronediamine And polyester polyol or polyester amide polyol obtained by a dehydration condensation reaction with one or more low molecular weight amino alcohol compounds such as low molecular weight amine compounds such as monoethanolamine and diethanolamine. Moreover, for example, 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 polyether polyol compound include, for example, low molecular alcohol compounds, low molecular amine compounds, low molecular amino alcohol compounds used for the synthesis of the above-described polyester polyol, and ethylene oxide, propylene oxide, butylene oxide using phenols as initiators. Examples include ring-opening polymerization of alkylene oxides such as tetrahydrofuran, and the like. Specifically, polyoxyethylene polyols such as polyethylene glycol, polyoxypropylene polyols such as polypropylene glycol, polytetramethylene ether polyols, polyoxyethylene Examples include polyoxyethylene polyoxypropylene polyol such as polyoxypropylene glycol.

  Examples of the polyether polyester polyol compound include polyether polyesters having the above-described polyester polyol and polycarbonate polyol as initiators. Preferably, what added the alkylene oxide by ring-opening polymerization is mentioned. The alkylene oxide may be added in any form such as random addition or block addition.

  Examples of the amine compound include aliphatic amine compounds such as ethylenediamine, tetramethylenediamine, and hexamethylenediamine, cyclic amine compounds such as piperazine, aromatic amine compounds such as toluenediamine, phenylenediamine, and diphenylethanediamine, monoethanolamine, and monoamine. Examples include alkanol primary amine compounds such as isopropanolamine.

  Examples of the thiol compound include thioglycol.

  Among these, as the active hydrogen compound, the polyol compound is preferable in that it can be a polyurethane resin having suitable elasticity and hardness. Further, the aliphatic monoether polyol compound, the polyether polyol compound, etc. An ether polyol compound having a plurality of hydroxyl groups in the molecule and having at least one ether group is more preferred. Specifically, the active hydrogen compound is preferably the aliphatic monoether polyol compound such as diethylene glycol or dipropylene glycol, or the polyether polyol compound such as polyethylene glycol, polypropylene glycol or polyoxyethylene polyoxypropylene glycol. . Of these, dipropylene glycol, polyethylene glycol, polypropylene glycol, and polyoxyethylene polyoxypropylene glycol are particularly preferable.

  Specifically, as the polyol composition of the present embodiment, a polycarboxylic acid having three carboxyl groups in the molecule and one in the molecule in that it can be a polyol composition having a lower viscosity. A product obtained by dehydrating and condensing a hydroxy monocarboxylic acid having a hydroxyl group and having 5 to 30 carbon atoms and the ether polyol compound having a plurality of hydroxyl groups in the molecule and having at least one ether group is preferable. . More specifically, those obtained by dehydrating and condensing citric acid, monohydroxystearic acid or ricinoleic acid, and an aliphatic monoether polyol compound having one ether group in the molecule are preferable.

Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, glycidol, butylene oxide, tetrahydrofuran, and mixtures thereof. Among these, ethylene oxide or propylene oxide is preferable in that it has excellent compatibility with other polyols and other additives described later. That is, ethylene oxide, propylene oxide, and mixtures thereof are preferred.
Usually, the hydroxyl group produced by addition polymerization of ethylene oxide becomes a primary hydroxyl group, and the hydroxyl group produced by addition polymerization of propylene oxide becomes a secondary hydroxyl group. Therefore, when a mixture of ethylene oxide and propylene oxide is used, these two types are used. By changing the mixing ratio of the alkylene oxide, the ratio of the primary hydroxyl group to the secondary hydroxyl group in the polyol composition can be appropriately adjusted.
As described above, in the polyol composition of the present embodiment, a predetermined amount of a predetermined alkylene oxide is added and polymerized to a reaction product obtained by subjecting the polycarboxylic acid, the hydroxycarboxylic acid, and the active hydrogen compound to a dehydration condensation reaction. Therefore, the aspect of the hydroxyl group present in the polyol composition can be sufficiently adjusted.

  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 using it as a polyurethane resin raw material, the viscosity of the reaction solution when producing a polyurethane resin can be relatively low, so that there is an advantage that workability such as workability can be good, and there is a low elasticity. There is an advantage that a polyurethane resin having a hardness 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.

  The viscosity of the polyol composition of the present embodiment is preferably 50 to 2500 mPa · s, and more preferably 100 to 1000 mPa · s. If it is in the said range, it will be easy to handle and it will be excellent in workability, such as handling property. In addition, the said viscosity can be calculated | required by the method described in the Example.

  In addition, although the polyol composition of this embodiment has a polyol compound as a main component, it may contain by-products or the like generated in association with the dehydration condensation reaction. Further, for example, when a dehydration condensation reaction is performed using a mixture containing the polycarboxylic acid, a mixture containing the hydroxycarboxylic acid, and a mixture containing the active hydrogen compound, impurities contained in the mixture, etc. Can be included in the polyol composition of the present embodiment.

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

  The method for producing a polyol composition of the present embodiment comprises a polycarboxylic acid having 3 or more carboxyl groups in the molecule, a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule, In addition, an alkylene oxide having 2 to 4 carbon atoms is subjected to addition polymerization to a reaction product obtained by subjecting an active hydrogen compound having at least two active hydrogens to a dehydration condensation reaction.

  The manufacturing method of the polyol composition of this embodiment can make the viscosity of the manufactured polyol composition lower than the conventional one. Therefore, the manufactured polyol composition can be easily mixed with the polyisocyanate compound, and can be easily handled and have good workability such as handling properties and workability.

  As the polycarboxylic acid, the hydroxycarboxylic acid, the active hydrogen compound, and the alkylene oxide having 2 to 4 carbon atoms, the same as those described in the embodiment of the polyol composition can be used.

  The dehydration condensation reaction of the polycarboxylic acid, the hydroxycarboxylic acid, and the active hydrogen compound can be performed by employing a conventionally known method performed using a catalyst. Specifically, the dehydration condensation reaction can be performed by a reaction similar to an esterification reaction employing a conventionally known esterification technique.

  Representative examples of the esterification reaction include a method of performing an esterification reaction under normal pressure, a method of performing an esterification reaction under vacuum, and an esterification reaction in the presence of an inert solvent such as toluene. Thereafter, a method of removing the condensed water and the solvent azeotropically and removing them from the reaction system is exemplified.

  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.

In the esterification reaction, the polycarboxylic acid, the hydroxycarboxylic acid, and the active hydrogen compound are preferably reacted at the same time in that the polyol composition can be produced by a single reaction. By reacting all of them at the same time, there is an advantage that a polyol composition having a relatively low viscosity can be easily produced in one reaction.
In addition, in order to produce a more controlled polyol composition to impart desired physical properties to the polyurethane resin, first, any two components are subjected to a dehydration condensation reaction, and then the remaining one component is subjected to a dehydration condensation reaction. It is preferable to make it. Specifically, for example, in the production method in which the active hydrogen compound is further reacted after the polycarboxylic acid and the hydroxycarboxylic acid are reacted, a polyol compound having a more similar molecular structure is included in the polyol composition. It is preferable in terms of obtaining.

  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, the viscosity of the reaction liquid obtained by mixing the polyol composition and the polyisocyanate compound is relatively low because the polyol composition is low in viscosity so as to be excellent in workability. It becomes low and workability | operativity, such as workability at the time of polyurethane resin manufacture, can become favorable. In addition, the method for producing a polyurethane resin according to the present embodiment makes it easy to obtain desired properties of 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 form a polyol component and used for producing a polyurethane resin. 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 compound which can become a raw material of a polyurethane resin, and what is normally obtained by addition-polymerizing alkylene oxide is mentioned. The proportion of the polyol composition in the polyol component is preferably 10% by weight or more, and more preferably 15% by weight or more in that the viscosity of the polyol component can be relatively low.

  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 of the other polyol compound include succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid. , One or more of polycarboxylic acids such as naphthalenedicarboxylic acid and trimellitic acid, acid esters thereof, or acid anhydrides thereof, and 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, die Lenglycol, dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide or propylene oxide adduct of bisphenol A, low molecular alcohol compounds such as trimethylolpropane, glycerin, pentaerythritol, hexamethylenediamine, xylylenediamine, isophoronediamine And polyester polyol or polyester amide polyol obtained by a dehydration condensation reaction with one or more low molecular weight amino alcohol compounds such as low molecular weight amine compounds such as monoethanolamine and diethanolamine. Further, for example, lactone polyester polyols obtained by ring-opening polymerization of cyclic ester (lactone) monomers such as ε-caprolactone and γ-valerolactone using a low molecular alcohol compound, a low molecular amino alcohol, etc. as an initiator can be mentioned.

  Examples of the polycarbonate polyol of the other polyol compound include a dehydrochlorination reaction of a low molecular alcohol compound and phosgene used in the synthesis of the polyester polyol of the above other polyol compound, or the low molecular alcohol compound and diethylene carbonate. , Dimethyl carbonate, diethyl carbonate, diphenyl carbonate and the like obtained by transesterification.

  Examples of the polyether polyol of the other polyol compound include, for example, low molecular alcohol compounds, low molecular amine compounds, low molecular amino alcohol compounds used for the synthesis of the above-described polyester polyol, ethylene oxide, phenols as initiators, Examples thereof include polyoxyethylene polyol, polyoxypropylene polyol, polytetramethylene ether polyol, polyoxyethylene polyoxypropylene polyol and the like obtained by ring-opening polymerization of alkylene oxide such as propylene oxide and butylene 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 of the other polyol compound is a method of polymerizing an ethylenically unsaturated monomer in a polyether polyol, a method of mixing separately produced polymer fine particles in a polyether polyol, or a macromonomer having an ethylenically unsaturated group. And an ethylenically unsaturated monomer 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 exceeds 5 parts by weight, the moldability deteriorates.

The cross-linking agent is preferably a low-molecular active hydrogen compound having a molecular weight of less than 500, such as a low-molecular alcohol compound, a low-molecular amine compound, or a low-molecular amino alcohol compound used for the synthesis of the polyester polyol.
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) Active hydrogen compound having at least two active hydrogens in the molecule>
(C1) Dipropylene glycol (Brand name: Dipropylene glycol Nacalai Tesque)
(C2) Polyethylene glycol (number average molecular weight 390, trade name: PEG400, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(C3) polyoxyethylene polyoxypropylene glycol (number average molecular weight 990, random polymerization of propylene glycol with a mixture of ethylene oxide and propylene oxide (30/70 [weight ratio]))
(C4) Polypropylene glycol (number average molecular weight 392, trade name: PPG400, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.)
(C5) Diethanolamine (molecular weight 105)
(C6) Polyester polyol (Number average molecular weight 1000, trade name: Nipponporan 4009, manufactured by Nippon Polyurethane Co., Ltd.)
(C7) Ethylene glycol (molecular weight 62)

<(D) C2-C4 alkylene oxide>
(D1) Ethylene oxide (D2) Propylene oxide

  Polyol compositions 1 to 17 were produced using the above polycarboxylic acid, hydroxycarboxylic acid, and active hydrogen compound as necessary.

(Polyol composition 1)
In a reactor equipped with a stirrer, thermometer, nitrogen inlet tube and reflux condenser, 57.6 g (0.3 mol) of citric acid, 487 g (1.8 mol) of monohydroxystearic acid and 181 g of dipropylene glycol (1. 35 mol) was added, and the reaction was carried out at 220 ° C. for 8 hours while removing by-product water from the reaction system. Subsequently, the reaction solution was transferred to an autoclave, and 4.5 g of 48% potassium hydroxide aqueous solution (0.3 parts by weight with respect to 100 parts by weight of reaction solution as KOH) was added, and the temperature was maintained at 130 ° C. and the pressure was 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 (viscosity: 920 mPa · s, average hydroxyl value: 68 mgKOH / g).

(Polyol composition 2-17)
“(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” Types and amounts used, types and amounts of “(C) active hydrogen compounds having at least two active hydrogens in the molecule”, and types and uses of “(D) alkylene oxides having 2 to 4 carbon atoms” Except that the amount was changed as described in Table 1, polyol compositions 2 to 17 were produced in the same manner as polyol composition 1.

(Polyol composition 18)
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 166 g (1 mol) of terephthalic acid, 81 g (0.3 mol) of monohydroxystearic acid and 186 g (3 mol) of ethylene glycol. The reaction was carried out at 220 ° C. while removing by-product water from the reaction system for 8 hours to produce a polyol composition 18 (viscosity: 10400 mPa · s, average hydroxyl value 228 mgKOH / g).

(Polyol composition 19)
A reactor equipped with a stirrer, a thermometer, a nitrogen inlet tube and a reflux condenser was charged with 166 g (1 mol) of terephthalic acid, 81 g (0.3 mol) of monohydroxystearic acid and 186 g (3 mol) of ethylene glycol. The reaction was carried out at 220 ° C. for 8 hours while removing by-product water from the reaction system. Subsequently, the reaction solution was transferred to an autoclave, and 2.7 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, 132 g (3 mol) of ethylene oxide was introduced, and the polyol composition 19 (viscosity: 9600 mPa · s, average hydroxyl value: 199 mgKOH / g) was produced by further aging reaction for 1 hour.

(Polyol composition 20)
“(A) a polycarboxylic acid having three or more carboxyl groups in the molecule”, “(B) a hydroxycarboxylic acid having one or two carboxyl groups and a hydroxyl group in the molecule”, “(C) molecule” The same as the polyol composition 19 except that the amount of the "active hydrogen compound having at least two active hydrogens" and "(D) alkylene oxide having 2 to 4 carbon atoms" was changed as shown in Table 1. The polyol composition 20 was produced by the method described above.

<Viscosity>
The viscosity of the polyol composition was measured at 25 ° C. with a BL type viscometer (manufactured by Toki Sangyo Co., Ltd.) according to JIS K-7117-1. For the polyol compositions 1 to 19, the rotor No. 2 and the polyol composition 20 was measured using a rotor No. 4 was measured.

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

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

  As can be recognized from Table 1, it can be said that the viscosity of the polyol composition of the present invention is relatively low. Moreover, it can be said that although the viscosity is relatively low, the average hydroxyl value is relatively low.

  Then, the polyurethane foam was manufactured using each said polyol composition. In addition to the polyol composition, the following raw materials were used. Table 2 shows the blending amounts of these raw materials.

<Other polyols>
(E-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.) ))
(E-2)
Polymer polyol obtained by addition-polymerizing propylene oxide to glycerin and further polymerizing styrene monomer (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) )

  The polyol compositions 1 to 20, other polyols, water as a foaming agent, a catalyst and a foam stabilizer were mixed so that the weight ratio shown in Table 2 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.

As can be recognized from Table 2, the polyurethane foam using the polyol composition of each example was able to obtain good physical properties.
On the other hand, as in Comparative Examples 1 to 3, when an attempt was made to produce a polyurethane foam using a conventional polyol composition, the respective raw materials could be mixed uniformly due to the high viscosity of the polyol composition. could not.

  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 (5)

A polycarboxylic acid having three or more carboxyl groups in the molecule, a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule, and an active hydrogen compound having at least two active hydrogens in the molecule preparative to the reaction product obtained by dehydration condensation reaction, a polyol composition ing by addition polymerization of alkylene oxide having 2 to 4 carbon atoms,
The polycarboxylic acid is citric acid or pyromellitic acid;
The hydroxycarboxylic acid is monohydroxystearic acid, glycolic acid, or ricinoleic acid;
The active hydrogen compound is ethylene glycol, an aliphatic monoether polyol compound having one ether group in the molecule and a number average molecular weight of 50 to 1000, a polyester polyol compound having a number average molecular weight of 50 to 1000, and a number average molecular weight. A polyol composition, which is a polyether polyol compound having 50 to 1000 or an amino group-containing polyol compound having a number average molecular weight of 50 to 1000 .   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, which is for a polyurethane resin raw material. A polycarboxylic acid having three or more carboxyl groups in the molecule, a hydroxycarboxylic acid having a hydroxyl group and one or two carboxyl groups in the molecule, and an active hydrogen compound having at least two active hydrogens in the molecule the door to a reaction product obtained by dehydration condensation reaction, a process for the preparation of a polyol composition Ru by addition polymerization of alkylene oxide having 2 to 4 carbon atoms,
The polycarboxylic acid is citric acid or pyromellitic acid;
The hydroxycarboxylic acid is monohydroxystearic acid, glycolic acid, or ricinoleic acid;
The active hydrogen compound is ethylene glycol, an aliphatic monoether polyol compound having one ether group in the molecule and a number average molecular weight of 50 to 1000, a polyester polyol compound having a number average molecular weight of 50 to 1000, and a number average molecular weight. A method for producing a polyol composition, which is a polyether polyol compound having 50 to 1000 or an amino group-containing polyol compound having a number average molecular weight of 50 to 1000.   A method for producing a polyurethane resin, comprising reacting the polyol composition according to any one of claims 1 to 3 with a polyisocyanate compound.