JP2010202762A - Polyol composition and application of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyol composition containing a polyester polyol and a polyether polyol, the composition hardly causing phase separation and suitable to be used as a raw material for polyurethane foam. <P>SOLUTION: The polyol composition contains a polyester polyol, a polyether polyol and a compatibilizing agent, wherein the compatibilizing agent is at least one kind of compound selected from trimethylolpropane and compounds obtained by adding an alkylene oxide to trimethylolpropane, and the composition contains 0.1 to 10 mass% of the compatibilizing agent per 100 mass% of the composition. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyol composition and use thereof. Specifically, the present invention relates to a polyol composition containing a polyester polyol, a polyether polyol and a specific compatibilizing agent, and uses thereof.

Polyol compositions containing polyester polyols and polyether polyols are widely used as raw materials for urethane resins such as polyurethane foam.
However, phase separation of polyester polyol and polyether polyol usually tends to occur. Therefore, a polyol composition containing a polyester polyol and a polyether polyol is usually used in a state where it is forcibly mixed by stirring and mixing before use. However, inadequate stirring / mixing may cause deterioration of physical properties of the product, and it is industrially complicated to perform such stirring / mixing.

Therefore, there is a demand for a polyol composition that hardly causes phase separation between the polyester polyol and the polyether polyol, that is, excellent in storage stability.
By the way, from the viewpoint of environmental load reduction in recent years, materials obtained from plant resources are becoming widespread as alternatives to materials obtained from petroleum resources. Plant resources are resources obtained from plants which grow by photosynthesis while taking in CO ₂ in air, CO ₂ of the combustion process CO ₂ also results in the air being discharged into the atmosphere after use Is a resource corresponding to so-called carbon neutral that does not increase.

  As urethane resins using plant resources, resins in which part of petroleum-based polyols are replaced with vegetable oil-based polyols derived from vegetable oils such as castor oil have been proposed (see, for example, Patent Documents 1 and 2). .

  However, generally, phase separation is likely to occur between vegetable oil-based polyols and petroleum-based polyols. Therefore, when a polyol composition containing these polyols is used as a raw material for urethane resin, it is necessary to sufficiently stir and mix before use and use it in a forcibly mixed state. When using a composition that is not sufficiently stirred and mixed, or a composition that is not used immediately after stirring and mixing and phase separation occurs, it is difficult to control the physical properties of the urethane resin. However, it was difficult to control physical properties such as the degree of foaming, hardness, tensile strength, elongation, and tear strength.

  Under such circumstances, Patent Document 3 discloses that a specific polyester-polyether block polymer is used for mixing the polyester polyol and the polyether polyol. However, in order to improve the compatibility of the polyester-polyether block polymer, it is necessary to add about 20%, and there is a concern that the physical properties may be adversely affected. Patent Document 3 discloses that it is possible to prepare a flexible foam using a polyester-polyether block polymer, but does not disclose any physical properties thereof.

  Patent Document 4 discloses a polyol composition in which phase separation between a vegetable oil-derived polyol and a petroleum-based polyol does not occur. The composition includes a specific nonionic emulsifier having an HLB value greater than about 17 to prevent phase separation.

  Since the nonionic emulsifier has a functional group number of 1, when a polyurethane foam is produced using a polyol composition containing the emulsifier as a raw material, foaming does not work and a foam having desired physical properties is obtained. I could not.

US Pat. No. 2,787,601 International Publication No. 2006/118995 Pamphlet Special table 2003-511532 gazette JP 2007-277560 A

  The present invention is intended to solve the problems associated with the prior art as described above, and is unlikely to cause phase separation, and can be suitably used as a raw material for urethane resins such as polyurethane foams. It aims at providing the polyol composition containing this.

The present inventors have intensively studied to solve the above problems. As a result, it has been found that the above problem can be solved by using a specific compatibilizing agent, and the present invention has been completed.
That is, the polyol composition of the present invention is a polyol composition containing a polyester polyol, a polyether polyol and a compatibilizing agent,
The compatibilizer is at least one compound selected from trimethylolpropane and a compound obtained by adding an alkylene oxide to trimethylolpropane;
The compatibilizer is contained in an amount of 0.1 to 10% by mass per 100% by mass of the composition.

The hydroxyl value of the compatibilizer is preferably 400 to 1254 mg KOH / g.
It is preferable that the said polyester polyol contains the polyester polyol obtained by condensation with carboxylic acid and a polyhydric alcohol.

The carboxylic acid preferably contains a carboxylic acid having 10 to 22 carbon atoms.
The carboxylic acid preferably contains a hydroxyl group-containing fatty acid.
The hydroxyl group-containing fatty acid preferably contains castor oil fatty acid obtained from castor oil.

It is preferable that the castor oil fatty acid is 50 mol% or more in 100 mol% of the hydroxyl group-containing fatty acid.
The polyurethane composition of the present invention contains the polyol composition and a polyisocyanate.

The composition for polyurethane foam of the present invention contains the polyol composition and a polyisocyanate.
The polyurethane foam of the present invention is obtained by reacting the polyurethane foam composition.

The composition for flexible polyurethane foams of the present invention contains the polyol composition and a polyisocyanate.
The flexible polyurethane foam of the present invention is obtained by reacting the composition for flexible polyurethane foam.

  The seat cushion of this invention consists of the said flexible polyurethane foam.

  The polyol composition of the present invention can be suitably used as a raw material for urethane resins such as polyurethane foams because phase separation between the polyester polyol and the polyether polyol hardly occurs and the storage stability is excellent.

  In particular, since the polyol composition of the present invention has improved compatibility of the above two types of polyols, the physical properties of the polyurethane foam are unlikely to deteriorate due to insufficient stirring and mixing. For this reason, the polyurethane foam manufactured from the polyol composition of the present invention is excellent in mechanical properties such as hardness, elongation, tensile strength and tear strength.

  Hereinafter, the polyol composition of the present invention and its use will be described in detail including preferred embodiments thereof. The polyol composition of the present invention is suitably used as a raw material for urethane resins such as polyurethane foam.

[Polyol composition]
The polyol composition of the present invention is characterized by containing a polyester polyol, a polyether polyol, and a specific compatibilizer (hereinafter also simply referred to as “compatibility agent”) in a specific range.

  Furthermore, the polyol composition of the present invention is a polyol other than the above two types, a catalyst, a crosslinking agent, a foaming agent, a foam stabilizer, depending on the purpose of use (for example, a raw material of urethane resin such as polyurethane foam). You may contain an additive etc. In the present invention, the “polyol” is a concept including the polyester polyol, the polyether polyol, and other polyols.

<Compatibilizer>
As the compatibilizing agent, at least one compound selected from trimethylolpropane and a compound obtained by adding alkylene oxide to trimethylolpropane is used.

  The compound obtained by addition polymerization of alkylene oxide to trimethylolpropane is a compound obtained by adding alkylene oxide such as ethylene oxide or propylene oxide to at least a part, preferably all of the hydroxyl groups of trimethylolpropane. .

The number of functional groups of the compatibilizer is 3.
The hydroxyl value of the compatibilizer is usually 400 to 1254 mg KOH / g, preferably 500 to 1254 mg KOH / g, and particularly preferably 600 to 1254 mg KOH / g.

In the present invention, the compatibilizer may be used alone or in combination of two or more.
The polyol composition of the present invention contains 0.1 to 10% by mass, preferably 0.5 to 5% by mass, particularly preferably 1 to 3% by mass of a compatibilizer per 100% by mass of the composition. It is preferable that the content of the compatibilizing agent is in the above range because the physical properties of the polyurethane resin can be maintained while maintaining a good compatibility state.

<Polyester polyol>
As polyester polyol, the conventionally well-known thing used for manufacture of a urethane resin can be used. For example, polyester polyol obtained by condensation of carboxylic acid and polyhydric alcohol, polyester polyol obtained by condensation of carboxylic acid ester and polyhydric alcohol, condensation of polyhydric alcohol with a mixture of carboxylic acid and carboxylic acid ester Examples thereof include polyester polyols obtained, polycaprolactone diols obtained by ring-opening polymerization of ε-caprolactone, polyester polyols obtained by condensing hydroxycarboxylic acids with polyhydric alcohols, and the like.

<Carboxylic acid>
Carboxylic acids include glutaric acid, adipic acid, sebacic acid, terephthalic acid, isophthalic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid Examples thereof include low molecular weight dicarboxylic acids such as acid, nonadecanedioic acid, icosanedioic acid, and henicosanedioic acid; dimer acid; oligomeric acid; and hydroxyl group-containing fatty acid. These carboxylic acids may be used alone or in combination of two or more.

  Among the carboxylic acids, a carboxylic acid having 6 to 22 carbon atoms is preferable, and a carboxylic acid having 10 to 20 carbon atoms is more preferable. It is preferable to use a carboxylic acid having a carbon number within the above-mentioned range because it expresses preferable physical properties as a polyester polyol for preparing a polyurethane resin.

  Among the carboxylic acids, hydroxyl group-containing fatty acids are preferred. When a hydroxyl group-containing fatty acid is used as the carboxylic acid, the condensate obtained by condensation of the fatty acid may be condensed with a polyhydric alcohol, or after the fatty acid and the polyhydric alcohol are condensed, Hydroxyl group-containing fatty acids may be condensed.

  Examples of the hydroxyl group-containing fatty acid include lactic acid, glycolic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, γ-hydroxybutyric acid, ricinoleic acid, 12-hydroxystearic acid, hydroxyundecanoic acid, and cerebronic acid.

  The hydroxyl group-containing fatty acid is preferably used in an amount of 85 to 100 mol% or more, more preferably 90 to 100 mol%, still more preferably 95 to 100 mol% with respect to 100 mol% of the carboxylic acid. When the amount of the hydroxyl group-containing fatty acid is within the above range, when the polyester polyol is obtained by condensing the carboxylic acid and the polyhydric alcohol, the ratio of the hydroxyl group at the end of the molecular chain is capped by the carboxylic acid not containing a hydroxyl group. Since it is low, a polyurethane foam excellent in impact resilience can be produced.

  Among the hydroxyl group-containing fatty acids, hydroxy group-containing fatty acids derived from vegetable oils or animal oils are preferable because they can contribute to reducing the environmental burden. Examples of vegetable oils include castor oil, soybean oil, palm oil, sesame oil, rapeseed oil, and coconut oil. Examples of animal oils include beef tallow and lard. Among these oils, in order to obtain hydroxyl group-containing fatty acids from vegetable oils such as soybean oil, palm oil, sesame oil, rapeseed oil, coconut oil and animal oils such as beef tallow and lard, the oil is obtained by hydrolysis. It is necessary to add a hydroxyl group to the unsaturated fatty acid obtained by a method such as air oxidation, epoxidation or hydroformylation. On the other hand, when a hydroxyl group-containing fatty acid is obtained from castor oil, it is obtained by hydrolyzing castor oil. The hydroxyl group-containing fatty acid is preferably a hydroxyl group-containing fatty acid derived from castor oil obtained by a simple process.

  As the hydroxyl group-containing fatty acid derived from castor oil, castor oil-derived ricinoleic acid and 12-hydroxystearic acid are more preferable; castor oil-derived ricinoleic acid is particularly preferable in that the viscosity thereof is reduced during the production of the polyester polyol. In addition, the hydroxyl group containing fatty acid derived from castor oil obtained from castor oil is also called "castor oil fatty acid".

  The castor oil fatty acid is preferably used in an amount of 50 mol% or more, more preferably 70 to 100 mol%, still more preferably 80 to 100 mol% with respect to 100 mol% of the hydroxyl group-containing fatty acid. When the amount of castor oil fatty acid used is within the above range, it can contribute to reducing the environmental load.

  In purifying castor oil fatty acid, known methods such as distillation, extraction and crystallization can be used. When the castor oil fatty acid is distilled, the castor oil fatty acid is thermally decomposed at about 200 ° C., or a side reaction that causes intramolecular dehydration occurs. Therefore, it is possible to perform distillation at a temperature of 180 ° C. or less using a thin film evaporator. preferable. The thin film distillation apparatus is not particularly limited, and a rotating thin film distillation apparatus, a falling thin film distillation apparatus, and the like are used. In particular, a rotating thin film distillation apparatus under high vacuum called molecular distillation is preferable from the viewpoint of evaporation efficiency.

  For extraction of castor oil fatty acid, a general solvent extraction method is used. Although there is no restriction | limiting in particular about the solvent to be used, Hexane etc. are used from viewpoints, such as the solubility of a castor oil fatty acid and the ease of solvent removal after extraction. Castor oil fatty acid and hexane are mixed at an arbitrary ratio, and the mixture is allowed to stand at an arbitrary temperature, and the hexane phase and castor oil fatty acid phase are separated to remove hexane partially dissolved in castor oil fatty acid. Thus, high purity castor oil fatty acid can be obtained.

  Thus, it can contribute to environmental load reduction more by manufacturing a polyester polyol using a castor oil fatty acid. Further, by using the polyester polyol, it is possible to obtain a urethane resin such as polyurethane foam having excellent mechanical properties such as hardness, elongation, tensile strength and tear strength.

  The ratio of the hydroxyl group-containing fatty acid in the polyol composition of the present invention is the hydroxyl value A of the hydroxyl group-containing fatty acid measured by the method of JIS K1557-1 and the hydroxyl group-containing value measured by the method of JIS K1557-1. It is determined by the ratio A / B of the acid value B of the fatty acid.

  Moreover, when using the polyester polyol obtained by condensation with a carboxylic acid ester and a polyhydric alcohol as a polyester polyol, the carboxylic acid ester which esterified the said carboxylic acid is used.

As the carboxylic acid ester, it is preferable to use a hydroxyl group-containing fatty acid ester obtained by esterifying the hydroxyl group-containing fatty acid.
Examples of the hydroxy group-containing fatty acid ester include lactic acid ester, glycolic acid ester, 2-hydroxybutyric acid ester, 3-hydroxybutyric acid ester, γ-hydroxybutyric acid ester; methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate, butyl ricinoleate, etc. Ricinoleic acid ester; 12-hydroxystearic acid ester such as methyl 12-hydroxystearate, ethyl 12-hydroxystearate, propyl 12-hydroxystearate, butyl 12-hydroxystearate; methyl cerebrate, ethyl cerebronate, cerebronic acid Cerebronate esters such as propyl and butyl cerebronate; methyl hydroxyundecanoate, ethyl hydroxyundecanoate, propyl hydroxyundecanoate, Such as hydroxy undecanoic acid ester, such as mud carboxybutyl undecanoic acid.

  Among these, ricinoleic acid esters derived from castor oil such as methyl ricinoleate, ethyl ricinoleate, propyl ricinoleate, and butyl ricinoleate; methyl 12-hydroxystearate, ethyl 12-hydroxystearate, 12-hydroxystearic acid 12-hydroxystearic acid esters such as propyl and 12-hydroxystearic acid butyl ester are preferred; ricinoleic acid esters derived from castor oil are particularly preferred in that the viscosity of the polyester polyol is reduced during production.

The esterification is not particularly limited as long as it is a general esterification, and esterification of methanol, ethanol, n-propanol, iso-propanol, n-butanol, tert-butanol and the like with a hydroxyl group-containing fatty acid. Is mentioned. Such esterification can be performed by a known method such as performing in the presence of an alkali catalyst.
Castor oil fatty acid ester can be obtained by esterifying castor oil fatty acid, and can also be obtained by transesterification of castor oil using alcohol.

<Polyhydric alcohol>
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 1,5-pentanediol, 1,6- C 2-10 dihydric alcohols such as hexanediol, 3-methyl-1,5-pentanediol, 1,9-nonanediol; 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, hydrogenated bisphenol A, alicyclic dihydric alcohols such as hydrogenated bisphenol F; aromatic dihydric alcohols such as bisphenol A and bisphenol F; trihydric alcohols having 2 to 10 carbon atoms such as trimethylolpropane and glycerin; 8 polyhydric alcohol. Further, an alkylene oxide adduct of a polyhydric alcohol obtained by adding ethylene oxide, propylene oxide or the like to a part or all of the hydroxyl groups of these polyhydric alcohols can also be used. These may be used alone or in combination of two or more.

  Examples of polyhydric alcohols having 4 to 8 hydroxyl groups include tetravalent alcohols such as diglycerin, pentaerythritol, and α-methylglucoside; hexavalent alcohols such as dipentaerythritol; glucose, sorbitol, dextrose, fructose, sucrose, etc. Saccharides and derivatives thereof; phenols having 7 to 8 hydroxyl groups are exemplified. These may be used alone or in combination of two or more.

  In order to increase the degree of crosslinking of the polyurethane foam and to ensure its mechanical properties, the average number of hydroxyl groups of the polyhydric alcohol is preferably 3.5 or more and 8 or less. When the average number of hydroxyl groups exceeds 8, the viscosity of the polyester polyol increases, making it difficult to use it in a foaming machine when producing polyurethane foam.

When castor oil fatty acid is used as the carboxylic acid, the mass ratio ((i) / (ii) of castor oil fatty acid (i) and polyhydric alcohol (ii) having an average number of hydroxyl groups of 3.5 or more and 8 or less. )) Is preferably 1 to 100, more preferably 5 to 70, and even more preferably 5 to 50. If the mass ratio is less than the above range, it tends to be difficult to design a polyester polyol capable of producing a desired polyurethane foam, in particular, a flexible polyurethane foam. It tends to be smaller.

<Physical properties of polyester polyol>
The hydroxyl value of the polyester polyol is preferably 15 to 100 mgKOH / g, more preferably 25 to 80 mgKOH / g, and further preferably 25 to 60 mgKOH / g. If the hydroxyl value is 15 mgKOH / g or more, curing during the production of polyurethane foam proceeds in a short time, and if it is 100 mgKOH / g or less, it is preferable because it exhibits appropriate resilience and hardness as a flexible polyurethane foam.

  The acid value of the polyester polyol is preferably 0 to 3 mgKOH / g, more preferably 0 to 2 mgKOH / g. When the acid value exceeds the above range, when the urethanization reaction of the composition containing the polyol composition and the polyisocyanate is carried out, the reactivity may decrease and the reaction rate may decrease. The acid value is measured by the method described in JIS K-1557-5.

  The viscosity at 25 ° C. of the polyester polyol is preferably 20000 mPa · s or less, more preferably 15000 mPa · s or less, and still more preferably 10,000 mPa · s or less. The lower limit is usually about 500 mPa · s. The viscosity is measured at 25 ° C. using a conical plate type rotational viscometer (E type viscometer).

  In addition, since the polyurethane foam obtained by using the polyester polyol synthesized from castor oil fatty acid in the present invention can greatly increase the content of plant (castor oil) -derived components in the foam, the environmental load is further reduced. Can contribute. If the concept of carbon neutral is used, the amount of carbon dioxide emitted when a polyester polyol or polyurethane foam prepared using the plant (castor oil) -derived component is burned can be reduced. In addition, the fact that the polymer uses the biomass raw material is determined by measuring the content of carbon having a mass number of 14 and the content of carbon having a mass number of 12 and a mass number of 13 as specified in ASTM D6866. It can be determined by obtaining the carbon content ratio (14C concentration) of 14.

Specifically, ASTM (American Standard tests) D6866 (Standard Test Method for Determining the Biobased Content of Natural Range Materials Using Radiocarbon and Isotope Ratio Mass Spectrometry Analysis) , as described in, by burning sample CO ₂ The CO ₂ gas, which was accurately quantified, was put into an AMS (Accelerated Mass Spectrometry) apparatus, the carbon content of mass number 14, the carbon content of mass number 12 and the mass number 13 was measured, and the atmosphere or petrochemical It can be determined by comparing with the abundance ratio of carbon having a mass number of 14 present in the product.

Furthermore, burning the sample, the CO ₂ obtained is absorbed by the CO ₂ absorbent, or measuring the amount of carbon having a mass number of 14 with a liquid scintillation counter, and converting the resulting CO ₂ into benzene, liquid scintillation counter Can be determined by measuring the amount of carbon having a mass number of 14 and comparing it with that derived from petroleum.

  When a polyester polyol is synthesized from only petroleum-derived raw materials, carbon having a mass number of 14 is not observed, and when plant-derived raw materials are used, carbon having a mass number of 14 is observed. In order to obtain the effect of reducing the carbon dioxide emission, the value of the 14C concentration in the polyurethane foam may be 10 pMC (Percent Modern Carbon) or more, preferably 20 pMC or more, and more preferably 30 pMC.

<Polyether polyol>
As polyether polyol, the conventionally well-known thing used for manufacture of a urethane resin can be used. For example, polyalkylene oxide (for example, polyethylene glycol, polypropylene, etc.) obtained by addition polymerization of alkylene oxide using, as an initiator, polyhydric alcohol exemplified in the column of <Polyester polyol>, aliphatic polyamine such as ethylenediamine, or aromatic polyamine. Glycol, polyethylene polypropylene glycol and the like); and polytetramethylene ether glycol obtained by ring-opening polymerization of tetrahydrofuran.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, and phenyl. C2-C12 alkylene oxides, such as glycidyl ether, are mentioned. Among these, ethylene oxide, propylene oxide, 1,2-butylene oxide and styrene oxide are preferable, and ethylene oxide and propylene oxide are particularly preferable.

  An alkylene oxide may be used individually by 1 type, and may use 2 or more types together. In addition, when using alkylene oxide together, the method of performing addition polymerization of several alkylene oxide simultaneously, the method of carrying out addition polymerization sequentially, the method of repeating the method of carrying out addition polymerization sequentially, etc. are employable.

  When a polyurethane foam is obtained using the polyol composition of the present invention, it is preferable to use a polyether polyol called a communicating agent as at least a part of the polyether polyol. Specific examples of the communication agent include Actol-EP505S (manufactured by Mitsui Chemicals Polyurethane, polyalkylene oxide having a weight average molecular weight of 3400 obtained by addition polymerization of ethylene oxide and propylene oxide to glycerin, and a hydroxyl value of 50 mg / KOH. Is).

The hydroxyl value of the polyether polyol is preferably 15 to 100 mgKOH / g, more preferably 15 to 60 mgKOH / g.
The viscosity of the polyether polyol is preferably 5000 mPa · s or less, more preferably 3000 mPa · s or less.

《Other polyols》
The polyol composition of the present invention may contain other polyols in addition to the polyester polyol and polyether polyol. Examples of other polyols include low molecular weight polyhydric alcohols, polycarbonate diols, and modified polyols.

<Low molecular weight polyhydric alcohol>
Examples of the low molecular weight polyhydric alcohol include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, 2,2-dimethyl-1,3-propanediol, 1,5 -Pentanediol, 1,6-hexadiol, 3-methyl-1,5-pentanediol, 2-methyl-2,4-pentanediol, 2-ethyl-1,3-hexanediol, 1,3-dihydroxy Benzene, 1,3-bis (2-hydroxyethoxy) benzene, 1,4-bis (2-hydroxyethoxy) benzene, 4,4'-dihydroxydiphenylpropane, 4,4'-dihydroxydiphenylmethane, 1,2hedihydroxy Cyclohexane, 1,3-dihydroxycyclohexane, 1,4-di Droxycyclohexane, 1,2-dihydroxymethylcyclohexane, 1,3-dihydroxymethylcyclohexane, 1,4-dihydroxymethylcyclohexane, 1,2-bishydroxyethoxycyclohexane, 1,3-bishydroxyethoxycyclohexane, 1,4- Bishydroxyethoxycyclohexane, 1,2-bishydroxyethoxycarbonylcyclohexane, 1,3-bishydroxyethoxycarbonylcyclohexane, 1,4-bishydroxyethoxycarbonylcyclohexane, 2,5-dihydroxymethylbicyclo [2.2.1] heptane , 2,6-dihydroxy-methyl bicyclo [2.2.1] heptane, 3,8-dihydroxy methyl - tricyclo [5.2.1.0 ^2.6] decane, 3,9-dihydroxy methyl Tricyclo [5.2.1.0 ^2.6] decane, 4,8-dihydroxy methyl - tricyclo [5.2.1.0 ^2.6] 2 dihydric alcohols such as decane;
Glycerin, 2-hydroxymethyl-2-methyl-1,3-diol, 2-ethyl-2-hydroxymethyl-1,3-diol, 1,2,5-hexanetriol, 1,2,6-hexanetriol, Trihydric alcohols such as 1,2,3-cyclohexanetriol, 1,3,5-cyclohexanetriol;
Pentaerythritol, glucose, sucrose, fructose, sorbitol, 1,2,3,4-cyclohexanetetrol, 1,2,4,5-cyclohexanetetrol, cyclohexanepentol (quercitol), cyclohexanehexol (inositol), Examples include tetrahydric or higher polyhydric alcohols such as xylitol.

<Polycarbonate diol>
Examples of the polycarbonate diol include polycarbonate diols obtained by condensation of dihydric alcohols such as 1,4-butanediol and 1,6-hexanediol with dicarbonates such as dimethyl carbonate and diethyl carbonate.

<Modified product of polyol>
In the present invention, the polyol may be used as it is, but a modified polyol such as a polymer-dispersed polyol (hereinafter also referred to as “polymer polyol”) may be used. Such a polymer polyol is suitable as a raw material for a flexible polyurethane foam.

  The polymer polyol is obtained by dispersing polymer fine particles obtained by polymerizing an ethylenically unsaturated compound in a polyol using a radical initiator such as azobisisobutyronitrile. The polymer fine particle may be a polymer fine particle composed of a polymer of an ethylenically unsaturated compound, but is preferably a polymer fine particle in which at least a part of the ethylenically unsaturated compound is grafted to a polyol as a dispersion medium at the time of polymerization. .

  Examples of the ethylenically unsaturated compound include acrylonitrile, styrene, acrylamide, (meth) acrylate, and the like. These ethylenically unsaturated compounds may be used individually by 1 type, and may use 2 or more types together. Moreover, when manufacturing a polymer polyol, you may use a dispersion stabilizer, a chain transfer agent, etc. with an ethylenically unsaturated compound.

  The polymer polyol is preferably contained in the range of 0 to 80% by mass, more preferably 0 to 50% by mass, and still more preferably 0 to 30% by mass with respect to 100% by mass of all the polyol components. If the content of the polymer polyol exceeds the above range, it may not be possible to contribute to reducing the environmental load.

"catalyst"
The polyol composition of the present invention may contain a catalyst. As the catalyst, a conventionally known catalyst used for the reaction of polyol and polyisocyanate can be used. Specifically, triethylenediamine, bis- (2-dimethylaminoethyl) ether, 1-isobutyl-2-methylimidazole, Aliphatic amines such as phosphorus; organotin compounds such as tin octoate and dibutyltin dilaurate. These catalysts may be used individually by 1 type, and may use 2 or more types together.

In addition, a commercial item can be used as said catalyst, for example, 1-isobutyl-2-methylimidazole is marketed by Active Material Chemical Co., Ltd. as brand name R-9000.
When using a catalyst, in the polyol composition of this invention, it is preferable that this catalyst is contained in 0.1-10 mass parts with respect to 100 mass parts of all the polyol components.

<Crosslinking agent>
The polyol composition of the present invention may further contain a crosslinking agent. As the crosslinking agent, a conventionally known crosslinking agent can be used, but a compound having a hydroxyl value of 200 to 1800 mgKOH / g is preferably used.

Examples of the crosslinking agent having a hydroxyl value of 200 to 1800 mg KOH / g include alkanolamines such as diethanolamine and triethanolamine. Further, a polyoxyalkylene polyol having a hydroxyl value of 200 to 1800 mgKOH / g (for example, Actol KL-210 manufactured by Mitsui Chemicals Polyurethanes Co., Ltd .: polyoxyalkylene polyol having a functional group number of 3.75, OHV = 840 mgKOH / g) Can also be used as a crosslinking agent.
When using a crosslinking agent, in the polyol composition of the present invention, the crosslinking agent is preferably included in the range of 0.5 to 10 parts by mass with respect to 100 parts by mass of all the polyol components.

《Foaming agent》
When the intended use of the polyol composition of the present invention is a raw material for polyurethane foam, it is preferable to further contain a foaming agent. As the foaming agent, a physical foaming agent such as liquefied carbon dioxide can be used, but it is most preferable to use water.

  When water is used as the blowing agent, in the polyol composition of the present invention, water is preferably 1.3 to 6.0 parts by mass, more preferably 1.8 to 5 parts per 100 parts by mass of all polyol components. It is contained in a range of 2.0 parts by mass, particularly preferably 2.0 to 4.0 parts by mass. When the amount of water as the foaming agent is within the above range, foaming is performed stably and effectively.

  In addition, physical foaming agents such as hydroxyfluorocarbons (HFC-245fa, etc.), hydrocarbons (cyclopentane, etc.), carbon dioxide, liquefied carbon dioxide, etc., developed for the purpose of protecting the global environment, are used in combination with water. can do. Among these physical foaming agents, carbon dioxide and liquefied carbon dioxide are preferable from the viewpoint of reducing environmental burden.

<Foam stabilizer>
When the intended use of the polyol composition of the present invention is a raw material for polyurethane foam, it is preferable to further contain a foam stabilizer. As the foam stabilizer, a conventionally known foam stabilizer can be used, and it is usually preferable to use an organosilicon surfactant.

  As the organosilicon surfactant, FV-1013-16 (manufactured by Toray Dow Corning Silicone Co., Ltd.), SRX-274C, SF-2969, SF-2961, SF-2962, L-5309, L-3601 , L-5307, L-3600, L-5366, SZ-1325, SZ-1328, Y-10366 (manufactured by GE Toshiba Silicone Co., Ltd.), and the like.

  When a foam stabilizer is used, in the polyol composition of the present invention, the foam stabilizer is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts by mass with respect to 100 parts by mass of all the polyol components. Included in part range.

"Additive"
In addition to the above components, the polyol composition of the present invention is generally used for producing urethane resins such as polyurethane foams such as chain extenders, flame retardants, pigments, ultraviolet absorbers, antioxidants and antifoaming agents. You may mix | blend the additive used for in the range which does not impair the objective of this invention.

  Additives include Nobutaka Matsudaira and Tetsuro Maeda, “Polyurethane” 8th Printing Bookstore (1964), pages 134-137, Hitoshi Matsuo, Nobuaki Kunii, Kiyoshi Tanabe “Functional Polyurethane” 1st Printing CMC Co., Ltd. (1989) pages 54 to 68, and the like.

<< Preparation of polyol composition >>
In the polyol composition of the present invention, the polyester polyol is contained in an amount of preferably 15 to 80% by mass, more preferably 20 to 70% by mass, per 100% by mass of the composition. Further, the polyether polyol is preferably contained in the range of 10 to 80% by mass, more preferably 20 to 75% by mass per 100% by mass of the composition. When the content of these two kinds of polyols is in the above range, the compatibility effect by the compatibilizing agent is expressed well, and phase separation of the polyol composition can be prevented.

  Moreover, when using other polyol, per 100 mass% of the polyol composition of the present invention, the total polyol component is preferably 40 to 99 mass%, and more preferably 70 to 98 mass%. It is desirable to use other polyols.

  The polyol composition of the present invention comprises a polyester polyol, a polyether polyol and a compatibilizing agent and other polyols, which are optional components, a catalyst, a crosslinking agent, a foaming agent, a foam stabilizer, an additive, etc., in a predetermined composition ratio. It is prepared by mixing by a conventionally known method so that

[Polyurethane composition, polyurethane foam composition]
The composition for polyurethane or the composition for polyurethane foam of the present invention contains the above-described polyol composition and polyisocyanate. Furthermore, the composition for polyurethane or the composition for polyurethane foam of the present invention has the above-described other polyols, catalysts, crosslinking agents, and foaming agents depending on the purpose of use (for example, raw materials for urethane resins such as polyurethane foam). Further, it may contain a foam stabilizer, an additive and the like.

  The composition for polyurethane of the present invention may be a composition for obtaining a non-foaming polyurethane resin, but is a composition for obtaining a polyurethane foam that is a foaming polyurethane resin, that is, a composition for polyurethane foam. It is preferable that

  In particular, the polyurethane foam composition of the present invention is preferably a flexible polyurethane foam composition that is suitably used as a raw material for a flexible polyurethane foam having an appropriate resilience, elongation and molding.

<Polyisocyanate>
As the polyisocyanate, conventionally known ones used in the production of urethane resins can be used, and examples thereof include aromatic, aliphatic or alicyclic isocyanates having two or more isocyanate groups in one molecule. It is done.

  Examples of aromatic isocyanates include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, and isomer mixtures of these tolylene diisocyanates (for example, 2,4: 2,6 = 80: 20 (mass ratio). ) Mixture (TDI-80 / 20), 2,4: 2,6 = 65: 35 (mass ratio) mixture (TDI-65 / 35)), 4,4′-diphenylmethane diisocyanate (4,4 '-MDI), 2,4'-diphenylmethane diisocyanate (2,4'-MDI), 2,2'-diphenylmethane diisocyanate (2,2'-MDI), any isomeric mixture of diphenylmethane diisocyanate (MDI), polymeric MDI, toluylene diisocyanate, xylylene diisocyanate, paraphenylene diisocyanate, naphtha Such as emissions diisocyanate, and the like.

  Aliphatic isocyanates include ethylene diisocyanate, 1,4-butane diisocyanate, 1,6-hexane diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 2,2,4-trimethylhexane diisocyanate, lysine diisocyanate, and the like. Can be mentioned.

  Examples of the alicyclic isocyanate include isophorone diisocyanate, norbornane diisocyanate, dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, methylcyclohexylene diisocyanate, and the like.

  Furthermore, modified isocyanates such as urethane-modified products, biuret-modified products, allophanate-modified products, carbodiimide-modified products, and isocyanurate-modified products of the above polyisocyanates can also be used.

These polyisocyanates may be used alone or in combination of two or more.
It is preferable to use tolylene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI) as the polyisocyanate used for obtaining the polyurethane foam.

  As TDI, isomers can be used alone or as a mixture. That is, 2,4-tolylene diisocyanate (2,4-TDI) 100% product, isomer mixture of tolylene diisocyanate (for example, a mixture of 2,4: 2,6 = 80: 20 (mass ratio)) TDI-80 / 20), 2,4: 2,6 = 65: 35 (mass ratio) mixture (TDI-65 / 35)), and mixtures thereof, and further contains a multifunctional tar Crude TDI (for example, TDI-TRC manufactured by Mitsui Chemicals Polyurethane Co., Ltd.) can also be used.

  MDI includes 4,4′-diphenylmethane diisocyanate (4,4′-MDI) as a main component, and polymeric MDI containing trinuclear or higher polynuclear (for example, Cosmonate manufactured by Mitsui Chemical Polyurethane Co., Ltd.) Series) can be suitably used.

Moreover, as a polyisocyanate, the mixture (For example, Cosmonate TM-20 by Mitsui Chemicals Polyurethane Co., Ltd.) etc. can be used conveniently.
Also, polyisocyanates such as nurate-modified polyisocyanate, carbodiimide-modified polyisocyanate, prepolymer-modified polyisocyanate (a prepolymer having an isocyanate group at the molecular end obtained from polyisocyanate and the above-mentioned polyol), uretdione-modified polyisocyanate, etc. Polyisocyanate can also be used.

These polyisocyanates can be used singly or in combination of two or more.
The polyisocyanate used for obtaining the non-foaming type polyurethane resin is 4,4′-diphenylmethane diisocyanate (hereinafter also referred to as “4,4′-MDI”), dicyclohexylmethane diisocyanate (hydrogenated MDI: hereinafter “HMDI”). ), Paraphenylene diisocyanate (hereinafter also referred to as “PPDI”), naphthalene diisocyanate (hereinafter also referred to as “NDI”), hexamethylene diisocyanate (hereinafter also referred to as “HDI”), isophorone diisocyanate (hereinafter referred to as “IPDI”). ), Norbornane diisocyanate (hereinafter also referred to as “NBDI”), bis (isocyanatomethyl) cyclohexane, and urethane-modified, biuret-modified, and allophanate-modified products thereof are preferable; 4,4′-MDI, MDI, PPDI, organic diisocyanates such as NDI, and these urethane modified product, a biuret modified product, an allophanate modified product is particularly preferred.

  In the present invention, the NCO index is preferably 0.70 to 1.30, more preferably 0.80 to 1.20, still more preferably 0.90 to 1.10, and particularly preferably 0.94 to 1.08. It is desirable to mix the above-mentioned polyol composition, polyisocyanate, and optional components so that When the NCO index is within the above range, it is possible to obtain a polyurethane foam having a suitable hardness and mechanical strength as a cushioning material and also having a suitable impact resilience, elongation and moldability. The NCO index means a value obtained by dividing the total number of isocyanate groups in the polyisocyanate by the total number of active hydrogens that react with amino groups such as polyol hydroxyl groups, crosslinking agents, and isocyanate groups such as water. For example, when the number of active hydrogens that react with an isocyanate group and the isocyanate group in the polyisocyanate are stoichiometrically equal, the NCO index is 1.0.

<< Preparation of polyurethane composition and polyurethane foam composition >>
The polyurethane composition or polyurethane foam composition of the present invention comprises the above polyol composition, polyisocyanate, and other optional polyols, catalysts, crosslinking agents, foaming agents, foam stabilizers, additives, and the like. The mixture is prepared by a conventionally known method so as to obtain a predetermined composition ratio. The polyurethane foam composition of the present invention is particularly suitable as a composition for obtaining a flexible polyurethane foam, that is, a flexible polyurethane foam composition.

  Other polyols, catalysts, crosslinking agents, foaming agents, foam stabilizers, additives, and the like may be preliminarily blended with the polyol composition. For this reason, when these other components are newly blended, the content of these other components with respect to all the polyol components in the polyurethane composition or polyurethane foam composition is described in the [Polyol composition] column. The range should be within the range.

[Polyurethane (urethane resin)]
The polyurethane (urethane resin) of the present invention can be produced according to a conventionally known production method. Specifically, by preparing a resin premix composed of the above polyol composition, this resin premix, polyisocyanate and an optional component are mixed to obtain a composition for polyurethane, and the composition is reacted. A polyurethane can be obtained.

  As another method, an isocyanate group-terminated prepolymer obtained by reacting a part of a polyol composition with a polyisocyanate in advance is produced, and a polyurethane is obtained by reacting the prepolymer with the remaining polyol composition. it can. Alternatively, a polyurethane can be obtained by producing a hydroxyl group-terminated prepolymer obtained by reacting a polyol composition with a part of a polyisocyanate in advance, and reacting the prepolymer with the remaining polyisocyanate.

The polyurethane thus obtained can be pulverized and refined using a cutter, a pelletizer or the like, and then molded into a desired shape such as a pellet using an extruder or the like.
In the production of non-foaming polyurethane, it is preferable to sufficiently heat and dehydrate the polyol to reduce the water content. For example, the water content in the polyol composition or polyurethane composition is preferably 0.05% by mass or less, more preferably 0.03% by mass or less, and particularly preferably 0.02% by mass or less.

[Polyurethane foam]
The polyurethane foam of the present invention can be produced according to a conventionally known production method. Specifically, any of a slab foam method, a hot cure mold foam method, and a cold cure mold foam method can be adopted. When manufacturing a vehicle seat pad such as an automobile, the cold cure mold foam method is preferable.

  As a method for producing a polyurethane foam by the cold cure mold foam method, for example, after preparing a resin premix composed of the above polyol composition, the resin premix, the polyisocyanate and an optional component are mixed with a high pressure foaming machine or a low pressure foaming. Using a machine, mix to achieve a predetermined NCO index. Alternatively, the polyurethane foam composition prepared to have a predetermined NCO index is kneaded using a high-pressure foaming machine or a low-pressure foaming machine. This mixture or kneaded material is poured into a mold and reacted, foamed and cured to obtain a polyurethane foam having a fixed shape.

In particular, by using the composition for a flexible polyurethane foam of the present invention, a flexible polyurethane foam having an appropriate resilience, elongation and molding can be obtained.
The curing time is usually from 30 seconds to 30 minutes, the mold temperature is usually from about room temperature to about 80 ° C., and the curing temperature is preferably from about room temperature to about 150 ° C. You may heat hardened | cured material in the range of 80-180 degreeC in the range which is not impaired.

  The resin premix is usually mixed with polyisocyanate in a high-pressure foaming machine or a low-pressure foaming machine, but when a hydrolyzable compound such as an organic tin compound is used as a catalyst and the foaming agent is water, In order to avoid these contacts, it is preferable to inject water and the organotin compound into the foaming machine through different routes and mix them with the mixing head of the foaming machine. The viscosity of the resin premix to be used is preferably 3000 mPa · s or less from the viewpoints of mixing properties in a foaming machine, foam moldability, and the like.

  Thus, by using the polyol composition of the present invention having improved compatibility, a polyurethane foam excellent in mechanical properties such as hardness, elongation, tensile strength and tear strength can be obtained.

  The preferred range of these mechanical properties of polyurethane foam generally varies depending on its application, but the polyurethane foam of the present invention, particularly the flexible polyurethane foam, can be suitably used as a cushioning material for seat cushions, seat pads and the like. . In particular, the (soft) polyurethane foam of the present invention is preferably used for applications such as a vehicle seat cushion and a vehicle seat back that require high impact resilience.

For example, in a vehicle seat cushion application such as an automobile having a core density generally in the range of 40 to 75 kg / m ³ , the appropriate hardness range is 25% ILD, preferably 150 to 400 N / 314 cm ² , more preferably. Is 200 to 300 N / 314 cm ² .

  The elongation of the polyurethane foam of the present invention is preferably 50 to 200%, more preferably 60 to 150%; the tensile strength is preferably 60 to 300 kPa, more preferably 70 to 200 kPa; Is preferably 3.0 to 8.0 N / cm, more preferably 4.0 to 7.0 N / cm.

  These physical property values are measured under the conditions described in the following examples.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further in detail, this invention is not limited to these Examples. “Part” and “%” in the examples represent “part by mass” and “% by mass”, respectively. Analysis and measurement in Examples and Comparative Examples were performed according to the following methods.

(1) Core density (In Table 2, the core density is abbreviated as “D _CO ”.)
The measurement was performed in accordance with the apparent density measurement method described in JIS K-6400. In the present invention, the skin was removed from the polyurethane foam sample, a cuboid foam sample was prepared, and the core density was measured.

(2) Hardness of foam (In Table 2, the hardness of foam is abbreviated as “25% ILD”.)
Measurement was carried out in accordance with method A described in JIS K-6400. However, measurement was performed on a polyurethane foam having a thickness of 100 mm.

(3) Elongation rate Measurement was performed by the method described in JIS K-6400.
(4) Tensile strength Measurement was carried out by the method described in JIS K-6400 (1997).

(5) Tear strength Measurement was carried out by the method described in JIS K-6400 (1997).
(6) Compatibility The resin premixes obtained in Examples and Comparative Examples were transferred to test tubes, and the separation state after standing for 2 weeks in a horizontal place in a room where the room temperature was 23 ° C. was confirmed with the naked eye. . The state in which separation was not confirmed at all was evaluated as good compatibility (◯), and the case where separation was confirmed even a little was evaluated as poor compatibility (×).

(7) Hydroxyl value (OHV)
The measurement was carried out by the method described in JIS K-1557-1.
(8) Molecular weight The molecular weight of the compatibilizer was determined by substituting the hydroxyl value into the following formula.
Molecular weight = 56108 × (number of functional groups of compatibilizer) ÷ (hydroxyl value of compatibilizer)
The number of functional groups and hydroxyl value of the compatibilizer used in Examples and Comparative Examples are shown in Table 2.

(9) Acid value It measured by the method of JISK-1557-5.
(10) Viscosity (mPa · s / 25 ° C)
Using a conical plate type rotational viscometer (E type viscometer), the viscosity at 25 ° C. was measured.

(11) Purity Measurement of Castor Oil Fatty Acid The purity of castor oil fatty acid is determined based on the hydroxyl value A of castor oil fatty acid measured by the method of JIS K1557-1 and the acid value of castor oil fatty acid measured by the method of JIS K1557-5. The ratio B was obtained by the ratio A / B.

(12) Plant-derived component content The plant-derived component content was determined as the proportion of components derived from plants contained in the polyurethane foam. As an example, 60 parts of a polyester polyol obtained from a hydroxycarboxylic acid produced using a raw material obtained from a plant and a polyhydric alcohol derived from a plant, 40 parts of a polyether polyol not containing a component obtained from a plant When the resin is prepared using a total of 10 parts of a cross-linking agent, a catalyst, a foam stabilizer, etc. that do not contain components obtained from plants, and 40 parts of isocyanate that does not contain components obtained from plants, the plant-derived component content Is 40%.

<Purification of castor oil fatty acid>
(Purification Example 1)
A castor oil fatty acid obtained by hydrolyzing castor oil (manufactured by Ito Oil Co., Ltd .: trade name CO-FA, purity: 86%), a molecular distillation apparatus having an evaporation surface area of 0.03 m ² (Shibata) A high-purity castor oil fatty acid was obtained by removing hydroxyl-free components, which are low boiling components, using Kagaku Co., Ltd.). The evaporation conditions at this time were a charging speed of 200 g / h, an evaporation surface temperature of 160 ° C., a pressure of 15 Pa, and a wiper rotation speed of 300 rpm. The acid value of the high purity castor oil fatty acid obtained at that time was 180.7 mgKOH / g, and the hydroxyl value was 172.9 mgKOH / g. The purity of the high purity castor oil fatty acid (1) determined from these was 95.7%. there were. The high purity castor oil fatty acid (1) was confirmed to be ricinoleic acid.

<Synthesis of polyester polyol>
[Synthesis Example 1] Polyester polyol A-1
Purity 95.0% of high purity castor oil fatty acid (1) and castor oil fatty acid (made by Ito Oil Co., Ltd .: trade name CO-FA, purity (ricinoleic acid content): 86%) obtained in Purification Example 1 1944 g of high-purity castor oil fatty acid mixed in advance so as to be, 78 g of SOR-400 (manufactured by Mitsui Chemicals Polyurethanes Co., Ltd., polyol obtained by adding propylene oxide to sorbitol, hydroxyl value 400 mg KOH / g), PE-450 (Mitsui Chemical Polyurethane Co., Ltd., polyol obtained by adding propylene oxide to pentaerythritol, hydroxyl value 450 mgKOH / g) (above, average number of functional groups of polyhydric alcohol: 4.6), thermometer / stirring device / generated water Was charged into a 2 L glass flask equipped with a device for separating the water and subjected to a condensation reaction at 180 ° C. under a nitrogen stream. It was. When the acid value became 10 mgKOH / g or less, 0.2 g of tetrabutyl orthotitanate (reagent made by Tokyo Chemical Industry Co., Ltd.) was added as a catalyst, and then the condensation reaction was carried out at 180 ° C. to carry out the condensation reaction for 45 hours. . The obtained polyester polyol A-1 had a hydroxyl value (OHV) of 49.0 mgKOH / g, an average functional group number (calculated value) of 4.4, a viscosity of 4300 mPa · s / 25 ° C., and an HLB value of 2.622. It was.

<Synthesis of low monool polyol>
[Synthesis Example 2]: Polyether polyol (B-1)
After adding 0.01 mol of tetrakis [tris (dimethylamino) phosphoranylideneamino] phosphonium hydroxide to 1 mol of glycerin and dehydrating under reduced pressure at 100 ° C. for 6 hours, propylene oxide was reacted at a reaction temperature of 80 ° C. Addition polymerization was performed at a reaction pressure of 3.8 kg / cm ² . Next, ethylene polyol was subjected to addition polymerization at a reaction temperature of 100 ° C. and a maximum reaction pressure of 3.8 kg / cm ² to obtain a polyether polyol (B-1). This polyol (B-1) had a total unsaturation of 0.025 meq / g, a hydroxyl value of 24 mgKOH / g, a terminal oxyethylene group content of 15% by mass, and an HLB value of 5.50.

<Synthesis of polymer polyol>
[Synthesis Example 3]: Polymer polyol (PB-1)
A polyether polyol (B-1) having a hydroxyl value of 24 mgKOH / g obtained in Synthesis Example 2 is fully filled in a pressure-resistant autoclave equipped with a thermometer, a stirrer, a pressure gauge, and a liquid feeding device. The temperature was raised to 120 ° C. while stirring. A mixture of a polyether polyol (B-1), a radical polymerization initiator, acrylonitrile and a dispersion stabilizer was continuously charged into the mixture, and the reaction temperature was 120 ° C., the reaction pressure was 400 kPa, and the residence time was 50 minutes. After the initial polymerization was removed from the outlet, a reaction solution was continuously obtained. In addition, the usage-amount of a raw material is as follows.
Polyether polyol (B-1): 7200 g (total of the amount charged in the autoclave and the amount used in the mixture)
Radical polymerization initiator: 50 g
Acrylonitrile: 1800 g

Moreover, the following were used for the radical polymerization initiator.
Radical polymerization initiator: 2,2′-azobis (2-isobutyronitrile)
The obtained reaction liquid was subjected to a heating and decompression treatment for 3 hours under the conditions of 120 ° C. and 655 Pa or less to remove unreacted acrylonitrile and a decomposition product of a radical polymerization initiator, and a polymer polyol having a hydroxyl value of 19 mgKOH / g ( PB-1) was obtained. The vinyl polymer content of the polymer polyol (PB-1) is 20% by mass (the total amount of acrylonitrile used is 20% by mass with respect to the total amount of polyether polyol (B-1) and acrylonitrile used of 100% by mass). there were.

[Compatibilizer]
The compatibilizers used in the examples and comparative examples are shown in Table 1.

なお、相溶化剤の各物性は表２に示す。

The physical properties of the compatibilizer are shown in Table 2.

[Example 1]
58 parts of polyester polyol (A-1), 42 parts of polyether polyol (B-1), compatibilizer 1: 2 parts of compatibilizer A, foam stabilizer 2: FV-1013-16 (Toray Dow Corning) 0.7 parts, water: 2.3 parts, catalyst: 1.2 parts of R-9000 (manufactured by Active Materials Chemical Co., Ltd.), communication agent: Actol EP505S (Mitsui Chemical Polyurethane) Resin premix was prepared by mixing 2.5 parts of Co., Ltd. and 0.5 parts of a crosslinking agent: diethanolamine (manufactured by Nippon Shokubai Co., Ltd.). Table 2 shows the evaluation results regarding the compatibility of this resin premix.

  The above resin premix and 32 parts of polyisocyanate (trade name Cosmonate TM-20, manufactured by Mitsui Chemicals Polyurethanes Co., Ltd.) were mixed so that the NCO index was 1.00, and the internal dimensions were immediately adjusted to 60 ° C. in advance. The mixture was poured into a 300 mm × 300 mm × 100 mm mold, and the lid was closed and foamed. After proceeding the curing reaction for 8 minutes while keeping the mold at 60 ° C., the flexible polyurethane foam was taken out from the mold, and the physical properties (1) to (5) were measured. The measurement results are shown in Table 2.

[Examples 2 to 4, Comparative Examples 1 to 5]
In Example 1, a polyurethane foam was produced in the same manner as in Example 1 except that a resin premix was prepared with the composition shown in Table 2. Table 2 shows the measurement results of the above physical properties (1) to (5) of the polyurethane foam.

表２中、各成分は下記のとおり。
架橋剤：アクトコールＫＬ−２１０（三井化学ポリウレタン（株）製）
整泡剤１：Ｙ−１０３６６（ＧＥ東芝シリコーン（株）製）
整泡剤２：ＦＶ−１０１３−１６（東レ・ダウコーニング（株）製）
触媒：Ｒ−９０００（活材ケミカル（株）製）
連通化剤：アクトコールＥＰ５０５Ｓ（三井化学ポリウレタン（株）製）

In Table 2, each component is as follows.
Cross-linking agent: Actcol KL-210 (Mitsui Chemical Polyurethane Co., Ltd.)
Foam stabilizer 1: Y-10366 (GE Toshiba Silicone Co., Ltd.)
Foam stabilizer 2: FV-1013-16 (manufactured by Dow Corning Toray)
Catalyst: R-9000 (manufactured by Active Material Chemical Co., Ltd.)
Communication agent: Actcol EP505S (manufactured by Mitsui Chemicals Polyurethanes)

Claims (13)

A polyol composition containing a polyester polyol, a polyether polyol and a compatibilizer,
The compatibilizer is at least one compound selected from trimethylolpropane and a compound obtained by adding an alkylene oxide to trimethylolpropane;
A polyol composition comprising 0.1 to 10% by mass of the compatibilizer per 100% by mass of the composition.   2. The polyol composition according to claim 1, wherein the compatibilizing agent has a hydroxyl value of 400 to 1254 mg KOH / g.   The polyol composition according to claim 1 or 2, wherein the polyester polyol includes a polyester polyol obtained by condensation of a carboxylic acid and a polyhydric alcohol.   The said carboxylic acid contains C10-C22 carboxylic acid, The polyol composition of Claim 3 characterized by the above-mentioned.   The polyol composition according to claim 3 or 4, wherein the carboxylic acid contains a hydroxyl group-containing fatty acid.   The polyol composition according to claim 5, wherein the hydroxyl group-containing fatty acid contains castor oil fatty acid obtained from castor oil.   The polyol composition according to claim 6, wherein the castor oil fatty acid is 50 mol% or more in 100 mol% of the hydroxyl group-containing fatty acid.   The composition for polyurethanes containing the polyol composition and polyisocyanate as described in any one of Claims 1-7.   The composition for polyurethane foams containing the polyol composition and polyisocyanate as described in any one of Claims 1-7.   A polyurethane foam obtained by reacting the polyurethane foam composition according to claim 9.   The composition for flexible polyurethane foams containing the polyol composition and polyisocyanate as described in any one of Claims 1-7.   A flexible polyurethane foam obtained by reacting the composition for a flexible polyurethane foam according to claim 11.   A seat cushion comprising the flexible polyurethane foam according to claim 12.