JP5169752B2 - Method for producing flexible polyurethane foam - Google Patents

Description

  The present invention relates to a method for producing a flexible polyurethane foam using a polyol derived from castor oil.

Flexible polyurethane foams widely used in various applications such as heat insulating materials, automobile seats, furniture, cushions, etc., generally react polyols and polyisocyanates in the presence of urethanization catalysts, foaming agents, foam stabilizers, etc. Manufactured by.
Polyols used as a main raw material are generally derived from petroleum, and in recent years, when used urethane products are incinerated, there is a problem of increasing carbon dioxide in the atmosphere. Therefore, development of a flexible polyurethane foam that suppresses the increase in carbon dioxide in the atmosphere even after incineration is considered in consideration of global warming.

Examples of polyols replacing petroleum-derived polyols include vegetable oil-derived polyols. Since vegetable oil is a compound in which carbon dioxide in the air is fixed, even if a urethane product using a polyol derived from vegetable oil is incinerated, the amount of carbon dioxide in the natural world is substantially equivalent to the amount used. Does not increase. The following flexible polyurethane foams are shown as those using vegetable oil-derived polyols.
A flexible polyurethane obtained by reacting a polyisocyanate with a polyol comprising a polyhydric alcohol condensed with a vegetable oil-derived hydroxycarboxylic acid and a polyol containing a low monool polyol having a total unsaturation of 0.05 meq / g or less Form (Patent Document 1).
Moreover, there exists the following patent document about the manufacturing method of the polyol which made the caster oil condensed the hydroxycarboxylic acid derived from vegetable oil, and the curable composition using the same (patent document 2).
International Publication No. 07/020904 Pamphlet Japanese Patent No. 39449797

However, in Patent Document 1, it is necessary to use a low monool polyol having a total unsaturation degree of 0.05 meq / g or less in order to prevent deterioration of various physical properties such as a hysteresis loss rate of the obtained flexible polyurethane foam.
In order to obtain a polyol having a total unsaturation level of 0.05 meq / g or less, a double metal cyanide complex catalyst (DMC catalyst) or a cesium hydroxide catalyst must be used as a polymerization catalyst for ring-opening polymerization of alkylene oxide as an initiator. I must. These polymerization catalysts are more expensive than generally used potassium hydroxide catalysts.
On the other hand, the curable composition described in Patent Document 2 is a non-foamed material, and there is no description of the production method and characteristics of the flexible polyurethane foam.

  Thus, in order to produce a flexible polyurethane foam using a polyol derived from vegetable oil, it is necessary to highly control the total unsaturation of the polyol used together, and a corresponding burden must be imposed during production.

  The present invention provides, as a method for producing a flexible polyurethane foam, a method in which a polyol derived from castor oil, which is a vegetable oil, is used, and a flexible polyurethane foam excellent in various physical properties such as a hysteresis loss rate is obtained.

The method for producing a flexible polyurethane foam of the present invention comprises a polyol (A) and a polyol (B) comprising the following polyol (A1) and / or polyol (A2) in the presence of a urethanization catalyst, a foaming agent and a foam stabilizer. And a polyisocyanate compound (I) are reacted with each other.
Polyol (A1): castor oil and / or hydrogenated castor oil as initiator (a1-1), the condensation of the following hydroxycarboxylic acid (a1-2) and / or the following hydroxycarboxylic acid condensate (a1-3) Polyester polyol.
Hydroxycarboxylic acid (a1-2): at least one selected from the group consisting of castor oil fatty acid, hydrogenated castor oil fatty acid, ricinoleic acid, 12-hydroxystearic acid, 10-hydroxystearic acid and 9-hydroxystearic acid.
Hydroxycarboxylic acid condensate (a1-3): a condensate of the hydroxycarboxylic acid (a1-2).
Polyol (A2): A polyether ester polyol obtained by ring-opening polymerization of alkylene oxide (a2-2) using the polyol (A1) as an initiator (a2-1) in the presence of a polymerization catalyst.
Polyol (B): A polyol having a hydroxyl value of 10 to 100 mgKOH / g, obtained by ring-opening polymerization of alkylene oxide (b2) to an initiator (b1) having an average functional group number of 4 or more in the presence of a polymerization catalyst.

In the method for producing a flexible polyurethane foam of the present invention, the polyol (B) preferably has a total degree of unsaturation of 0.06 meq / g or more.
Moreover, it is preferable that content in the polyol composition (P) (100 mass%) of the said polyol (B) is 30 mass% or more.
Moreover, it is preferable that the polymerization catalyst used for manufacture of the said polyol (B) is a potassium hydroxide catalyst .
Moreover, it is preferable that the said polyol composition (P) contains a polymer dispersion | distribution polyol (C) further.

  According to the production method of the present invention, it is possible to produce a flexible polyurethane foam excellent in various physical properties such as a hysteresis loss rate by using a polyol derived from castor oil.

  The method for producing a flexible polyurethane foam of the present invention comprises a polyol composition (P) containing a polyol (A) and a polyol (B) in the presence of a urethanization catalyst, a foaming agent and a foam stabilizer, and a polyisocyanate compound (I). ) Is reacted.

<Polyol composition (P)>
[Polyol (A)]
The polyol (A) is a polyol composed of the following polyol (A1) and / or polyol (A2), and is a polyol derived from castor oil. Castor oil has ricinoleic acid glyceride as a main component, and the ricinoleic acid has one secondary hydroxyl group.

(Polyol (A1))
Polyol (A1) was obtained by condensing hydroxycarboxylic acid (a1-2) and / or hydroxycarboxylic acid condensate (a1-3) using castor oil and / or hydrogenated castor oil as initiator (a1-1). Polyester polyol.

Examples of castor oil used as the initiator (a1-1) include refined castor oil, semi-refined castor oil, and unrefined castor oil. Specific examples of castor oil include URIC • H-30 manufactured by Ito Oil, but are not limited thereto.
Moreover, the hydrogenated castor oil used as an initiator (a1-1) can use what added hydrogen to the said castor oil.

The hydroxycarboxylic acid (a1-2) to be condensed with the initiator (a1-1) is a fatty acid having one or more hydroxy groups in the molecule.
It is preferable that carbon number of hydroxycarboxylic acid (a1-2) is 14-25, and it is more preferable that it is 16-20.
When the carbon number of the hydroxycarboxylic acid (a1-2) is 14 or more, a flexible polyurethane foam having an appropriate cushion feeling is easily obtained. When the carbon number of the hydroxycarboxylic acid (a1-2) is 25 or less, the viscosity of the polyol does not become too high and handling is easy.

  Examples of the hydroxycarboxylic acid (a1-2) include saturated fatty acids such as 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, sabinic acid, 2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid; And unsaturated fatty acids such as ricinoleic acid; or hydrogenated products of these unsaturated fatty acids.

As the hydroxycarboxylic acid (a1-2), it is preferable to use a plant-derived hydroxycarboxylic acid from the viewpoint of improving the degree of biomass of the foam (the ratio of the portion derived from castor oil in the resulting flexible polyurethane foam).
Particularly preferred hydroxycarboxylic acids (a1-2) include castor oil fatty acid (fatty acid containing a small amount of oleic acid and linoleic acid in addition to ricinoleic acid), hydrogenated castor oil fatty acid (small amount of 12-hydroxystearic acid and Fatty acids containing stearic acid and palmitic acid).
Hydroxycarboxylic acid (a1-2) may be used alone or in combination of two or more.

The amount of the hydroxycarboxylic acid (a1-2) to be condensed with the initiator (a1-1) is preferably 1 to 30 mol with respect to 1 mol of the hydroxyl group of the initiator (a1-1), and 1 to 20 More preferably, it is a mole.
When the amount of the hydroxycarboxylic acid (a1-2) to be condensed is 1 mol or more, a flexible polyurethane foam having an appropriate cushion feeling is easily obtained. When the amount of the hydroxycarboxylic acid (a1-2) to be condensed is 30 mol or less, the viscosity of the polyol does not become too high and handling is easy.

As the hydroxycarboxylic acid condensate (a1-3) to be condensed with the initiator (a1-1), one obtained by condensing the hydroxycarboxylic acid (a1-2) can be used.
The hydroxycarboxylic acid condensate (a1-3) is preferably a 2-30 mer, and more preferably a 2-20 mer.
The amount of the hydroxycarboxylic acid condensate (a1-3) to be condensed with the initiator (a1-1) is preferably 1 to 15 mol with respect to 1 mol of the hydroxyl group of the initiator.
When the amount of the hydroxycarboxylic acid condensate (a1-3) to be condensed is 1 mol or more, a flexible polyurethane foam having an appropriate cushion feeling is easily obtained. When the amount of the hydroxycarboxylic acid condensate (a1-3) to be condensed is 15 mol or less, the viscosity of the polyol does not become too high and handling is easy.
As for the hydroxycarboxylic acid monomer which comprises a hydroxycarboxylic acid condensate (a1-3), only 1 type may be sufficient and 2 or more types may be sufficient.

The acid value of the polyol (A1) is preferably 0.001 to 3.0 mgKOH / g, and more preferably 0.001 to 1.0 mgKOH / g. When the acid value of the polyol (A1) is within the above range, it becomes easy to obtain a flexible polyurethane foam having a sufficient strength by keeping the amount of fatty acid not condensed in castor oil low.
Moreover, it is preferable that it is 10-100 mgKOH / g, and, as for the hydroxyl value of a polyol (A1), it is more preferable that it is 15-80 mgKOH / g.
When the hydroxyl value of the polyol (A1) is 10 mgKOH / g or more, the resulting flexible polyurethane foam has good physical properties. Moreover, if the hydroxyl value of a polyol (A1) is 100 mgKOH / g or less, the flexible polyurethane foam obtained will be excellent in a softness | flexibility.

The content of the polyol (A1) in the polyol composition (P) (100% by mass) is preferably 10 to 90% by mass, and more preferably 15 to 60% by mass.
If the content of the polyol (A1) is 10% by mass or more, the biomass degree of the foam is improved, which is preferable. Moreover, if content of a polyol (A1) is 90 mass% or less, it will be easy to maintain various physical properties of the flexible polyurethane foam obtained.

(Polyol (A2))
Polyol (A2) is a polyether ester polyol obtained by ring-opening polymerization of alkylene oxide (a2-2) using polyol (A1) as an initiator (a2-1) in the presence of a polymerization catalyst.
A polyol (A2) may be used individually by 1 type, and may use 2 or more types together.

Examples of the alkylene oxide (a2-2) include ethylene oxide, propylene oxide, butylene oxide, and the like. Of these, propylene oxide and ethylene oxide are preferable, and only propylene oxide or a combination of propylene oxide and ethylene oxide is particularly preferable.
When two or more kinds of alkylene oxides are used in combination, a block polymerization method and a random polymerization method may be used, and further, one kind of polyol can be produced by combining both the block polymerization method and the random polymerization method.

Examples of the polymerization catalyst for ring-opening polymerization of the alkylene oxide (a2-2) to the initiator (a2-1) include one or more selected from the group consisting of a coordination anionic polymerization catalyst and a cationic polymerization catalyst. A more preferred polymerization catalyst is a coordination anion polymerization catalyst.
(Coordination anionic polymerization catalyst)
A well-known thing can be used suitably for a coordination anion polymerization catalyst. In particular, a double metal cyanide complex catalyst having an organic ligand (hereinafter sometimes referred to as a DMC catalyst) is preferable.
Double metal cyanide complexes having an organic ligand are disclosed in known production methods (Japanese Unexamined Patent Publication Nos. 2003-165636, 2005-15786, 7-196778, and 2000-513647). And the like, etc.).

Examples of the method for producing the DMC catalyst include the following methods (α) to (γ).
(Α) An organic ligand is coordinated to a reaction product obtained by reacting a metal halide salt with an alkali metal cyanometalate in an aqueous solution, then the solid component is separated, and the separated solid component is organically separated. Further washing with an aqueous ligand solution.
(Β) A metal halide salt and an alkali metal cyanometalate are reacted in an organic ligand aqueous solution to separate the resulting reaction product (solid component), and the separated solid component is further added to the organic ligand aqueous solution. How to wash.
(Γ) In the method of (α) or (β), a cake (solid component) obtained by washing and filtering and separating the reaction product is treated with an organic compound containing 3% by mass or less of a polyether compound. A method of preparing a slurry-like DMC catalyst by redispersing in a ligand aqueous solution and then distilling off volatile components.

As the DMC catalyst, a slurry-like DMC catalyst obtained by the method (γ) is preferable because it can produce a polyoxyalkylene polyol (A2) having high activity and a narrow molecular weight distribution.
The polyether compound used in the method (γ) is preferably a polyether polyol or a polyether monool, and an alkali catalyst or a cationic catalyst is used, and an alkylene oxide is ring-opening polymerized to an initiator (polyhydric alcohol or monoalcohol). A polyether polyol or polyether monool having an average number of hydroxyl groups per molecule of 1 to 12 and a mass average molecular weight of 300 to 5000 is more preferred.

As the DMC catalyst, a zinc hexacyanocobaltate complex having an organic ligand is preferable.
Examples of the organic ligand include alcohols, ethers, ketones, esters, amines, amides, and the like. Specifically, tert-butyl alcohol, n-butyl alcohol, iso-butyl alcohol, tert-pentyl alcohol, iso- Examples include pentyl alcohol, N, N-dimethylacetamide, ethylene glycol mono-tert-butyl ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), triethylene glycol dimethyl ether (triglyme), iso-propyl alcohol, dioxane and the like.
Examples of dioxane include 1,4-dioxane or 1,3-dioxane, and 1,4-dioxane is preferable.
An organic ligand may be used individually by 1 type, and may be used in combination of 2 or more type.

  As the organic ligand, tert-butyl alcohol is preferred. Therefore, as the DMC catalyst, a double metal cyanide complex catalyst having tert-butyl alcohol as at least a part of the organic ligand is preferable. The DMC catalyst can produce a polyoxyalkylene polyol (A2) having high activity and low total unsaturation. Further, if a highly active DMC catalyst is used, the amount of the polymerization catalyst can be reduced, so that the polyether before purification has less polymerization catalyst, and therefore, the polymerization catalyst remaining in the purified polyol can be reduced.

(Cation polymerization catalyst)
Cationic polymerization catalysts include lead tetrachloride, tin tetrachloride, titanium tetrachloride, aluminum trichloride, zinc chloride, vanadium trichloride, antimony trichloride, metal acetylacetonate, phosphorus pentafluoride, antimony pentafluoride, trifluoride. Boron fluoride, Boron trifluoride coordination compound (Boron trifluoride diethyl etherate, Boron trifluoride dibutyl etherate, Boron trifluoride dioxanate, Boron trifluoride acetate anhydrate, Boron trifluoride triethylamine complex compound Etc.), inorganic acids (perchloric acid, acetyl perchlorate, tert-butyl perchlorate, etc.), organic acids (hydroxyacetic acid, trichloroacetic acid, trifluoroacetic acid, p-toluenesulfonic acid, trifluoromethanesulfonic acid, etc.) , Organic acid metal salts, complex salt compounds (triethyloxon Mutetrafluoroborate, triphenylmethylhexafluoroantimonate, allyldiazonium hexafluorophosphate, allyldiazonium tetrafluoroborate, etc.), alkyl metal salts (diethyl zinc, triethylaluminum, diethylaluminum chloride, etc.), heteropolyacid, isopolyacid And an aluminum or boron compound having at least one aromatic hydrocarbon group containing a fluorine element or an aromatic hydrocarbon oxy group containing a fluorine element.

Examples of the cationic polymerization catalyst include MoO ₂ (diketonate) Cl, MoO ₂ (diketonate) OSO ₂ CF ₃ , trifluoromethanesulfonic acid, boron trifluoride, boron trifluoride coordination compound (boron trifluoride diethyl etherate, three Boron fluoride dibutyl etherate, boron trifluoride dioxanate, boron trifluoride acetate anhydrate or boron trifluoride triethylamine complex)), or an aromatic hydrocarbon group containing fluorine element or fluorine element Aluminum or boron compounds having at least one aromatic hydrocarbon oxy group are preferred.

Examples of the aromatic hydrocarbon group containing fluorine element include pentafluorophenyl, tetrafluorophenyl, trifluorophenyl, 3,5-bis (trifluoromethyl) trifluorophenyl, and 3,5-bis (trifluoromethyl) phenyl. , Β-perfluoronaphthyl, 2,2 ′, 2 ″ -perfluorobiphenyl, and the like.
As the aromatic hydrocarbon oxy group containing a fluorine element, a hydrocarbon oxy group in which an oxygen element is bonded to the aromatic hydrocarbon group containing the fluorine element is preferable.

  As an aluminum or boron compound having at least one aromatic hydrocarbon group containing an elemental fluorine or aromatic hydrocarbon oxy group containing an elemental fluorine, JP-A No. 2000-344881, JP-A No. 2005-82732, Alternatively, a boron compound or an aluminum compound as a Lewis acid described in International Publication No. 03/000750 pamphlet, or a boron compound or an aluminum compound which is an onium salt described in JP-A No. 2003-501524 or JP-A No. 2003-510374 Is preferred.

Examples of Lewis acids include tris (pentafluorophenyl) borane, tris (pentafluorophenyl) aluminum, tris (pentafluorophenyloxy) borane, and tris (pentafluorophenyloxy) aluminum. (Pentafluorophenyl) borane is particularly preferred.
The counter cation of the onium salt is preferably a trityl cation or an anilinium cation.
As the onium salt, trityltetrakis (pentafluorophenyl) borate or N, N′-dimethylaniliniumtetrakis (pentafluorophenyl) borate is particularly preferable.

  As a usage-amount of a polymerization catalyst, it is preferable that it is 0.0005-3 mass% with respect to the polyol (A2) obtained, and it is more preferable that it is 0.002-0.5 mass%. When the amount of the polymerization catalyst used is within the above range, the reactivity with the alkylene oxide (a2-2) and the production cost are excellent.

The acid value of the polyol (A2) is preferably 0.001 to 0.5 mgKOH / g, and more preferably 0.001 to 0.1 mgKOH / g.
The hydroxyl value of the polyol (A2) is preferably 5 to 100 mgKOH / g, and more preferably 10 to 80 mgKOH / g. When the hydroxyl value of the polyol (A2) is 5 mgKOH / g or more, the physical properties of the resulting flexible polyurethane foam are good. Moreover, if the hydroxyl value of a polyol (A1) is 100 mgKOH / g or less, the flexible polyurethane foam obtained will be excellent in a softness | flexibility.

The content of the polyol (A2) in the polyol composition (P) (100% by mass) is preferably 10 to 90% by mass, and more preferably 15 to 60% by mass.
If the content of the polyol (A2) is 10% by mass or more, the biomass degree of the foam is improved, which is preferable. Moreover, if content of a polyol (A2) is 90 mass% or less, it will be easy to maintain various physical properties of the flexible polyurethane foam obtained.

  The polyol (A) is a polyol composed of the polyol (A1) and / or the polyol (A2), and the content of the polyol (A) in the polyol composition (P) (100% by mass) is 10 to 90. It is preferable to set it as the mass%, and it is more preferable to set it as 15-60 mass%.

[Polyol (B)]
In the production method of the present invention, the polyol composition (P) contains the following polyol (B). When the polyol composition (P) contains the polyol (B), the hysteresis loss rate of the obtained flexible polyurethane foam is lowered, and the durability is further improved.
Polyol (B) is a polyether polyol obtained by ring-opening polymerization of alkylene oxide (b2) to initiator (b1) in the presence of a polymerization catalyst.

The initiator (b1) is a compound having an average functional group number of 4 or more, and examples thereof include polyhydric alcohols, polyhydric phenols, and amines.
Examples of the polyhydric alcohols include diglycerin, pentaerythritol, and sorbitol.
Examples of the polyhydric phenols include 2,3,3 ′, 4-tetrahydroxybenzophenone, 2,2 ′, 3,4,4′-pentahydroxybenzophenone, 2,3,3 ′, 4,4 ′, And 5′-hexahydroxybenzophenone.
Examples of amines include ethylenediamine and diethylenetriamine.
As the initiator (b1), the aforementioned compounds may be used alone or in combination of two or more.

Examples of the alkylene oxide (b2) include ethylene oxide, propylene oxide, and butylene oxide. Of these, propylene oxide and ethylene oxide are preferable, and only propylene oxide or a combination of propylene oxide and ethylene oxide is particularly preferable.
The content of ethylene oxide is preferably 5 to 30% by mass and more preferably 7 to 25% by mass with respect to the total mass of the polyol (B). If content of ethylene oxide is 5 mass% or more, the curing property (curability) at the time of manufacture of a flexible polyurethane foam will become favorable, and productivity can be improved. On the other hand, if it is 30% by mass or less, the reaction at the time of foaming of the flexible polyurethane foam is easy to control without being too fast, and the foamability of the obtained flexible polyurethane foam is suppressed, and appropriate air permeability can be imparted. it can.
When two or more types of alkylene oxides are used in combination, either a block polymerization method or a random polymerization method may be used, and a single polyol can also be produced by combining both the block polymerization method and the random polymerization method.

  As the polymerization catalyst for ring-opening polymerization of the alkylene oxide (b2) to the initiator (b1), a known polymerization catalyst can be used. For example, an alkali metal compound catalyst or an alkaline earth metal compound catalyst such as potassium hydroxide, cesium hydroxide, cesium methoxide and the like can be mentioned. In the present invention, a potassium hydroxide catalyst can be preferably used. By using a potassium hydroxide catalyst, production costs can be reduced.

  The amount of the polymerization catalyst used is preferably 0.01 to 3% by mass and more preferably 0.1 to 1% by mass with respect to the resulting polyol (B). When the amount of the polymerization catalyst used is within the above range, the reactivity with the alkylene oxide (b2) and the production cost are excellent.

The average number of functional groups of the polyol (B) is 4 or more, preferably 4-8.
When the average number of functional groups of the polyol (B) is within the above range, it becomes easy to achieve both mechanical properties such as elasticity and hardness of the resulting flexible polyurethane foam.

The total unsaturation degree of a polyol (B) can use 0.06 meq / g or more. The total unsaturation degree of the polyol (B) is preferably 0.06 to 0.15 meq / g, and more preferably 0.06 to 0.10 meq / g.
However, the total degree of unsaturation is a monool having an unsaturated group at the terminal, which is produced as a by-product with an increase in the molecular weight of the polyether polyol when the initiator is subjected to ring-opening polymerization of alkylene oxide to obtain a polyether polyol. Is a value representing the content of. Since the monool is monofunctional, the average number of functional groups of the entire polyol is lowered, and various physical properties of the resulting flexible polyurethane foam are lowered.
However, in this invention, since a polyol (B) is used with a polyol (A), the total unsaturation degree of a polyol (B) can be 0.06 meq / g or more. If the total degree of unsaturation of the polyol (B) can be 0.06 meq / g or more, it is preferable in that it is not necessary to use an expensive cesium hydroxide or phosphazene catalyst as a polymerization catalyst.

  Particularly preferred polyol (B) is that the resulting flexible polyurethane foam has a low hysteresis loss rate and is excellent in durability of the flexible polyurethane foam, so that propylene oxide and ethylene oxide are added to the initiator (b1) having an average functional group number of 4 or more. The polyol is ring-opening polymerized in this order.

The hydroxyl value of the polyol (B) is 10 to 100 mgKOH / g, preferably 15 to 80 mgKOH / g, and more preferably 20 to 60 mgKOH / g. When the hydroxyl value is 10 mgKOH / g or more, the viscosity of the polyol does not become too high and handling is easy. When the hydroxyl value is 100 mgKOH / g or less, a flexible polyurethane foam having an appropriate cushion feeling can be obtained.
One type of polyol B may be used, or two or more types may be used in combination.

The content of the polyol (B) in the polyol composition (P) (100% by mass) is preferably 10 to 90% by mass, more preferably 30 to 70% by mass, and 35 to 60% by mass. More preferably.
When the content of the polyol (B) is within the above range, various physical properties such as a hysteresis loss rate of the obtained flexible polyurethane foam are improved.

[Polymer-dispersed polyol (C)]
The polyol composition (P) of the present invention may contain the following polymer-dispersed polyol (C) in addition to the polyol (A) and the polyol (B). However, the polymer-dispersed polyol means a dispersion system in which polymer fine particles (dispersoid) are stably dispersed in a base polyol (dispersion medium).
When the polyol composition (P) contains the polymer-dispersed polyol (C), it is effective for improving the physical properties of the resulting flexible polyurethane foam, such as increased hardness and air permeability.

  The polymer fine particles are preferably dispersed in the polyol composition (P). Specifically, the polymer dispersed polyol (C) in which the polymer particles are dispersed in the polyol (C ′) (base polyol). It is preferable to prepare and contain the polymer-dispersed polyol (C) in the polyol composition (P).

The polyol (C ′) may be any polyol that can stably disperse the polymer fine particles, and generally available polyols and the like can be used.
The polymer-dispersed polyol (C) may be a polymer-dispersed polyol using the polyol (A1), the polyol (A2), or the polyol (B) as the polyol (C ′).

Examples of the polymer that can be used as the polymer fine particles include addition polymerization polymers and condensation polymerization polymers.
Examples of the addition polymerization polymer include polymers obtained by homopolymerizing or copolymerizing monomers such as acrylonitrile, styrene, methacrylic acid ester, acrylic acid ester, and vinyl acetate.
Examples of the polycondensation polymer include polyester, polyurea, polyurethane, and polymethylol melamine.

Examples of the method for preparing the polymer-dispersed polyol (C) include the following two methods.
(1) A method of directly depositing polymer particles by polymerizing a monomer having a polymerizable unsaturated bond, for example, acrylonitrile, methyl methacrylate, vinyl acetate, etc. in the polyol (C ′) in the presence of a solvent as necessary. .
(2) In the presence of a grafting agent that stabilizes the particles as necessary, a monomer having a polymerizable unsaturated bond is polymerized in a solvent to precipitate polymer fine particles, and then a polyol (C ′), a solvent, To obtain a stable dispersion.
In the present invention, it is preferable to prepare the polymer-dispersed polyol (C) by the method (1).

The content of the polymer fine particles in the polymer-dispersed polyol (C) (100% by mass) may be any as long as the effect of improving the physical properties is obtained, and is preferably 5 to 60% by mass, and more preferably 10 to 55% by mass. % Is more preferable.
Various physical properties (unsaturation, hydroxyl value, etc.) of the polymer-dispersed polyol as a polyol are considered for the base polyol excluding the polymer fine particles.

[Polyol (D)]
The polyol composition (P) of the present invention may contain a polyol (D) together with the polyol (A), the polyol (B), and the polymer-dispersed polyol (C).
The polyol (D) is a polyol other than the polyol (A) and the polyol (B).

Examples of the polyol (D) include polyether polyol, polyester polyol, polycarbonate polyol, and acrylic polyol.
The polyol (D) is a polyether polyol obtained by ring-opening polymerization of the alkylene oxide (d2) to the initiator (d1) and having an average functional group number of 2 to 3 and a hydroxyl value of 10 to 100 mgKOH / g. preferable.

The polyether polyol initiator (d1) is preferably a compound having an average number of functional groups of 2 to 3, and examples thereof include polyhydric alcohols, polyhydric phenols, and amines.
Examples of the polyhydric alcohols include ethylene glycol, propylene glycol, 1,4-butanediol, diethylene glycol, dipropylene glycol, glycerin, and trimethylolpropane.
Examples of the polyhydric phenols include bisphenol A.
Examples of amines include monoethanolamine, diethanolamine, triethanolamine, and piperazine.

Examples of the alkylene oxide (d2) include ethylene oxide, propylene oxide, butylene oxide, and the like. Of these, propylene oxide and ethylene oxide are preferable, and only propylene oxide or a combination of propylene oxide and ethylene oxide is particularly preferable.
When two or more kinds of alkylene oxides are used in combination, a block polymerization method and a random polymerization method may be used, and further, one kind of polyol can be produced by combining both the block polymerization method and the random polymerization method.

  The content of the polyol (D) in the polyol composition (P) is preferably 40% by mass or less, and preferably 35% by mass or less with respect to the entire polyol composition (P) (100% by mass). More preferred.

  Specific examples of suitable compositions of the polyol composition (P) of the present invention include 0 to 90 parts by weight of polyol (A1), 0 to 90 parts by weight of polyol (A2), and 10 to 90 parts by weight of polyol (B). Parts, a polyol composition (P) containing 0 to 60 parts by mass of the polymer-dispersed polyol (C) and 0 to 40 parts by mass of the polyol (D) (however, the polyol (A1), the polyol (A2), and the polyol) The total of (B) is 100 parts by mass.)

<Polyisocyanate compound (I)>
Examples of the polyisocyanate compound (I) include aromatic, alicyclic, and aliphatic polyisocyanates having two or more isocyanate groups; mixtures of two or more of the above polyisocyanates; The modified polyisocyanate obtained is mentioned.

  Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HMDI), and the like. These polyisocyanates, or their prepolymer-type modified products, nurate-modified products, urea-modified products, and carbodiimide-modified products.

As the polyisocyanate compound (I), TDI, MDI, crude MDI, or a modified product thereof is preferably used, and a modified product of crude MDI is preferably used. Especially, it is more preferable to use TDI, crude MDI, or this modified body (especially a prepolymer type modified body is preferable) from the point which the foaming stability and durability of the flexible polyurethane foam obtained improve.
Polyisocyanate compound (I) may be used alone or in combination of two or more.

  The amount of the polyisocyanate compound (I) used is preferably 80 to 130, more preferably 85 to 125 in terms of isocyanate index (INDEX). However, the isocyanate index is represented by multiplying the numerical value obtained by dividing the number of isocyanate groups by 100 with the total number of active hydrogens of the polyol composition (P) and other active hydrogen compounds.

<Urethane catalyst>
The reaction between the polyol composition (P) and the polyisocyanate composition (I) is performed in the presence of a urethanization catalyst. A urethanization catalyst is a catalyst which accelerates | stimulates a urethanation reaction, for example, a metal catalyst and an amine catalyst are mentioned.

  Examples of the metal catalyst include carboxylic acid metal salts such as potassium acetate, potassium 2-ethylhexanoate and tin 2-ethylhexanoate; tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, And organic metal compounds such as dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate.

Examples of the amine catalyst include triethylamine, tripropylamine, polyisopropanolamine, tributylamine, trioctylamine, hexamethyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, diethylenetriamine, N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetramethylpropylenediamine, N, N, N ′, N′-tetramethylbutanediamine, N, N, N ′, N′— Tetramethyl-1,3-butanediamine, N, N, N ′, N′-tetramethylhexamethylenediamine, bis [2- (N, N-dimethylamino) ethyl] ether, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N, N ′, N′-pentamethyldiethyl Tertiary amines such as N-triamine and triethylenediamine; organic and inorganic salts of the above compounds; oxyalkylene adducts of amino groups of primary and secondary amines; azacyclic compounds such as N, N-dialkylpiperazines; N, N ′, N ″ -trialkylaminoalkylhexahydrotriazines may be mentioned.
The said metal catalyst and amine catalyst may be used individually by 1 type, and may use 2 or more types together.

The amount of the metal catalyst used as the urethanization catalyst is preferably 0.001 to 2.0 parts by mass, and 0.002 to 1.5 parts by mass with respect to 100 parts by mass of the polyol composition (P). Is more preferable.
The amount of the amine catalyst used as the urethanization catalyst is preferably 0.01 to 2.0 parts by mass, and 0.05 to 1.5 parts by mass with respect to 100 parts by mass of the polyol composition (I). Is more preferable.

<Foaming agent>
Examples of the foaming agent include known foaming agents such as water, inert gas, and fluorinated hydrocarbon. Of these, water is preferably used.
Examples of the inert gas include air, nitrogen, and carbon dioxide gas.
When water is used as the foaming agent, the amount of the foaming agent used is preferably 10 parts by mass or less with respect to 100 parts by mass of the polyol composition (P), and 0.1 to 8.0 parts by mass It is preferable to do this.

<Foam stabilizer>
In the production method of the present invention, good bubbles can be formed by using a foam stabilizer.
Examples of the foam stabilizer include silicone foam stabilizers and fluorine foam stabilizers. The amount of the foam stabilizer used can be appropriately selected, and is preferably 0.1 to 10 parts by mass with respect to 100 parts by mass of the polyol composition (P).

<Other ingredients>
In the production method of the present invention, a crosslinking agent may be used as necessary.
As the crosslinking agent, a compound having an average functional group number of 2 to 8 and a hydroxyl value of 150 to 2000 mgKOH / g is preferable. Moreover, as a crosslinking agent, the compound which has 2 or more of functional groups selected from the group which consists of a hydroxyl group, a primary amino group, and a secondary amino group is mentioned.
A crosslinking agent may be used individually by 1 type, and may use 2 or more types together.

As the crosslinking agent having a hydroxyl group, a compound having 2 to 8 hydroxyl groups is preferable. A polyhydric alcohol, a low molecular weight polyoxyalkylene polyol obtained by ring-opening polymerization of an alkylene oxide with a polyhydric alcohol, a tertiary amino group, The polyol which has is mentioned.
Specific examples of the crosslinking agent having a hydroxyl group include ethylene glycol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, diethylene glycol, triethylene glycol, dipropylene glycol, monoethanolamine, diethanolamine, and triethanol. Amine, glycerin, N-alkyldiethanol, bisphenol A-alkylene oxide adduct, glycerin-alkylene oxide adduct, trimethylolpropane-alkylene oxide adduct, pentaerythritol-alkylene oxide adduct, sorbitol-alkylene oxide adduct, sucrose -Alkylene oxide adduct, aliphatic amine-alkylene oxide adduct, alicyclic amine-alkylene oxide adduct, heterocyclic polyamine-a Alkylene oxide adducts, aromatic amines - alkylene oxide adduct and the like, from the viewpoint of the hysteresis loss ratio and excellent low diethanolamine are preferable.

  Heterocyclic polyamine-alkylene oxide adducts include piperazine, short-chain alkyl-substituted piperazine (2-methylpiperazine, 2-ethylpiperazine, 2-butylpiperazine, 2-hexylpiperazine, 2,5-, 2,6-, 2, 3- or 2,2-dimethylpiperazine, 2,3,5,6- or 2,2,5,5-tetramethylpiperazine, etc.), aminoalkyl-substituted piperazine (1- (2-aminoethyl) piperazine, etc.). ) And the like are obtained by ring-opening polymerization of alkylene oxide.

  Examples of the crosslinking agent (amine-based crosslinking agent) having a primary amino group or a secondary amino group include aromatic polyamines, aliphatic polyamines, and alicyclic polyamines.

As the aromatic polyamine, an aromatic diamine is preferable. The aromatic diamine is preferably an aromatic diamine having one or more substituents selected from an alkyl group, a cycloalkyl group, an alkoxy group, an alkylthio group, and an electron-withdrawing group in the aromatic nucleus to which the amino group is bonded. Diaminobenzene derivatives are particularly preferred.
The substituent other than the electron-withdrawing group is preferably bonded to 2 to 4 aromatic nuclei to which the amino group is bonded, and is bonded to one or more of the ortho positions with respect to the binding site of the amino group. It is more preferable that it is bonded to all.
It is preferable that one or two electron-withdrawing groups are bonded to the aromatic nucleus to which the amino group is bonded. An electron-withdrawing group and another substituent may be bonded to one aromatic nucleus.
The number of carbon atoms of the alkyl group, alkoxy group, and alkylthio group is preferably 4 or less.
As the cycloalkyl group, a cyclohexyl group is preferable.
As the electron withdrawing group, a halogen atom, a trihalomethyl group, a nitro group, a cyano group, and an alkoxycarbonyl group are preferable, and a chlorine atom, a trifluoromethyl group, and a nitro group are particularly preferable.

Aliphatic polyamines include diaminoalkanes having 6 or less carbon atoms, polyalkylene polyamines, polyamines obtained by converting some or all of the hydroxyl groups of low molecular weight polyoxyalkylene polyols to amino groups, and two or more aminoalkyl groups. An aromatic compound etc. are mentioned.
Examples of the alicyclic polyamine include cycloalkanes having two or more amino groups and / or aminoalkyl groups.

  Specific examples of the amine-based crosslinking agent include 3,5-diethyl-2,4 (or 2,6) -diaminotoluene (DETDA), 2-chloro-p-phenylenediamine (CPA), 3,5-dimethylthio- 2,4 (or 2,6) -diaminotoluene, 1-trifluoromethyl-3,5-diaminobenzene, 1-trifluoromethyl-4-chloro-3,5-diaminobenzene, 2,4-toluenediamine, 2,6-toluenediamine, bis (3,5-dimethyl-4-aminophenyl) methane, 4,4-diaminodiphenylmethane, ethylenediamine, m-xylenediamine, 1,4-diaminohexane, 1,3-bis (amino) Methyl) cyclohexane, isophoronediamine and the like, and diethyltoluenediamine [that is, 3,5-diethyl-2, (Or 2,6) - one or more mixture of diaminotoluene, dimethylthiotoluenediamine, monochlorodisilane aminobenzene, diaminobenzene derivative such as trifluoromethyl-diaminobenzene are preferred.

  It is preferable that the usage-amount of a crosslinking agent shall be 0.1-10 mass parts with respect to 100 mass parts of polyol compositions (P).

Moreover, you may use a chain extender as needed.
The chain extender is a compound having two functional groups capable of reacting with an isocyanate group, preferably having a molecular weight of 500 or less, more preferably 300 or less. The functional group is preferably a hydroxy group, a primary or secondary amino group.
Examples of chain extenders include dihydric alcohols such as ethylene glycol, propylene glycol, 1,4-butanediol, 1,5-pentanediol, and 1,6-hexanediol, ethanolamine, aminopropyl alcohol, and 3-amino. Cyclohexyl alcohol, amino alcohols such as p-aminobenzyl alcohol, ethylenediamine, 1,2-propylenediamine 1,4-butylenediamine, 2,3-butylenediamine, hexamethylenediamine, cyclohexanediamine, piperazine, xylylenediamine, Diamines such as tolylenediamine, phenylenediamine, diphenylmethanediamine, 3,3′-dichlorodiphenylmethanediamine, hydrazine, monoalkylhydrazine, 1,4-dihydrazinodiethylene, etc. And hydrazines, carbohydrazides, dihydrazides such as adipic acid hydrazide, and the like. Of these, dihydric alcohols are preferred.
A chain extender may be used individually by 1 type, and may use 2 or more types together.

Moreover, you may use a communication agent as needed.
As the communicating agent, a polyoxyalkylene polyol having an average number of functional groups of 2 to 8, a hydroxyl value of 20 to 100 mgKOH / g, and an oxyethylene group content in the oxyalkylene group of 25 to 100% by mass is preferable.

In the production method of the present invention, the following additives may be used.
Additives include, for example, fillers such as potassium carbonate and barium sulfate; surfactants such as emulsifiers; anti-aging agents such as antioxidants and ultraviolet absorbers; Agents, colorants, antifungal agents, foam breakers, dispersants, anti-discoloring agents.

<Manufacturing method>
Examples of the method for producing the flexible polyurethane foam of the present invention include a method of foam-molding the raw material in a sealed mold (molding method) and a method of foaming the raw material in an open system (slab method).

[Mold method]
Examples of the molding method include a method of directly injecting a raw material into a sealed mold (reaction injection molding method), and a method of sealing after injecting a raw material into an open mold, and the latter method is preferable. As the latter method, a method of injecting the reactive mixture into the mold using a low pressure foaming machine or a high pressure foaming machine is preferable.
As the high-pressure foaming machine, a type in which two liquids are mixed is preferable. Of the two liquids, one liquid is preferably polyisocyanate compound (I), and the other liquid is preferably a mixture of all components other than polyisocyanate compound (I) (polyol system liquid). Depending on the case, it is good also as a type which mixes 3 liquid which makes a urethanization catalyst another component.

The temperature of the raw material is preferably 10 to 40 ° C. If this temperature is 10 degreeC or more, the viscosity of a raw material will not become high too much and the mixability of a liquid will become favorable. If this temperature is 40 degrees C or less, the reactivity will not become quick too much and a moldability etc. will become favorable.
The mold temperature is preferably 10 to 80 ° C, particularly preferably 30 to 70 ° C.
The curing time is preferably 1 to 20 minutes, more preferably 1 to 10 minutes, and particularly preferably 1 to 7 minutes. If the curing time is 1 minute or longer, the curing is sufficiently performed. If the curing time is 20 minutes or less, the productivity will be good.

[Slab method]
Examples of the slab method include known methods such as a one-shot method, a semi-prepolymer method, and a prepolymer method. A known production apparatus can be used for producing the flexible polyurethane foam.

In the production method of the present invention described above, a polyol (A) derived from castor oil, which is a vegetable oil, is used, and a flexible polyurethane foam having excellent physical properties such as a hysteresis loss rate can be obtained. This reason is considered to be because the polyol (B) having an average functional group number of 4 or more is used in combination with the polyol (A).
Moreover, in the manufacturing method of this invention, the polyol whose total unsaturation is 0.06 meq / g or more can be used together. This reason is considered to be because the polyol (A) derived from castor oil used in the present invention can sufficiently function as a trifunctional polyol.

That is, if the average number of functional groups of the polyol used for the production of the flexible polyurethane foam is small, the crosslinked structure of the resulting flexible polyurethane foam becomes insufficient, and various physical properties such as hysteresis loss rate, hardness, and durability are lowered. Therefore, in order to produce a flexible polyurethane foam, it is necessary to consider that the average functional group number of the polyol does not become too low. For example, when a polyol obtained by condensing a hydroxycarboxylic acid and / or a hydroxycarboxylic acid condensate is used with glycerin, which is a polyhydric alcohol, as an initiator, it is used in combination in order to prevent deterioration of various physical properties of the resulting flexible polyurethane foam. It is necessary to control the total unsaturation of the polyol to 0.05 meq / g or less.
This is because when glycerin is used as an initiator, a condensation reaction at the tertiary hydroxyl group site of glycerin hardly occurs due to steric hindrance or the like, and a polyol in which the condensation reaction occurs only at the primary hydroxyl group site is obtained. The polyol is considered to be a bifunctional polyol substantially because the reactivity of the tertiary hydroxyl group is very low even in the reaction with polyisocyanate. Therefore, it is necessary to use a low monool polyol having a total unsaturation level of 0.05 meq / g or less so that the polyol used in combination does not lower the average number of functional groups of the whole polyol.

On the other hand, it was confirmed by NMR analysis that the polyol (A) of the present invention had a completely different structure from the polyol using glycerin as an initiator.
The polyol (A) of the present invention is a polyol using castor oil and / or hydrogenated castor oil as an initiator. Castor oil is mainly composed of ricinoleic acid glyceride, and all the hydroxyl groups of castor oil are hydroxyl groups of ricinoleic acid, which is a fatty acid. That is, castor oil does not have a hydroxyl group with low reactivity due to steric hindrance or the like, and all hydroxyl groups exhibit sufficient reactivity.
Therefore, polyol (A1) obtained by condensing hydroxylcarboxylic acid (a1-2) and / or hydroxycarboxylic acid condensate (a1-3) using castor oil and / or hydrogenated castor oil as initiator (a1-1) A polyol (A2) obtained by ring-opening polymerization of an alkylene oxide (a2-2) using the polyol (A1) as an initiator (a2-1) is a trifunctional trifunctional group having a hydroxyl group exhibiting sufficient reactivity. It becomes a polyol.
Therefore, in this invention which manufactures a flexible polyurethane foam using a polyol (A), even if it uses together the polyol whose total unsaturation is 0.06 meq / g or more, the flexible polyurethane foam excellent in various physical properties is obtained.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by these description. However, “part” in Examples and Comparative Examples indicates “part by mass”.
The raw materials used in the examples and comparative examples are as follows.

[Polyol composition (P)]
(Polyol (A))
Polyol A1-1: Purified castor oil (930 parts, hydroxyl group) was added to a 3 L four-necked separable flask (hereinafter referred to as a reactor) equipped with a stirrer, thermometer, Dean stack trap with cooling pipe, and nitrogen gas introduction pipe. 162.5 mg KOH / g, acid value 0.6 mg KOH / g), condensed castor oil fatty acid (1200 parts, average tetramer), and stannous octylate (0.5 parts) were charged, and the produced water was Dean Stack. While discharging from the reaction apparatus with a trap, the reaction was carried out at 200 ° C. for 12 hours to obtain polyol A1-1.
The obtained polyol A1-1 had an acid value of 0.4 mgKOH / g and a hydroxyl value of 56 mgKOH / g.

Polyol A1-2: Purified castor oil (930 parts, hydroxyl value 162.5 mgKOH / g, acid value 0.6 mgKOH / g), castor oil fatty acid (1200 parts), and stannous octylate (0. 5 parts) was charged, and the reaction was carried out at 200 ° C. for 12 hours while discharging the produced water from the reactor by a Dean stack trap to obtain polyol A1-2.
The obtained polyol A1-2 had an acid value of 0.3 mgKOH / g and a hydroxyl value of 63 mgKOH / g.

Example of preparation of slurry catalyst (DMC-TBA catalyst):
Using a zinc hexacyanocobaltate complex coordinated with tert-butyl alcohol (DMC catalyst) as a polymerization catalyst, a slurry catalyst (DMC-TBA catalyst) in which the DMC catalyst and the following polyol X are mixed is prepared by the following method. did. The concentration (active component concentration) of the DMC catalyst (solid catalyst component) contained in the slurry catalyst was 5.33% by mass.
Polyol X: Polyoxypropylene diol having a hydroxyl group equivalent of 501 obtained by ring-opening polymerization of propylene oxide with propylene glycol using a KOH catalyst, and dealkal purification.

[Production of slurry catalyst]
A zinc chloride aqueous solution consisting of zinc chloride (10.2 g) and water (10 g) is placed in a 500 mL flask, and potassium hexacyanocobaltate (K ₃ Co (CN) ₆ ) (4.2 g) and water are added to the zinc chloride aqueous solution. An aqueous solution composed of (75 g) was added dropwise over 30 minutes while stirring at 300 rpm (number of rotations / minute). During this time, the mixed solution in the flask was kept at 40 ° C. After completion of the dropwise addition, the mixed solution in the flask was further stirred for 30 minutes, and then a mixture of tert-butyl alcohol (hereinafter referred to as TBA) (80 g), water (80 g), and polyol X (0.6 g) was added. The mixture was added and stirred at 40 ° C. for 30 minutes and further at 60 ° C. for 60 minutes.
Subsequently, the obtained mixture was filtered under pressure (0.25 MPa) using a circular filter plate having a diameter of 125 mm and a quantitative filter paper for fine particles (No. 5C manufactured by ADVANTEC Co., Ltd.) to obtain a composite metal cyanide complex. The containing solid (cake) was isolated.
Next, the cake containing the obtained double metal cyanide complex was transferred to a flask, a mixture of TBA (36 g) and water (84 g) was added and stirred for 30 minutes, and then pressure filtration was performed under the same conditions as above to obtain a cake. Got. Thereafter, the obtained cake was transferred to a flask, and a mixture of TBA (108 g) and water (12 g) was further added and stirred for 30 minutes to obtain a liquid (slurry) in which the DMC catalyst was dispersed in the TBA-water mixed solvent. It was. After adding and mixing polyol X (120 g) to the slurry, volatile components were distilled off under reduced pressure at 80 ° C. for 3 hours and further at 115 ° C. for 3 hours to obtain a slurry catalyst (DMC-TBA catalyst). .

Polyol A2-1: The polyol A1-1 was used as an initiator, and a polyol A2-1 was produced using the slurry catalyst.
That is, a stainless steel 500 ml pressure-resistant reactor equipped with a stirrer was used as a reactor, and the polyol A1-1 (250.5 g) and the slurry catalyst (682 mg, 36 mg as a solid catalyst component) were charged into the reactor. After the atmosphere in the reactor was replaced with nitrogen, the temperature was raised to 120 ° C. and vacuum dehydration was performed for 2 hours. Thereafter, a mixed liquid of propylene oxide (hereinafter referred to as PO) (20.1 g) and ethylene oxide (hereinafter referred to as EO) (4.8 g) was supplied into the reactor over 40 minutes, Stirring was continued for 2 hours and 30 minutes, and it was confirmed that pressure drop disappeared to obtain polyol A2-1. During this time, the reaction was allowed to proceed while maintaining the internal temperature of the reactor at 120 ° C. and the stirring speed at 500 rpm.
The appearance of the obtained polyol A2-1 was a transparent liquid at room temperature. Polyol A2-1 had an acid value of 0.28 mgKOH / g and a hydroxyl value of 51 mgKOH / g.

Polyol A2-2: Synthesis of the polyol A2-1 except that the polyol A1-2 (248.3 g) as the initiator and PO (19.8 g) and EO (4.5 g) as the alkylene oxide were used. Polyol A2-2 was obtained in the same manner.
The obtained polyol A2-2 had an acid value of 0.19 mgKOH / g and a hydroxyl value of 57 mgKOH / g.

(Polyol (B))
Polyol B1: An average number of functional groups of 4, obtained by ring-opening polymerization of PO and EO in this order using pentaerythritol as an initiator under a potassium hydroxide catalyst, a hydroxyl value of 28 mgKOH / g, and a total unsaturation of 0.06 meq / G polyoxypropyleneoxyethylene polyol. The mass ratio of EO to the total mass of PO and EO used for ring-opening polymerization is 13% by mass.

(Polymer-dispersed polyol (C))
Polymer-dispersed polyol C1: Polyoxypropyleneoxyethylene polyol having an average number of functional groups of 3 and a hydroxyl value of 34 mgKOH / g by ring-opening polymerization of PO and EO in this order using glycerol as an initiator under a potassium hydroxide catalyst ( Polyol C1 ′) was obtained. The mass ratio of EO to the total mass of PO and EO used for ring-opening polymerization is 14.5 mass%.
Subsequently, acrylonitrile (27 parts) and styrene (8 parts) were copolymerized in the polyol C1 ′ (65 parts) to obtain a polymer-dispersed polyol C1 having a hydroxyl value of 24 mgKOH / g and a fine particle polymer amount of 35%. . As the polymerization initiator, azobismethylbutyronitrile (AMBN) (0.8 parts) was used.

(Other polyols)
Polyol A'1: A reactor is charged with glycerin (92 parts), condensed castor oil fatty acid (1800 parts, average hexamer), and stannous octylate (0.5 parts), and the generated water is Dean stack trap. The polyol A′1 was obtained by reacting at 200 ° C. for 12 hours while discharging from the reactor.
The obtained polyol A′1 had an acid value of 0.5 mgKOH / g and a hydroxyl value of 63 mgKOH / g.
Polyol B′1: The average number of functional groups is 3, the hydroxyl value is 28 mgKOH / g, and the total unsaturation degree is 0. 0, obtained by ring-opening polymerization of PO and EO in this order using glycerol as an initiator under a potassium hydroxide catalyst. 06 meq / g polyoxypropyleneoxyethylene polyol. The mass ratio of EO to the total mass of PO and EO used in the ring-opening polymerization is 17% by mass.

[Polyisocyanate Compound (I)]
Polyisocyanate I1: Mixture of TDI-80 and Crude MDI in a mass ratio of 80/20 (trade name: Coronate 1021, manufactured by Nippon Polyurethane Industry Co., Ltd.)

[Urethane catalyst]
Urethane catalyst M1: 33% dipropylene glycol solution of triethylenediamine (trade name: TEDA L33, manufactured by Tosoh Corporation)
Urethane catalyst M2: 70% dipropylene glycol solution of bis- (2-dimethylaminomethyl) ether (trade name: TOYOCAT ET, manufactured by Tosoh Corporation)

[Foaming agent]
Foaming agent: water

[Foam stabilizer]
Foam stabilizer S1: Silicone foam stabilizer (trade name: SZ-1325, manufactured by Toray Dow Corning)
Foam stabilizer S2: Silicone foam stabilizer (trade name: SZ-1327, manufactured by Toray Dow Corning)

[Combination agent]
(Communicating agent)
Communication agent G1: Polyoxypropylene oxyethylene polyol having an average number of functional groups of 3, a hydroxyl value of 48 mg KOH / g, and an oxyethylene group content of 80% by mass in the oxyalkylene group.

(Crosslinking agent)
Crosslinker H1: Diethanolamine

Hereinafter, examples and comparative examples will be described.
[Example 1]
Polyol A1-1 (21 parts), Polyol B1 (39 parts), Polymer-dispersed polyol C1 (40 parts), Urethane catalyst M1 (0.6 parts), Urethane catalyst M2 (0.07 parts), Water (2 0.5 part), foam stabilizer S1 (0.4 part), foam stabilizer S2 (0.4 part), communicating agent G1 (1 part), and crosslinking agent H1 (0.5 part) A polyol system liquid was prepared and the liquid temperature was adjusted to 30 ± 1 ° C. Further, the amount of polyisocyanate I1 corresponding to INDEX100 was weighed and the liquid temperature was adjusted to 25 ± 1 ° C.
Next, the polyisocyanate I1 was added to the polyol system liquid (isocyanate index 100), stirred for 5 seconds with a mixer (3000 rpm), and immediately poured into a mold heated to 60 ° C. and sealed. As the mold, an aluminum mold having an inner dimension of 400 mm in length and width and 100 mm in height was used.
Next, after curing at 60 ° C. for 6 minutes, the flexible polyurethane foam obtained from the mold was taken out, crushed, and left in the room (temperature 23 ° C., relative humidity 50%) for 24 hours. Was measured.

[Examples 2 to 8]
A flexible polyurethane foam was obtained in the same manner as in Example 1 except that the composition of the polyol system liquid and the polyisocyanate I1 was changed as shown in Table 1, and each physical property value was measured.

[Comparative Examples 1-5]
A flexible polyurethane foam was obtained in the same manner as in Example 1 except that the composition of the polyol system liquid and the polyisocyanate I1 was changed as shown in Table 1, and each physical property value was measured.

[Evaluation of the physical properties]
(Density, hardness, breathability, impact resilience, tear strength, tensile strength, compression set, hysteresis loss rate)
About the flexible polyurethane foam obtained in Examples 1-8 and Comparative Examples 1-5, the density of the whole, the density of a core part, 25% hardness (25% ILD hardness), 50% hardness (50% ILD hardness) , 65% hardness (65% ILD hardness), core breathability, overall impact resilience, core impact resilience, tear strength, tensile strength, elongation, dry heat compression set, wet heat compression set, and hysteresis The loss rate was measured according to JIS K6400 (1997 edition).
However, the density of the core part, the breathability of the core part, and the rebound resilience of the core part were evaluated by using a sample at the center part cut out in a dimension of 100 mm in length and width and 50 mm in height after removing the skin part from the foam.

(Vibration characteristics)
For the vibration characteristics, resonance frequency (Hz), resonance magnification (absolute displacement measurement), transmission rate of 6 Hz, and transmission rate of 10 Hz were evaluated. The measurement was performed according to JASO B407-87. As a measurement condition of the vibration characteristics, a Tekken type (490N) was used as a pressure plate, and the total amplitude of vibration was 5 mm.
The results of physical property evaluation are shown in Table 2.

As shown in Table 2, when compared with a flexible polyurethane foam having a foam biomass degree of 15%, Examples 1 and 3 have a lower hysteresis loss rate (excellent in foam durability) than Comparative Example 1, and Various physical properties such as hardness, air permeability and impact resilience were also excellent. Moreover, Examples 1 and 3 are good in low wet heat compression set, dry heat compression set, and hysteresis loss rate as compared with Comparative Examples 3-5. In addition, Examples 4 to 8 also had low hysteresis loss ratios and excellent physical properties as compared with Comparative Examples 1 and 3 to 5.
Further, when compared with a flexible polyurethane foam having a foam biomass degree of 20%, Examples 2 and 4 have a better hysteresis loss rate than Comparative Example 2, and various physical properties such as hardness, air permeability and rebound resilience. Was also excellent.

  The method for producing a flexible polyurethane foam according to the present invention uses a castor oil-derived polyol (A) to obtain a flexible polyurethane foam having excellent physical properties. Therefore, it can utilize suitably as a manufacturing method of various flexible polyurethane foams, such as a heat insulating material, a motor vehicle seat, furniture, and a cushion.

Claims (5)

A polyol composition (P) comprising a polyol (A) and a polyol (B) comprising the polyol (A1) and / or the polyol (A2) shown below in the presence of a urethanization catalyst, a foaming agent and a foam stabilizer; A method for producing a flexible polyurethane foam, comprising reacting a polyisocyanate compound (I).
Polyol (A1): castor oil and / or hydrogenated castor oil as initiator (a1-1), the condensation of the following hydroxycarboxylic acid (a1-2) and / or the following hydroxycarboxylic acid condensate (a1-3) Polyester polyol.
Hydroxycarboxylic acid (a1-2): at least one selected from the group consisting of castor oil fatty acid, hydrogenated castor oil fatty acid, ricinoleic acid, 12-hydroxystearic acid, 10-hydroxystearic acid and 9-hydroxystearic acid.
Hydroxycarboxylic acid condensate (a1-3): a condensate of the hydroxycarboxylic acid (a1-2).
Polyol (A2): A polyether ester polyol obtained by ring-opening polymerization of alkylene oxide (a2-2) using the polyol (A1) as an initiator (a2-1) in the presence of a polymerization catalyst.
Polyol (B): A polyol having a hydroxyl value of 10 to 100 mgKOH / g, obtained by ring-opening polymerization of alkylene oxide (b2) to an initiator (b1) having an average functional group number of 4 or more in the presence of a polymerization catalyst.   The manufacturing method of the flexible polyurethane foam of Claim 1 whose total unsaturation of the said polyol (B) is 0.06 meq / g or more.   The manufacturing method of the flexible polyurethane foam of Claim 1 or 2 whose content in the polyol composition (P) (100 mass%) of the said polyol (B) is 30 mass% or more. The manufacturing method of the flexible polyurethane foam as described in any one of Claims 1-3 whose polymerization catalyst used for manufacture of the said polyol (B) is a potassium hydroxide catalyst. The method for producing a flexible polyurethane foam according to any one of claims 1 to 4 , wherein the polyol composition (P) further contains a polymer-dispersed polyol (C).