JP2008019353A - Method of manufacturing polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane foam which exhibits excellent moldability and shows a small compression set and wet heat set, and a method of manufacturing the same. <P>SOLUTION: The method of manufacturing the polyurethane foam comprises reacting a polyol component (A) containing a caster oil polyol (a1) having a terminal hydroxy group of a tertiary or secondary hydroxy group and a hydroxyl value of 20-350, which is prepared by adding a caster oil or a derivative thereof with a 2-4C alkylene oxide, and a polyol (a2) other than the caster oil polyol with an isocyanate compound (B). The polyurethane foam, which is obtained by the method, has a compression set at a core portion measured on the basis of JIS K 6400-4 of not greater than 20%, and has a value found by dividing the compression set by the wet heat set measured on the basis of JIS K 6400-4 of not less than 1. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for producing a polyurethane foam, and a polyurethane foam obtained by the production method.

  Currently, technological development efforts are being carried out on a global scale with the aim of preventing global warming and building a recycling-oriented society. Carbon dioxide is one of the gases that cause the global warming, and there is a need to reduce the amount of carbon dioxide emitted.

  For example, many of the polyurethane foams currently used are made from petroleum-derived materials. Therefore, when the production amount of the polyurethane foam increases, the amount of carbon dioxide generated during the incineration process at the time of disposal increases, thereby increasing the amount of carbon dioxide stored in water, plants, etc. The balance with the amount of carbon may be lost, and this may cause a gradual increase in the amount of carbon dioxide in the entire atmosphere.

Therefore, as a polyol which is a raw material component of polyurethane foam, aerated soybean oil (see Patent Document 1) or castor oil (see Patent Document 2) which is a plant-derived raw material instead of the petroleum-derived material. Attempts have been made to produce polyurethane foams. However, when the polyurethane foam described in Patent Document 1 or 2 is used for, for example, a vehicle seat such as an automobile seat that requires high comfort and safety, the foam physical properties prevent heat aging and aging. There is a drawback that it is insufficient to exhibit durability.
JP-T-2002-524627 JP 2005-320437 A

  The present invention has been made in view of the drawbacks of the prior art, and in one aspect, the present invention can provide a polyurethane foam that exhibits excellent moldability and has a low compression set and a low wet heat set. One object is to provide a method for producing a polyurethane foam, which can achieve at least one of being able to be easily produced. In another aspect, another object of the present invention is to provide a polyurethane foam that exhibits excellent moldability and exhibits small compression set and wet heat set.

That is, the gist of the present invention is as follows.
[1] A castor oil polyol (a1), which is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to castor oil or a derivative thereof, a terminal hydroxyl group is a secondary or tertiary hydroxyl group, and a hydroxyl value of 20 to 350 And a polyol component (A) containing a polyol (a2) other than the castor oil polyol,
An isocyanate compound (B);
A process for producing a polyurethane foam, characterized in that
[2] Production of polyurethane foam according to [1] above, wherein the polyol (a2) other than the castor oil polyol is a polyol having an average functional group number of 2.0 to 6.0 and a hydroxyl value of 20 to 800. Method,
[3] The polyol component (A) comprises a castor oil polyol (a1) and a polyol (a2) other than the castor oil polyol in a weight ratio of 10/90 to 70/30 [(a1) / (a2 )]], The polyurethane foam production method according to [1] or [2], and [4] the production method according to any one of [1] to [3]. It is obtained
The compression set in the core measured in accordance with JIS K 6400-4 is 20% or less, and the value of the compression set is measured in accordance with JIS K 6400-4. Polyurethane foam whose value divided by 1 is 1 or more,
About.

  According to the method for producing a polyurethane foam of the present invention, it is possible to provide a polyurethane foam that exhibits excellent moldability and has a small compression set and a low wet heat permanent strain, and that the polyurethane foam can be produced easily. There is an excellent effect that one can be achieved. Moreover, according to the polyurethane foam of this invention, there exists the outstanding effect that the outstanding moldability was expressed and the small compression set and wet heat permanent set were shown. Therefore, according to the polyurethane foam of the present invention, there is an excellent effect that it can be widely used in applications that require durability against moisture and heat, such as furniture, automobile seats, and headrests.

In one aspect, the present invention is a compound in which a C2-C4 alkylene oxide is added to castor oil or a derivative thereof, the terminal hydroxyl group is a secondary or tertiary hydroxyl group, and the hydroxyl value is 20 to 350. A polyol component (A) containing a certain castor oil polyol (a1) and a polyol (a2) other than the castor oil polyol;
An isocyanate compound (B);
It is related with the manufacturing method of the polyurethane foam characterized by making these react.

  The method for producing a polyurethane foam according to the present invention is characterized in that the polyol used for producing the polyurethane foam contains the castor oil polyol (a1). Therefore, according to the production method of the present invention, for example, an excellent effect that the load on the environment represented by an increase in the amount of carbon dioxide in the atmosphere can be reduced is exhibited. In addition, according to the production method of the present invention, an excellent effect that a polyurethane foam exhibiting excellent durability can be formed is exhibited.

  In addition, the production method of the present invention is characterized in that the polyol used for the production of polyurethane foam contains the castor oil polyol (a1) and a polyol (a2) other than the castor oil polyol. is there. Therefore, according to the manufacturing method of this invention, the outstanding effect that a polyurethane foam can be formed favorable is exhibited.

  The castor oil polyol (a1) is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to castor oil or a derivative thereof.

  The castor oil only needs to contain 75% by weight or more of ricinoleic acid having a hydroxyl group. In the present invention, a derivative of the castor oil (castor oil generally distributed in the market) can also be used. As the castor oil derivative, for example, the castor oil (castor oil generally marketed) is publicly known such as oxidative polymerization, transesterification by reaction with a polyhydric alcohol (for example, polyalkylene glycol). Examples thereof include derivatives containing hydroxy fatty acids obtained by derivatization by a technique. In the present invention, it is desirable to use castor oil generally distributed in the market as it is without processing from the viewpoint of easy availability and low cost.

  The alkylene oxide is preferably a compound having 2 to 4 carbon atoms from the viewpoint of increasing the reactivity of the polyol and easily obtaining a foam with good moldability. Although it does not specifically limit as said alkylene oxide, For example, ethylene oxide, propylene oxide, butylene oxide, tetramethylene oxide (tetrahydrofuran) etc. are mentioned. In the present invention, the alkylene oxide may be added to castor oil or a derivative thereof alone or in combination of two or more. Further, the addition form of the alkylene oxide to castor oil or a derivative thereof may be any of random addition, block addition, and mixed addition thereof.

  In the castor oil polyol (a1), the terminal hydroxyl group is preferably a secondary or tertiary hydroxyl group from the viewpoint of reducing wet heat permanent strain. As described above, in the castor oil polyol (a1), when the terminal hydroxyl group is a secondary or tertiary hydroxyl group, the ratio of oxyethylene groups in the castor oil polyol (a1) is reduced, and the obtained polyurethane is obtained. It exhibits an excellent effect that the wet heat permanent set of the foam can be reduced.

  The castor oil polyol (a1) has a hydroxyl value of 20 or more, preferably 25 or more, from the viewpoint of appropriately maintaining the ratio of natural fats and oils (castor oil) or derivatives thereof in the foam. From the viewpoint of maintaining a good degree of crosslinking and obtaining a foam having a low permanent set, it is 350 or less, preferably 300 or less.

  In the polyol (a2), the average number of functional groups is preferably 2.0 or more, more preferably 2.3 or more, from the viewpoint of reducing the compression residual strain of the obtained polyurethane foam. From the viewpoint of exhibiting sufficient elongation, it is preferably 6.0 or less.

  In the polyol (a2), the hydroxyl value is preferably 20 or more, more preferably 25 or more, from the viewpoint of exhibiting sufficient mechanical strength for the obtained polyurethane foam, and is sufficient for the obtained polyurethane foam. From the viewpoints of exhibiting mechanical strength and reducing the isocyanate content in the obtained polyurethane foam, it is preferably 800 or less, and more preferably 750 or less. The hydroxyl value can be measured based on, for example, JIS K 0070.

  The polyol (a2) may be a mixture of two or more. In this case, the average number of functional groups may be an average value of 2.0 to 6.0 as the whole mixture. Moreover, the hydroxyl value should just be an average value 20-800 as the whole mixture.

  Although it does not specifically limit as said polyol (a2), For example, polyester polyol, polycarbonate polyol, polyether polyol, polymer polyol, these copolyols, these arbitrary 2 or more types of mixtures, etc. are mentioned. Of these, polyether polyols and polymer polyols are preferable from the viewpoint of obtaining a foam having a lower permanent set at low cost.

  The polyester polyol is not particularly limited. For example, at least one selected from the group consisting of a polycarboxylic acid, an acid ester thereof, and an acid anhydride thereof, a low molecular alcohol compound, a low molecular amine compound, and a low molecular amino compound. Examples thereof include polyester polyols and polyester amide polyols obtained by dehydration condensation with at least one selected from the group consisting of alcohol compounds. The polycarboxylic acid is not particularly limited. For example, succinic acid, adipic acid, sebacic acid, azelaic acid, terephthalic acid, isophthalic acid, orthophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, hexahydroorthophthalic acid , Naphthalenedicarboxylic acid, trimellitic acid and the like. Moreover, the low molecular alcohol compound is not particularly limited, and examples thereof include ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, neopentyl glycol, 1,8-octanediol, 1,9-nonanediol, diethylene glycol, Examples include dipropylene glycol, 1,4-cyclohexanedimethanol, ethylene oxide adduct of bisphenol A, propylene oxide adduct of bisphenol A, trimethylolpropane, glycerin, pentaerythritol and the like. Although it does not specifically limit as said low molecular amine compound, For example, hexamethylenediamine, xylylenediamine, isophoronediamine etc. are mentioned. Although it does not specifically limit as said low molecular amino alcohol compound, For example, a monoethanolamine, a diethanolamine, etc. are mentioned. The polyester polyol can be obtained, for example, by ring-opening polymerization of a cyclic ester (lactone) monomer such as ε-caprolactone or γ-valerolactone using the low molecular alcohol compound, low molecular amino alcohol compound or the like as an initiator. Lactone polyester polyols are also included.

  The polycarbonate polyol is not particularly limited. For example, a dehydrochlorination reaction between the low molecular alcohol compound and phosgene, or an ester of the low molecular alcohol compound with diethylene carbonate, dimethyl carbonate, diethyl carbonate, diphenyl carbonate, or the like. Examples thereof include those obtained by exchange reaction.

  The polyether polyol is not particularly limited. For example, the low molecular alcohol compound, the low molecular amine compound, the low molecular amino alcohol compound, the phenol compound, or the like is used as an initiator, and ethylene oxide, propylene oxide, tetramethylene oxide. Polyoxyethylene polyol, polyoxypropylene polyol, polytetramethylene ether polyol, polyoxyethylene polyoxypropylene polyol obtained by ring-opening polymerization of alkylene oxide, etc .; dehydrating condensation of the polyester polyol, polycarbonate polyol, etc. Polyester ether polyol obtained etc. are mentioned. Among the polyether polyols, ethylene oxide, propylene oxide or butylene oxide is preferably used from the viewpoint of exhibiting good reactivity and exhibiting good moldability in a polyurethane foam obtained using the polyether polyol. The polyether polyol obtained in this way is desirable. The polyether polyol obtained using ethylene oxide, propylene oxide, or butylene oxide may be any of a random polymer, a block polymer, and a polymer in which random polymerization and block polymerization are mixed.

  The polymer polyol is, for example, a method of polymerizing an ethylenically unsaturated monomer in a polyether polyol, a method of mixing polymer fine particles with a polyether polyol, a macromonomer having an ethylenically unsaturated group, and an ethylenically unsaturated monomer. And the like in a polyether polyol. Although it does not specifically limit as said ethylenically unsaturated monomer, For example, styrene, acrylonitrile, etc. are mentioned. Among the polymer polyols, a compound obtained by polymerizing an ethylenically unsaturated monomer in a polyether polyol is preferable. In particular, the polymer polyol is preferably a compound obtained by polymerizing an ethylenically unsaturated monomer in polyoxypropylene triol. When polymer polyol is produced by mixing polymer fine particles with polyether polyol, the viscosity of the resulting polymer polyol is reduced, and the workability during molding of polyurethane foam obtained using the polymer polyol is improved. In view of the above, preferably, the content of the polymer fine particles is 50% by weight or less.

  In the polyol component (A), the compounding ratio (weight ratio) of the castor oil polyol (a1) and the polyol (a2) allows the resulting polyurethane foam to exhibit good rebound resilience and lowers compression set. From the viewpoint of shortening the curing time and improving productivity during the production of polyurethane foam, 10/90 or more, preferably 15/85 or more, more preferably 20/80 or more, 70/30 or less, Preferably, it is 60/40 or less, more preferably 50/50 or less.

  The isocyanate compound (B) is not particularly limited. For example, toluene diisocyanate, diphenyl diisocyanate, polymethylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, naphthalene diisocyanate, xylylene diisocyanate, tolylene diisocyanate, triphenylmethane tri Isocyanate compounds such as isocyanate. In the production method of the present invention, the isocyanate compound (B) may be a modified product of the isocyanate compound as long as the object of the present invention is not impaired. The modified product of the isocyanate compound is not particularly limited. For example, a dimerized modified product, a trimerized modified product, a urea modified product, or a carbodiimide modified product modified with a polyhydric alcohol such as polyether polyol or trimethylolpropane. Such as things. These isocyanate compounds may be used alone or in combination of two or more. Among these, from the viewpoint of expressing good moldability in the obtained polyurethane foam, preferably, toluene diisocyanate alone, diphenylmethane diisocyanate alone, or a combination of toluene diisocyanate and diphenylmethane diisocyanate, and a modified product of the diphenylmethane diisocyanate by polyether polyol. From the viewpoint of exhibiting good moldability and impact resilience in the resulting polyurethane foam, a modified product of the diphenylmethane diisocyanate with a polyether polyol is more desirable.

  In the production method of the present invention, the polyol component (A) and the isocyanate compound (B) have an isocyanate index of at least 90, preferably 90 or more from the viewpoint of reducing the wet heat permanent distortion of the resulting polyurethane foam. From the viewpoint of exhibiting good rebound resilience in the obtained polyurethane foam, it is desirable that the blending is performed so that it is 150 or less, more preferably 120 or less.

  In the production method of the present invention, the polyurethane foam can be formed by a method such as a slab method, a one-shot method, a semi-premer method, or a prepolymer method. Specifically, a polyurethane foam mix | blends a polyol component (A) and an isocyanate compound (B), for example so that it may become the said isocyanate index, mixes, and injects a reactive mixture in a metal mold | die. , Reaction, foaming, curing, and molding (molding method).

  Examples of the foaming agent used for forming the polyurethane foam include water, hydrogen atom-containing halogenated hydrocarbons, methylene chloride, low-boiling hydrocarbons, and liquefied carbon dioxide. Such foaming agents may be used alone or in combination of two or more. Although it does not specifically limit as said hydrogen atom containing halogenated hydrocarbon, For example, HFC-134a, HFC-152a, HFC356mff, HFC236ea, HFC-245ca, HFCHFC365-mfc etc., for example, etc. Is mentioned. Moreover, examples of the low boiling point hydrocarbon include hydrocarbons having a boiling point of −5 to 70 ° C., and examples thereof include butane, pentane, cyclopentane, and mixtures thereof. Among these, water is particularly preferable from the viewpoint of a low global warming potential and a low influence on the global environment.

  In the production method of the present invention, a catalyst, a foam stabilizer, a crosslinking agent and the like may be blended as necessary.

  The catalyst is not particularly limited as long as it is a compound usually used in the production of urethane resins, and examples thereof include tertiary amines, diazabicycloalkene compounds, salts thereof, and organometallic compounds. The tertiary amine is not particularly limited. For example, triethylenediamine, triethylamine, tri-n-butylamine, bis (2-dimethylaminoethyl) ether, N, N, N ′, N′-tetramethylhexamethylene Examples thereof include diamine and 1,2-dimethylimidazole. Although it does not specifically limit as said organometallic compound, Metal salts of metals, such as zinc, tin, lead, zirconium, bismuth, cobalt, manganese, iron, and organic acids, such as octenoic acid and naphthenic acid; dibutyltin dilaurate, dioctyl Examples thereof include metal chelate compounds such as tin dilaurate, dibutyltin diacetylacetonate, zirconium tetraacetylacetonate, titanium acetylacetonate, acetylacetone aluminum, acetylacetone cobalt, acetylacetone iron, acetylacetone copper, and acetylacetone zinc. The said catalyst may be used independently and may mix and use 2 or more types. In addition, the usage-amount of the said catalyst should just be 0.1-10 weight part with respect to 100 weight part of polyol components (A), and can be adjusted suitably.

  The foam stabilizer is not particularly limited as long as it is usually used for producing a polyurethane resin, and examples thereof include a polyalkylsiloxane-polyoxyalkylene block copolymer. The said foam stabilizer may be used independently and may be used in mixture of 2 or more types. The amount of the foam stabilizer used is 5 parts by weight or less with respect to 100 parts by weight of the polyol component (A) from the viewpoint of obtaining a foam that exhibits good foamability and does not substantially cause shrinkage. Preferably, it is 3 parts by weight or less.

  Although it does not specifically limit as said crosslinking agent, For example, the low molecular active hydrogen compound of molecular weight less than 500, such as the low molecular alcohol compound used for the synthesis | combination of the above-mentioned polyester polyol, a low molecular amine compound, a low molecular amino alcohol compound, etc. Is mentioned. The said crosslinking agent may be used independently and may mix and use 2 or more types. From the viewpoint of reducing the compression set of the resulting polyurethane foam, the crosslinking agent is 10 parts by weight or less, preferably 5 parts by weight or less, based on 100 parts by weight of the polyol component (A).

  In the production method of the present invention, in addition to the above-mentioned foaming agent, catalyst, foam stabilizer, and crosslinking agent, any desired additive may be used as long as it does not impair the object of the present invention. Examples of the additive include, but are not limited to, fillers such as potassium carbonate and barium sulfate; surfactants such as emulsifiers and foam stabilizers; antioxidants such as antioxidants and ultraviolet absorbers; flame retardants; , Colorants, antifungal agents, deodorants, foam breakers, dispersants, anti-discoloring agents, plasticizers, solvents, film-forming aids, dispersants, fragrances and the like.

  According to the production method of the present invention, the amount of castor oil polyol which is a plant-derived raw material is remarkably high. Therefore, according to the production method of the present invention, the load on the environment is remarkably less than that of the prior art, and the moldability and curing properties are good. In particular, the compression residual strain and the wet heat residual strain are small, and the permanent strain And a polyurethane foam having a small difference between heat and heat permanent set.

  In another aspect of the present invention, the compression set in the core part obtained by the production method of the present invention and measured according to JIS K 6400-4 is 20% or less, and the value of the compression set It is related with the polyurethane foam whose value divided by the value of the wet heat permanent strain measured based on JIS K 6400-4 is one or more.

  Since the polyurethane foam of the present invention is obtained by the production method of the present invention, it exhibits excellent properties such as excellent moldability and low compression set and wet heat set.

  EXAMPLES Hereinafter, although an Example etc. demonstrate this invention in detail, this invention is not limited by this Example.

(Experimental example 1)
Castor oil (Ito Oil Co., Ltd., castor oil D) 16 g of potassium hydroxide was added to 1000 g, dehydrated under reduced pressure, and the temperature was raised to 110 ° C. To the resulting product, 2400 g of propylene oxide was added in portions while maintaining the reaction pressure at 4 kg / cm ² . The mixture was then maintained until no pressure drop was observed. To the obtained product, 26 g of phosphoric acid was added, neutralized and dehydrated. Thereafter, the obtained product was filtered to remove the salt to obtain polyol (a1) -1.

The hydroxyl value of the obtained polyol (a1) -1 was measured according to JIS K 1557-1970. As a result, the hydroxyl value was 50. Moreover, the average functional group number of the said polyol (a1) -1 was computed by the analysis of < ¹³ > C-NMR. As a result, the average number of functional groups of the polyol (a1) -1 was about 2.7. Furthermore, the terminal hydroxyl group of the polyol (a1) -1 was confirmed to be a secondary hydroxyl group by analysis of the ¹³ C-NMR.

(Experimental example 2)
Polyol (a1) -2 was obtained in the same manner as in Experimental Example 1 except that 29 g of potassium hydroxide, 4400 g of propylene oxide, and 42 g of phosphoric acid were used. Further, the hydroxyl value and the average number of functional groups of the obtained polyol (a1) -2 were measured by the same method as in Experimental Example 1. As a result, the polyol (a1) -2 had a hydroxyl value of 30, and an average functional group number of about 2.7. Moreover, the terminal hydroxyl group of the polyol (a1) -2 was a secondary hydroxyl group.

(Experimental example 3)
Castor oil (Ito Oil Co., Ltd., castor oil D) 13 g of potassium hydroxide was added to 1000 g, dehydrated under reduced pressure, and the temperature was raised to 110 ° C. To the resulting product, 3330 g of propylene oxide was added in portions while maintaining the reaction pressure at 4 kg / cm ² . The mixture was then maintained until no pressure drop was observed. Next, 1100 g of ethylene oxide was added to the obtained product in portions while maintaining the reaction pressure at 4 kg / cm ² . The mixture was then maintained until no pressure drop was observed. To the obtained product, 21 g of phosphoric acid was added, neutralized and dehydrated. Thereafter, the obtained product was filtered to remove the salt to obtain a polyol (a1 ′). Further, the hydroxyl value and the average number of functional groups of the obtained polyol (a1 ′) were measured by the same method as in Experimental Example 1. As a result, the polyol (a1 ′) had a hydroxyl value of 30, and an average functional group number of about 2.7. Moreover, the terminal hydroxyl group of the polyol (a1 ′) was a primary hydroxyl group.

(Experimental example 4)
23 g of potassium hydroxide was added to 100 g of glycerin, dehydrated under reduced pressure, and the temperature was raised to 110 ° C. To the resulting product, 5000 g of propylene oxide was added in portions while maintaining the reaction pressure at 4 kg / cm ² . The mixture was then maintained until no pressure drop was observed. Subsequently, 900 g of ethylene oxide was added to the obtained product in portions while maintaining the reaction pressure at 4 kg / cm ² . The mixture was then maintained until no pressure drop was observed. To the obtained product, 37 g of phosphoric acid was added, neutralized and dehydrated. Then, the obtained product was filtered to remove the salt to obtain polyol (a2) -1. Further, the obtained polyol (a2) -1 hydroxyl value and average functional group number were examined by the same method as in Experimental Example 1. As a result, the polyol (a2) -1 had a hydroxyl value of 28 and was glycerin-based trifunctional. Moreover, the terminal oxyethylene group terminal content of the said polyol (a2) -1 was measured. As a result, it was found that the polyol (a2) -1 had an oxyethylene group terminal content of 15%.

(Experimental example 5)
Polyol (a2) -2 was obtained in the same manner as in Experimental Example 4 except that 20 g of potassium hydroxide, 4700 g of propylene oxide, 1200 g of ethylene oxide, and 32 g of phosphoric acid were used. Further, the hydroxyl value, the average number of functional groups, and the oxyethylene group terminal content of the obtained polyol (a2) -2 were measured by the same method as in Experimental Example 1. As a result, the polyol (a2) -2 has a hydroxyl value of 28, an average functional group number of about 3.0, and an oxyethylene group terminal content of 20% polyoxyethylene polyoxypropylene. It was found to be a polyol.

(Experimental example 6)
Polyol (a2) -3 was obtained in the same manner as in Experimental Example 4 except that 23 g of potassium hydroxide, 4150 g of propylene oxide, 750 g of ethylene oxide, and 37 g of phosphoric acid were used. Further, the hydroxyl value, the average number of functional groups, and the oxyethylene group terminal content of the obtained polyol (a2) -3 were measured by the same method as in Experimental Example 1. As a result, the hydroxyl value of the polyol (a2) -3 was 28, the average number of functional groups was about 3.0, and the oxyethylene group terminal content was 20%.

(Experimental example 7)
Polymer polyol (Daiichi Kogyo Seiyaku Co., Ltd., trade name: Hiflex ND825C was used as polyol (a2) -4 of Experimental Example 7). The polyol (a2) -4 has a hydroxyl value of 28 and an average number of functional groups of about 3.0.

(Test Example 1)
At least one of the polyols of Experimental Examples 1 to 7, the rack teaching material a (diethanolamine), and the catalyst a (33% by weight of triethylenediamine in dipropylene glycol so that the blending ratio (weight ratio) shown in Table 1 is obtained. Manufactured by Tosoh Corporation, trade name: TEDA L-33), catalyst b [70% by weight dipropylene glycol solution of bis (2-methylaminoethyl) ether, manufactured by Tosoh Corporation, trade name: TOYOCAT ET], Foam stabilizer a (silicone foam stabilizer, manufactured by Toray Dow Corning Co., Ltd., trade name: SZ-1313) or foam stabilizer b (silicone foam stabilizer, manufactured by Toray Dow Corning Co., Ltd., trade name: L -5366) and isocyanate compound [reacting polyoxyethylene polyoxypropylene polyol to diphenylmethane diisocyanate The obtained diphenylmethane diisocyanate-based isocyanate compound, free NCO = 29.0%, manufactured by Daiichi Kogyo Seiyaku Co., Ltd., trade name: DK System B-73E], and the resulting mixture was subjected to mold temperature. : 55 ° C., mold shape: 325 × 155 × 50 cm, 22 ± 1 ° C., foamed by hand mixing. The curing condition was 55 ° C. for 5 minutes. After foaming the foam and leaving it to stand at 20 ° C. for one day, foam physical properties (overall density, core density, compression residual strain, wet heat residual strain, 25% hardness) were measured as follows (Examples 1 to 9, Comparative examples 1 and 2).

  The overall density and core density of each foam obtained were measured in accordance with JIS K 7222 (2005).

  The compression set was measured according to JIS K 6400-4.

  Furthermore, the wet heat permanent strain was measured according to JIS K 6400-4.

  Moreover, 25% hardness (ILD) of each obtained foam was measured using 5581 type made from Instron Japan Company Limited based on JIS K 6400-2.

  Formability of each foam obtained was evaluated by its self-foaming and curing properties, that is, there was no occurrence of shrinkage even after skin peeling or all day and night, and it did not deform even when a load was applied to the demolded foam. did.

  The results are shown in Table 1.

  As a result, as shown in Table 1, as shown in Examples 1 to 9, propylene oxide having 2 to 4 carbon atoms was added to castor oil, and the terminal hydroxyl group was a secondary hydroxyl group. And a castor oil polyol (a1) -1 or (a1) -2 having a hydroxyl value in the range of 20 to 350 (hydroxyl value 50) and polyols (a2) -1 and (a2) -2 other than the castor oil polyol When (a2) -3 or (a2) -4 is blended, the moldability is good and the compression set and the wet heat set are also reduced. Moreover, in the case of Example 1- Example 9, it turns out that a moldability is also favorable.

  On the other hand, in the case of Comparative Example 1 in which the castor oil polyol alone was blended, no foam was formed. Moreover, when the castor oil polyol whose terminal hydroxyl group is a primary hydroxyl group and a polyol other than the castor oil polyol are blended, it can be seen that the wet heat permanent strain is increased as compared with Examples 1 to 9.

  According to the method for producing a polyurethane foam of the present invention, it is possible to easily and efficiently provide a polyurethane foam that can be widely used for applications requiring durability against wet heat, such as furniture, automobile seats, and headrests. Further, according to the polyurethane foam of the present invention, it is possible to use the polyurethane foam for applications such as furniture, automobile seats, headrests and the like that require durability against wet heat.

Claims (4)

Castor oil polyol (a1), which is a compound obtained by adding an alkylene oxide having 2 to 4 carbon atoms to castor oil or a derivative thereof, a terminal hydroxyl group is a secondary or tertiary hydroxyl group and a hydroxyl value of 20 to 350; A polyol component (A) containing a polyol (a2) other than the castor oil polyol;
An isocyanate compound (B);
A process for producing a polyurethane foam, characterized by reacting   The method for producing a polyurethane foam according to claim 1, wherein the polyol (a2) other than the castor oil polyol is a polyol having an average functional group number of 2.0 to 6.0 and a hydroxyl value of 20 to 800.   The polyol component (A) comprises a castor oil polyol (a1) and a polyol (a2) other than the castor oil polyol in a weight ratio [(a1) / (a2)] of 10/90 to 70/30. The method for producing a polyurethane foam according to claim 1 or 2, wherein the mixture is a blended composition. It is obtained by the manufacturing method according to any one of claims 1 to 3,
The compression set in the core measured in accordance with JIS K 6400-4 is 20% or less, and the value of the compression set is measured in accordance with JIS K 6400-4. Polyurethane foam whose value divided by 1 is 1 or more.