Methods for reducing volatile organic compounds, methods for producing polyurethane foam, and resin premixes.

Abstract

31 / 07 / 2560 (OCR) Page 1 of 1 Summary of the invention. In methods for reducing volatile organic compounds, polyurethane foam contains these compounds. which is shown by the following formula(1): [Chemical Formula 1] (chemical formula) (Where -N=R represents the following substructure formula (A) or the following substructure formula (B), (And X represents an anion) [Chemical Formula 2] (chemical formula) (Where R1 is appropriately the methyl group) [Chemical Formula 3] (chemical formula) (where R2 appropriately represents the methyl group and n” appropriately represents 1) ------------

Description

Method for reducing volatile organic compounds, method for producing polyurethane foam, and resin premix The present invention relates to a method for reducing volatile organic compounds, a method for producing polyurethane foam, and a resin premix. Polyurethane foam is obtained by reacting a resin premix containing a polyol, a catalyst, and a blowing agent with a polyisocyanate. Polyurethane foam is used in a wide range of fields, such as cushions. On the other hand, polyurethane foam may contain volatile organic compounds (VOCs) such as acetaldehyde and formaldehyde. When these volatile organic compounds (VOCs) are released into the atmosphere, they may affect the global environment and the human body. Therefore, it is required to reduce the volatile organic compounds (VOCs) from polyurethane foam. More specifically, for example, when molding a polyurethane molded article from a polyisocyanate and a polyol mixture containing a polyol, a catalyst, and a crosslinking agent, a hydrazine compound (for example, adipic acid dihydrazide) as an aldehyde scavenger is added to the polyol mixture in advance. This has been proposed (see, for example, Patent Document 1 below). Japanese Patent Application Laid-Open No. 2006-182825 On the other hand, since the required reduction amounts of volatile organic compounds (VOCs) in various fields vary depending on the purpose and application, it is desired to efficiently meet the required level of reduction amount. However, although the hydrazine compound as described in Patent Document 1 can reduce volatile organic compounds (VOCs), the reduction amount of volatile organic compounds (VOCs) is constant regardless of the amount of the hydrazine compound used and has a limit. Furthermore, there is also a problem that the degree of reduction of volatile organic compounds (VOCs) cannot be adjusted. The present invention provides a method for reducing volatile organic compounds (VOCs) that can adjust the degree of reduction of volatile organic compounds (VOCs) and can efficiently reduce volatile organic compounds (VOCs). Further, the present invention provides a method for producing polyurethane foam and a resin premix in which volatile organic compounds (VOCs) are reduced. The present invention [1] is a method for reducing volatile organic compounds in a polyurethane foam, which includes a method for reducing volatile organic compounds by incorporating a compound represented by the following formula (1) into the polyurethane foam. (In the formula, -N=R represents the following partial structural formula (A) or the following partial structural formula (B), and X － represents an anion.) (In the formula, R １ are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １ may be bonded to each other to form a ring structure.) (In the formula, R ２ are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R ２ may be bonded to each other to form a ring structure. Also, n represents an integer of 0 to 3. However, n corresponding to at least one of the four Rs in formula (1) is not 0.) The present invention [2] includes the method for reducing volatile organic compounds according to the above [1], in which the volatile organic compounds are linearly reduced according to the content of the compound represented by the above formula (1). The present invention [3] includes the method for reducing volatile organic compounds according to the above [1] or [2], in which the polyurethane foam is a reaction product of a resin premix containing a polyol and a polyisocyanate, and the content ratio of the cationic part of the compound represented by the above formula (1) is 500 ppm or more based on the total amount of the polyol. The present invention [4] includes the method for reducing volatile organic compounds according to any one of the above [1] to [3], which comprises a preparation step of preparing a resin premix containing a polyol and a polyisocyanate, an addition step of adding the compound represented by the above formula (1) to the resin premix, and a foaming step of mixing and foaming the resin premix and the polyisocyanate. The present invention [5] relates to a method for producing a polyurethane foam with reduced volatile organic compounds, comprising a preparation step of preparing a resin premix containing a polyol and a polyisocyanate, an addition step of adding a compound represented by the following formula (1) to the resin premix, and a foaming step of mixing and foaming the resin premix and the polyisocyanate. (In the formula, -N=R represents the following partial structural formula (A) or the following partial structural formula (B), and X － represents an anion.) (In the formula, R １ represents, independently of one another, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １ may be bonded to each other to form a ring structure.) (In the formula, R ２ represents, independently of one another, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R ２ may be bonded to each other to form a ring structure. Also, n represents an integer of 0 to 3. However, n corresponding to at least one of the four Rs in formula (1) is not 0.) The present invention [6] relates to a resin premix used in the method for producing a polyurethane foam described in [5] above, and contains a polyol and a compound represented by the following formula (1). (In the formula, -N=R represents the following partial structural formula (A) or the following partial structural formula (B), and X － represents an anion.) (In the formula, R １ represents, independently of one another, a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １ may be bonded to each other to form a ring structure.) (In the formula, R２ are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R ２ may be bonded to each other to form a ring structure. Further, n represents an integer of 0 to 3. However, n corresponding to at least one of the four Rs in formula (1) is not 0.) In the method for reducing a volatile organic compound (VOC) of the present invention, since the compound represented by the above formula (1) is contained in the polyurethane foam, the volatile organic compound (VOC) can be efficiently reduced, and depending on the content of the compound represented by the above formula (1), the degree of reduction of the volatile organic compound (VOC) can be arbitrarily adjusted. Further, according to the method for producing a polyurethane foam and the resin premix of the present invention, a polyurethane foam in which the volatile organic compound (VOC) is reduced to an arbitrary degree can be produced. FIG. 1 is a correlation diagram showing the relationship between the content ratio of the cationic part of the VOC reducing agent and the reduction amount of acetaldehyde. FIG. 2 is a correlation diagram showing the relationship between the content ratio of the cationic part of the VOC reducing agent and the reduction amount of propionaldehyde. FIG. 3 is a correlation diagram showing the relationship between the amount of ADH (hydrazide-based antioxidant) used and the reduction amounts of acetaldehyde and propionaldehyde. FIG. 4 is a correlation diagram showing the relationship between the amount of VDH (hydrazide-based antioxidant) used and the reduction amounts of acetaldehyde and propionaldehyde. The polyurethane foam (for example, a flexible polyurethane foam) contains a volatile organic compound (VOC). In other words, the polyurethane foam is a VOC-containing foam (foam composition) containing the polyurethane foam and the volatile organic compound. The volatile organic compound (VOC) is an organic compound having a vapor pressure at 20°C of 2500 Pa or less, preferably 150 Pa or less. Examples of volatile organic compounds (VOCs) include aldehyde compounds such as acetaldehyde, formaldehyde, and propionaldehyde; aromatic organic compounds such as styrene, toluene, and benzene; ester compounds such as ethyl acetate and butyl acetate; alcohol compounds such as methanol, ethanol, isopropanol, and butanol; ketone compounds such as acetone and methyl ethyl ketone; aliphatic cyclic compounds such as cyclohexane and cyclopentane; phthalate ester compounds such as di-n-butyl phthalate and n-ethylhexyl phthalate; nitrile compounds such as acetonitrile; fluorine-containing organic compounds; and chlorine-containing organic compounds such as chloroform, methylene chloride, vinyl chloride, ethylbenzene, p-dichlorobenzene, and o-dichlorobenzene. Preferably, the volatile organic compound (VOC) is at least one selected from the group consisting of aldehyde compounds selected from acetaldehyde, formaldehyde, and propionaldehyde; aromatic organic compounds selected from styrene, toluene, and benzene; ester compounds selected from ethyl acetate and butyl acetate; alcohol compounds selected from methanol, ethanol, isopropanol, and butanol; ketone compounds selected from acetone and methyl ethyl ketone; aliphatic cyclic compounds selected from cyclohexane and cyclopentane; phthalate ester compounds selected from di-n-butyl phthalate and n-ethylhexyl phthalate; nitrile compounds selected from acetonitrile; fluorine-containing organic compounds; and chlorine-containing organic compounds selected from chloroform, methylene chloride, vinyl chloride, ethylbenzene, p-dichlorobenzene, and o-dichlorobenzene. More preferably, the volatile organic compound (VOC) is at least one selected from acetaldehyde, formaldehyde, and propionaldehyde, and even more preferably, at least one selected from the group consisting of acetaldehyde and propionaldehyde. One or more of these volatile organic compounds (VOCs) may be contained in the polyurethane foam. Therefore, in the method for reducing volatile organic compounds (VOCs) of the present invention, the volatile organic compounds (VOCs) in the polyurethane foam are reduced. More specifically, in this method, in order to reduce the volatile organic compounds (VOCs), the polyurethane foam is made to contain a compound represented by the following formula (1) (hereinafter referred to as a VOC reducing agent). (In the formula, -N=R represents the following partial structural formula (A) or the following partial structural formula (B), and X － represents an anion.) (In the formula, R １ are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and R １ may be bonded to each other to form a ring structure.) (In the formula, R ２ are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R ２ may be bonded to each other to form a ring structure. Also, n represents an integer of 0 to 3. However, n corresponding to at least one of the four Rs is not 0.) In the above formula (1), when R is represented by the partial structural formula (A), the VOC reducing agent is a compound represented by the following formula (2). (In the formula, R １ has the same meaning as R １ in the above formula (A), and X － has the same meaning as X － in the above formula (1).) In the above partial structural formula (A) and formula (2), R １ are the same as or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms which may have a substituent, or an aralkyl group having 7 to 20 carbon atoms which may have a substituent. Preferably, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is included. Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include linear saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, 2-butyl group, 1-pentyl group, 2-pentyl group, 3-pentyl group, 2-methyl-1-butyl group, isopentyl group, tert-pentyl group, 3-methyl-2-butyl group, neopentyl group, n-hexyl group, 4-methyl-2-pentyl group, 1-heptyl group, 3-heptyl group, 1-octyl group, 2-octyl group, 2-ethyl-1-hexyl group, 1,1-dimethyl-3,3-dimethylbutyl group, 1-nonyl group, 1-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group; cyclic saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group; linear unsaturated aliphatic hydrocarbon groups having 2 to 20 carbon atoms such as vinyl group, 2-propenyl group; cyclic unsaturated aliphatic hydrocarbon groups having 3 to 20 carbon atoms such as cyclohexenyl group. Preferably, linear saturated aliphatic hydrocarbon groups having 1 to 20 carbon atoms are included. More preferably, methyl group, ethyl group, n-propyl group, isopropyl group, tert-butyl group, tert-pentyl group, 1,1-dimethyl-3,3-dimethylbutyl group are included. Even more preferably, methyl group is included. Examples of the aryl group having 6 to 20 carbon atoms which may have a substituent include a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2,3-xylyl group, 2,4-xylyl group, 2,5-xylyl group, 2,6-xylyl group, 3,4-xylyl group, 3,5-xylyl group, 2,3,4-trimethylphenyl group, 3,4,5-trimethylphenyl group, 2,4,6-trimethylphenyl group, 2,3,4,5-tetramethylphenyl group, 2,3,4,6-tetramethylphenyl group, 2-ethylphenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 1-naphthyl group, 2-naphthyl group and the like. Examples of the substituent of the aryl group having 6 to 20 carbon atoms which may have a substituent include a hydroxyl group, a halogeno group (e.g., chloro group, fluoro group, bromo group, iodo group, etc.), a cyano group, an amino group, a carboxy group, an alkoxy group (e.g., an alkoxy group having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, etc.), an aryloxy group (e.g., phenoxy group, etc.), an alkoxycarbonyl group (e.g., an alkoxycarbonyl group having 1 to 6 carbon atoms such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, hexyloxycarbonyl, etc.), an alkylthio group (e.g., an alkylthio group having 1 to 4 carbon atoms such as methylthio, ethylthio, propylthio, butylthio, etc.) and an arylthio group (e.g., phenylthio group, etc.). The substitution position and the number of substituents of the substituent can be arbitrarily determined. Examples of the C7-20 aralkyl group which may have a substituent include benzyl group, 1-phenylethyl group, 2-phenylethyl group, 1-phenylpropyl, 2-phenylpropyl, 3-phenylpropyl, o-methylbenzyl, m-methylbenzyl, p-methylbenzyl, o-ethylbenzyl, m-ethylbenzyl, p-ethylbenzyl, o-isopropylbenzyl, m-isopropylbenzyl, p-isopropylbenzyl, 2,3,4-trimethylbenzyl, 3,4,5-trimethylbenzyl, 2,4,6-trimethylbenzyl, etc. Examples of the substituent of the C7-20 aralkyl group which may have a substituent include the substituents of the C6-20 aryl group which may have the above-mentioned substituents. Also, R １ may be bonded to each other to form a ring structure. Preferably, R １ bonded to the same guanidine structure are bonded to each other to form a ring structure. R １ When R １ forms a ring structure, examples of R include C2-20 alkylene groups such as dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, etc., C3-20 cycloalkylene groups such as cyclohexylene group, etc., C2-20 alkenylene groups such as vinylene group, etc., C3-20 cycloalkenylene groups such as cyclohexenylene group, etc., C6-20 arylene groups such as phenylene group, naphthylene group, etc., C8-20 aralkylene groups such as phenylethylene group, etc. Preferably, C2-20 alkylene groups are included. More preferably, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group are included. Even more preferably, tetramethylene group is included. １ Examples of the ring structure in which R are bonded to each other include pyrrolidinyl group, pyrrolyl group, piperidinyl group, indolyl group, isoindolyl group, etc. １are preferably identical to each other. R １ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and particularly preferably a methyl group. In the above formula (1), X － represents an anion, preferably a hydroxyanion (hydroxide ion), an alkoxyanion (alkoxide), a carboxyanion, a sulfonyl anion, a hydrogen carbonate anion, or a halide ion. Examples of the alkoxyanion include methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, sec-butoxide, tert-butoxide, cyclohexoxide, 2-heptoxide, 1-octoxide, and phenoxide. Examples of the carboxyanion include formate anion, acetate anion, propionate anion, butyrate anion, isobutyrate anion, caproate anion, laurate anion, palmitate anion, stearate anion, benzoate anion, decylbenzoate, dodecylbenzoate anion, lactate anion, malate anion, tartrate anion, citrate anion, and ricinoleate anion. Examples of the sulfonyl anion include p-toluenesulfonate anion, dodecylbenzenesulfonate anion (including linear and branched types), benzenesulfonate anion, methanesulfonate anion, and camphorsulfonate anion. Examples of the halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion, and preferably chloride ion. X － is more preferably a sulfonyl anion, a hydroxyanion, or a halide ion, and still more preferably a sulfonyl anion or a halide ion. Specific examples of the compound represented by the above formula (2) include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium chloride, tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide, tetrakis(1,3-diisopropylimidazolidinimino)phosphonium chloride, and tetrakis(1,3-dimethylimidazolidinimino)phosphonium chloride. Preferred examples include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium chloride and tetrakis(1,1,3,3-tetramethylguanidino)phosphonium hydroxide. More preferred examples include tetrakis(1,1,3,3-tetramethylguanidino)phosphonium chloride. These compounds represented by the above formula (2) can be used alone or in combination of two or more kinds. The compound represented by the above formula (2) can be produced, for example, by the method for producing a phosphonium salt described in German Patent Application DE102006010034A1. When R in the above formula (1) is represented by partial structural formula (B), the VOC reducing agent is, for example, a compound represented by the following formula (3). (In the formula, R ２ is R in the above formula (B). ２ and X － is X in the above formula (1). － and n may be the same or different and has the same meaning as n in the above formula (B). In the partial structural formula (B) and the formula (3), R ２ are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. Examples of the hydrocarbon group having 1 to 20 carbon atoms include the above-mentioned hydrocarbon groups having 1 to 20 carbon atoms. Also, R ２ and R directly bonded to the same nitrogen atom may be the same or different and may be bonded to each other to form a ring structure. ２ They bond to each other to form a ring structure. R ２ When R groups form a ring structure, examples of R ２ include a dimethylene group, a trimethylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, etc., and preferably, a dimethylene group, a trimethylene group, a tetramethylene group are included. R ２ are preferably the same as each other. R ２ As R, preferably, an aliphatic hydrocarbon group having 1 to 20 carbon atoms is included, more preferably, a linear aliphatic hydrocarbon group having 1 to 20 carbon atoms is included, still more preferably, a methyl group, an ethyl group, an n-propyl group, an isopropyl group are included, and particularly preferably, a methyl group is included. In addition, in the above partial structural formula (B) and the above formula (3), n is the same as or different from each other and represents an integer of 0 to 3, preferably, the same as or different from each other and represents an integer of 1 or 2, more preferably, at least three of the n in the above formula (3) are 1 and the rest are 2, still more preferably, n represents that all of the n in the above formula (3) are 1. Specific examples of the compound represented by the above formula (3) include tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium hydroxide, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium chloride, tetrakis[tris(diethylamino)phosphoranilideneamino]phosphonium chloride, tetrakis[tris(1-azacyclononyl)phosphoranilideneamino]phosphonium chloride, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium bromide, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium dodecylbenzenesulfonyl, etc., and more preferably, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium chloride, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium dodecylbenzenesulfonyl are included. These compounds represented by the above formula (3) can be used alone or in combination of two or more. The compound represented by the above formula (3) can be synthesized, for example, by the synthesis method of phosphazenium compounds described on pages 12 to 13 of European Patent Application Publication No. EP0791600A1 or a similar method. These VOC reducing agents can be used alone or in combination of two or more. As the VOC reducing agent, preferably, the compound represented by the above formula (3) is mentioned, and more preferably, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium dodecylbenzenesulfonyl (in the above formula (3), R ２ is a methyl group, and X － is a compound which is a linear dodecylbenzenesulfonate anion). According to such a VOC reducing agent, a volatile organic compound (VOC) can be efficiently reduced, and a polyurethane foam with an arbitrarily adjusted degree of reduction can be obtained. To incorporate a VOC reducing agent into a polyurethane foam, during the production of the polyurethane foam, the raw material components (resin premix and / or polyisocyanate) are made to contain the VOC reducing agent and reacted. Preferably, the resin premix is made to contain the VOC reducing agent, and the resin premix and polyisocyanate (described later) are reacted. The method of incorporating a VOC reducing agent into the resin premix is not particularly limited. For example, during the production of a polyol (described later), the VOC reducing agent is used as an addition polymerization catalyst, and a resin premix containing the VOC reducing agent can be prepared using the obtained polyol (including the VOC reducing agent). Also, after preparing a polyol without using the VOC reducing agent and then adding the VOC reducing agent to the polyol, a resin premix containing the VOC reducing agent can be prepared. Further, during the production of a polyol (described later), the VOC reducing agent is used as an addition polymerization catalyst, and the obtained polyol (including the VOC reducing agent) can also be added with the VOC reducing agent. More specifically, in this method, first, a resin premix containing a polyol and a polyisocyanate are prepared (preparation step). The resin premix contains, for example, a polyol, a urethanization catalyst, and a foaming agent. The polyol preferably contains a macro polyol. The macro polyol is a high molecular weight polyol having a number average molecular weight of 400 or more and 10,000 or less (including a high molecular weight polyol in which polymer fine particles are dispersed), and examples thereof include a polyether polyol, a polyester polyol, a polyester amide polyol, a polycarbonate polyol, a polyurethane polyol, an epoxy polyol, a vegetable oil polyol, a polyolefin polyol, an acrylic polyol, and a polymer polyol (vinyl monomer-modified polyol). These macro polyols can be used alone or in combination of two or more. Preferred examples of the macro polyol include a polyether polyol and a polymer polyol. More preferably, the macro polyol contains a polyether polyol and a polymer polyol. The number average molecular weight is measured by gel permeation chromatography (GPC) analysis (in terms of polyethylene glycol conversion) in accordance with JIS K 7252-1 (2008) (the same shall apply hereinafter). Examples of the polyether polyol include polyoxyalkylene polyol. The polyoxyalkylene polyol is, for example, an addition polymer of an alkylene oxide using a low molecular weight polyol, a low molecular weight polyamine, etc. as an initiator in the presence of an addition polymerization catalyst such as an alkali metal hydroxide (sodium hydroxide, potassium hydroxide, etc.) (including a random and / or block copolymer of two or more alkylene oxides). When an alkali metal hydroxide is used as the addition polymerization catalyst as described above, a polyoxyalkylene polyol (and thus a resin premix) that does not contain a VOC reducing agent can be obtained. When a VOC reducing agent is used as the addition polymerization catalyst as described later, a polyoxyalkylene polyol (and thus a resin premix) that contains a VOC reducing agent can be obtained. The low molecular weight polyol is a compound having two or more hydroxyl groups and a molecular weight of 40 or more and less than 400. Examples thereof include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,2,2-trimethylpentanediol, 3,3-dimethylolheptane, alkane (C7-20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol and other dihydric alcohols, for example, glycerin, trimethylolpropane, triisopropanolamine and other trihydric alcohols, for example, tetramethylolmethane (pentaerythritol), diglycerin and other tetravalent alcohols, for example, xylitol and other pentavalent alcohols, for example, sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol and other hexavalent alcohols, for example, perseitol and other heptavalent alcohols, for example, sucrose and other octavalent alcohols and the like. These low molecular weight polyols can be used alone or in combination of two or more. Low molecular weight polyamines are compounds having two or more amino groups and a molecular weight of 40 or more and less than 400. Examples include low molecular weight diamines such as ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,6-hexamethylenediamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, 1,3-bis(aminomethyl)cyclohexane, hydrazine, o, m or p-tolylenediamine (TDA, OTD), etc., low molecular weight triamines such as diethylenetriamine, etc., and low molecular weight polyamines having four or more amino groups such as triethylenetetramine, tetraethylenepentamine, etc. These low molecular weight polyamines can be used alone or in combination of two or more. Examples of the alkylene oxide include alkylene oxides having 2 to 12 carbon atoms such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether, etc. These alkylene oxides can be used alone or in combination of two or more. Preferred examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, and styrene oxide, and more preferred examples include ethylene oxide and propylene oxide. Preferred examples of the polyoxyalkylene polyol include, for example, polyethylene glycol, polypropylene glycol, propylene oxide-ethylene oxide copolymer (random and / or block copolymer), etc. When a propylene oxide-ethylene oxide copolymer is used as the polyoxyalkylene polyol, its ethylene oxide content is, for example, 5% by mass or more, preferably 10% by mass or more, and, for example, 50% by mass or less, preferably 30% by mass or less. The ethylene oxide content is calculated from the formulation of the charge (the same applies hereinafter). When a propylene oxide-ethylene oxide copolymer is used as the polyoxyalkylene polyol, its terminal oxyethylene group content is, for example, 5% by mass or more, preferably 10% by mass or more, and, for example, 50% by mass or less, preferably 30% by mass or less. The terminal oxyethylene group content is calculated from the formulation of the charge. The number average molecular weight of the polyoxyalkylene polyol is, for example, 400 or more, preferably 1000 or more, and, for example, 15000 or less, preferably 10000 or less. The average functionality of the polyoxyalkylene polyol is, for example, 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, and, for example, 6 or less, preferably 4 or less. The average functionality of the polyoxyalkylene polyol is calculated from the formulation of the charge. The hydroxyl value of the polyoxyalkylene polyol is, for example, 10 mg KOH / g or more, preferably 15 mg KOH / g or more, more preferably 20 mg KOH / g or more, still more preferably 25 mg KOH / g or more, and, for example, 80 mg KOH / g or less, preferably 60 mg KOH / g or less, more preferably 50 mg KOH / g or less, still more preferably 30 mg KOH / g or less. When the hydroxyl value of the polyoxyalkylene polyol is within the above range, the polyurethane foam obtained using the polyol containing the polyoxyalkylene polyol can maintain physical properties such as hardness. The hydroxyl value is measured in accordance with the description in JIS K-1557-1 (2007) (the same applies hereinafter). These polyoxyalkylene polyols can be used alone or in combination of two or more. Polymer polyol (vinyl monomer-modified polyol) can be obtained by dispersion polymerization of vinyl monomers in high molecular weight polyols. In polymer polyol, the high molecular weight polyol is a dispersion medium for vinyl monomers, and has a number average molecular weight of, for example, 400 or more, preferably 1000 or more, and, for example, 10000 or less, preferably 8000 or less. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, etc., and preferably polyether polyol. These high molecular weight polyols can be used alone or in combination of two or more. Examples of the vinyl monomer include styrene, acrylamide, alkyl (meth)acrylate, vinyl cyanide (acrylonitrile), vinylidene cyanide, etc. These vinyl monomers can be used alone or in combination of two or more. Among these, preferably, styrene, vinyl cyanide (acrylonitrile), and the combination of styrene and vinyl cyanide are mentioned. The content of the polymer of the vinyl monomer in the polymer polyol is, for example, 2% by mass or more, preferably 5% by mass or more, and, for example, 50% by mass or less, preferably 45% by mass or less. And the polymer polyol can be obtained by reacting vinyl monomers in high molecular weight polyols, for example, in the presence of a radical polymerization initiator (such as persulfate, organic peroxide, azo compounds (such as azobisisobutyronitrile), etc.), and further, if necessary, in the presence of a dispersion stabilizer, a chain transfer agent, etc. More specifically, the polymer polyol is prepared by polymerizing the above vinyl monomers by a radical initiator in high molecular weight polyols, and the resulting polymer fine particles are dispersed in the high molecular weight polyols. The polymer microparticles are polymer microparticles composed of a polymer of vinyl monomers. In addition, in the polymer microparticles, at least a part of the vinyl monomer can be grafted onto a high molecular weight polyol during polymerization. The number average molecular weight of the polymer polyol is, for example, 400 or more, preferably 1000 or more, and for example, 15000 or less, preferably 10000 or less. Also, the average functionality of the polymer polyol is, for example, 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, and for example, 6 or less, preferably 4 or less. In addition, the average functionality of the polymer polyol is calculated from the formulation of the charge. Also, the hydroxyl value of the polymer polyol is, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 25 mgKOH / g or more, and for example, 80 mgKOH / g or less, preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 30 mgKOH / g or less. When the hydroxyl value of the polymer polyol is within the above range, the polyurethane foam obtained using the polyol containing the polymer polyol can maintain physical properties such as hardness. These polymer polyols can be used alone or in combination of two or more. When the macro polyol contains a polyoxyalkylene polyol and a polymer polyol, the blending ratio of the polyoxyalkylene polyol and the polymer polyol is, based on 100 parts by mass of the macro polyol, for example, the polyoxyalkylene polyol is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less. Also, the polymer polyol is, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, and for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass or less. Also, the blending ratio of the polyoxyalkylene polyol and the polymer polyol is, on a mass basis, for example, 10 / 90 or more, preferably 30 / 70 or more, more preferably 40 / 60 or more, and also, for example, 90 / 10 or less, preferably 70 / 30 or less, more preferably 60 / 40 or less. When the blending ratio or blending proportion of the polyoxyalkylene polyol and the polymer polyol in the macro polyol is within the above range, the polyurethane foam obtained using the polyol containing the macro polyol can maintain physical properties such as hardness. The hydroxyl value of the macro polyol is, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, still more preferably 25 mgKOH / g or more, and for example, 80 mgKOH / g or less, preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, still more preferably 30 mgKOH / g or less. When the hydroxyl value of the macro polyol is within the above range, the polyurethane foam obtained using the polyol containing the macro polyol can maintain physical properties such as hardness. Also, the average functionality of the macro polyol is, for example, 1.5 or more, preferably 2 or more, more preferably 2.5 or more, and for example, 6 or less, preferably 4 or less. In addition to the above-mentioned macro polyol, the polyol can contain the above-mentioned low molecular weight polyol. When the polyol contains a low molecular weight polyol, the content ratio is appropriately set according to the purpose and application within the range that does not inhibit the excellent effects of the present invention. Preferably, the polyol does not contain a low molecular weight polyol. The content ratio of the polyol in the resin premix is, for example, 98.00% by mass or more, preferably 99.70% by mass or more, more preferably 99.80% by mass or more, still more preferably 99.90% by mass or more, based on the total amount of the resin premix. Also, for example, it is less than 100% by mass, preferably 99.999% by mass or less, more preferably 99.99% by mass or less, still more preferably 99.98% by mass or less. The urethanization catalyst is not particularly limited, and known urethanization catalysts can be mentioned. Specifically, for example, aliphatic amines such as triethylamine, triethylenediamine, bis-(2-dimethylaminoethyl) ether, morpholines (e.g., N-methylmorpholine, etc.), quaternary ammonium salts such as tetraethylammonium hydroxide, imidazoles such as imidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, organic tin compounds such as tin octanoate (tin octylate), tin acetate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin mercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin dilaurate), dibutyltin dineodecanoate, dioctyltin mercaptide, dioctyltin dilaurate, dibutyltin dichloride, organic lead compounds such as lead octanoate, lead naphthenate, organic nickel compounds such as nickel naphthenate, organic cobalt compounds such as cobalt naphthenate, organic copper compounds such as copper octenoate, organic bismuth compounds such as bismuth octylate, bismuth neodecanoate, etc. Furthermore, examples of the urethanization catalyst also include potassium salts such as potassium carbonate, potassium acetate, potassium octylate, etc. In addition, the urethanization catalyst can be obtained as a commercially available product. For example, Kaolizer No. 31 (amine catalyst, manufactured by Kao Corporation), Kaolizer No. 120 (amine catalyst, 1-isobutyl-2-methylimidazole, manufactured by Kao Corporation), Kaolizer No. 12 (amine catalyst, manufactured by Kao Corporation), Kaolizer No. 25 (amine catalyst, manufactured by Kao Corporation), DABCO 33LV (amine catalyst, 33% by mass diethylene glycol solution of triethylenediamine, manufactured by Air Products Japan Co., Ltd.), Niax A-1 (amine catalyst, manufactured by Momentive Performance Materials Japan LLC (hereinafter referred to as "manufactured by Momentive")), TOYOCAT-NCE (amine catalyst, manufactured by Tosoh Corporation), Neostan U-100 (organic tin catalyst, dibutyltin dilaurate, manufactured by Nitto Kasei Co., Ltd.), Formate TK-1 (organic tin catalyst, manufactured by Mitsui Chemicals, Inc.), and the like can be mentioned. These urethanization catalysts can be used alone or in combination of two or more. The blending ratio of the urethanization catalyst is, for example, 0.1 part by mass or more, preferably 0.3 part by mass or more, and, for example, 5 parts by mass or less, preferably 1 part by mass or less, based on 100 parts by mass of the polyol (preferably, macro polyol) in the resin premix. The blowing agent is not particularly limited, and known blowing agents can be mentioned, and preferably, water can be mentioned. In addition, as the blowing agent, water and a physical blowing agent (for example, hydrofluorocarbons, hydrocarbons (for example, cyclopentane, etc.), carbon dioxide gas, liquefied carbon dioxide gas, etc.) can be used in combination at an appropriate ratio. As the physical blowing agent, from the viewpoint of reducing environmental impact, preferably, carbon dioxide gas and liquefied carbon dioxide gas can be mentioned. These physical blowing agents can be used alone or in combination of two or more. The blending ratio of the blowing agent is, for example, 0.5 part by mass or more, preferably 1 part by mass or more, and, for example, 10 parts by mass or less, preferably 7 parts by mass or less, based on 100 parts by mass of the polyol (preferably, macro polyol) in the resin premix. If the content ratio of the blowing agent is within the above range, excellent foamability can be obtained. In addition, the resin premix can contain additives such as a crosslinking agent, a linking agent, a foam stabilizer, etc., if necessary. Preferably, the resin premix contains additives. The crosslinking agent is not particularly limited, and known crosslinking agents can be mentioned. Specifically, for example, alkanolamine, a polyol having a valency of 3 or more, an alkylene oxide-added polyol, etc. can be mentioned. Examples of the alkanolamine include polyalkanolamines such as trialkanolamines (tri C2-4 alkanolamines) such as trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, and dialkanolamines (di C2-4 alkanolamines) such as diethanolamine. Preferably, diethanolamine can be mentioned. Examples of the polyol having a valency of 3 or more include trihydric alcohols such as glycerin and trimethylolpropane, and polyhydric alcohols having 4 or more hydroxyl groups such as tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, and D-mannitt. The alkylene oxide-added polyol is a polyol obtained by adding an alkylene oxide to the above-mentioned polyol having a valency of 3 or more. For example, polyoxyalkylene polyols having a hydroxyl value of 200 mgKOH / g or more and 2000 mgKOH / g or less can be mentioned. Preferably, the crosslinking agent includes a polyol having a valency of 3 or more and / or an alkylene oxide-added polyol. In addition, as the polyol having a valency of 3 or more, preferably, glycerin can be mentioned, and as the alkylene oxide-added polyol, preferably, Actocol KL-210 (a polyoxyalkylene polyol having an average functionality of 3.75, hydroxyl value (OHV)=840 mgKOH / g, manufactured by Mitsui Chemicals, Inc.) can be mentioned. The hydroxyl value of the crosslinking agent is, for example, 200 mg KOH / g or more, preferably 800 mg KOH / g or more, and, for example, 2000 mg KOH / g or less, preferably 1850 mg KOH / g or less. These crosslinking agents can be used alone or in combination of two or more. The compounding ratio of the crosslinking agent is, for example, 0.5 part by mass or more, preferably 1 part by mass or more, and, for example, 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the polyol (preferably macro polyol) in the resin premix. The crosslinking agent is not particularly limited, and known crosslinking agents can be mentioned. Specifically, for example, polyether polyol (for example, a random copolymer of propylene oxide - ethylene oxide) can be mentioned. When a propylene oxide - ethylene oxide copolymer is used as the crosslinking agent, the ethylene oxide content thereof is, for example, more than 50% by mass, preferably 60% by mass or more, and, for example, 90% by mass or less, preferably 80% by mass or less. In addition, the crosslinking agent can be obtained as a commercially available product. For example, Actocol EP - 505S (manufactured by Mitsui Chemicals, Inc.), MF - 19 (manufactured by Mitsui Chemicals, Inc.), Excenol 3040 (manufactured by Asahi Glass Co., Ltd.), EL - 985 (manufactured by Asahi Glass Co., Ltd.) and the like can be mentioned. These crosslinking agents can be used alone or in combination of two or more. The compounding ratio of the crosslinking agent is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and, for example, 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the polyol (preferably macro polyol) in the resin premix. The foam stabilizer is not particularly limited, and known foam stabilizers can be mentioned. For example, silicone foam stabilizers can be mentioned. In addition, the foam stabilizer can be obtained as a commercially available product. For example, DC-6070 (manufactured by Air Products Japan), DC-2525 (manufactured by Air Products Japan), B-8715LF2 (manufactured by Evonik), SZ-1966 (manufactured by Toray Dow Corning), SRX-274C, SF-2969, SF-2961, SF-2962, L-5309 (manufactured by Momentive), L-3601 (manufactured by Toray Dow Corning), L-5307, L-3600, L-5366, SZ-1325, SZ-1328, Y-10366 (manufactured by Momentive), etc. can be mentioned. These foam stabilizers can be used alone or in combination of two or more kinds. The blending ratio of the foam stabilizer is, for example, 0.1 part by mass or more, preferably 0.5 part by mass or more, and for example, 10 parts by mass or less, preferably 5 parts by mass or less, based on 100 parts by mass of the polyol (preferably, macro polyol) in the resin premix. In addition to the above additives, other known additives such as antioxidants can be appropriately blended in the resin premix at an appropriate ratio within the range that does not impair the excellent effects of the present invention, if necessary. Examples of the antioxidant include hindered phenol-based antioxidants and other antioxidants (antioxidants excluding hindered phenol-based antioxidants). As hindered phenol antioxidants, specifically, for example, 4-methyl-2,6-di-tert-butylphenol (BHT), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate] (trade name: Irganox 245, manufactured by Ciba Japan), 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 259, manufactured by Ciba Japan), pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] (trade name: Irganox 1010, manufactured by Ciba Japan), octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (trade name: Irganox 1076, manufactured by Ciba Japan), N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide) (trade name: Irganox 1098, manufactured by Ciba Japan), isooctyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (trade name: Irganox 1135, manufactured by Ciba Japan), 3,5-di-t-butyl-4-hydroxybenzylphosphonate-diethyl ester (trade name: Irganox 1222, manufactured by Ciba Japan), 2,4,-bis[(octylthio)methyl]-O-cresol (trade name: Irganox 1520L, manufactured by Ciba Japan), tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl)isocyanurate (trade name: Irganox 3790, manufactured by Ciba Japan), 3,9-bis[1,1-dimethyl-2-[(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]ethyl] 2,4,8,10-tetraoxaspiro[5.5]undecane (trade name: ADK STAB AO-80, manufactured by Adeka), and the like can be mentioned. Examples of other antioxidants include hydrazide antioxidants such as lauryl hydrazide, salicylic acid hydrazide, formyl hydrazide, acetyl hydrazide, propionic acid hydrazide, p-hydroxybenzoic acid hydrazide, naphthoic acid hydrazide, 3-hydroxy-2-naphthoic acid hydrazide, oxalic acid dihydrazide, malonic acid dihydrazide, succinic acid dihydrazide, adipic acid dihydrazide, azelaic acid dihydrazide, sebacic acid dihydrazide, dodecane-2-dicarboxylic acid dihydrazide, maleic acid dihydrazide, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid dihydrazide, dimer acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,4-dioxo-5-propyl-1,3-imidazolidinedipropanoic acid dihydrazide, polyacrylic acid hydrazide, etc. Further, phosphorus antioxidants such as tris(2,4-di-t-butylphenyl) phosphite (trade name: Irgafos 168, manufactured by Ciba Japan), bis(2,4-di-t-butylphenyl)pentaerythritol diphosphite (trade name: Adeka Stab PEP-24G, manufactured by Adeka), trisnonylphenyl phosphite (trade name: Adeka Stab 1178, manufactured by Adeka), tridecyl phosphite (trade name: Adeka Stab 3010, manufactured by Adeka), etc. Also, thiophene antioxidants such as 2,5-thiophenediylbis(5-t-butyl-1,3-benzoxazole) (trade name: Chinopal OB, manufactured by Ciba Japan), etc. can be mentioned. These antioxidants can be used alone or in combination of two or more. Furthermore, in addition to the above additives, if necessary, known other additives such as pigments (color pigments), dyes, ultraviolet absorbers, antioxidants, curing accelerators, heat stabilizers, light stabilizers, matting agents, adhesion promoters, silane coupling agents, chain extenders, antifoaming agents, plasticizers, antiblocking agents, heat resistance stabilizers, light resistance stabilizers, mold release agents, lubricants, fillers, hydrolysis inhibitors, etc. can be blended in an appropriate ratio within the range not impairing the excellent effects of the present invention. To prepare the resin premix, a polyol, a urethanization catalyst, a foaming agent, and, if necessary, an additive are blended at the above-described ratios and mixed by a known method. Thereby, the resin premix can be prepared. The additive may be added during the synthesis of each component of the resin premix, or may be added during the blending or mixing of each component, or may even be added after the mixing of each component. Examples of the polyisocyanate include a polyisocyanate monomer and a polyisocyanate derivative. Examples of the polyisocyanate monomer include an aromatic polyisocyanate, an araliphatic polyisocyanate, and an aliphatic polyisocyanate. Examples of the aromatic polyisocyanate include aromatic diisocyanates such as tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or a mixture thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or a mixture thereof), 4,4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisocyanate (4,4'-, 2,4'- or 2,2'-diphenylmethane diisocyanate or a mixture thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), and 4,4'-diphenyl ether diisocyanate. Examples of the araliphatic polyisocyanate include araliphatic diisocyanates such as xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetramethylxylylene diisocyanate or a mixture thereof) (TMXDI), and ω,ω'-diisocyanate-1,4-diethylbenzene. Examples of the aliphatic polyisocyanate include aliphatic diisocyanates such as ethylene diisocyanate, trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate (tetramethylene diisocyanate, 1,2-butylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate), 1,5-pentamethylene diisocyanate (PDI), 1,6-hexamethylene diisocyanate (HDI), 2,4,4- or 2,2,4-trimethylhexamethylene diisocyanate, 2,6-diisocyanatomethyl caproate, dodecamethylene diisocyanate, and the like. The aliphatic polyisocyanate also includes alicyclic polyisocyanate. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl-3,5,5-trimethylcyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylene bis(cyclohexyl isocyanate) (4,4'-, 2,4'- or 2,2'-methylene bis(cyclohexyl isocyanate), these Trans,Trans-form, Trans,Cis-form, Cis,Cis-form, or a mixture thereof) (H １２ MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or a mixture thereof) (NBDI), bis(isocyanatomethyl)cyclohexane (1,3- or 1,4-bis(isocyanatomethyl)cyclohexane or a mixture thereof) (H ６ XDI), and other alicyclic diisocyanates. These polyisocyanate monomers can be used alone or in combination of two or more. Examples of the polyisocyanate derivative include multimers of the above-described polyisocyanate monomers (e.g., dimers, trimers (e.g., isocyanurate-modified products, iminooxadiazinedione-modified products), pentamers, heptamers, etc.), allophanate-modified products (e.g., allophanate-modified products produced by the reaction of the above-described polyisocyanate monomers with low molecular weight polyols, etc.), polyol-modified products (e.g., polyol-modified products (alcohol adducts) produced by the reaction of the above-described polyisocyanate monomers with low molecular weight polyols, etc.), biuret-modified products (e.g., biuret-modified products produced by the reaction of the above-described polyisocyanate monomers with water or amines, etc.), urea-modified products (e.g., urea-modified products produced by the reaction of the above-described polyisocyanate monomers with diamines, etc.), oxadiazinetrione-modified products (e.g., oxadiazinetrione produced by the reaction of the above-described polyisocyanate monomers with carbon dioxide gas, etc.), carbodiimide-modified products (e.g., carbodiimide-modified products produced by the decarboxylation condensation reaction of the above-described polyisocyanate monomers, etc.), uretdione-modified products, uretonimine-modified products, and the like. Furthermore, examples of the polyisocyanate derivative also include polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI), etc. These polyisocyanate derivatives can be used alone or in combination of two or more. Preferred examples of the polyisocyanate include aromatic polyisocyanates and their derivatives, and more preferred examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), and polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI). These polyisocyanates can be used alone or in combination of two or more. More preferably, examples of the polyisocyanate include a combination of tolylene diisocyanate, and a combination of tolylene diisocyanate and diphenylmethane diisocyanate. Particularly preferably, a combination of tolylene diisocyanate and diphenylmethane diisocyanate is included. Next, in this method, a VOC reducing agent is added to the resin premix and / or the polyisocyanate. Preferably, the VOC reducing agent is added to the resin premix (addition step). The addition amount of the VOC reducing agent is appropriately set so that the content of the VOC reducing agent in the polyurethane foam falls within a desired range. And the content of the VOC reducing agent in the polyurethane foam is appropriately determined according to the required reduction amount of the volatile organic compound (VOC). More specifically, in this method for reducing the volatile organic compound (VOC), as shown in the following formula (I), the content of the cationic part of the VOC reducing agent in the polyurethane foam and the reduction amount of the volatile organic compound (VOC) (the VOC content in the polyurethane foam) are represented by a linear function. Formula (I): [VOC content in polyurethane foam] = a × [content of cationic part of VOC reducing agent] + b In the above formula (I), a and b are constants set according to the type of VOC, the type of polyurethane foam, the type of VOC reducing agent, etc. For example, as the VOC reducing agent, tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium dodecylbenzenesulfonyl (in the above formula (3), R ２ is a methyl group, and X － is a compound that is a linear dodecylbenzenesulfonate anion.) When used, acetaldehyde (AA) in the polyurethane foam is reduced linearly, for example, according to the following formula (II), based on tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium (cationic part) (see Figure 1). Formula (II): [Acetaldehyde content in polyurethane foam] = a ＡＡ × [content of cationic part of VOC reducing agent] + b ＡＡ In the above formula (II), a ＡＡ is, for example, -3 × 10 －４ or more, preferably, -1.5 × 10－４ is as above, for example, -0.5×10 －４ or less, preferably, -1.0×10 －４ is the following constant. a ＡＡ as, particularly preferably, -1.30×10 －４ is. Further, in the above formula (II), b ＡＡ is, for example, 0.3 or more, preferably 0.33 or more, and is, for example, 0.7 or less, preferably 0.5 or less as a constant. b ＡＡと and, particularly preferably, 0.348. Note that, in the above formula (II), the acetaldehyde content in the polyurethane foam is measured in accordance with the examples described later. Further, the content of the cationic part of the VOC reducing agent is calculated as a ratio to 100 parts by mass of the polyol in accordance with the examples described later. Further, for example, when tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium dodecylbenzenesulfonyl (in the above formula (3), R ２ is a methyl group and X － is a linear dodecylbenzenesulfonate anion compound) is used as the VOC reducing agent, the propionaldehyde (PA) in the polyurethane foam is linearly reduced according to, for example, the following formula (III) with reference to tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium (cationic part) (see FIG. 2). Formula (III): [Propionaldehyde content in polyurethane foam] = a ＰＡ × [Content of cationic part of VOC reducing agent] + b ＰＡ In the above formula (III), a ＰＡ is, for example, -3×10 －３ or more, preferably, -1.5×10 －３ or more, and is, for example, -0.5×10 －３ or less, preferably, -1.0×10 －３ or less as a constant. a ＰＡ as, particularly preferably, -1.16×10 －３It is as follows. Further, in the above formula (III), b ＰＡ is, for example, a constant of 1.5 or more, preferably 2.0 or more, and for example, 5 or less, preferably 3 or less. b ＰＡと Thus, particularly preferably, it is 2.31. Incidentally, in the above formula (III), the propionaldehyde content in the polyurethane foam is measured in accordance with the examples described later. Further, the content of the cationic part of the VOC reducing agent is calculated as a ratio to 100 parts by mass of the polyol in accordance with the examples described later. Thus, in the method for reducing volatile organic compounds (VOCs), the volatile organic compounds (VOCs) can be linearly reduced according to the content of the cationic part of the above-described VOC reducing agent. In other words, the content of the cationic part of the VOC reducing agent in the polyurethane foam is appropriately set according to a linear function formula such as the above formulas (I) to (III). The content of the cationic part of the VOC reducing agent in the polyurethane foam is, on a mass basis, for example, 5 ppm or more, preferably 50 ppm or more, more preferably 500 ppm or more, with respect to the total amount of the polyurethane foam, and also, for example, 15000 ppm or less, preferably 10000 ppm or less, more preferably 8000 ppm or less. Further, the addition amount of the VOC reducing agent is specifically, for example, 0.0005 parts by mass or more, preferably 0.002 parts by mass or more, more preferably 0.003 parts by mass or more, further preferably 0.005 parts by mass or more, further preferably 0.010 parts by mass or more, further preferably 0.025 parts by mass or more, further preferably 0.035 parts by mass or more, further preferably 0.045 parts by mass or more, particularly preferably 0.05 parts by mass or more, with respect to 100 parts by mass of the polyol in the resin premix, and also, for example, 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, further preferably 0.3 parts by mass or less, further preferably 0.15 parts by mass or less, particularly preferably 0.10 parts by mass or less. Also, as a quality standard, from the perspective of sufficiently reducing VOC, for example, based on 100 parts by mass of the polyol in the resin premix, it is 5 ppm or more, preferably 15 ppm or more, more preferably 25 ppm or more, still more preferably 50 ppm or more, still more preferably 100 ppm or more, still more preferably 200 ppm or more, still more preferably 300 ppm or more, still more preferably 400 ppm or more, particularly preferably 500 ppm or more. Also, from the perspective of cost reduction, for example, it is 20,000 ppm or less, preferably 3,000 ppm or less, more preferably 2,000 ppm or less. Thereby, a resin premix containing a VOC reducing agent (VOC reducing agent-containing resin premix) can be obtained. Next, in this method, the resin premix and the polyisocyanate are mixed and foamed (foaming step). More specifically, polyisocyanate is added to the resin premix (containing a VOC reducing agent), stirred and reacted, and foamed by a known foaming method such as a slab method, a mold method, a spray method, etc. The blending ratio of the polyisocyanate to the resin premix is, for example, the isocyanate index (the ratio of the isocyanate group to 100 of the active hydrogens such as the hydroxyl group in the macro polyol in the resin premix, the hydroxyl group and amino group in the crosslinking agent, and water as the blowing agent (stoichiometric ratio)), for example, 70 or more, preferably 85 or more, and for example, 140 or less, preferably 120 or less. Thereby, a polyurethane foam can be produced. As described above, the resin premix is used to reduce the volatile organic compounds (VOC) of the polyurethane foam. And in such a method for reducing volatile organic compounds (VOC), since the VOC reducing agent is contained in the polyurethane foam, the volatile organic compounds (VOC) can be efficiently reduced, and the degree of reduction can be arbitrarily adjusted. That is, hydrazine compounds (such as hydrazide antioxidants like adipic acid dihydrazide), which are generally used to reduce volatile organic compounds (VOCs), can reduce volatile organic compounds (VOCs), but the amount of reduction of volatile organic compounds (VOCs) is constant regardless of the amount of hydrazine compound used and has a limit. Furthermore, there is also the problem that the degree of reduction of volatile organic compounds (VOCs) cannot be adjusted. In this regard, according to the above-mentioned VOC reducing agent (the compound represented by the above formula (1)), not only can volatile organic compounds (VOCs) be reduced, but the degree of reduction can be arbitrarily adjusted. Therefore, according to the required reduction amount, the addition amount of the VOC reducing agent can be adjusted, and the efficiency and cost reduction of reducing volatile organic compounds (VOCs) can be achieved. Also, according to the above-mentioned method for producing a polyurethane foam and the resin premix, a polyurethane foam with volatile organic compounds (VOCs) reduced to an arbitrary degree can be produced. In the above-mentioned addition step, the VOC reducing agent was added to the resin premix and / or the polyisocyanate before mixing the resin premix not containing the VOC reducing agent and the polyisocyanate not containing the VOC reducing agent. However, for example, the VOC reducing agent can also be separately added and mixed during their mixing, or after mixing them, the VOC reducing agent can be added to the mixture and further mixed. Furthermore, a plurality of these can also be combined. Also, without adding a VOC reducing agent, for example, by using the VOC reducing agent as a production catalyst (addition polymerization catalyst) for a polyol, the polyol can be pre-containing the VOC reducing agent. More specifically, for example, in the production of polyoxyalkylene polyol, the compound represented by the above formula (1) can be used as a reaction catalyst for the addition polymerization of alkylene oxide. When a compound represented by the above formula (1) is used as a reaction catalyst (addition polymerization catalyst) for the addition polymerization of alkylene oxide, preferably, a compound represented by the above formula (3) is used. More preferably, in the above formula (3), X － is a compound represented by a hydroxyanion or an alkoxy anion. Particularly preferably, in the above formula (3), X － is a compound represented by a hydroxyanion. In the presence of such an addition polymerization catalyst (compound represented by the above formula (1)), by subjecting an initiator such as a low molecular weight polyol or a low molecular weight polyamine to addition polymerization of alkylene oxide, a polyoxyalkylene polyol containing the compound represented by the above formula (1) can be obtained. When the obtained polyoxyalkylene polyol is used in the production of a polyurethane foam, the resulting polyurethane foam contains the compound represented by the above formula (1). At this time, the compound represented by the above formula (1) can act as a VOC reducing agent. That is, the compound represented by the above formula (1) in the polyoxyalkylene polyol can be also used as a VOC reducing agent. In such a case, the amount of the compound represented by the above formula (1) used is appropriately adjusted so that the content ratio of the VOC reducing agent with respect to 100 parts by mass of the polyol in the resin premix is within the above range. Furthermore, for example, a polyoxyalkylene polyol containing the compound represented by the above formula (1) can also be used as a raw material for a polymer polyol, a polyurethane polyol, etc. Preferably, the above polyoxyalkylene polyol is used as a raw material for a polymer polyol. In such a case, the resulting polymer polyol contains the compound represented by the above formula (1). When the obtained polymer polyol is used in the production of a polyurethane foam, the resulting polyurethane foam contains the compound represented by the above formula (1). At this time, the compound represented by the above formula (1) can act as a VOC reducing agent. That is, even in such a case, the compound represented by the above formula (1) in the polyol can also be used as a VOC reducing agent. In such a case, the amount of the compound represented by the above formula (1) used is appropriately adjusted so that the content ratio of the VOC reducing agent to 100 parts by mass of the polyol in the resin premix is within the above range. Furthermore, as described above, by using the VOC reducing agent as a production catalyst (addition polymerization catalyst) for the polyol, even when the resin premix is preliminarily contained with the VOC reducing agent, the VOC reducing agent can be further added to the obtained resin premix. In such a case, before mixing the resin premix containing the VOC reducing agent and the polyisocyanate, the VOC reducing agent may be added to the resin premix and / or the polyisocyanate. For example, at the time of mixing them, the VOC reducing agent can be separately added and mixed. Furthermore, after mixing them, the VOC reducing agent can be added to the mixture and further mixed. Furthermore, a plurality of these combinations can also be made. In addition, the polyol obtained by using the VOC reducing agent as a production catalyst for the polyol and the polyol obtained by using an alkali metal hydroxide or the like without using the VOC reducing agent as a production catalyst for the polyol can be mixed and used at an appropriate ratio. In such a case, the resin premix containing the polyol contains the VOC reducing agent. Therefore, the resin premix can be used for the production of polyurethane foam without separately adding the VOC reducing agent, and if necessary, the VOC reducing agent can be further added and used for the production of polyurethane foam. Furthermore, as a production catalyst for the polyol, the polyol can be produced by using the VOC reducing agent and the alkali metal hydroxide in combination. In such a case, the resin premix containing the polyol contains the VOC reducing agent. Therefore, the resin premix can be used for the production of polyurethane foam without separately adding the VOC reducing agent, and if necessary, the VOC reducing agent can be further added and used for the production of polyurethane foam. Further, if necessary, after the production of the polyoxyalkylene polyol and before the production of the polyurethane foam, X of the compound represented by the above formula (1) － can be appropriately exchanged. More specifically, for example, as the reaction catalyst in the production of the above polyoxyalkylene polyol, when a compound represented by the above formula (1) in which X － is a hydroxyanion is used, the resulting polyoxyalkylene polyol contains a compound represented by the above formula (1) in which X － is a hydroxyanion. This polyoxyalkylene polyol can be used as it is for the production of the polyurethane foam. However, for example, to the polyoxyalkylene polyol, a compound that supplies other X － , for example, a sulfonic acid (for example, p-toluenesulfonic acid, dodecylbenzenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, camphorsulfonic acid, etc.) is added, and by mixing and stirring, X － can be exchanged for a sulfonyl anion. Thereby, the types of the addition polymerization catalyst in the production of the polyoxyalkylene polyol and the VOC reducing agent contained in the polyurethane foam can be changed. That is, in the addition polymerization of the alkylene oxide, a compound suitable for the addition polymerization of the alkylene oxide (for example, a compound represented by the above formula (1) in which X － is a hydroxyanion) is used, and then by changing X － , the polyurethane foam can contain a compound suitable as a VOC reducing agent (for example, a compound represented by the above formula (1) in which X － is a sulfonyl anion). Even by such a method, volatile organic compounds (VOCs) can be efficiently reduced, and the degree of reduction can be arbitrarily adjusted. Next, the present invention will be described based on Examples and Comparative Examples, but the present invention is not limited by the following Examples. Note that "parts" and "%" are based on mass unless otherwise specified. Also, specific numerical values such as the blending ratio (content ratio), physical property values, parameters, etc. used in the following description can be replaced with the upper limit values (numerical values defined as "hereinafter", "less than") or lower limit values (numerical values defined as "above", "exceeding") of the corresponding blending ratio (content ratio), physical property values, parameters, etc. described in the above "Mode for Carrying Out the Invention". <Explanation of Raw Materials> PZN compound: Tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium (PZN cation (hereinafter referred to as PZN)) dodecylbenzenesulfonyl (in the above formula (3), R ２ is a methyl group, X － is a compound of a linear dodecylbenzenesulfonate anion.) EP828; Actocol EP-828 (polyoxyalkylene polyol (block copolymer of propylene oxide-ethylene oxide), ethylene oxide content (terminal oxyethylene group content): 15% by mass, number average molecular weight: 6000, average functionality: 3, hydroxyl value: 28 mgKOH / g, manufactured by Mitsui Chemicals, Inc.) EP330N; Actocol EP-330N (polyoxyalkylene polyol (block copolymer of propylene oxide-ethylene oxide), ethylene oxide content (terminal oxyethylene group content): 15% by mass, number average molecular weight: 5000, average functionality: 3, hydroxyl value: 34 mgKOH / g, manufactured by Mitsui Chemicals, Inc.) POP-3623; Actocol POP-3623 (polymer polyol, hydroxyl value: 22 mgKOH / g, manufactured by Mitsui Chemicals, Inc.) EP-505S; Actocol EP-505S (compatibilizer, polyether polyol (polyoxyalkylene polyol (random copolymer of propylene oxide - ethylene oxide)), ethylene oxide content: 70% by mass, number average molecular weight: 3300, average functionality: 3, hydroxyl value: 52 mg KOH / g, manufactured by Mitsui Chemicals, Inc.) KL-210; Actocol KL-210 (crosslinking agent, average functionality: 3.75, hydroxyl value: 840 mg KOH / g, manufactured by Mitsui Chemicals, Inc.) IRGANOX 1135; Antioxidant manufactured by BASF ADH: Dihydrazide adipate, hydrazide-based antioxidant manufactured by Nippon Fine Chemical Co., Ltd. VDH: Amicure VDH, hydrazide-based antioxidant manufactured by Ajinomoto Fine-Techno Co., Inc. 33LV; DABCO 33LV (amine catalyst (urethane-forming catalyst), 33% by mass diethylene glycol solution of triethylenediamine, manufactured by Air Products Japan, Ltd.) A-1; Niax A-1 (amine catalyst (urethane-forming catalyst), manufactured by Momentive) L5309; L-5309 (silicone foam stabilizer, manufactured by Momentive) L3601; L-3601 (silicone foam stabilizer, manufactured by Toray Dow Corning Co., Ltd.) DC2525; DC-2525 (silicone foam stabilizer, manufactured by Air Products Japan, Ltd.) TM20; Cosmonate TM-20 (polyisocyanate (mixture of 80:20 mass ratio of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI) 80% by mass and diphenylmethane diisocyanate (MDI) 20% by mass), isocyanate group content: 45% by mass, manufactured by Mitsui Chemicals, Inc.) Synthesis Example 1 (Polyoxyalkylene Polyol A Containing VOC Reducing Agent) An autoclave equipped with a stirring device, a thermometer, and a pressure gauge was charged with glycerin and an amount of tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide corresponding to 0.18 mol% / mol OH as an addition polymerization catalyst relative to the hydroxyl groups of glycerin. After dehydration under reduced pressure at 100 °C for 6 hours, propylene oxide was continuously introduced at a reaction temperature of 120 °C and a maximum reaction pressure of 3.8 kg / cm2 for addition polymerization. Subsequently, ethylene oxide was continuously introduced at a reaction temperature of 120 °C and a maximum reaction pressure of 3.8 kg / cm ２ for addition polymerization. Then, dodecylbenzenesulfonic acid was added in an amount of 2.1 equivalents relative to tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide, and the mixture was stirred at 100 °C for 2 hours. Thereby, a polyoxyalkylene polyol A (hereinafter referred to as polyol A) containing tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium dodecylbenzenesulfonate (PZN compound) was obtained. The average functionality of this polyol A was 3, the hydroxyl value was 36 mg KOH / g, and the terminal oxyethylene group content was 17% by mass. The content ratio of PZN (cationic part) of the PZN compound with respect to polyol A was calculated to be 840 ppm from the charged amount. Synthesis Example 2 (Polyoxyalkylene Polyol B Containing a VOC Reducing Agent) An autoclave equipped with a stirring device, a thermometer, and a pressure gauge was charged with glycerin and an amount of tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide corresponding to 0.18 mol% / mol OH as an addition polymerization catalyst relative to the hydroxyl groups of glycerin. After dehydration under reduced pressure at 100 °C for 6 hours, propylene oxide was continuously introduced at a reaction temperature of 90 °C and a maximum reaction pressure of 3.8 kg / cm2 for addition polymerization. Subsequently, ethylene oxide was continuously introduced at a reaction temperature of 100 °C and a maximum reaction pressure of 3.8 kg / cm2 for addition polymerization. Then, dodecylbenzenesulfonic acid was added in an amount of 2.3 equivalents relative to PZN, and the mixture was stirred at 100 °C for 2 hours to obtain a polyoxyalkylene polyol B (hereinafter referred to as polyol B). The average functionality of this polyol B was 3, the hydroxyl value was 24 mg KOH / g, and the terminal oxyethylene group content was 15% by mass. The content ratio of PZN (cationic part) of the PZN compound to polyol B was calculated to be 550 ppm from the charged amount. Synthesis Example 3 (Polyoxyalkylene polyol C containing a VOC reducing agent) Into an autoclave equipped with a stirrer, a thermometer, and a pressure gauge, tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium hydroxide in an amount of 0.18 mol% / mol OH as an addition polymerization catalyst was added to glycerin and the hydroxyl groups of glycerin, and dehydration under reduced pressure was carried out at 100°C for 6 hours. Then, propylene oxide was continuously introduced and addition polymerized at a reaction temperature of 120°C and a maximum reaction pressure of 3.8 kg / cm ２ Then, ethylene oxide was continuously introduced and addition polymerized at a reaction temperature of 110°C and a maximum reaction pressure of 3.8 kg / cm ２ Then, dodecylbenzenesulfonic acid was added in an amount of 2.0 equivalents based on tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium hydroxide and stirred at 100°C for 2 hours to obtain polyoxyalkylene polyol C (hereinafter referred to as polyol C). The average functionality of this polyol C was 3, the hydroxyl value was 28 mg KOH / g, and the terminal oxyethylene group content was 15% by mass. The content ratio of PZN (cationic part) of the PZN compound to polyol C was calculated to be 640 ppm from the charged amount. Synthesis Example 4 (Polymer polyol D containing a VOC reducing agent) An autoclave equipped with a stirring device, a thermometer, a pressure gauge, and a liquid feeding device was charged with polyol A until it was full, and while stirring, the temperature was raised to 120 °C. A mixed solution of polyol A, 2,2'-azobis(isobutyronitrile), acrylonitrile, and styrene was continuously charged into the autoclave. The initial reaction solution obtained continuously from the discharge port was discarded, and the subsequent reaction solution was used in the next step. The reaction conditions were a reaction temperature of 120 °C and a reaction pressure of 440 kPa, and the residence time was 50 minutes. Under the condition of 655 Pa or less, a heat decompression treatment was performed for 3 hours to remove unreacted ethylenically unsaturated monomers and decomposition products of the polymerization initiator, and polymer polyol D (hereinafter referred to as polyol D) was obtained. The average functionality of this polyol D was 3, the hydroxyl value was 22 mg KOH / g, the content rate of the component derived from polyol A was 60% by mass, the content rate of the polymer component derived from acrylonitrile was 16% by mass, and the content rate of the polymer component derived from styrene was 24% by mass. These content rates were calculated from the charged amount and the amount of unreacted monomers quantified by gas chromatography. Further, the content ratio of PZN (cationic part) of the PZN compound derived from polyol A to polyol D was calculated to be 504 ppm. <Manufacture of Polyurethane Foam> (Example 1) 100 parts by mass of EP828 (polyoxyalkylene polyol), 0.35 parts by mass of 33LV (amine catalyst), 0.06 parts by mass of A-1 (amine catalyst), 2.7 parts by mass of water (foaming agent), 3.0 parts by mass of KL210 (crosslinking agent), 0.5 parts by mass of EP-505S (continuous agent), 1.0 parts by mass of L-3601 (foam stabilizer), and 672 ppm ( / 100 parts by mass of polyol) of tetrakis[tris(dimethylamino)phosphoranilideneamino]phosphonium dodecylbenzenesulfonyl (VOC reducing agent, PZN compound) were blended, and they were mixed to prepare a resin premix. Next, the obtained resin premix was temperature-controlled to 22 ± 1°C, and 32.1 parts by mass of TM20 (polyisocyanate) temperature-controlled to 22 ± 1°C (isocyanate index: 95) was added thereto. Immediately, it was vigorously stirred at 5000 rpm for 5 seconds using a homogenizer, and immediately injected into a mold with an inner dimension of 400 mm × 400 mm × 100 mm previously adjusted to 65°C. The lid was closed and foamed. Thereafter, the mold was kept at 65°C and the curing reaction was allowed to proceed for 6 minutes, and the polyurethane foam was taken out of the mold. Thereby, a flexible polyurethane foam was produced. (Examples 2 to 12 and Comparative Examples 1 to 5) According to the formulation described in Table 1, a polyurethane foam was produced in the same manner as in Example 1. In Examples 2 to 8, in the same manner as in Example 1, a PZN compound as a VOC reducing agent was added during the preparation of the resin premix. In Examples 9 to 12, no PZN compound was added during the preparation of the resin premix, and the PZN compound contained in Polyols A to D was used as a VOC reducing agent. Further, in Comparative Example 1, no VOC reducing agent was added. In Comparative Examples 2 to 4, adipic acid dihydrazide (ADH) was added as a VOC reducing agent instead of the compound represented by the above formula (1). In Comparative Examples 5 to 7, Amicure VDH (manufactured by Ajinomoto Fine-Techno Co., Inc., VDH) was added as a VOC reducing agent instead of the compound represented by the above formula (1). In Table 1, the content of PZN (based on the cation moiety) is shown as the ratio (ppm) to 100 parts by mass of the polyol in the resin premix. <Measurement of Aldehyde in Polyurethane Foam> The aldehyde in the polyurethane foams produced in Examples 1 to 12 and Comparative Examples 1 to 5 was measured by the following measurement method, and the results for the amount of acetaldehyde and the amount of propionaldehyde were obtained. The results are shown in a table. <Measurement Method> (1) Density After foaming, the size and weight of the polyurethane foam after 24 hours were measured, and the density was calculated. (2) Measurement of acetaldehyde (AA) and propionaldehyde (PA) After the measurement of the density in (1) above, the polyurethane foam was cut into 80 mm × 100 mm to obtain samples. Also, the obtained samples were placed in a sealed container and stored for one week. Then, the samples were placed in a 10 L fluororesin bag and purged three times with pure nitrogen. Next, about 4 L of pure nitrogen was introduced, and the mixture was heated in a constant temperature room at 65°C for 2 hours. Next, 3.0 L was collected at a flow rate of 0.5 L / min. using a DNPH cartridge for aldehyde analysis, and then the remaining total gas was aspirated to calculate the total gas volume. Then, the derivative was eluted through acetonitrile in the DNPH cartridge for aldehyde analysis, and the volume was fixed to 5 mL and measured by HPLC. And from the calculation results, the amount of each aldehyde was converted per total gas volume (sample). Also, from the results of Examples 2 to 6, the relationship between the content ratio of the cationic part of the VOC reducer and the reduction amount of acetaldehyde is shown in FIG. 1, and further, the relationship between the usage amount of the content ratio of the cationic part of the VOC reducer and the reduction amount of propionaldehyde is shown in FIG. 2, respectively. (Discussion) From Examples 1 to 12 and Comparative Example 1, it was confirmed that if PZN is contained in the polyurethane foam, acetaldehyde (AA) and propionaldehyde (PA) as volatile organic compounds (VOCs) can be reduced. Also, from FIGS. 1 and 2, it was confirmed that the volatile organic compound (VOC) is linearly reduced according to the content of PZN, and thus, the reduction amount of the volatile organic compound (VOC) can be adjusted and can be set to an arbitrary reduction amount. On the other hand, from FIGS. 3 and 4, it was confirmed that even when the hydrazide-based antioxidant can reduce volatile organic compounds (VOCs), the amount of reduction of volatile organic compounds (VOCs) is constant regardless of the amount of the hydrazide-based antioxidant used and has a limit. The above invention has been provided as an exemplary embodiment of the present invention, but this is merely an example and should not be construed in a limiting manner. Modifications of the present invention that are apparent to those skilled in the art are included in the following claims. The method for reducing volatile organic compounds, the method for producing a polyurethane foam, and the resin premix of the present invention are widely used in various industrial fields where polyurethane foams are used.

Claims

------31 / 07 / 2017------(OCR)Page 1 of 5 pages Claims 1. Method for reducing volatile organic compounds in polyurethane foam, where the polyurethane foam contains compounds represented by the following formula(1):[Chemical Formula 1](Chemical Formula)(where, -N=R represents the following substructure(A) or substructure(B), and X- represents anion)[Chemical Formula 2](Chemical Formula)(where, R1 is the same or different, representing a hydrogen atom or hydrocarbon group with 1 to 20 carbon atoms, and may (are bonded to each other to form a ring structure) page 2 of 5 pages [Chemical Formula 3] (Chemical Formula) (where R2 is the same or different and represents a hydrogen atom or hydrocarbon group with 1 to 20 carbon atoms. R2 may be bonded to each other to form a ring structure. n” represents an integer of 0 to 3. n” corresponding to at least one of the four R groups in Formula (1) will not be 0) 2. Method for reducing volatile organic compounds according to claim 1,Where volatile organic compounds are reduced by a linear function according to the number of compounds represented by the formula(1) described above.

3. Method for reducing volatile organic compounds according to claim 1, where polyurethane foam is the product of the reaction of a resin premix containing polyols, and polyisocyanates, and the volume ratio of the cation portion of the compounds represented by the formula(1) described above relative to the total amount of polyols is 500 ppm or more.

4. Method for reducing volatile organic compounds. The method for the production of polyurethane foam with reduced volatile organic compounds is easily obtained according to claim 1, which includes: the preparation procedure of the resin premix containing polyols and polyisocyanates, the addition procedure of adding the compounds shown by formula (1) described above into the resin premix, and the foaming procedure of the mixing and foaming of the resin premix and polyisocyanates. Page 3 of Number 5. Page 5. Method for the production of polyurethane foam with reduced volatile organic compounds which includes: the preparation procedure of the resin premix containing polyols and polyisocyanates,The doping procedure of the compounds shown by the following formula(1) into the resin premix, and the foaming procedure of the mixing and foaming of the resin and polyisocyanate premix [Chemical Formula 4] (Chemical Formula) (where -N=R represents the following substructure(A) or substructure(B), and X- represents anion) [Chemical Formula 5] (Chemical Formula) (where R1 is the same or different, representing a hydrogen atom or hydrocarbon group with 1 to 20 carbon atoms, and may be bonded to each other to form a ring structure). Page 4 of 5 of the number of pages [Chemical Formula 6] (Chemical Formula) (where R2 is the same or different and represents a hydrogen atom or hydrocarbon group with 1 to 20 carbon atoms. R2 may be bonded to each other to form a ring structure. n” represents an integer of 0 to 3. n” corresponding to at least one of the four R groups in Formula (1) shall not be 0.) 6. The premix of resins used in the method for the manufacture of polyurethane foam pursuant to claim 5, which consists of: polyols and compounds represented by the following Formula (1) [Chemical Formula 7] (Chemical Formula) (where,-N=R represents the following substructure(A) or the following substructure(B), and X- represents anion) page 5 of 5 pages [Chemical Formula 8](Chemical Formula) (where, R1 is either identical or different, representing a hydrogen atom or hydrocarbon group with 1 to 20 carbon atoms, and may be bonded to each other to form a ring structure. [Chemical Formula 9](Chemical Formula) (where, R2 is either identical or different and represents a hydrogen atom or hydrocarbon group with 1 to 20 carbon atoms. R2 may be bonded to each other to form a ring structure. n” represents an integer from 0 to 3. n” corresponding to at least one of the four R groups in formula(1) is not 0)------------;,