Technical field
[0001]
　The present invention is a method for reducing volatile organic compounds, a process for producing and resin premix of polyurethane foam.
BACKGROUND
[0002]
　Polyurethane foams are polyols, and resin premix containing a catalyst and a blowing agent is obtained by reacting a polyisocyanate. Polyurethane foams, for example, such as cushion, have been used in a wide range of fields.
[0003]
　On the other hand, the polyurethane foam may acetaldehyde, volatile organic compounds such as formaldehyde (VOC) is contained. When these volatile organic compounds (VOC) are released into the atmosphere, because it may affect the global environment and the human body, it is possible to reduce volatile organic compounds from the polyurethane foam (VOC) has been required.
[0004]
　More specifically, for example, a polyisocyanate, a polyol, a polyol mixture comprising a catalyst and a crosslinking agent, upon molding the polyurethane molded article, a hydrazine compound as an aldehyde scavenger (e.g., such as adipic acid dihydrazide) , be added to the pre-polyol mixture has been proposed (e.g., Patent Document 1 see.).
CITATION
Patent Document
[0005]
Patent Document 1: JP 2006-182825 JP
Summary of the Invention
Problems that the Invention is to Solve
[0006]
　On the other hand, the amount of reduction required volatile organic compounds in various fields (VOC) are the various depending on the purpose and application, it is desirable to meet the required level of efficiency reduction amount.
[0007]
　However, the hydrazine compounds as described in Patent Document 1, although it is possible to reduce volatile organic compounds (VOC), reducing the amount of volatile organic compound (VOC), regardless of the amount of the hydrazine compound it is constant, and there is a limit. Furthermore, there is also a problem that can not adjust the degree of reduction of volatile organic compounds (VOC).
[0008]
　The present invention can adjust the degree of reduction of volatile organic compounds (VOC), also a method for reducing volatile organic compounds capable of reducing efficiently the volatile organic compounds (VOC), further, volatile organic compounds (VOC) are the manufacturing method and resin premix of reduced polyurethane foam.
Means for Solving the Problems
[0009]
　The present invention [1] is a method for reducing volatile organic compounds in the polyurethane foam, is contained the indicated polyurethane foam by the following formula (1) compound, include a method of reducing volatile organic compounds there.
[0010]
[Formula 1]

[0011]
(Wherein, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - represents an anion.)
[0012]
[Formula 2]

[0013]
(Wherein, R 1 is the same or different from each other, a hydrocarbon group of a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[0014]
[Formula 3]

[0015]
(Wherein, R 2 is the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. also, n is an integer of 0-3. However, n corresponding to at least one of R of the four R in the formula (1) not 0.)
　the present invention [2], the above formula depending on the content of the compound represented by (1) reducing the volatile organic compound as a linear function includes a method for reducing volatile organic compound according to the above [1].
[0016]
　The present invention [3], wherein the polyurethane foam, the resin premix containing a polyol, a reaction product of a polyisocyanate, the content of the cationic moiety of the compound represented by the formula (1) is of the polyol the total amount, is 500ppm or more, includes a method for reducing volatile organic compound according to the above [1] or [2].
[0017]
　The present invention [4], the resin premix containing a polyol, preparation step of preparing a polyisocyanate, adding step of adding a compound represented by the formula (1) in the resin premix, and the Rejinpure comprising a mix and the polyisocyanate mixture and foamed to the foaming process, and includes a reduction method of [1] to volatile organic compound according to any one of [3].
[0018]
　The present invention [5] is a method for producing polyurethane foams volatile organic compounds have been reduced, and the resin premix containing a polyol, preparation step of preparing a polyisocyanate, wherein the resin premix by the following formula ( adding step of adding a compound represented by 1), and comprises a foaming step of mixing and foaming the resin premix and the polyisocyanate comprises a method for producing polyurethane foams.
[0019]
[Chemical Formula 4]

[0020]
(Wherein, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - represents an anion.)
[0021]
[Formula 5]

[0022]
(Wherein, R 1 is the same or different from each other, a hydrocarbon group of a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[0023]
[Formula 6]

[0024]
(Wherein, R 2 is the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. also, n is an integer of 0-3. However, n corresponding to at least one of R of the four R in the formula (1) not 0.)
　the present invention [6], the [ 5] used in the method for producing polyurethane foam according to, and includes a polyol, containing a compound represented by the following formula (1), the resin premix.
[0025]
[Chemical Formula 7]

[0026]
(Wherein, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - represents an anion.)
[0027]
[Formula 8]

[0028]
(Wherein, R 1 is the same or different from each other, a hydrocarbon group of a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[0029]
[Formula 9]

[0030]
(Wherein, R 2 is the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. also, n is an integer of 0-3. Here, n corresponding to at least one of R of the four R in the formula (1) is not 0.)
Effect of the invention
[0031]
　The method for reducing volatile organic compounds of the present invention (VOC), for compounds represented by the above formula (1) is contained in the polyurethane foam, can be reduced efficiently volatile organic compounds (VOC), also, the formula (1) in accordance with the content of the compound represented by, it is possible to arbitrarily adjust the degree of reduction of volatile organic compounds (VOC).
[0032]
　Further, according to the polyurethane foam production process and resin premix of the present invention, it is possible to volatile organic compound (VOC) to produce a reduced polyurethane foam in any degree.
BRIEF DESCRIPTION OF THE DRAWINGS
[0033]
[1] Figure 1 is a correlation diagram showing the content of the cationic portion of the VOC reducing agent, the relation between the reduction amount of acetaldehyde.
FIG. 2 is a correlation diagram showing the content of the cationic portion of the VOC reducing agent, the relation between the reduction amount of propionaldehyde.
FIG. 3 is a correlation diagram showing the amount of ADH (hydrazide antioxidants), the relation between the reduction amount and reduction amount of propionaldehyde of acetaldehyde.
[4] FIG. 4 is a correlation diagram showing the amount of the VDH (hydrazide antioxidants), the relation between the reduction amount and reduction amount of propionaldehyde of acetaldehyde.
DESCRIPTION OF THE INVENTION
[0034]
　Polyurethane foam (e.g., flexible polyurethane foam) contains volatile organic compounds (VOC). In other words, the polyurethane foam is VOC-containing foam containing polyurethane foam with volatile organic compounds (foam composition).
[0035]
　Volatile organic compound (VOC) vapor pressure at 20 ° C. is, 2500 Pa or less, preferably, the following organic compound 150 Pa.
[0036]
　The volatile organic compounds (VOC), e.g., acetaldehyde, formaldehyde, aldehyde compounds such as propionaldehyde, for example, styrene, toluene, aromatic organic compounds such as benzene, for example, ethyl acetate, esters such as butyl acetate compounds, e.g. , methanol, ethanol, isopropanol, alcohol compounds such as butanol, such as acetone, ketone compounds such as methyl ethyl ketone, for example, cyclohexane, aliphatic cyclic compounds such as cyclopentane, for example, phthalate -n- butyl phthalate -n - phthalic acid ester compounds, such as ethylhexyl, for example, nitrile compounds such as acetonitrile, for example, fluorine-containing organic compounds, for example, chloroform, methylene chloride, vinyl chloride, ethylbenzene, p - dichlorobenzene, such as chlorine-containing organic compounds such as o- dichlorobenzene, and the like.
[0037]
　Preferably, the volatile organic compounds (VOC), acetaldehyde, formaldehyde, an aldehyde compound selected from propionaldehyde, styrene, toluene, aromatic organic compound selected from benzene, ethyl acetate, ester compound selected from butyl acetate , methanol, ethanol, isopropanol, alcohol compound selected from butanol, acetone, ketone compounds selected from methyl ethyl ketone, cyclohexane, aliphatic cyclic compound selected from cyclopentane, phthalate -n- butyl phthalate -n - phthalic acid ester compound selected from ethylhexyl, nitrile compound selected from acetonitrile, fluorine-containing organic compounds, chloroform, methylene chloride, vinyl chloride, ethylbenzene, p- dichloro Benzene, at least one selected from the group consisting of chlorine-containing organic compound selected from o- dichlorobenzene.
[0038]
　More preferably, the volatile organic compound (VOC) acetaldehyde, is at least one selected from formaldehyde and propionaldehyde, more preferably at least one selected from the group consisting of acetaldehyde and propionaldehyde.
[0039]
　One or more of these volatile organic compounds (VOC), which may be contained in the polyurethane foam.
[0040]
　Therefore, in the method for reducing volatile organic compounds of the present invention (VOC), to reduce volatile organic compounds in the polyurethane foam (VOC). More specifically, in this method, to reduce volatile organic compounds (VOC), the polyurethane foam, a compound represented by the following formula (1) (hereinafter referred to as VOC reducing agent.) Is contained.
[0041]
[Formula 10]

[0042]
(Wherein, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - represents an anion.)
[0043]
[Of 11]

[0044]
(Wherein, R 1 is the same or different from each other, a hydrocarbon group of a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[0045]
[Chem. 12]

[0046]
(Wherein, R 2 is the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. also, n is an integer of 0-3. Here, n corresponding to at least one of R of the four R of said not zero.)
　in the above formula (1), R is the partial structural formula as shown by (a), VOC reduction agent is a compound represented by the following formula (2).
[0047]
[Formula 13]

[0048]
(Wherein, R 1 is the formula R a (A) 1 and the same meaning, X - is X in the formula (1) - . And the same significance)
　the partial structural formula (A) and Formula in (2), R 1 are each the same or different and are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
[0049]
　Examples of the hydrocarbon group having 1 to 20 carbon atoms, for example, organic aliphatic hydrocarbon group having 1 to 20 carbon atoms, optionally substituted aryl group having 6 to 20 carbon atoms, or a substituted group even an aralkyl group which may having 7 to 20 carbon atoms have been, preferably, include aliphatic hydrocarbon group having 1 to 20 carbon atoms.
[0050]
　Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms, such as methyl group, ethyl group, n- propyl group, an isopropyl group, n- butyl group, sec- butyl group, tert- butyl group, 2-butyl group, 1-pentyl, 2-pentyl, 3-pentyl, 2-methyl-1-butyl group, an isopentyl group, tert- pentyl group, 3-methyl-2-butyl group, a neopentyl group, n- hexyl group, 4 - methyl-2-pentyl group, 1-heptyl, 3-heptyl, 1-octyl, 2-octyl, 2-ethyl-1-hexyl, 1,1-dimethyl-3,3-dimethylbutyl group , 1-nonyl, 1-decyl group, undecyl group, dodecyl group, tridecyl group, tetradecyl group, pentadecyl group, hexadecyl group, heptadecyl group, octadecyl group, nonadecyl group, etc. Chain saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, and 1 carbon atoms such as cyclodecyl 20 cyclic saturated aliphatic hydrocarbon group include a vinyl group, 2-propenyl chain unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms, such groups, e.g., 1-3 carbon atoms such as a cyclohexenyl group 20 cyclic unsaturated aliphatic hydrocarbon group and the like, preferably, include chain saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably, a methyl group, an ethyl group, n- propyl group, isopropyl, tert- butyl group, tert- pentyl, 1,1-dimethyl-3,3-dimethylbutyl group and the like, more preferably, methyl And the like.
[0051]
　Examples of the aryl group having 6 to 20 carbon atoms an aryl group having 6 to carbon atoms, which may 20 have a substituent, for example, a phenyl group, 2-tolyl group, 3-tolyl group, 4-tolyl group, 2 , 3-xylyl group, 2,4-xylyl, 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, a 2,4,6-trimethylphenyl group, 2,3,4,5-methylphenyl group, 2,3,4,6-tetramethyl-phenyl group, 2-ethyl phenyl group, 3-ethylphenyl group, 4-ethylphenyl group, a 1-naphthyl group, 2-naphthyl group.
[0052]
　As the substituent of the aryl group to 6 carbon atoms which may have a substituent group 20, for example, a hydroxyl group, a halogeno group (e.g., chloro group, fluoro group, such as bromo, and iodo), cyano group, an amino group, a carboxy group, an alkoxy group (e.g., methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec- butoxy, tert- butoxy, pentyloxy, isopentyloxy, neopentyloxy, carbon such hexyloxy an alkoxy group having 1 to 6), an aryloxy group (e.g., phenoxy group), an alkoxycarbonyl group (e.g., methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec- Bed Butoxycarbonyl, tert- butoxycarbonyl, pentyloxycarbonyl, iso-pentyloxycarbonyl, neopentyloxy carbonyl, an alkoxycarbonyl group having 1 to 6 carbon atoms such as hexyl oxycarbonyl), an alkylthio group (e.g., methylthio, ethylthio, propylthio, an alkylthio group having 1 to 4 carbon atoms, etc.), and arylthio groups such as butylthio (e.g., phenylthio group). Incidentally, the substitution position and number of substituents the substituents can be arbitrarily determined.
[0053]
　The aralkyl group having 7 to 20 carbon atoms in the aralkyl group which has carbon atoms 7 be ~ 20 have a substituent, for example, benzyl, 1-phenylethyl, 2-phenylethyl, 1-phenylpropyl , 2-phenylpropyl, 3-phenylpropyl, o- methylbenzyl, m- methylbenzyl, p- methylbenzyl, o- ethylbenzyl, m- ethylbenzyl, p- ethylbenzyl, o- isopropyl benzyl, m- isopropylbenzyl , p- isopropylbenzyl, 2,3,4-trimethyl benzyl, 3,4,5-trimethyl benzyl, 2,4,6-trimethyl benzyl and the like.
[0054]
　As the substituent of the aralkyl group which has carbon atoms 7 be ~ 20 have a substituent, for example, substituents of the aryl group for the substituent ~ carbon atoms 6 have a 20 and the like.
[0055]
　Further, R 1 each other may be bonded to form a ring structure. Preferably, R attached to the same guanidine structure 1 with each other to form a ring structure together.
[0056]
　R 1 if each other to form a ring structure, R 1 as, for example, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, an alkylene group having 2 to 20 carbon atoms, such as a hexamethylene group, e.g., cyclohexylene cycloalkylene group having 3 to 20 carbon atoms, such groups, for example, an alkenylene group having 2 to 20 carbon atoms, such as vinylene group, for example, cycloalkenylene group having 3 to 20 carbon atoms such as cyclohexylene group, such as a phenylene group , an arylene group having 6 to 20 carbon atoms such as a naphthylene group, such as an aralkylene group having 8 to 20 carbon atoms, such as phenylethylene group and the like, preferably, include an alkylene group having 2 to 20 carbon atoms. More preferably, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, and more preferable example is a tetramethylene group.
[0057]
　Further, R 1 as the ring structure with each other are bonded to each other, for example, pyrrolidinyl group, pyrrolyl group, piperidinyl group, an indolyl group, etc. isoindolyl group.
[0058]
　R 1 is preferably identical to each other.
[0059]
　R 1 as, preferably, include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably, include a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably, a methyl group, ethyl, n- propyl group, and isopropyl group, particularly preferably, methyl group.
[0060]
　In the above formula (1), X - represents an anion, preferably represents hydroxy anion (hydroxide ion), alkoxy anion (alkoxide), carboxy anion, sulfonyl anion, bicarbonate anion, halide ions .
[0061]
　The alkoxy anion, e.g., methoxide, ethoxide, n- propoxide, isopropoxide, n- butoxide, sec- butoxide, tert- butoxide, cyclohexoxy de, Putokishido to 2, 1 Okutokishido, phenoxide, and the like .
[0062]
　The carboxy anion, such as formic acid anions, acetate anions, propionic acid anion, butyric acid anion, isobutyric acid anion, caproic acid anion, lauric acid anion, palmitic acid anion, stearic acid anion, benzoic acid anion, decyl benzoate, dodecyl benzoate anion, lactic anion, malic acid anions, tartrate anions, citrate anions, like ricinoleic acid anion.
[0063]
　The sulfonyl anion, for example, p- toluenesulfonic acid anion, dodecylbenzenesulfonic acid anion (linear, including branched), benzenesulfonic acid anion, methanesulfonic acid anion, and a camphorsulfonate anion.
[0064]
　The halide ions, e.g., fluoride ion, chloride ion, bromide ion, include iodide ions, preferably include chloride ion.
[0065]
　X - as, more preferably, sulfonyl anion, hydroxy anion, include halide ions, more preferably, sulfonyl anion include halide ions.
[0066]
　Compound represented by the formula (2), specifically, tetrakis (1,1,3,3-tetramethyl-guanidino) phosphonium chloride, tetrakis (1,1,3,3-tetramethyl-guanidino) phosphonium hydroxide , tetrakis (1,3-diisopropyl-imidazolidinone phosphorus imino) phosphonium chloride, tetrakis (1,3-dimethylimidazolidinone phosphorus imino), such as phosphonium chloride and the like, preferably, tetrakis (1,1,3,3-tetramethyl guanidino) phosphonium chloride, tetrakis (1,1,3,3-tetramethyl-guanidino) phosphonium hydroxide and the like, and more preferable example tetrakis (1,1,3,3-tetramethyl-guanidino) phosphonium chloride.
[0067]
　Compounds represented by these above formula (2) may be used alone or in combination of two or more kinds.
[0068]
　Compound represented by the formula (2), for example, can be manufactured by the manufacturing method of the phosphonium salts described in German Patent Application Publication Specification No. DE102006010034A1.
[0069]
　In the above formula (1), R is, when represented by the partial structural formula (B), VOC reduction agent is, for example, a compound represented by the following formula (3).
[0070]
[Formula 14]

[0071]
(Wherein, R 2 is the formula R a (B) 2 and the same meaning, X - is X in the formula (1) - indicates the same meaning, n is the same or different from each other, the same meaning as n in formula (B).)
　the above partial structural formula (B) and the formula (3), R 2 are each the same or different and carbonization of hydrogen atoms or a C 1-20 It represents hydrogen radical.
[0072]
　Examples of the hydrocarbon group having 1 to 20 carbon atoms, for example, the above hydrocarbon group with carbon number of 1 to 20.
[0073]
　Further, R 2 to each other are the same or different from each other, they may be bonded together to form a ring structure. Preferably, R which is directly bonded to the same nitrogen 2 to each other to form a ring structure together.
[0074]
　R 2 if each other to form a ring structure, R 2 as, dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group and the like, preferably, dimethylene group, trimethylene group, tetramethylene group and the like.
[0075]
　R 2 is preferably identical to each other.
[0076]
　R 2 as, preferably, include an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably, include a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably, a methyl group, ethyl, n- propyl group, and isopropyl group, particularly preferably, methyl group.
[0077]
　In the above partial structural formula (B) and the formula (3), n is the same or different from each other, an integer of 0 to 3, preferably, same or different from each other, an integer of 1 or 2 are shown, more preferably, the formula (3) at least three of the first n in the rest represents 2, more preferably, n is all the n in the formula (3) indicates the 1.
[0078]
　Compounds represented by the above formula (3), specifically, tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium hydroxide, tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium chloride, tetrakis [tris (diethylamino) phosphoranylidene two isopropylidene amino] phosphonium chloride, tetrakis [tris (1-Azoshikurononiru) phosphoramidate two isopropylidene amino] phosphonium chloride, tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium bromide, tetrakis [tris (dimethylamino) phospho- such Rani isopropylidene amino] phosphonium dodecylbenzene sulfonyl, and more preferably include tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium Chloride, tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium dodecylbenzene sulfonyl and the like.
[0079]
　Compounds represented by these above formula (3) may be used alone or in combination of two or more kinds.
[0080]
　The compound represented by formula (3) is, for example, can be synthesized by synthetic methods or similar methods of phosphazenium compounds described in European pages 12 to 13 pages of Patent Application Publication specification EP0791600A1.
[0081]
　These VOC reduction agents can be used alone or in combination of two or more kinds.
[0082]
　As VOC reducing agent, preferably a compound represented by the formula (3), and more preferably include tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium dodecylbenzene sulfonyl (the above formula (3), R 2 is a methyl group, X - . is linear dodecylbenzene sulfonate anion at which compounds).
[0083]
　According to such a VOC reducing agents, it can be reduced efficiently volatile organic compounds (VOC), also can be the degree of the reduction obtained arbitrarily adjusted polyurethane foam.
[0084]
　To contain a VOC reduction agent in polyurethane foams, at the time of manufacture of the polyurethane foams, the ingredients (resin premix and / or polyisocyanate) to contain a VOC reducing agent, reacting them. Preferably, it contains a VOC reducing agent to the resin premix is ​​reacted with the resin premix and polyisocyanate (described later).
[0085]
　As a method for containing the VOC reducing agent to the resin premix, it is not particularly limited, for example, using a VOC reduction agent as addition polymerization catalysts in the production of the polyol (described later), including the resulting polyol (VOC reducing agent. ) can be used to prepare the resin premix containing a VOC reducing agent. Also, after preparation of the polyol without the use of VOC reducing agent, by the addition of VOC reduction agent to the polyol, it can be prepared resin premix containing VOC reducing agent. Further, by using the VOC reducing agent as addition polymerization catalysts in the production of the polyol (described later), the resulting polyol (. Containing VOC reducing agent), may also be added a VOC reducing agent.
[0086]
　More specifically, in this method, first prepared a resin premix containing a polyol, a polyisocyanate (preparation step).
[0087]
　Resin premix contains, for example, a polyol and a urethane-forming catalyst and blowing agent.
[0088]
　Polyols preferably contain macro polyol.
[0089]
　Macro polyol, number average molecular weight of 400 to 10,000 molecular weight polyol (including a high molecular weight polyol polymer fine particles are dispersed), for example, polyether polyols, polyester polyols, polyesteramide polyols, polycarbonate polyols, polyurethane polyols , epoxy polyol, vegetable oil polyols, polyolefin polyols include acrylic polyols, polymer polyols (vinyl monomer-modified polyol). These macropolyols may be used alone or in combination of two or more kinds.
[0090]
　As a macro polyol, preferably polyether polyols, polymer polyols and the like. Further, the macro polyol, more preferably, contains a polyether polyol and polymer polyol.
[0091]
　The number average molecular weight is measured by gel permeation chromatography conforming to JIS K 7252-1 (2008) (GPC) analysis (in terms of polyethylene glycol) (hereinafter the same.).
[0092]
　The polyether polyols, polyoxyalkylene polyols.
[0093]
　Polyoxyalkylene polyols, for example, alkali metal hydroxides (sodium hydroxide, potassium hydroxide, etc.) in addition polymerization catalysts the presence of such low molecular weight polyols, addition weight of alkylene oxide and a low molecular weight polyamine, such as an initiator polymer (including random and / or block copolymers of two or more alkylene oxide) and the like.
[0094]
　Incidentally, the polyoxyalkylene polyol, when an alkali metal hydroxide as an addition polymerization catalyst as described above, polyoxyalkylene polyol containing no VOC reducing agent (and thus resin premix containing no VOC reducing agent) to obtain , when using a VOC reduction agent as addition polymerization catalysts, as described below, the polyoxyalkylene polyol (hence resin premix containing VOC reduction agent) is obtained which contains a VOC reducing agent.
[0095]
　Low molecular weight polyol is a compound having a molecular weight of less than 40 to 400 having two or more hydroxyl groups, such as 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-trimethyl pentanediol, 3,3 - dimethylol heptane, alkanes (C7 ~ 20) diol, 1,3- or 1,4-cyclohexanedimethanol and mixtures thereof, 1,3- or 1,4-cyclohexanediol, and mixtures thereof, hydrogenated bisphenol a , 1,4-dihydroxy-2-butene, 2,6-di Chill-1-octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dihydric alcohols such as dipropylene glycol, for example, glycerol, trimethylolpropane, trihydric alcohols such as triisopropanolamine, for example, tetra methylol methane (pentaerythritol), tetravalent alcohols such as diglycerin, for example, pentavalent alcohols such as xylitol, for example, sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, hexahydric alcohols such as dipentaerythritol, for example, 7-valent alcohols such as perseitol, for example, 8 monohydric alcohol and sucrose.
[0096]
　These low molecular weight polyols can be used alone or in combination of two or more.
[0097]
　Low molecular weight polyamine is a compound having a molecular weight of less than 40 to 400 having two or more amino groups, 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'-dicyclohexylmethane diamine, 2,5 (2,6) - bis ( aminomethyl) bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, o, m or p- tolylene diamine (TDA, OTD) low molecular weight diamines such as, for example, diethylenetriamine low molecular weight triamines, for example, triethylenetetramine, tetraethylene pen A low molecular weight polyamine having an amino group such as Min 4 or more can be mentioned.
[0098]
　These low molecular weight polyamines can be used alone or in combination of two or more.
[0099]
　The alkylene oxide, e.g., ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, allyl glycidyl ether include alkylene oxide having 2 to 12 carbon atoms, such as phenyl glycidyl ether.
[0100]
　These alkylene oxides may be used alone or in combination of two or more kinds.
[0101]
　As alkylene oxide, preferably ethylene oxide, propylene oxide, 1,2-butylene oxide, styrene oxide and the like, more preferably ethylene oxide, propylene oxide.
[0102]
　Polyoxyalkylene polyols, preferably, for example, polyethylene glycol, polypropylene glycol, propylene oxide - ethylene oxide copolymer (random and / or block copolymer) and the like.
[0103]
　Propylene oxide polyoxyalkylene polyol - If ethylene oxide copolymer is used, the ethylene oxide content, for example, 5 wt% or more, or preferably 10 mass% or more, e.g., 50 wt% or less, preferably is 30% by mass or less.
[0104]
　Incidentally, the ethylene oxide content is calculated from the formulation of the feed (same hereinafter.).
[0105]
　Also, propylene oxide as polyoxyalkylene polyols - If ethylene oxide copolymer is used, the terminal oxyethylene group content, for example, 5 wt% or more, or preferably 10 mass% or more, e.g., 50 wt % or less, preferably 30 mass% or less.
[0106]
　Incidentally, terminal oxyethylene group content is calculated from the formulation of the feed.
[0107]
　The number average molecular weight of the polyoxyalkylene polyol, for example, 400 or more, preferably, 1,000 or more, for example, 15000 or less, preferably 10,000 or less.
[0108]
　The average functionality of the polyoxyalkylene polyols may, for example, 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, e.g., 6 or less, or preferably 4 or less .
[0109]
　The average functionality of the polyoxyalkylene polyols is calculated from the formulation of the feed.
[0110]
　Further, the hydroxyl value of the polyoxyalkylene polyol, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably, 20 mgKOH / g or more, more preferably not 25 mg KOH / g or more, 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 not more than 30 mgKOH / g.
[0111]
　The hydroxyl value of the polyoxyalkylene polyol is within the above range, polyurethane foam obtained by using a polyol containing the polyoxyalkylene polyols can maintain the physical properties such as hardness.
[0112]
　The hydroxyl value is measured according to the description of JIS K-1557-1 (2007 years) (hereinafter the same.).
[0113]
　These polyoxyalkylene polyols can be used alone or in combination of two or more.
[0114]
　Polymer polyol (a vinyl monomer-modified polyol) can be obtained by dispersion polymerization of vinyl monomers in the high molecular weight polyol.
[0115]
　In the polymer polyol, a high molecular weight polyol is a dispersion medium of a vinyl monomer, the number average molecular weight, for example, 400 or more, or preferably 1000 or more, and is, for example, 10000 or less, or preferably 8000 or less . The high molecular weight polyols, e.g., polyether polyols, polyester polyols, and polycarbonate polyols can be mentioned, preferably, the polyether polyol.
[0116]
　These high molecular weight polyols can be used alone or in combination of two or more.
[0117]
　As the vinyl monomer, e.g., styrene, acrylamide, alkyl (meth) acrylates, vinyl cyanide (acrylonitrile), and the like cyanide vinylidene. These vinyl monomers may be used alone or in combination of two or more kinds. Further, among these, preferably, styrene, vinyl cyanide (acrylonitrile), and a combination of styrene and a vinyl cyanide.
[0118]
　The content of the polymer of vinyl monomer to polymer polyols, for example, 2 mass% or more, or preferably 5 mass% or more, and is, for example, 50 wt% or less, preferably 45 mass% or less.
[0119]
　Then, the polymer polyol is in a high molecular weight polyol, a vinyl monomer, for example, a radical polymerization initiator (e.g., persulfate, organic peroxides, azo compounds (such as azobisisobutyronitrile)), further can be obtained as required, the dispersion stabilizer, by reacting the like the presence of a chain transfer agent.
[0120]
　More specifically, the polymer polyol, the above vinyl monomer in a high molecular weight polyol is polymerized by a radical initiator, the resulting polymer microparticles are prepared by being dispersed in a high molecular weight polyol.
[0121]
　Polymer microparticles are polymer particles comprising a polymer of vinyl monomers.
[0122]
　In the polymer particles, at least a portion of the vinyl monomers may be grafted on high molecular weight polyol during the polymerization.
[0123]
　The number average molecular weight of the polymer polyol may, for example, 400 or more, preferably, 1,000 or more, for example, 15000 or less, or preferably 10000 or less.
[0124]
　The average functionality of the polymer polyols are, for example, 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, e.g., 6 or less, preferably 4 or less.
[0125]
　The average functionality of the polymer polyols is calculated from the formulation of the feed.
[0126]
　Further, the hydroxyl value of polymer polyol may, for example, 10 mgKOH / g or more, preferably, 15 mgKOH / g or more, more preferably, 20 mgKOH / g or more, more preferably not 25 mg KOH / g or more, 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 not more than 30 mgKOH / g.
[0127]
　Hydroxyl value of polymer polyol is within the above range, polyurethane foam obtained by using a polyol containing the polymer polyol can maintain the physical properties such as hardness.
[0128]
　These polymer polyols may be used alone or in combination of two or more kinds.
[0129]
　When the macro polyol contains a polyoxyalkylene polyol and polymer polyol, mixing ratio of the polyoxyalkylene polyols and polymer polyols, to the macro polyol 100 parts by weight polyoxyalkylene polyols, for example, for example, 10 mass parts or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably, not more than 60 parts by mass, also, polymer polyols are, for example, 10 parts by mass or more, preferably 30 parts by mass or more, more preferably 40 parts by mass or more, for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably, 60 parts by mass or less.
[0130]
　The mixing ratio of the polyoxyalkylene polyol and polymer polyol, by weight, for example, 10/90 or more, preferably, 30/70 or more, more preferably 40/60 or more, and for example, 90 / 10 or less, preferably, 70/30 or less, more preferably 60/40 or less.
[0131]
　The mixing ratio or mixing ratio of the polyoxyalkylene polyol and polymer polyol in the macro polyol is within the above range, polyurethane foam obtained by using a polyol containing the macro polyol, to maintain the physical properties such as hardness it can.
[0132]
　The hydroxyl value of the macro polyol, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably, 20 mgKOH / g or more, more preferably not 25 mg KOH / g or more, for example, 80 mg KOH / g or less, preferably is, 60 mg KOH / g or less, more preferably, 50 mg KOH / g or less, still more preferably not more than 30 mgKOH / g.
[0133]
　Hydroxyl value macro polyol is within the above range, polyurethane foam obtained by using a polyol containing the macro polyol, it is possible to maintain the physical properties such as hardness.
[0134]
　The average functionality of macro polyol, for example, 1.5 or more, preferably 2 or more, more preferably 2.5 or more, e.g., 6 or less, preferably 4 or less.
[0135]
　Further, polyols, other macros polyols described above can contain a low molecular weight polyols described above. If the polyol contains a low molecular weight polyol, the content is excellent does not inhibit the effect scope of the present invention, depending on the purpose and application, are set appropriately. Preferably, the polyol does not contain low molecular weight polyols.
[0136]
　The content of the polyol in the resin premix, based on the total amount of the resin premix, for example, 98.00 wt% or more, preferably 99.70 wt% or more, more preferably, 99.80% by mass or more, further preferred is a 99.90 wt% or more, and is, for example, less than 100% by weight, preferably 99.999% by mass or less, more preferably 99.99 wt% or less, more preferably, 99.98 weight % or less.
[0137]
　The urethanization catalyst, not particularly limited, include known urethanization catalyst, specifically, for example, triethylamine, triethylenediamine, bis - (2-dimethylaminoethyl) ether, morpholine compounds (e.g., N - aliphatic amines such as methyl morpholine, etc.), for example, quaternary ammonium salts such as tetraethyl ammonium hydroxide, for example, imidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-imidazole, such as methylimidazole s, for example, stannous octoate (tin octylate), tin acetate, tin oleate, laurate, dibutyltin diacetate, dimethyl tin dilaurate, dibutyl tin Shimerukapuchido, dibutyltin maleate, dibutyltin dilaurate (dibutyltin dilaurate), Djibouti Tin dineodecanoate, dioctyl tin dimercaptide, dioctyl tin dilaurate, organic tin compounds such as dibutyltin dichloride, for example, lead octoate, organic lead compounds such as lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example, organic cobalt compounds such as cobalt naphthenate, for example, organic copper compound such as octene copper, for example, bismuth octylate, and an organic bismuth compounds such as bismuth neodecanoate.
[0138]
　Further, as a urethanization catalyst, for example, potassium carbonate, potassium acetate, may also be mentioned, such as potassium salts such as potassium octoate.
[0139]
　Urethane catalysts may be obtained commercially, for example, Kao riser No. 31 (amine catalyst manufactured by Kao Corporation), Kao riser No. 120 (amine catalyst, 1-isobutyl-2-methylimidazole, manufactured by Kao Corporation), Kao riser No. 12 (amine catalyst manufactured by Kao Corporation), Kao riser No. 25 (amine catalyst manufactured by Kao Corporation), DABCO 33LV (amine catalyst, 33 wt% diethylene glycol solution of triethylenediamine, manufactured by Air Products Japan, Inc.), Niax A-1 (amine catalyst, Momentive Performance Materials Japan LLC company made (hereinafter referred to as "Momentive Co., Ltd.".)), TOYOCAT-NCE (amine catalysts, manufactured by Tosoh Corporation), Neostann U-100 (organic tin catalyst, dibutyl tin dilaurate, manufactured by Nitto Kasei Co., Ltd.), formate TK -1 (organotin catalyst manufactured by Mitsui Chemicals, Inc.) and the like.
[0140]
　These urethanization catalysts may be used alone or in combination of two or more kinds.
[0141]
　The mixing ratio of the urethanization catalyst (preferably, a macro polyol) polyol in the resin premix with respect to 100 parts by weight, for example, 0.1 parts by mass or more, or preferably, 0.3 parts by mass or more, and is , for example, 5 parts by mass or less, preferably not more than 1 part by weight.
[0142]
　The foaming agent is not particularly limited and a known foaming agent and the like, preferably include water.
[0143]
　As the foaming agent, and water, physical blowing agents (e.g., hydrofluorocarbons, hydrocarbons (e.g., cyclopentane), carbon dioxide gas, liquefied and carbonic gas) and, be combined at an appropriate ratio it can. The physical foaming agent, from the viewpoint of environmental load reduction, preferably, carbon dioxide, and liquefied carbon dioxide.
[0144]
　These physical blowing agents may be used alone or in combination of two or more kinds.
[0145]
　Mixing ratio of the foaming agent (preferably, a macro polyol) polyol in the resin premix with respect to 100 parts by weight, for example, 0.5 parts by mass or more, or preferably, 1 part by mass or more, e.g., 10 wt parts or less, preferably not more than 7 parts by mass.
[0146]
　When the content ratio of the foaming agent is within the above range, it is possible to obtain excellent foaming.
[0147]
　Further, the resin premix is ​​necessary, a crosslinking agent, communicating agent may contain additives such as foam stabilizers. Preferably, resin premix contains additives.
[0148]
　The crosslinking agent is not particularly limited, include known crosslinking agent, specifically, for example, alkanolamines, trihydric or higher polyols, such as alkylene oxide addition polyol.
[0149]
　The alkanolamine, e.g., triethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, trialkanolamine (tri C2 ~ 4 alkanol amines), such as tributanolamine or dialkanolamine (di C2 of diethanolamine such as 1-4 alkanolamine), poly alkanolamines and the like, preferably diethanolamine.
[0150]
　Examples of the trivalent or more polyols, such as glycerin, trihydric alcohols such as trimethylolpropane, for example, tetramethylolmethane, pentaerythritol, dipentaerythritol, D- sorbitol, xylitol, D- mannitol, such as D- mannitol and polyhydric alcohols having hydroxyl four or more thereof.
[0151]
　Alkylene oxide addition polyol is a polyol obtained by adding an alkylene oxide to trivalent or higher polyols described above, for example, hydroxyl value and a polyoxyalkylene polyol or less 200 mg KOH / g or more 2000mgKOH / g.
[0152]
　As a crosslinking agent, preferably, a trivalent or higher polyols and / or alkylene oxide addition polyol.
[0153]
　Further, as the trivalent or more polyols, preferably glycerol, and examples of the alkylene oxide addition polyols, preferably ACTCOL KL-210 (polyoxyalkylene polyol average functionality of 3.75, a hydroxyl value (OHV) = 840mgKOH / g, manufactured by Mitsui Chemicals, Inc.), and the like.
[0154]
　The hydroxyl value of the crosslinking agent, for example, 200 mg KOH / g or more, preferably not 800 mg KOH / g or more, for example, 2000mgKOH / g or less, or preferably less 1850mgKOH / g.
[0155]
　These crosslinking agents may be used alone or in combination of two or more kinds.
[0156]
　The mixing ratio of crosslinking agent (preferably, a macro polyol) polyol in the resin premix with respect to 100 parts by weight, for example, 0.5 parts by mass or more, or preferably, 1 part by weight or more, and is, for example, 10 parts by weight or less, or preferably 5 parts by mass or less.
[0157]
　The communication agent is not particularly limited, include known communication agent, specifically, for example, polyether polyols (e.g., propylene oxide - random copolymers of ethylene oxide) and the like.
[0158]
　Also, propylene oxide as communicating agent - if ethylene oxide copolymer is used, the ethylene oxide content, for example, more than 50 wt%, or preferably 60 mass% or more, e.g., 90 wt% or less, or preferably 80 mass% or less.
[0159]
　Further, communication agent may be commercially available, for example, (manufactured by Mitsui Chemicals, Inc.) ACTCOL EP-505S, 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.
[0160]
　These communication agent can be used alone or in combination of two or more.
[0161]
　The mixing ratio of the communicating agent (preferably, a macro polyol) polyol in the resin premix with respect to 100 parts by weight, for example, 0.1 parts by mass or more, or preferably, 0.5 parts by mass or more, e.g. , 10 parts by weight or less, preferably not more than 5 parts by mass.
[0162]
　The foam stabilizer is not particularly limited and a known foam stabilizer may be mentioned, for example, silicone foam stabilizer.
[0163]
　Also, a foam stabilizer may be commercially available, for example, DC-6070 (manufactured by Air Products Japan, Inc.), DC-2525 (manufactured by Air Products Japan, Inc.), B-8715LF2 (Evonikku Co.) , SZ-1966 (manufactured by Dow Corning Toray Co., Ltd.), SRX-274C, SF-2969, SF-2961, SF-2962, L-5309 (manufactured by Momentive, Inc.), L-3601 (manufactured by Dow Corning Toray Co., Ltd.), L-5307, L-3600, L-5366, SZ-1325, SZ-1328, Y-10366 (manufactured by Momentive Co., Ltd.).
[0164]
　These foam stabilizers may be used alone or in combination of two or more kinds.
[0165]
　The mixing ratio of the foam stabilizer, (preferably, a macro polyol) polyol in the resin premix with respect to 100 parts by weight, for example, 0.1 parts by mass or more, or preferably, 0.5 parts by mass or more, e.g. , 10 parts by weight or less, preferably not more than 5 parts by mass.
[0166]
　Further, the resin premix, mixing in addition to the above additives, if necessary, for example, the other known additives such as antioxidants, in excellent not to impair the effects scope of the present invention, at an appropriate ratio can do.
[0167]
　Examples of the antioxidant include hindered phenolic antioxidants, and other antioxidants (antioxidant excluding hindered phenol antioxidant) and the like.
[0168]
　As hindered phenol antioxidant, 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 - bis [3- (3,5-di -t- butyl-4-hydroxyphenyl ) propionate] (trade name: Irganox 259, manufactured by Ciba Japan KK), pentaerythritol tetrakis [3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] (trade name: Irganox 1010, manufactured by Ciba Inc.), octadecyl-3- (3,5-di -t- butyl-4-hydroxyphenyl) pro Onato (trade name: Irganox 1076, manufactured by Ciba Japan), N, N'-hexamethylene-bis (3,5-di -t- butyl-4-hydroxy - hydrocinnamate raw bromide) (trade name: Irganox 1098, manufactured by Ciba Inc.), isooctyl-3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate (trade name: Irganox 1135, manufactured by Ciba Japan), 3,5-di -t- butyl-4-hydroxybenzyl phosphonate - 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) Isoshi 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 Corporation).
[0169]
　Other antioxidants, for example, lauric acid hydrazide, salicylic acid hydrazide, Holm hydrazide, acetic 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, dodecanoic -2 acid dihydrazide, maleic acid, fumaric acid dihydrazide, diglycolic acid dihydrazide, tartaric acid dihydrazide, malic acid dihydrazide, isophthalic acid dihydrazide, terephthalic acid, dimer acid dihydrazide, 2,6-naphthoic acid dihydrazide, 2,4-dioxo-5-propyl-1, - imidazolidine di propanoic acid dihydrazide, hydrazides antioxidants such as polyacrylic acid hydrazide, furthermore, 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: ADK STAB PEP-24G, manufactured by Adeka Corporation), tris nonylphenol phosphite (trade name: Adeka Stab 1178, manufactured by Adeka Corporation), tridecyl phosphite (trade name: Adeka Stab 3010, manufactured by ADEKA Corporation) phosphorus-based antioxidant such as, for example, 2,5-thiophenediylbis (5-t-butyl-1,3-benzoxazole) (trade name: Tinopal OB , manufactured by Ciba Japan KK), and the like thiophene-based antioxidants such as It is.
[0170]
　These antioxidants may be used alone or in combination of two or more.
[0171]
　Further, the resin premix, in addition to the above additives, if necessary, for example, pigments (coloring pigments), dyes, UV absorbers, antioxidants, accelerators, heat stabilizers, light stabilizers, matting agents , adhesion imparting agent, a silane coupling agent, a chain extender, a defoaming agent, a plasticizer, antiblocking agent, heat stabilizer, light stabilizer, mold release agents, lubricants, fillers, known such as hydrolysis inhibitor other additives, in excellent not to impair the effects scope of the present invention may be formulated in an appropriate ratio.
[0172]
　Then, to prepare a resin premix, a polyol, and a urethane catalyst, a blowing agent, and an additive if necessary, in proportions described above, are mixed in a known manner.
[0173]
　This makes it possible to prepare a resin premix.
[0174]
　Incidentally, the additives may be added during synthesis of each component of the resin premix, or may be added during compounding or during mixing of the components, further, it may be added after mixing of the components .
[0175]
　The polyisocyanate, for example, polyisocyanate monomers, such as polyisocyanate derivatives.
[0176]
　The polyisocyanate monomers, for example, aromatic polyisocyanates, araliphatic polyisocyanates, and aliphatic polyisocyanates.
[0177]
　Examples of the aromatic polyisocyanates include tolylene diisocyanate (2,4- or 2,6-tolylene diisocyanate or mixtures thereof) (TDI), phenylene diisocyanate (m-, p-phenylene diisocyanate or mixtures thereof), 4, 4'-diphenyl diisocyanate, 1,5-naphthalene diisocyanate (NDI), diphenylmethane diisopropyl Société sulfonate (4,4 '-, 2,4'- or 2,2'-diphenylmethane diisopropyl Société sulfonates or mixtures thereof) (MDI), 4,4'-toluidine diisocyanate (TODI), and aromatic diisocyanates such as 4,4'-diphenyl ether diisocyanate.
[0178]
　Examples of the aromatic aliphatic polyisocyanates, for example, xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or mixtures thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra methyl xylylene diisocyanate or mixtures thereof) (TMXDI), ω, etc. aromatic aliphatic diisocyanates such as ω'- diisocyanate-1,4-diethylbenzene, and the like.
[0179]
　Examples of the aliphatic polyisocyanates include 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-diisocyanate methyl Cap benzoate , and aliphatic diisocyanates such as dodecamethylene diisocyanate.
[0180]
　Furthermore, the aliphatic polyisocyanate include aromatic polyisocyanates. Examples of the alicyclic polyisocyanates, such as 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), 3-isocyanatomethyl--3 , 5,5-trimethyl cyclohexyl isocyanate (isophorone diisocyanate) (IPDI), methylenebis (cyclohexyl isocyanate) (4,4 '-, 2,4'- or 2,2'-methylenebis (cyclohexyl isocyanate, these Trans, Trans - body, Trans, Cis body, Cis, Cis body, or mixtures thereof)) (H 12 MDI), methylcyclohexane diisocyanate (methyl-2,4-cyclohexane Isocyanate, methyl-2,6-cyclohexane diisocyanate), norbornane diisocyanate (various isomers or mixtures thereof) (NBDI), bis (isocyanatomethyl) cyclohexane (1,3-or 1,4-bis (isocyanatomethyl) cyclohexane or mixtures thereof) (H 6 XDI) include alicyclic diisocyanates such as.
[0181]
　These polyisocyanate monomers can be used alone or in combination of two or more kinds.
[0182]
　The polyisocyanate derivatives, for example, multimers of the polyisocyanate monomers mentioned above (e.g., dimers, trimers (e.g., isocyanurate-modified product, iminooxadiazinedione modified product), 5-mer, 7 etc. mer), allophanate-modified products (e.g., a polyisocyanate monomer described above, such as allophanate modified product which from the reaction of a low molecular weight polyol), polyol modified (e.g., low and polyisocyanate monomer described above polyol-generating from the reaction between the molecular weight polyol (alcohol adduct), etc.), biuret modified products (e.g., a polyisocyanate monomer mentioned above, biuret modified products formed by the reaction of water and amines, etc.), urea modified products (e.g., for reaction with the polyisocyanate monomer and the diamine described above Ri etc. resulting urea-modified product), oxadiazinetrione-modified products (e.g., oxadiazinetrione produced by reaction of the polyisocyanate monomers with carbon dioxide as described above), carbodiimide modified product (the above-mentioned polyisocyanate single carbodiimide modified products produced by decarboxylation condensation reaction of dimer, etc.), uretdione modified product, like uretonimine modified product.
[0183]
　Furthermore, as the polyisocyanate derivatives, polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI) can also be mentioned such.
[0184]
　These polyisocyanates derivatives can be used alone or in combination of two or more kinds.
[0185]
　Polyisocyanate, preferably, include aromatic polyisocyanates and derivatives thereof, more preferably, tolylene diisocyanate (TDI), diphenylmethane diisopropyl Société sulfonate (MDI), polymethylene polyphenylene polyisocyanates (crude MDI, polymeric MDI) is and the like.
[0186]
　These polyisocyanates may be used alone or in combination of two or more kinds.
[0187]
　As the polyisocyanate, more preferably tolylene diisocyanate, include combination of tolylene diisocyanate and diphenylmethane diisopropyl Société sulfonates, particularly preferably include the combination of tolylene diisocyanate and diphenylmethane diisopropyl Société sulfonates.
[0188]
　Next, in this method, the resin premix and / or polyisocyanate, adding a VOC reducing agent. Preferably, the addition of VOC reducing agent to the resin premix (addition step).
[0189]
　Amount of VOC reduction agent, so that the content of VOC reduction agent in the polyurethane foam has a desired range is set appropriately.
[0190]
　Then, the content of VOC reduction agent in the polyurethane foam is appropriately determined depending on the amount of reduction required volatile organic compounds (VOC).
[0191]
　More specifically, in the method of decreasing the volatile organic compounds (VOC), as shown in the following formula (I), the the content of the cationic portion of VOC reduction agent in the polyurethane foam, volatile organic compounds (VOC ) and low loss (VOC content in the polyurethane foam), but represented by a linear function.
[0192]
　Formula (I):
　[content of the cationic portion of VOC reduction agent] Polyurethane VOC content in the foam] = a × + b
　Note, a and b in the above formula (I), the type of VOC, polyurethane foam type is a constant which is set according to the type of VOC reduction agent.
[0193]
　For example, the tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium dodecylbenzene sulfonyl (the above formula (3) as a VOC reducing agent, R 2 is a methyl group, X - is a straight-chain dodecylbenzenesulfonate anion If a compound.) is used, acetaldehyde in the polyurethane foam (AA), based on the tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium (cation portion), for example, according to the following formula (II), 1 degree function will be reduced (see Figure 1).
[0194]
　Formula (II):
　[acetaldehyde content in the polyurethane foam] = a AA [content of the cationic portion of VOC reduction agent] × + b AA
　in the above formula (II), a AA , for example, -3 × 10 -4 or more, preferably, -1.5 × 10 -4 or more, for example, -0.5 × 10 -4 or less, preferably, -1.0 × 10 -4 or less constant. a AA as, especially preferably, -1.30 × 10 -4 is.
[0195]
　In the above formula (II), b AA , for example, 0.3 or more, or preferably 0.33 or more, for example, 0.7 or less, preferably, 0.5 or less constant. b and AA and, particularly preferably, is 0.348.
[0196]
　Incidentally, in the above-mentioned formula (II), acetaldehyde content in the polyurethane foam, as measured according to the Examples below. The content of the cationic portion of VOC reduction agents, in conformity with the examples described below, is calculated as a percentage of 100 parts by weight polyol.
[0197]
　Further, for example, in the tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium dodecylbenzene sulfonyl (the above formula (3) as a VOC reducing agent, R 2 is a methyl group, X - is linear dodecylbenzenesulfonate anionic compounds wherein. If) is used, propionaldehyde in the polyurethane foam (PA) include tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium (the cation moiety) as a reference, for example, the following formula (III) accordingly be reduced as a linear function (see FIG. 2).
[0198]
　Formula (III):
　[Polyurethane propionaldehyde content of the foam] = a PA [content of the cationic portion of VOC reduction agent] × + b PA
　above formula (III), a PA , for example, -3 × 10 - 3 or more, preferably, -1.5 × 10 -3 or more, for example, -0.5 × 10 -3 or less, preferably, -1.0 × 10 -3 or less constant. a PA as, especially preferably, -1.16 × 10 -3 is.
[0199]
　In the above formula (III), b PA , for example, 1.5 or more, preferably, is 2.0 or more, e.g., 5 or less, preferably, 3 or less constant. b the PA and, particularly preferably, is 2.31.
[0200]
　Incidentally, In the above formula (III), propionaldehyde content in the polyurethane foam, as measured according to the Examples below. The content of the cationic portion of VOC reduction agents, in conformity with the examples described below, is calculated as a percentage of 100 parts by weight polyol.
[0201]
　Thus, in the method for reducing volatile organic compounds (VOC), it can be in accordance with the content of the cationic portion of the VOC reducing agent as described above, to reduce volatile organic compound (VOC) 1 linear function.
[0202]
　In other words, the content of the cationic portion of VOC reduction agent in the polyurethane foams, according to first-order function equation as the equation (I) ~ (III), is set appropriately.
[0203]
　The content of the cationic portion of VOC reduction agent in the polyurethane foams, as mass, relative to the total amount of polyurethane foams, for example, 5 ppm or more, preferably, 50 ppm or more, more preferably 500ppm or more, also, for example, , 15000 ppm or less, preferably 10000 ppm or less, and more preferably not more than 8000 ppm.
[0204]
　The amount of VOC reduction agent, specifically, the polyol 100 parts by weight in the resin premix, 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 weight or more, more preferably, 0.045 parts by mass or more, particularly preferably, 0.05 parts by mass or more, and is, for example, 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, more preferably, 0.3 parts by mass or less, more preferably 0.15 parts by mass or less, particularly preferably not more than 0.10 parts by mass.
[0205]
　Further, as the mass of the polyol 100 parts by weight in the resin premix, from the viewpoint of sufficiently reducing the VOC, for example, 5 ppm or more, or preferably, 15 ppm or more, more preferably, 25 ppm or more, more preferably is, 50 ppm or more, more preferably, 100 ppm or more, more preferably, 200 ppm or more, more preferably, 300 ppm or more, more preferably, more than 400 ppm, especially preferably not less 500ppm or more, from the viewpoint of cost reduction , for example, 20000 ppm or less, preferably 3000 ppm or less, more preferably 2000ppm or less.
[0206]
　Thus, it is possible to obtain a resin premix containing a VOC reducing agent (VOC reducing agent-containing resin premix).
[0207]
　Next, in this method, mixing and foaming a resin premix and a polyisocyanate (foaming step).
[0208]
　More specifically, the polyisocyanate was added to the resin premix (VOC reducing agent-containing), with and reacted with stirring, for example, slab method, molding method, foaming by a known foaming method such as a spray method.
[0209]
　The mixing ratio of the polyisocyanate relative to resin premix, for example, hydroxyl groups in a macro polyol in the isocyanate index (resin premix, hydroxyl and amino groups in the crosslinking agent, and isocyanate groups to active hydrogen 100, such as water as a blowing agent as a percentage of the (stoichiometric ratio)), for example, for example, 70 or more, or preferably 85 or more, for example, 140 or less, preferably 120 or less.
[0210]
　As a result, it is possible to produce a polyurethane foam.
[0211]
　As described above, resin premix is ​​used to reduce the polyurethane foam of volatile organic compounds (VOC).
[0212]
　Then, in the method of decreasing such volatile organic compounds (VOC), for VOC reducing agent is contained in the polyurethane foam, it can be efficiently reduced volatile organic compounds (VOC), also optionally degree of reduction it can be adjusted to.
[0213]
　That is, generally volatile organic compounds Hydrazine is used to reduce (VOC) Compound (hydrazide antioxidants such as adipic acid dihydrazide) can be reduced volatile organic compounds (VOC) , reduce the amount of volatile organic compounds (VOC) is a constant irrespective of the amount of the hydrazine compound, and there is a limit. Furthermore, there is also a problem that can not adjust the degree of reduction of volatile organic compounds (VOC).
[0214]
　In this respect, according to the VOC reducing agent as described above (compound represented by the formula (1)), can not only reduce volatile organic compounds (VOC), it is possible to arbitrarily adjust the degree of reduction.
[0215]
　Therefore, in accordance with the reduced amount of required, it is possible to adjust the amount of VOC reduction agent, it is possible to volatile organic compound (VOC) efficiency reduction and cost reduction.
[0216]
　Further, according to the manufacturing method and the resin premix of the polyurethane foam can be volatile organic compound (VOC) to produce a reduced polyurethane foam in any degree.
[0217]
　In the addition step described above, the resin premix containing no VOC reducing agent, prior to mixing with the polyisocyanate containing no VOC reducing agent was added VOC reduction agent to resin premix and / or polyisocyanate but, for example, at the time of their mixing, separately, it can also be added to and mixed with VOC reduction agent and, after mixing them, may be further added to and mixed with VOC reduction agent to the mixture. Furthermore, it is also possible to combine a plurality of these.
[0218]
　Moreover, without the addition of VOC reduction agent, for example, a VOC reducing agent, by using as a polyol production catalyst (addition polymerization catalysts) can also be pre-contained VOC reducing agent to the polyol.
[0219]
　More specifically, for example, in the preparation of polyoxyalkylene polyol, as a reaction catalyst for addition polymerization of alkylene oxide, it is possible to use a compound represented by the above formula (1).
[0220]
　As a reaction catalyst for addition polymerization of alkylene oxide (addition polymerization catalysts), when the compounds represented by the above formula (1) is used, preferably a compound represented by the formula (3) can be mentioned, more preferably, the in the formula (3), X - is hydroxy anion, include compounds represented by the alkoxy anion, especially preferably, in the above formula (3), X - can be mentioned compounds represented by hydroxy anion.
[0221]
　In the presence of such additional polymerization catalyst (compound represented by the formula (1)), low molecular weight polyols, by addition polymerization of alkylene oxide to an initiator such as low molecular weight polyamine, represented by the formula (1) polyoxyalkylene polyol is obtained which contains the compound.
[0222]
　When the resulting polyoxyalkylene polyol used in the preparation of polyurethane foams, the resulting polyurethane foam, the compound represented by the formula (1) is contained. In this case, the compound represented by the formula (1) can act as a VOC reducing agent.
[0223]
　That is, the above formula in the polyoxyalkylene polyol a compound represented by (1), can also serve as a VOC reducing agent. Incidentally, in such a case, the amount of the compound represented by the formula (1) is such that the content of VOC reduction agent to the polyol 100 parts by weight in the resin premix is ​​in the range described above are appropriately adjusted.
[0224]
　Furthermore, for example, a polyoxyalkylene polyol containing a compound represented by the above formula (1), polymer polyols may also be used as a raw material, such as polyurethane polyols. Preferably, the above polyoxyalkylene polyol, is used as a raw material of the polymer polyol. In such a case, the resulting polymer polyol contains a compound represented by the formula (1).
[0225]
　When the resulting polymer polyol used in the preparation of polyurethane foams, the resulting polyurethane foam, the compound represented by the formula (1) is contained. In this case, the compound represented by the formula (1) can act as a VOC reducing agent.
[0226]
　That is, even in such a case, the compound of the above formula in the polyol (1), can also serve as a VOC reducing agent. Incidentally, in such a case, the amount of the compound represented by the formula (1) is such that the content of VOC reduction agent to the polyol 100 parts by weight in the resin premix is ​​in the range described above are appropriately adjusted.
[0227]
　Furthermore, the use of VOC reducing agent as described above as a polyol production catalyst (addition polymerization catalysts), even when the pre contain a VOC reducing agent to the resin premix, the obtained resin premix, Furthermore, it is possible to add a VOC reducing agent.
[0228]
　In the case such a resin premix containing a VOC reducing agent, prior to mixing with the polyisocyanate, may be added VOC reduction agent to resin premix and / or polyisocyanate, also, e.g. , upon their mixing, separately, can also be added to and mixed with VOC reducing agent, further, after mixing them, it may be further added to and mixed with VOC reduction agent to the mixture. Furthermore, it is also possible to combine a plurality of these.
[0229]
　Further, the polyols obtained using VOC reducing agent for producing a catalyst of the polyol, without the use of VOC reduction agent for producing a catalyst of the polyol, a polyol obtained by using an alkali metal hydroxide, an appropriate It may be used in a mixing ratio. In such a case, the resin premix containing a polyol, VOC reducing agent is contained. Therefore, additionally, the resin premix without the addition of VOC reducing agent can be used in the production of polyurethane foams and, if necessary, can be used in the production of polyurethane foams by adding a VOC reduction agent further .
[0230]
　Furthermore, as a production catalyst of the polyol, it is also possible to prepare the polyol in combination with VOC reducing agent and an alkali metal hydroxide, in such a case, the resin premix containing a polyol, VOC reduction agent is contained. Therefore, additionally, the resin premix without the addition of VOC reducing agent can be used in the production of polyurethane foams and, if necessary, can be used in the production of polyurethane foams by adding a VOC reduction agent further .
[0231]
　If necessary, after the preparation of polyoxyalkylene polyols, before the production of polyurethane foams, X of the compound represented by the formula (1) - a may be appropriately replaced.
[0232]
　More specifically, for example, as a reaction catalyst in the preparation of the above polyoxyalkylene polyol, represented by the above formula (1), X - if a compound is used is a hydroxy anion, polyoxyalkylene polyol obtained is , represented by the formula (1), X - contains a compound is hydroxy anion.
[0233]
　The polyoxyalkylene polyols, can also directly be used for the production of polyurethane foams, for example, polyoxyalkylene polyols, other X - compound supplying, for example, sulfonic acid (e.g., p- toluenesulfonic acid, dodecyl benzenesulfonic acid, benzenesulfonic acid, methanesulfonic acid, was added camphor like over acid), by mixing and stirring, X - it is possible to replace the sulfonyl anion.
[0234]
　This makes it possible to change the addition polymerization catalysts in the production of the polyoxyalkylene polyol, the type of the VOC reduction agent contained in the polyurethane foam.
[0235]
　That is, in the addition polymerization of alkylene oxide, compounds suitable for addition polymerization of alkylene oxide (e.g., shown by the above formula (1), X - compounds is a hydroxy anion) is used, then, X - to change the it makes the compounds suitable as VOC reduction agent in polyurethane foams (e.g., shown by the above formula (1), X - compounds is sulfonyl anion) may be contained.
[0236]
　In this way, can be efficiently reduced volatile organic compounds (VOC), it is also possible to adjust the degree of the reduction arbitrarily.
Example
[0237]
　Next, the present invention will be described with reference to examples and comparative examples, the present invention is not limited by the examples below. Incidentally, "parts" and "%", unless specifically stated, it is by weight. The mixing ratio used in the following description (content), physical properties, the specific values of such parameters are described in the "Description of the Invention" section above, the blending ratio corresponding to them ( content), physical properties, the upper limit of such appropriate according parameter ( "hereinafter" substitute defined numerical are) or the lower limit value as "less than" ( "or" numerical values is defined as "excess") be able to.
PZN compound: tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium (PZN cation (hereinafter, PZN to)) in dodecylbenzene sulfonyl (the equation (3), R 2 is a methyl group Yes, X - is linear dodecylbenzene sulfonate anionic compounds wherein).
　　EP828; ACTCOL EP828 (polyoxyalkylene polyols (propylene oxide - block copolymer of ethylene oxide), ethylene oxide content (terminal oxy ethylene content): 15 mass%, number average molecular weight: 6000, average functionality: 3, hydroxyl value: 28 mg KOH / g, manufactured by Mitsui Chemicals,
　　Inc.) EP330N; Actcol EP330N (polyoxyalkylene polyols (propylene oxide - ethyl Block copolymers of emissions oxide), ethylene oxide content (terminal oxyethylene group content): 15 mass%, number average molecular weight: 5000, average functionality: 3, hydroxyl value: 34 mg KOH / g, manufactured by Mitsui Chemicals, Inc.)
　　POP-3623; ACTCOL POP-3623 (polymer polyol, hydroxyl value: 22 mgKOH / g, manufactured by Mitsui Chemicals, Inc.)
　　EP-505S; ACTCOL EP-505S (communicating agent, polyether polyol (polyoxyalkylene polyol (propylene oxide - a random copolymer of ethylene oxide)), ethylene oxide content: 70 wt%, number average molecular weight: 3300, average functionality: 3, hydroxyl value: 52 mg KOH / g, manufactured by Mitsui Chemicals,
　　Inc.) KL-210; Actcol KL-210 (crosslinking agent, average functionality: 3. 75, hydroxyl value: 840mgKOH / g, manufactured by Mitsui Chemicals,
　　Inc.) IRGANOX1135; BASF Corp. of antioxidant
　　ADH: adipic acid dihydrazide, Japan FineChem Co., Ltd. of hydrazide antioxidant
　　VDH: AMICURE VDH, Ajinomoto Fine-Techno Co., Ltd. hydrazide antioxidants
　　33LV; DABCO 33LV (amine catalyst (urethanization catalyst), 33 wt% diethylene glycol solution of triethylenediamine, manufactured by air Products Japan,
　　Inc.) a-1; Niax a-1 (amine catalyst (urethane catalyst) , Momentive
　　Corp.) L5309; L5309 (silicone foam stabilizer, manufactured by Momentive
　　Co.) L3601; L3601 (silicone foam stabilizer, manufactured by Dow Corning Toray Co.,
　　Ltd.) DC2525; DC2525 (silicone foam stabilizer, the air - Productivity Shoes Japan
　　Co.) TM20; Cosmonate TM20 (mixture of 80:20 weight ratio of the polyisocyanate (2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI) and 80 wt%, diphenylmethane diisopropyl Soshineto (MDI) mixture of 20 wt%), isocyanate group content: 45 wt%, manufactured by Mitsui Chemicals, Inc.)
　　synthesis example 1 (polyoxyalkylene polyol a) containing the VOC reducing agent
　stirrer, a thermometer, a pressure gauge the equipment autoclave, relative to the hydroxyl group of glycerol and glycerol, addition polymerization catalysts 0.18mol% / molOH become amount of tetrakis [tris (dimethylamino) phosphonyl isopropylidene amino] phosphonium hydroxide was added as at 100 ° C. 6 after time dehydrated under reduced pressure, the reaction temperature 12 propylene oxide 0 ° C., was continuously introduced by addition polymerization at a maximum reaction pressure of 3.8 kg / cm @ 2.
[0238]
　Then, ethylene oxide the reaction temperature 120 ° C., maximum reaction pressure of 3.8 kg / cm 2 was continuously introduced by addition polymerization with. Then, dodecylbenzene sulfonic acid, and stirred for 2 hours at 2.1 equivalent added to 100 ° C. relative to tetrakis [tris (dimethylamino) phosphonyl isopropylidene amino] phosphonium hydroxide. Thus, tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium dodecylbenzene sulphonyl including (PZN compound) polyoxyalkylene polyol A (hereinafter, the polyol A) was obtained.
[0239]
　Average functionality of the polyol A is 3, a hydroxyl value of 36 mg KOH / g, the terminal oxyethylene group content was 17 wt%. Content of PZN (cation portion) of PZN compound to the polyol A was calculated to 840ppm from the charged amount.
[0240]
　　Synthesis Example 2 (polyoxyalkylene polyol B comprises a VOC reduction agent)
　stirrer, a thermometer, an autoclave equipped with a pressure gauge, relative to the hydroxyl group of glycerin and glycerin, and 0.18mol% / molOH as addition polymerization catalysts the amount of tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium hydroxide was added and after 6 hours under reduced pressure dehydration at 100 ° C., the reaction temperature 90 ° C. propylene oxide continuously at a maximum reaction pressure of 3.8 kg / cm @ 2 introduced by addition polymerization. Then, the reaction temperature 100 ° C. The ethylene oxide was continuously introduced by addition polymerization at a maximum reaction pressure of 3.8 kg / cm @ 2. Then, the polyoxyalkylene polyol B (hereinafter, the polyol B) by stirring for 2 hours dodecylbenzenesulfonate 2.3 by adding equivalent 100 ° C. relative PZN was obtained.
[0241]
　Average functionality of the polyol B is 3, a hydroxyl value of 24 mg KOH / g, the terminal oxyethylene group content was 15 wt%. Content of PZN (cation portion) of PZN compound to polyol B was calculated to 550ppm from the charged amount.
[0242]
　　Synthesis Example 3 (Polyoxyalkylene Polyol C contains a VOC reduction agent)
　stirrer, a thermometer, an autoclave equipped with a pressure gauge, relative to the hydroxyl group of glycerin and glycerin, and 0.18mol% / molOH as addition polymerization catalysts the amount of tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium hydroxide was added and after 6 hours under reduced pressure dehydration at 100 ° C., a propylene oxide reaction temperature 120 ° C., maximum reaction pressure of 3.8 kg / cm 2 continuously at It was introduced by addition polymerization to. Then, ethylene oxide the reaction temperature 110 ° C., maximum reaction pressure of 3.8 kg / cm 2 was continuously introduced by addition polymerization with. Then, dodecylbenzenesulfonate tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] by stirring for 2 hours against phosphonium hydroxide 2.0 equiv added to 100 ° C. polyoxyalkylene polyol C (hereinafter, a polyol to obtain a C).
[0243]
　Average functionality of the polyol C is 3, a hydroxyl value of 28 mg KOH / g, the terminal oxyethylene group content was 15 wt%. Content of PZN (cation portion) of PZN compound to polyol C was calculated to 640ppm from the charged amount.
[0244]
　　Synthesis Example 4 (Polymer Polyol D contains a VOC reduction agent)
　stirrer, a thermometer, an autoclave equipped with a pressure gauge and liquid feeder was charged until the polyol A to the flooded state, with stirring, the temperature to 120 ° C. It was allowed. Polyol A, 2,2'-azobis (isobutyronitrile), acrylonitrile and a mixture of styrene was continuously charging into the autoclave. Initial reaction solution obtained from the continuous outlet discarded, with subsequent reaction in the next step. The reaction conditions, reaction temperature 120 ° C., under the conditions of a reaction pressure 440 kPa, the residence time was 50 minutes. 655Pa under the following conditions, subjected to heat treatment under reduced pressure for 3 hours, unreacted ethylenically unsaturated monomer, to remove the degradation products of the polymerization initiator, a polymer polyol D (hereinafter, polyol D) was obtained. The average number of functional groups 3 of the polyol D, a hydroxyl value of 22 mgKOH / g, the polyol A derived component content of 60 wt%, the polymer component content of from acrylonitrile is 16 wt%, the polymer component content of from styrene 24 mass %Met. These content and charged amount was calculated from the amount of unreacted monomer was determined by gas chromatographic methods. Further, the content of the PZN (cation portion) of PZN compound derived from the polyol A to the polyol D was calculated as 504Ppm.
[0245]
　
　　(Example
　1) and EP828 (polyoxyalkylene polyol) 100 parts by weight, and 33LV (amine catalyst) 0.35 part by mass, A-1 (amine catalyst) 0.06 part by weight, of water (foaming agent) and 2.7 parts by mass, KL210 and (crosslinking agent) 3.0 parts by mass, EP-505S (communicating agent) and 0.5 parts by mass, L-3601 (foam stabilizer) 1.0 weight and parts, tetrakis [tris (dimethylamino) phosphoranylidene two isopropylidene amino] phosphonium dodecylbenzene sulfonyl (VOC reducing agent, PZN compound) 672Ppm (/ polyol 100 parts by weight) were blended and mixed them, the resin premix It was prepared.
[0246]
　Then, the resulting resin premix, leave controlled at 22 ± 1 ° C., TM20 controlled at there 22 ± 1 ° C. (polyisocyanate) 32.1 parts by weight (isocyanate index: 95) was added, immediately 5 seconds vigorously stirred at 5000rpm by a homogenizer, and injected immediately the inside dimension 400 mm × 400 mm × 100 mm was adjusted in advance to 65 ° C. to the mold and allowed to foam capped. Then, proceed with 6 minutes curing reaction while maintaining the mold 65 ° C., was removed polyurethane foam from the mold. As a result, to produce a flexible polyurethane foam.
[0247]
　　(Examples 2 to 12, and Comparative Examples 1 to 5)
　in accordance with the formulations set forth in Table 1, in the same manner as in Example 1 to produce a polyurethane foam.
[0248]
　In Examples 2-8, in the same manner as in Example 1, was added PZN compound as VOC reducing agent during the preparation of the resin premix.
[0249]
　In Examples 9-12, at the time of preparation of the resin premix without adding PZN compound was used PZN compound contained in the polyol A ~ D as VOC reducing agent.
[0250]
　In Comparative Example 1, without addition of VOC reduction agent, in Comparative Examples 2-4, as VOC reduction agent, was added adipic acid dihydrazide (ADH) in place of the compound represented by the formula (1), also in Comparative examples 5-7, as VOC reducing agent, the above formula (1) in place of the compound represented Amicure VDH (Ajinomoto Fine-Techno Co., VDH) was added.
[0251]
　In Table 1 shows the content of PZN (the cation moiety reference), as a percentage (ppm) to the polyol 100 parts by weight in the resin premix.
[0252]
　　
　measured aldehyde measurement of polyurethane foams prepared in Examples 1 to 12 and Comparative Examples 1 to 5 by the following measuring method, each amount of acetaldehyde, the results for the propionaldehyde amount Obtained.
[0253]
　The results are shown in the Table.

　(1) Density
　after foaming, was calculated measured density the size and weight of the polyurethane foam after 24 hours.
[0254]
　(2) acetaldehyde (AA), the measurement of propionaldehyde (PA)
　of the (1) after determining the density, the polyurethane foam was cut into 80 mm × 100 mm, to obtain a sample. Were also stored for one week put the obtained sample in a sealed container.
[0255]
　Then, put the sample in 10L fluorine resin bag, was purged three times with pure nitrogen.
[0256]
　Then placed pure nitrogen of approximately 4L, was heated at a constant temperature room of 65 ° C..
[0257]
　Then, in the DNPH cartridge for aldehyde analysis 0.5L / min. After 3.0L taken at a flow rate to calculate the total amount of gas sucked all the remaining gas.
[0258]
　Thereafter, the derivative product eluted through acetonitrile DNPH cartridge aldehyde analysis was determined by HPLC constant volume of 5 mL.
[0259]
　Then, by converting the respective aldehyde quantity than the calculated results based on the total gas volume (sample).
[0260]
　Further, from the results of Examples 2-6, the content of the cationic portion of the VOC reducing agent, in Figure 1 the relationship between the reduction amount of acetaldehyde, further the use of the content of the cationic portion of the VOC reducing agent, the relationship between the reduction amount of propionaldehyde in FIG 2, showing respectively.
[0261]
[Table 1]

[0262]
Discussion
　Examples 1 to 12 and Comparative Examples 1, that if PZN is contained in the polyurethane foam, it is possible to reduce the acetaldehyde (AA) and propionaldehyde (PA) as a volatile organic compound (VOC) There has been confirmed.
[0263]
　Further, from FIGS. 1 and 2, volatile organic compounds (VOC) is confirmed to be reduced as a linear function depending on the content of PZN, thereby, reducing the volatile organic compounds (VOC) can adjust the amount, it was confirmed that the set to any amount of reduction.
[0264]
　On the other hand, from FIGS. 3 and 4, hydrazide antioxidants, reduce the amount of the case can be reduced volatile organic compounds (VOC) is also volatile organic compounds (VOC), the amount of hydrazide-based antioxidant a constant irrespective of, and that there is a limit was confirmed.
[0265]
　The above invention has been provided as illustrative embodiments of the present invention, this is merely illustrative and should not be construed restrictively. Modification of the present invention that will be obvious to those skilled in the art will be covered by the following claims.
Industrial Applicability
[0266]
　Reduction method, manufacturing method, and resin premix of polyurethane foam of volatile organic compounds of the present invention, in various industrial fields where polyurethane foam is used, is used widely.

The scope of the claims
[Requested item 1]
　A method for reducing volatile organic compounds in the polyurethane foam,
　is contained the indicated polyurethane foam by the following formula (1) compound
, wherein the method for reducing volatile organic compounds.
[Chemical formula 1]

(In the formula, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - . Is showing an anion)
[Formula 2]

(wherein, R 1 are the same or different from each other, represents a hydrocarbon group having a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[formula 3]

(wherein among, R 2 may be the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. Further, n is an integer of 0-3. However, n corresponding to at least one of R of the four R in the formula (1) is not 0.)
[Requested item 2]
　Depending on the content of the compound represented by the formula (1), characterized in that to reduce the volatile organic compound as a linear function, a method for reducing volatile organic compound according to claim 1.
[Requested item 3]
　The polyurethane foam, the resin premix containing a polyol, a reaction product of a polyisocyanate,
　the content of the cationic moiety of the compound represented by the formula (1) is, relative to the total amount of the polyol, 500 ppm or more and characterized in that, a method for reducing volatile organic compound according to claim 1.
[Requested item 4]
　A resin premix containing a polyol, preparation step of preparing a polyisocyanate,
　adding step of adding a compound represented by the formula (1) in the resin premix, and,
　mixing the resin premix and the polyisocyanate and foamed to the foaming process
, characterized in that it comprises a method for reducing volatile organic compound according to claim 1.
[Requested item 5]
　A method of manufacturing a polyurethane foam volatile organic compounds have been reduced,
　and the resin premix containing a polyol, preparation step of preparing a polyisocyanate,
　a compound represented in the resin premix by the following formula (1) addition step, and, adding
　foaming step of mixing and foaming the resin premix and the polyisocyanate
, characterized in that it comprises a method for producing a polyurethane foam.
[Formula 4]

(wherein, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - . Is showing an anion)
[Chemical Formula 5]

(wherein, R 1 are the same or different from each other, represents a hydrocarbon group having a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[formula 6]

(wherein among, R 2 may be the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. Further, n is an integer of 0-3. However, n corresponding to at least one of R of the four R in the formula (1) is not 0.)
[Requested item 6]
　Used in producing a polyurethane foam according to claim 5,
　characterized in that it contains a polyol, a compound represented by the following formula (1), resin premix.
[Chemical Formula 7]

(wherein, -N = R represents the following partial structural formula (A) or the following partial structural formula (B), X - . Is showing an anion)
[Chem 8]

(wherein, R 1 are the same or different from each other, represents a hydrocarbon group having a hydrogen atom or a C 1 ~ 20, R 1 each other may be bonded to form a ring structure.)
[Chem 9]

(formula among, R 2 may be the same or different from each other, indicate a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. However, R 2 to each other may be bonded to form a ring structure. Further, n is an integer of 0-3. However, n corresponding to at least one of R of the four R in the formula (1) is not 0.)