JP2016102178A - Polyol composition, resin premix and polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polyol composition that can maintain the physical properties such as hardness of polyurethane foam, that can as well improve the flame retardancy; a resin premix containing the polyol composition; and polyurethane foam produced by using the resin premix.SOLUTION: Provided is polyurethane foam in which a resin premix comprising a polyol composition containing a polyol component comprising one kind selected from a polyoxyalkylene polyol or polymer polyol, and a flame retardant agent, and in which the flame retardant agent is a particular ionic compound comprising phosphorus and nitrogen, is used.SELECTED DRAWING: None

Description

  The present invention relates to a polyol composition, a resin premix, and a polyurethane foam. More specifically, the present invention relates to a polyol composition, a resin premix containing the polyol composition, and a polyurethane foam obtained using the resin premix.

  The polyurethane foam is obtained by reacting a resin premix containing a polyol component, a catalyst, and a foaming agent with an isocyanate component.

  In such a polyurethane foam, when flame retardancy is required, the polyurethane foam usually contains a flame retardant.

  As such a flame retardant, an organic phosphorus flame retardant is often used. Examples of the organic phosphorus flame retardant include TCEP (tris (chloroethyl) phosphate), TCPP (tris (chloropropyl) phosphate), TCP (tricresyl phosphate) and the like are known.

  And it is proposed to prepare a polyurethane foam by reacting a resin premix containing 10 to 15 parts by weight of an organic phosphorus flame retardant with an isocyanate component with respect to 100 parts by weight of a polyol component. (For example, refer to Patent Document 1).

JP 2005-015521 A

  However, as described in Patent Document 1, when a flame retardant is blended in the above ratio with polyurethane foam, there is a problem that the hardness of the obtained polyurethane foam is lowered.

  On the other hand, if the blending ratio of the flame retardant with respect to the polyurethane foam is decreased in order to maintain the hardness of the polyurethane foam, the improvement of the flame retardancy becomes insufficient.

  Accordingly, an object of the present invention is to provide a polyol composition capable of improving the flame retardancy while maintaining the hardness of the polyurethane foam, a resin premix containing the polyol composition, and a polyurethane obtained using the resin premix To provide a form.

  The polyol composition of the present invention includes a polyol component containing at least one selected from the group consisting of a polyoxyalkylene polyol and a polymer polyol, and a flame retardant, and the flame retardant is represented by the following formula (1). It is characterized by being a compound.

(In the formula, R ^{1 s} are the same or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ⁻ represents an anion. However, R ^{1 s} are bonded to each other to form a ring. A structure may be formed.)
Moreover, in the polyol composition of this invention, it is suitable that content of the said flame retardant is 5 ppm or more and 20000 ppm or less.

  In the polyol composition of the present invention, it is preferable that the polyol component has a hydroxyl value of 10 mgKOH / g or more and 80 mgKOH / g or less.

  Moreover, the resin premix of the present invention is characterized by containing the above-mentioned polyol composition, a catalyst, and a foaming agent.

  Moreover, in the resin premix of this invention, it is suitable that content of the said flame retardant is 5 ppm or more and 20000 ppm or less.

  The polyurethane foam of the present invention is characterized by being obtained by reacting the above resin premix with a polyisocyanate component.

  The polyol composition of the present invention contains a compound represented by the above formula (1) as a flame retardant.

  Therefore, the polyurethane foam obtained using the resin premix containing the polyol composition can improve the flame retardancy while maintaining physical properties such as hardness.

  The polyol composition of the present invention contains a polyol component and a flame retardant.

  The polyol component contains at least one selected from the group consisting of polyoxyalkylene polyols and polymer polyols, preferably contains polyoxyalkylene polyols and polymer polyols, more preferably polyoxyalkylene polyols and polymer polyols. It consists of.

  The polyoxyalkylene polyol is a polyether polyol, for example, an alkylene oxide addition polymer (a random and / or block copolymer of two or more alkylene oxides), which is initiated by a low molecular weight polyol, a low molecular weight polyamine, or the like. Are included).

  The low molecular weight polyol is a compound having two or more hydroxyl groups and a molecular weight of less than 400, 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-trimethylpentanediol, 3,3-di Methylol heptane, alkane (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-dimethyl- -Dihydric alcohols such as octene-3,8-diol, bisphenol A, diethylene glycol, triethylene glycol, dipropylene glycol, for example, trihydric alcohols such as glycerin, trimethylolpropane, triisopropanolamine, such as tetramethylolmethane ( Pentavalent alcohol such as pentaerythritol), pentahydric alcohol such as xylitol, for example, pentahydric alcohol such as xylitol, for example, hexavalent alcohol such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, for example, perseitol. And the like, for example, octavalent alcohols such as sucrose.

  These low molecular weight polyols can be used alone or in combination of two or more.

  The low molecular weight polyamine is a compound having two or more amino groups and a molecular weight of less than 400, for example, ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,6-hexamethylene. Diamine, 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5 (2,6) -bis (aminomethyl) ) Low molecular weight diamines such as bicyclo [2.2.1] heptane, 1,3-bis (aminomethyl) cyclohexane, hydrazine, o, m or p-tolylenediamine (TDA, OTD), for example, low such as diethylenetriamine Molecular weight triamines such as triethylenetetramine, tetraethylenepentamine Examples thereof include low molecular weight polyamines having 4 or more amino groups.

  These low molecular weight polyamines can be used alone or in combination of two or more.

  Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, cyclohexene oxide, epichlorohydrin, epibromohydrin, methyl glycidyl ether, and allyl glycidyl ether. And alkylene oxides having 2 to 12 carbon atoms such as phenyl glycidyl ether.

  These alkylene oxides can be used alone or in combination of two or more.

  The alkylene oxide is preferably ethylene oxide, propylene oxide, 1,2-butylene oxide, or styrene oxide, more preferably ethylene oxide or propylene oxide.

  Preferred examples of the polyoxyalkylene polyol include polyethylene glycol, polypropylene glycol, and propylene oxide-ethylene oxide copolymer (random and / or block copolymer).

  When a propylene oxide-ethylene oxide copolymer is used as the polyoxyalkylene polyol, the ethylene oxide content is, for example, 5% by mass or more, preferably 10% by mass or more, for example, 50% by mass or less, preferably Is 30% by mass or less.

  The ethylene oxide content is calculated from the blended recipe (the same applies hereinafter).

  When a propylene oxide-ethylene oxide copolymer is used as the polyoxyalkylene polyol, the terminal oxyethylene group content is, for example, 5% by mass or more, preferably 10% by mass or more, for example, 50% by mass. % Or less, preferably 30% by mass or less.

  In addition, terminal oxyethylene group content is computed from the preparation recipe of preparation.

  The number average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC) analysis of the polyoxyalkylene polyol is, for example, 400 or more, preferably 1000 or more, for example, 15000 or less, preferably 10,000. It is as follows.

  The average functional group number of the polyoxyalkylene polyol is, for example, 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, for example, 6 or less, preferably 4 or less. .

  The average number of functional groups of the polyoxyalkylene polyol is calculated from the blended recipe.

  The hydroxyl value of the polyoxyalkylene polyol is, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, and further preferably 25 mgKOH / g or more, for example, 80 mgKOH / g. g or less, preferably 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, and still more preferably 30 mgKOH / g or less.

  When the hydroxyl value of the polyoxyalkylene polyol is within the above range, the polyurethane foam (described later) obtained by using a resin premix (described later) containing a polyol component containing the polyoxyalkylene polyol has physical properties such as hardness. The flame retardancy can be improved while maintaining the above.

  The hydroxyl value is measured according to the description of JIS K-1557-1 (2007) (the same applies hereinafter).

  These polyoxyalkylene polyols can be used alone or in combination of two or more.

  The polymer polyol (vinyl monomer-modified polyol) can be obtained by dispersing and polymerizing a vinyl monomer in a high molecular weight polyol.

  The high molecular weight polyol is a dispersion medium of a vinyl monomer, and has a number average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC) analysis, for example, 400 or more, preferably 1000 or more, For example, it is 10,000 or less, preferably 8000 or less. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, and the like, 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, and the like. These vinyl monomers can be used alone or in combination of two or more. Of these, styrene, vinyl cyanide (acrylonitrile), styrene and vinyl cyanide are preferably used in combination.

  The content of the polymer of the vinyl monomer with respect to 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.

  The polymer polyol is a high molecular weight polyol in which a vinyl monomer is replaced with, for example, a radical polymerization initiator (for example, a persulfate, an organic peroxide, an azo compound (such as azobisisobutyronitrile)), and the like. Can be obtained by reacting in the presence of a dispersion stabilizer, a chain transfer agent or the like, if necessary.

  More specifically, the polymer polyol is prepared by polymerizing the above vinyl monomer with a radical initiator in a high molecular weight polyol and dispersing the resulting polymer fine particles in the high molecular weight polyol.

  The polymer fine particles are polymer fine particles made of a vinyl monomer polymer.

  In the polymer fine particles, at least a part of the vinyl monomer can be grafted to the high molecular weight polyol at the time of polymerization.

  The number average molecular weight (in terms of polyethylene glycol) measured by gel permeation chromatography (GPC) analysis of the polymer polyol is, for example, 400 or more, preferably 1000 or more, for example, 15000 or less, preferably 10,000 or less. is there.

  The average functional group number of the polymer polyol is, for example, 1.5 or more, preferably 2.0 or more, more preferably 2.5 or more, for example, 6 or less, preferably 4 or less.

  In addition, the average functional group number of the polymer polyol is calculated from the blended recipe.

  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, and further preferably 25 mgKOH / g or more, for example, 80 mgKOH / g or less. Preferably, it is 60 mgKOH / g or less, More preferably, it is 50 mgKOH / g or less, More preferably, it is 30 mgKOH / g or less.

  If the hydroxyl value of the polymer polyol is within the above range, the polyurethane foam (described later) obtained by using a resin premix containing a polyol component containing the polymer polyol (described later) must maintain physical properties such as hardness. It is possible to improve the flame retardancy.

  These polymer polyols can be used alone or in combination of two or more.

  When the polyol component contains a polyoxyalkylene polyol and a polymer polyol, the blending ratio of the polyoxyalkylene polyol and the polymer polyol is such that the polyoxyalkylene polyol is, for example, 10 masses per 100 mass parts of the polyol component. Part or more, preferably 30 parts by weight or more, more preferably 40 parts by weight or more, for example, 90 parts by weight or less, preferably 70 parts by weight or less, more preferably 60 parts by weight or less, 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, for example, 90 parts by mass or less, preferably 70 parts by mass or less, more preferably 60 parts by mass. It is below mass parts.

  Further, the blending ratio of the polyoxyalkylene polyol and the polymer polyol is, for example, 10/90 or more, preferably 30/70 or more, more preferably 40/60 or more, and 90, for example, on a mass basis. / 10 or less, preferably 70/30 or less, more preferably 60/40 or less.

  If the blending ratio or blending ratio of the polyoxyalkylene polyol and polymer polyol in the polyol component is within the above range, the polyurethane foam (described later) obtained by using a resin premix containing the polyol component (described later) has hardness and the like. While maintaining the physical properties, flame retardancy can be improved.

  The hydroxyl value of the polyol component is, for example, 10 mgKOH / g or more, preferably 15 mgKOH / g or more, more preferably 20 mgKOH / g or more, more preferably 25 mgKOH / g or more, for example, 80 mgKOH / g or less, preferably Is 60 mgKOH / g or less, more preferably 50 mgKOH / g or less, and still more preferably 30 mgKOH / g or less.

  When the hydroxyl value of the polyol component is within the above range, the polyurethane foam (described later) obtained using a resin premix (described later) containing the polyol component is difficult to maintain while maintaining physical properties such as hardness. Flammability can be improved.

  The content ratio of the polyol component in the polyol composition is, for example, 98.00% by mass or more, preferably 99.70% by mass or more, more preferably 99.80% by mass or more, based on the total amount of the polyol composition. More preferably, it is 99.90 mass% or more, for example, less than 100 mass%, Preferably, it is 99.999 mass% or less, More preferably, it is 99.99 mass% or less, More preferably, it is 99.98. It is below mass%.

  The flame retardant is a compound represented by the following formula (1).

(In the formula, R ^{1 s} are the same or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ⁻ represents an anion. However, R ^{1 s} are bonded to each other to form a ring. A structure may be formed.)
In the above formula (1), R ^{1 s} 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 a substituent. And an aralkyl group having 7 to 20 carbon atoms which may be used, and preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms.

  Examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms include 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, etc. C1-20 chain saturated aliphatic hydrocarbon group, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, etc. A cyclic saturated aliphatic hydrocarbon group such as a chain unsaturated aliphatic hydrocarbon group having 2 to 20 carbon atoms such as a vinyl group or 2-propenyl group, such as a cyclohexenyl group. Cyclic unsaturated aliphatic hydrocarbon groups, and the like, preferably a chain saturated aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, Examples thereof include isopropyl group, tert-butyl group, tert-pentyl group, 1,1-dimethyl-3,3-dimethylbutyl group, and more preferably methyl. And the like.

  Examples of the aryl group having 6 to 20 carbon atoms of the aryl group having 6 to 20 carbon atoms which may have a substituent include a phenyl group, a 2-tolyl group, a 3-tolyl group, a 4-tolyl group, and 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-ethyl A phenyl group, 3-ethylphenyl group, 4-ethylphenyl group, 1-naphthyl group, 2-naphthyl group, etc. are mentioned.

  Examples of the substituent of the aryl group having 6 to 20 carbon atoms that may have a substituent include a hydroxyl group, a halogeno group (for example, a chloro group, a fluoro group, a bromo group, and an iodo group), cyano Group, amino group, carboxy group, alkoxy group (for example, carbon such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, neopentyloxy, hexyloxy, etc. 1-6 alkoxy groups, aryloxy groups (eg, phenoxy groups), alkoxycarbonyl groups (eg, methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butyl) C1-C6 alkoxycarbonyl groups such as xyloxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, isopentyloxycarbonyl, neopentyloxycarbonyl, hexyloxycarbonyl, etc., alkylthio groups (for example, methylthio, ethylthio, propylthio, And an alkylthio group having 1 to 4 carbon atoms such as butylthio) and an arylthio group (for example, phenylthio group). In addition, the substitution position and the number of substitutions of the substituent can be arbitrarily determined.

  Examples of the aralkyl group having 7 to 20 carbon atoms of the aralkyl group having 7 to 20 carbon atoms which may have a substituent include, for example, 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 and the like.

  Moreover, as a substituent of a C7-20 aralkyl group which may have a substituent, for example, a substituent of a C6-20 aryl group which may have the above-described substituent may be mentioned. Can be mentioned.

R ¹ may be bonded to each other to form a ring structure. Preferably, R ¹ bonded to the same guanidine structure is bonded to each other to form a ring structure.

When R ¹ forms a ring structure, as R ¹ , for example, an alkylene group having 2 to 20 carbon atoms such as dimethylene group, trimethylene group, tetramethylene group, pentamethylene group, hexamethylene group, for example, cyclohexylene A cycloalkylene group having 3 to 20 carbon atoms such as a group, for example, an alkenylene group having 2 to 20 carbon atoms such as a vinylene group, for example, a cycloalkenylene group having 3 to 20 carbon atoms such as a cyclohexenylene group, for example, a phenylene group , An arylene group having 6 to 20 carbon atoms such as a naphthylene group, for example, an aralkylene group having 8 to 20 carbon atoms such as a phenylethylene group, and preferably an alkylene group having 2 to 20 carbon atoms. More preferably, a dimethylene group, a trimethylene group, a tetramethylene group, and a pentamethylene group are mentioned, More preferably, a tetramethylene group is mentioned.

Examples of the ring structure in which R ¹ are bonded to each other include a pyrrolidinyl group, a pyrrolyl group, a piperidinyl group, an indolyl group, and an isoindolyl group.

R ¹ is preferably identical to each other.

R ¹ is preferably an aliphatic hydrocarbon group having 1 to 20 carbon atoms, more preferably a chain aliphatic hydrocarbon group having 1 to 20 carbon atoms, still more preferably a methyl group, Examples thereof include an ethyl group, an n-propyl group, and an isopropyl group, and a methyl group is particularly preferable.

In the formula (1), X ⁻ represents an anion, preferably a hydroxy anion (hydroxide ion), an alkoxy anion (alkoxide), a carboxy anion, a sulfonyl anion, a hydrogen carbonate anion, or a halide ion. .

  Examples of the alkoxy anion include methoxide, ethoxide, n-propoxide, isopropoxide, n-butoxide, sec-butoxide, tert-butoxide, cyclohexoxide, 2-heptoxide, 1-octoxide, phenoxide and the like. .

  Examples of the carboxy anion include formate anion, acetate anion, propionate anion, butyrate anion, isobutyrate anion, caproate anion, laurate anion, palmitate anion, stearate anion, benzoate anion, decylbenzoate anion, dodecyl. Examples thereof include benzoate 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, camphorsulfonate anion and the like.

  Examples of the halide ion include fluoride ion, chloride ion, bromide ion, and iodide ion, and preferably include chloride ion.

X ^- is, more preferably, sulfonyl anion, hydroxy anion, include halide ions, more preferably, it includes a halide ion.

  Specifically, the compound represented by the above formula (1) includes tetrakis (1,1,3,3-tetramethylguanidino) phosphonium chloride, tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide. , Tetrakis (1,3-diisopropylimidazolidilinimino) phosphonium chloride, tetrakis (1,3-dimethylimidazolidilinimino) phosphonium chloride, and the like, preferably tetrakis (1,1,3,3-tetramethyl) Guanidino) phosphonium chloride and tetrakis (1,1,3,3-tetramethylguanidino) phosphonium hydroxide are exemplified, and tetrakis (1,1,3,3-tetramethylguanidino) phosphonium chloride is more preferred.

  These compounds represented by the above formula (1) can be used alone or in combination of two or more.

  The compound represented by the above formula (1) can be produced, for example, by a method for producing a phosphonium salt described in German Patent Application Publication DE102006010034A1.

  The content ratio of the flame retardant in the polyol composition is, 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, with respect to 100 parts by mass of the polyol component. More preferably, it is 0.005 parts by mass or more, more preferably 0.010 parts by mass or more, more preferably 0.025 parts by mass or more, more preferably 0.035 parts by mass or more, and still more preferably 0.0. 045 parts by mass or more, particularly preferably 0.05 parts by mass or more, and for example, 2 parts by mass or less, preferably 1 part by mass or less, more preferably 0.5 parts by mass or less, still more preferably, 0.3 parts by mass or less, more preferably 0.15 parts by mass or less, and particularly preferably 0.10 parts by mass or less.

  Further, the content of the flame retardant in the polyol composition is, for example, 5 ppm or more, preferably 15 ppm or more, more preferably 25 ppm or more, further preferably 50 ppm or more, more preferably 100 ppm or more as a mass standard. More preferably, it is 200 ppm or more, more preferably 300 ppm or more, more preferably 400 ppm or more, particularly preferably 460 ppm or more, and, for example, 20000 ppm or less, preferably 3000 ppm or less, more preferably 2000 ppm or less. More preferably, it is 1500 ppm or less, More preferably, it is 1000 ppm or less, Most preferably, it is 500 ppm or less.

  If the content ratio or content of the flame retardant is within the above range, the polyurethane foam (described later) obtained using a resin premix (described later) containing the polyol composition may maintain physical properties such as hardness. While possible, flame retardancy can be improved.

  And in order to obtain a polyol composition, the above-mentioned flame retardant is contained in the above-mentioned polyol component. In order to contain a flame retardant, a flame retardant is blended with the polyol component.

  Thereby, the polyol composition of the present invention can be obtained.

  The polyol composition thus obtained contains a polyol component containing at least one selected from the group consisting of a polyoxyalkylene polyol and a polymer polyol, and a flame retardant, and the flame retardant is represented by the above formula ( It is a compound shown by 1).

  Preferably, the polyol composition is composed of a polyol component and a flame retardant.

  Therefore, a polyurethane foam (described later) obtained using a resin premix (described later) containing the polyol composition can improve flame retardancy while maintaining physical properties such as hardness.

  Next, the resin premix of the present invention will be described.

  The resin premix of the present invention includes the above-described polyol composition, a catalyst, and a blowing agent.

  The content ratio of the polyol composition in the resin premix is, for example, 90% by mass or more, preferably 91.5% by mass or more, and, for example, 95% by mass or less, preferably with respect to the total amount of the resin premix. Is 93% by mass or less, more preferably 91.8% by mass or less.

  The content of the flame retardant in the resin premix is, for example, 5 ppm or more, preferably 15 ppm or more, more preferably 20 ppm or more, more preferably 25 ppm or more, further preferably 50 ppm or more, as a mass standard. Preferably, it is 100 ppm or more, more preferably 200 ppm or more, more preferably 300 ppm or more, more preferably 400 ppm or more, particularly preferably 450 ppm or more, and for example, 20000 ppm or less, preferably 3000 ppm or less, more Preferably, it is 2000 ppm or less, More preferably, it is 1500 ppm or less, More preferably, it is 1000 ppm or less, Most preferably, it is 500 ppm or less.

  If the content of the flame retardant is within the above range, the polyurethane foam (described later) obtained using the resin premix can improve the flame retardancy while maintaining physical properties such as hardness. it can.

  The catalyst is not particularly limited, and examples thereof include known urethanization catalysts. Specifically, for example, triethylamine, triethylenediamine, bis- (2-dimethylaminoethyl) ether, morpholines (for example, N-methyl) Aliphatic amines such as morpholine), for example, quaternary ammonium salts such as tetraethylammonium hydroxide, for example, imidazoles such as imidazole, 2-ethyl-4-methylimidazole, 1-isobutyl-2-methylimidazole, For example, tin octoate (tin octylate), tin acetate, tin oleate, tin laurate, dibutyltin diacetate, dimethyltin dilaurate, dibutyltin simercaptide, dibutyltin maleate, dibutyltin dilaurate (dibutyltin dilaurate), dibutyltin Gineo Organic tin compounds such as canoate, dioctyltin dimercaptide, dioctyltin dilaurate, dibutyltin dichloride, for example, organic lead compounds such as lead octoate and lead naphthenate, for example, organic nickel compounds such as nickel naphthenate, for example, cobalt naphthenate Organic cobalt compounds such as, for example, organic copper compounds such as copper octenoate, for example, organic bismuth compounds such as bismuth octylate and bismuth neodecanoate, and the like.

  Furthermore, examples of the urethanization catalyst include potassium salts such as potassium carbonate, potassium acetate, and potassium octylate.

  Moreover, a catalyst can be obtained as a commercial item, 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% by weight diethylene glycol solution of triethylenediamine, manufactured by Air Products Japan), Niax A-1 (amine catalyst, Momentive Performance Materials Japan Joint) Manufactured by company (hereinafter referred to as “Momotiv”), TOYOCAT-NCE (amine catalyst, manufactured by Tosoh Corporation), Neostan U-100 (organotin catalyst, dibutyltin dilaurate, manufactured by Nitto Kasei), Formate TK -1 (organotin catalyst, manufactured by Mitsui Chemicals, Inc.).

  These catalysts can be used alone or in combination of two or more.

  The mixing ratio of the catalyst is, for example, 0.1 parts by mass or more, preferably 0.3 parts by mass or more, and, for example, 5 parts by mass or less, preferably 100 parts by mass of the polyol component of the polyol composition. Is 1 part by mass or less.

  It does not restrict | limit especially as a foaming agent, A well-known foaming agent is mentioned, Preferably, water is mentioned.

  As the foaming agent, water and a physical foaming agent (for example, hydrofluorocarbons, hydrocarbons (for example, cyclopentane), carbon dioxide gas, liquefied carbon dioxide gas, etc.) may be used in an appropriate ratio. it can. The physical foaming agent is preferably carbon dioxide gas or liquefied carbon dioxide gas from the viewpoint of reducing environmental burden.

  These physical foaming agents can be used alone or in combination of two or more.

  The blending ratio of the foaming agent is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, for example, 10 parts by mass or less, preferably 7 parts by mass with respect to 100 parts by mass of the polyol component of the polyol composition. It is below mass parts.

  If the content rate of a foaming agent is the said range, the outstanding foamability can be obtained.

  In addition, the resin premix can contain additives such as a crosslinking agent, a communication agent, and a foam stabilizer as necessary.

  The crosslinking agent is not particularly limited, and examples thereof include known crosslinking agents. Specific examples include alkanolamines, trivalent or higher polyols, and alkylene oxide addition polyols.

  Examples of the alkanolamine include trialkanolamines (tri-C2-4 alkanolamines) such as trimethanolamine, triethanolamine, tripropanolamine, triisopropanolamine, tributanolamine, and dialkanolamines (diC2) such as diethanolamine. Polyalkanolamines, such as ˜4 alkanolamines, preferably diethanolamine.

  Examples of the trivalent or higher polyol include trihydric alcohols such as glycerin and trimethylolpropane, such as tetramethylolmethane, pentaerythritol, dipentaerythritol, D-sorbitol, xylitol, D-mannitol, and D-mannitol. Examples thereof include polyhydric alcohols having 4 or more hydroxyl groups.

  The alkylene oxide addition polyol is a polyol obtained by adding an alkylene oxide to the above trivalent or higher polyol, and examples thereof include a polyoxyalkylene polyol having a hydroxyl value of 200 mgKOH / g or more and 2000 mgKOH / g or less.

  As a crosslinking agent, Preferably, a trivalent or more polyol and / or alkylene oxide addition polyol are mentioned.

  Further, glycerin is preferably used as the trivalent or higher polyol, and as the alkylene oxide addition polyol, preferably Actol KL-210 (polyoxyalkylene polyol having an average functional group number of 3.75, hydroxyl value (OHV) = 840 mg KOH / g, manufactured by Mitsui Chemicals, Inc.).

  The hydroxyl value of the crosslinking agent is, for example, 200 mgKOH / g or more, preferably 800 mgKOH / g or more, for example, 2000 mgKOH / g or less, preferably 1850 mgKOH / g or less.

  These crosslinking agents can be used alone or in combination of two or more.

  The blending ratio of the crosslinking agent is, for example, 0.5 parts by mass or more, preferably 1 part by mass or more, and for example, 10 parts by mass or less, preferably 100 parts by mass of the polyol component of the polyol composition. 5 parts by mass or less.

  The communication agent is not particularly limited and may be a known communication agent. Specifically, for example, polyether polyol (for example, polyoxyethylene polyol, propylene oxide-ethylene oxide random copolymer, etc.) Etc.

  Further, when polyoxyethylene polyol or propylene oxide-ethylene oxide copolymer is used as the communicating agent, the ethylene oxide content is, for example, more than 50% by mass, preferably 60% by mass or more, 100% by mass or less, preferably 90% by mass or less.

  Further, the communication agent can be obtained as a commercial product, for example, Actol EP-505S (manufactured by Mitsui Chemicals), MF-19 (manufactured by Mitsui Chemicals), Exenol 3040 (manufactured by Asahi Glass Co., Ltd.), EL- 985 (manufactured by Asahi Glass Co., Ltd.).

  These communicating agents can be used alone or in combination of two or more.

  The blending ratio of the communicating agent is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 10 parts by mass or less, preferably 100 parts by mass of the polyol component of the polyol composition. Is 5 parts by mass or less.

  It does not restrict | limit especially as a foam stabilizer, A well-known foam stabilizer is mentioned, For example, a silicone foam stabilizer is mentioned.

  Moreover, a foam stabilizer can be obtained as a commercial item, for example, DC-6070 (made by Air Products Japan), DC-2525 (made by Air Products Japan), B-8715LF2 (made by Evonik). SZ-1966 (made by Toray Dow Corning), SRX-274C, SF-2969, SF-2961, SF-2962, L-5309 (made by Momentive), L-3601 (made by Toray Dow Corning), L-5307, L-3600, L-5366, SZ-1325, SZ-1328, Y-10366 (made by Momentive) etc. are mentioned.

  These foam stabilizers can be used alone or in combination of two or more.

  The blending ratio of the foam stabilizer is, for example, 0.1 parts by mass or more, preferably 0.5 parts by mass or more, for example, 10 parts by mass or less, preferably 100 parts by mass of the polyol component of the polyol composition. Is 5 parts by mass or less.

  In addition to the above-mentioned additives, the resin premix may further include, for example, a pigment (color pigment), a dye, an ultraviolet absorber, an antioxidant, a curing accelerator, a heat stabilizer, a light stabilizer, a matte. Other known additives such as an agent, an adhesion-imparting agent, and a silane coupling agent can be blended at an appropriate ratio as long as the excellent effects of the present invention are not impaired.

  Examples of the coloring pigment or dye include inorganic pigments such as carbon black and titanium oxide having good weather resistance, for example, organic pigments such as phthalocyanine blue, phthalocyanine green, quinacridone red, indanthrene orange, and isoindolinone yellow. And dyes.

  These color pigments or dyes can be used alone or in combination of two or more.

  Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, triazine-based, and cyanoacrylate-based ultraviolet absorbers, and more specifically, tinuvin 213, tinuvin 234, tinuvin 326, tinuvin 571 (and above,・ Products made in Japan and trade names).

  These ultraviolet absorbers can be used alone or in combination of two or more.

  Examples of the antioxidant include hindered phenolic antioxidants and other antioxidants (antioxidants other than hindered phenolic antioxidants).

  Specific examples of the hindered phenol antioxidant include 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, Ciba Japan), octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) pro Honate (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) Cyanurate (trade name: Irganox 3790, manufactured by Ciba Japan), 3,9-bis [1,1-dimethyl-2-[(3-tert-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.

  Other antioxidants include, for example, tris (2,4-di-t-butylphenyl) phosphite (trade name: Irgaphos 168, manufactured by Ciba Japan), bis (2,4-di-t-butylphenyl). Pentaerythritol diphosphite (trade name: ADK STAB PEP-24G, manufactured by Adeka), trisnonylphenol phosphite (trade name: ADK STAB 1178, manufactured by ADEKA), tridecyl phosphite (trade name: ADK STAB 3010, manufactured by ADEKA) Phosphorous antioxidants such as 2,5-thiophenediylbis (5-t-butyl-1,3-benzoxazole) (trade name: Tinopal OB, manufactured by Ciba Japan), etc. Agents and the like.

  These antioxidants can be used alone or in combination of two or more.

  Examples of the curing accelerator include dibutyltin dilaurate.

  Examples of the heat stabilizer include a compound containing a sulfonamide group.

  Examples of the compound containing a sulfonamide group include aromatic sulfonamides and aliphatic sulfonamides.

  Examples of aromatic sulfonamides include benzenesulfonamide, dimethylbenzenesulfonamide, sulfanilamide, o- and p-toluenesulfonamide, hydroxynaphthalenesulfonamide, naphthalene-1-sulfonamide, naphthalene-2-sulfonamide, m-nitrobenzenesulfonamide, p-chlorobenzenesulfonamide and the like can be mentioned.

  Examples of the aliphatic sulfonamides include methanesulfonamide, N, N-dimethylmethanesulfonamide, N, N-dimethylethanesulfonamide, N, N-diethylmethanesulfonamide, N-methoxymethanesulfonamide, N- Examples include dodecylmethanesulfonamide, N-cyclohexyl-1-butanesulfonamide, and 2-aminoethanesulfonamide.

  These heat stabilizers can be used alone or in combination of two or more.

  Examples of the light stabilizer include hindered amine light-resistant stabilizers (for example, ADK STAB LA62, ADK STAB LA67 (hereinafter, Adeka Argus Chemical Co., Ltd., trade name), Tinuvin 765, Tinuvin 144, Tinuvin 770, Tinuvin 622 (above, Ciba For example, Tinuvin B75, Tinuvin PUR866 (above, trade name, manufactured by Ciba Japan Co., Ltd.) and the like.

  These light stabilizers can be used alone or in combination of two or more.

  Examples of the matting agent include ultra fine powder synthetic silica.

  Examples of the adhesion-imparting agent include phosphorus oxyacids or derivatives thereof.

  Examples of the oxygen acid of phosphorus include phosphoric acids such as hypophosphorous acid, phosphorous acid, orthophosphoric acid and hypophosphoric acid, for example, condensed phosphorous such as metaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, polyphosphoric acid and ultraphosphoric acid. Examples include acids.

  Examples of phosphorus oxygen acid derivatives include phosphates or condensed phosphates such as sodium orthophosphate, potassium orthophosphate, sodium metaphosphate, potassium metaphosphate, such as monomethyl orthophosphate, monoethyl orthophosphate, orthophosphoric acid. Monoesters such as monopropyl acid, monobutyl orthophosphate, mono-2-ethylhexyl orthophosphate, monophenyl orthophosphate, for example, di-2-ethylhexyl orthophosphate, diphenyl orthophosphate, trimethyl orthophosphate, triethyl orthophosphate, orthophosphoric acid Tripropyl, tributyl orthophosphate, tri-2-ethylhexyl orthophosphate, triphenyl orthophosphate, dimethyl phosphite, diethyl phosphite, dipropyl phosphite, dibutyl phosphite, phosphorous acid 2-ethylhexyl, diphenyl phosphite, trimethyl phosphite, triethyl phosphite, tripropyl phosphite, tributyl phosphite, tri-2-ethylhexyl phosphite, triphenyl phosphite, etc. Examples include esters, or mono, di, and triesters obtained from condensed phosphoric acid and alcohols.

  These adhesion promoters can be used alone or in combination of two or more.

Examples of the silane coupling agent include structural formula R—Si≡ (X) ₃ or R—Si≡ (R ′) (X) ₂ (wherein R is a vinyl group, an epoxy group, an amino group, an imino group). , An organic group having an isocyanate group or a mercapto group, R ′ represents a lower alkyl group having 1 to 4 carbon atoms, and X represents a methoxy group, an ethoxy group, or a chloro atom.

  Specific examples of the silane coupling agent include chlorosilanes such as vinyltrichlorosilane, such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxy. Epoxy silanes such as cyclohexyl) ethyltrimethoxysilane, di (γ-glycidoxypropyl) dimethoxysilane, such as N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, Aminosilanes such as N-β- (aminoethyl) -γ-propylmethyldimethoxysilane, n- (dimethoxymethylsilylpropyl) ethylenediamine, n- (triethoxysilylpropyl) ethylenediamine, N-phenyl-γ-aminopropyltrimethoxysilane For example, bi Vinylsilane such as Le triethoxysilane, for example, .gamma.-isocyanatopropyltrimethoxysilane, such as isocyanatosilanes such as .gamma.-isocyanatopropyltriethoxysilane and the like.

  These silane coupling agents can be used alone or in combination of two or more.

  Furthermore, as other known additives, for example, chain extender, antifoaming agent, plasticizer, antiblocking agent, heat stabilizer, light stabilizer, mold release agent, lubricant, filler, hydrolysis inhibitor, etc. Can be blended at an appropriate ratio as long as the excellent effects of the present invention are not impaired.

  The additive preferably comprises a cross-linking agent, a communicating agent, and a foam stabilizer. The resin premix preferably comprises a polyol composition (that is, a polyol component and a flame retardant), a catalyst, a foaming agent, and an additive.

  And in order to obtain resin premix, a polyol composition, a catalyst, a foaming agent, and an additive as needed are mix | blended and mixed by a well-known method.

  Thereby, the resin premix of the present invention can be obtained.

  In addition, a polyol component and a flame retardant, a catalyst, a foaming agent, and an additive may be blended at the same time, and a polyol composition and a resin premix containing the polyol composition can be simultaneously prepared.

  The additive may be added at the time of synthesizing each component of the resin premix, or may be added at the time of mixing or mixing each component, or may be added after mixing each component. .

  And the resin premix obtained in this way contains the above-mentioned polyol composition, a catalyst, and a foaming agent.

  Therefore, the polyurethane foam (described later) obtained using the resin premix can improve the flame retardancy while maintaining physical properties such as hardness.

  Next, the polyurethane foam of the present invention will be described.

  A polyurethane foam can be obtained by reacting the above resin premix with a polyisocyanate component.

  Examples of the polyisocyanate component include polyisocyanate monomers and polyisocyanate derivatives.

  Examples of the polyisocyanate monomer include aromatic polyisocyanate, araliphatic polyisocyanate, and aliphatic polyisocyanate.

  Examples of the aromatic polyisocyanate include 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 mixtures thereof) (MDI), Examples include aromatic diisocyanates such as 4,4′-toluidine diisocyanate (TODI) and 4,4′-diphenyl ether diisocyanate.

  Examples of the araliphatic polyisocyanate include xylylene diisocyanate (1,3- or 1,4-xylylene diisocyanate or a mixture thereof) (XDI), tetramethylxylylene diisocyanate (1,3- or 1,4-tetra). Methyl xylylene diisocyanate or a mixture thereof (TMXDI), aromatic aliphatic diisocyanates such as ω, ω′-diisocyanate-1,4-diethylbenzene, and the like.

  Examples of the aliphatic polyisocyanate 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 capate And aliphatic diisocyanates such as dodecamethylene diisocyanate.

Aliphatic polyisocyanates include alicyclic polyisocyanates. Examples of the alicyclic polyisocyanate include 1,3-cyclopentane diisocyanate, 1,3-cyclopentene diisocyanate, cyclohexane diisocyanate (1,4-cyclohexane diisocyanate, 1,3-cyclohexane diisocyanate), and 3-isocyanatomethyl-3. , 5,5-trimethylcyclohexylisocyanate (isophorodiisocyanate) (IPDI), methylenebis (cyclohexylisocyanate) (4,4'-, 2,4'- or 2,2'-methylenebis (cyclohexylisocyanate, 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 a mixture thereof) (H ₆ XDI) and the like.

  These polyisocyanate monomers can be used alone or in combination of two or more.

  Examples of the polyisocyanate derivative include a multimer (for example, dimer, trimer (for example, isocyanurate-modified product, iminooxadiazinedione-modified product), pentamer, 7) of the polyisocyanate monomer described above. ), Allophanate-modified products (for example, allophanate-modified products produced from the reaction of the above-mentioned polyisocyanate monomer and low molecular weight polyol), polyol-modified products (for example, the above-mentioned polyisocyanate monomer and low Polyol-modified products (alcohol adducts, etc.) produced by reaction with molecular weight polyols), biuret-modified products (for example, biuret-modified products produced by reaction of the above-mentioned polyisocyanate monomer with water or amines), Urea modified products (for example, in the reaction of the above polyisocyanate monomer and diamine) Modified urea-modified products), oxadiazine trione-modified products (for example, oxadiazine trione produced by reaction of the above-mentioned polyisocyanate monomer and carbon dioxide gas), carbodiimide-modified products (such as the above-mentioned polyisocyanate single product). Carbodiimide-modified products produced by decarboxylation condensation reaction of monomers), uretdione-modified products, uretonimine-modified products, and the like.

  Furthermore, examples of the polyisocyanate derivative include polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI).

  These polyisocyanate derivatives can be used alone or in combination of two or more.

  The polyisocyanate component preferably includes aromatic polyisocyanate and derivatives thereof, more preferably tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenylene polyisocyanate (crude MDI, polymeric MDI). Is mentioned.

  These polyisocyanate components can be used alone or in combination of two or more.

  More preferable examples of the polyisocyanate component include a combination of tolylene diisocyanate, tolylene diisocyanate and diphenylmethane diisocyanate, and particularly preferable is a combination of tolylene diisocyanate and diphenylmethane diisocyanate.

  When tolylene diisocyanate and diphenylmethane diisocyanate are used in combination as the polyisocyanate component, the tolylene diisocyanate and diphenylmethane diisocyanate content is 100 parts by mass of tolylene diisocyanate and diphenylmethane diisocyanate. 40 parts by mass, preferably 50 parts by mass or more, preferably 60 parts by mass or more, for example, less than 100 parts by mass, preferably 90 parts by mass or less, and diphenylmethane diisocyanate is, for example, More than 0 parts by mass, preferably 10 parts by mass or more, for example, 60 parts by mass or less, preferably 50 parts by mass or less, more preferably 40 parts by mass or less.

  Further, the isocyanate group content in the polyisocyanate component is, for example, 15% by mass or more, preferably 30% by mass or more, more preferably 45% by mass or more, based on the total amount of the polyisocyanate component. 60 mass% or less, preferably 50 mass% or less.

  The blending ratio of the polyisocyanate component to the resin premix is, for example, isocyanate index (hydroxyl group in the polyol component in the resin premix, hydroxyl group and amino group in the crosslinking agent, and isocyanate relative to active hydrogen 100 such as water as a blowing agent) The group ratio (stoichiometric ratio)) is, for example, 70 or more, preferably 85 or more, for example, 140 or less, preferably 120 or less.

  And while making a resin premix and a polyisocyanate component react, it is made to foam by well-known foaming systems, such as a slab system, a mold system, and a spray system, for example. Thereby, a polyurethane foam can be obtained.

  Since the above-described polyol composition is used as a raw material for the polyurethane foam thus obtained, flame retardancy can be improved while maintaining properties such as hardness.

The hardness of the polyurethane foam (based on JIS K-6400 (1997)) is, for example, 50 N / 314 cm ² or more, preferably 120 N / 314 cm ² or more, more preferably 130 N / 314 cm ² or more, for example, 500 N / 314 cm ² or less, preferably 300 N / 314 cm ² or less, more preferably 150 N / 314 cm ² or less.

  Further, the combustibility of the polyurethane foam (score based on the description of combustibility evaluation (combustion test) in Examples described later) is, for example, 7 points or less, preferably 5 points or less, more preferably 4 points or less. More preferably, it is 3 points or less, particularly preferably 2 points or less, and usually 0 points or more.

  Examples of the polyurethane foam include a flexible polyurethane foam, a semi-rigid polyurethane foam, and a rigid polyurethane foam. When the polyol component is blended within the range of the hydroxyl value described above, a flexible polyurethane foam is obtained.

  Such a flexible polyurethane foam is suitably used as a cushion material, an impact absorbing material, a sound absorbing material, a vibration absorbing material, a body pressure dispersing material and the like.

  The case where the polyol composition of the present invention and the resin premix containing the polyol composition are used for the production of polyurethane foam has been described, but the use of the polyol composition of the present invention and the resin premix containing the polyol composition is as follows. It is not limited to the above, but can be used for the production of other polyurethane resins.

  Examples of polyurethane resins include elastomers (polyurethane solutions, water-based polyurethanes, hot melt molding (slush molding, rotational molding) urethane powder, thermoplastic urethane elastomers (TPU), thermosetting urethane elastomers (TSU), spray molded urethanes, and melts. Spinning or dry spinning elastic fiber), paint (mainly solution-based, powder-based curing agents: adduct, allophanate, burette, uretdione, polyisocyanurate, iminooxadiandione and mixtures thereof), industrial or hot melt Adhesives, sealants, gels, sealants and the like.

  For example, when the polyurethane resin is produced as a two-component curable polyurethane resin, other known additives described above can be added as necessary. For example, the two-component curable polyurethane resin can be used as a paint. In the case of using as a coloring pigment, dye, ultraviolet absorber, curing accelerator, light stabilizer, matting agent, etc., for example, when using a two-component curable polyurethane resin as an adhesive Can add an adhesion-imparting agent, a silane coupling agent, and the like.

Next, although this invention is demonstrated based on an Example and a comparative example, this invention is not limited by the following Example. In the following description, “part” and “%” are based on mass unless otherwise specified. In addition, the numerical value of the Example shown below can be substituted to the corresponding numerical value (namely, upper limit value or lower limit value) described in embodiment.
<Description of raw materials>
TTGPC: Tetrakis (1,1,3,3-tetramethylguanidino) phosphonium chloride (in the above formula (1), R ¹ is a methyl group and X ⁻ is a chloride ion.)
Ravitor FP-110: 2,2,4,4,6,6-hexaphenoxycyclotriphosphazene (phosphazene compound, manufactured by Fushimi Manufacturing Co., Ltd.)
TCPP: Tris (chloropropyl) phosphate (trade name: TMCPP, manufactured by Daihachi Chemical Industry Co., Ltd.)
EP330N; Actol EP-330N (polyoxyalkylene polyol (propylene oxide-ethylene oxide block copolymer)), ethylene oxide content (terminal oxyethylene group content): 15% by mass, number average molecular weight: 5000, average functionality Number of groups: 3, hydroxyl value: 34 mg KOH / g, manufactured by Mitsui Chemicals)
EP 828; Actol EP-828 (polyoxyalkylene polyol (propylene oxide-ethylene oxide block copolymer)), ethylene oxide content (terminal oxyethylene group content): 15% by mass, number average molecular weight: 6000, average functionality Number of groups: 3, hydroxyl value: 28 mgKOH / g, manufactured by Mitsui Chemicals)
EP 3033; Actol EP-3033 (polyoxyalkylene polyol (propylene oxide-ethylene oxide block copolymer)), ethylene oxide content (terminal oxyethylene group content): 16% by mass, number average molecular weight: 6600, average functionality Number of groups: 4, hydroxyl value: 34 mg KOH / g, manufactured by Mitsui Chemicals)
POP3628; Actol POP-3628 (polymer polyol, hydroxyl value: 28 mgKOH / g, manufactured by Mitsui Chemicals, Inc.)
POP3123; Actol POP-3123 (polymer polyol, hydroxyl value: 23 mgKOH / g, manufactured by Mitsui Chemicals)
33LV; DABCO 33LV (amine catalyst, 33% by weight diethylene glycol solution of triethylenediamine, manufactured by Air Products Japan)
A1; Niax A-1 (amine catalyst, manufactured by Momentive)
No. 25; Kaorizer No. 25 25 (Amine catalyst, manufactured by Kao Corporation)
NCE: TOYOCAT-NCE (amine catalyst, manufactured by Tosoh Corporation)
KL210; Actcol KL-210 (crosslinking agent, average number of functional groups: 3.75, hydroxyl value: 840 mg KOH / g, manufactured by Mitsui Chemicals, Inc.)
DEOA; diethanolamine (cross-linking agent, number of functional groups: 3, hydroxyl value: 1600 mgKOH / g)
EP505S; Actol EP-505S (communication agent, polyether polyol (polyoxyalkylene polyol (random copolymer of propylene oxide-ethylene oxide)), ethylene oxide content: 70% by mass, number average molecular weight: 3300, average Number of functional groups: 3, hydroxyl value: 52 mgKOH / g, manufactured by Mitsui Chemicals)
DC-6070; DC-6070 (silicone foam stabilizer, manufactured by Air Products Japan)
B8715LF2; B-8715LF2 (silicone foam stabilizer, manufactured by Evonik)
L-5309; L-5309 (silicone foam stabilizer, manufactured by Momentive)
L3601; L-3601 (silicone foam stabilizer, manufactured by Toray Dow Corning)
DC2525; DC-2525 (silicone foam stabilizer, manufactured by Air Products Japan)
TM20; Cosmonate TM-20 (polyisocyanate (80% by mass of a mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate in an 80:20 mass ratio (TDI) and diphenylmethane diisocyanate (MDI)) 20 mass% mixture), isocyanate group content: 45 mass%, manufactured by Mitsui Chemicals, Inc.)
TM50; Cosmonate TM-50 (polyisocyanate (50% by mass of 80:20 mass ratio mixture of 2,4-tolylene diisocyanate and 2,6-tolylene diisocyanate (TDI) and diphenylmethane diisocyanate (MDI)) 50 mass% mixture), isocyanate group content: 40 mass%, manufactured by Mitsui Chemicals, Inc.)
<Manufacture of polyurethane foam>
Example 1
EP330N (polyoxyalkylene polyol) 50 parts by mass, POP3628 (polymer polyol) 50 parts by mass, 33LV (amine catalyst) 0.4 part by mass, A1 (amine catalyst) 0.08 part by mass, water (foaming agent) ) 4.6 parts by mass, 1.5 parts by mass of KL210 (crosslinking agent), 1.0 part by mass of EP505S (communication agent), 1.0 part by mass of DC6070 (foam stabilizer), B8715LF2 (foam stabilizer) Agent) 0.5 part by mass and tetrakis (tetramethylguanidino) phosphonium chloride (TTGPC) (flame retardant) 0.05 part by mass were blended and mixed to prepare a resin premix.

Next, the temperature of the obtained resin premix was adjusted to 22 ± 1 ° C., and 55 parts by mass of TM20 (polyisocyanate) adjusted to 22 ± 1 ° C. (isocyanate index: 100) was immediately added. The mixture was vigorously stirred at 5000 rpm for 6 seconds with a homogenizer, and immediately poured into a mold having an inner size of 400 mm × 400 mm × 100 mm adjusted to 60 ° C. in advance, and the lid was closed and foamed. Thereafter, the curing reaction was allowed to proceed for 5 minutes while maintaining the mold at 60 ° C., and the polyurethane foam was taken out of the mold. This produced the flexible polyurethane foam.
(Examples 2 to 18 and Comparative Examples 1 to 9)
A flexible polyurethane foam was produced in the same manner as in Example 1 in accordance with the formulation described in Tables 1 to 3.
<Measurement of properties of polyurethane foam>
The physical properties of the polyurethane foams produced in Examples 1 to 18 and Comparative Examples 1 to 9 were measured by the following measuring methods. The density and physical properties (hardness, elongation, tearing) of each polyurethane foam were measured. Results were obtained for evaluation of strength, thermal compression set, rebound resilience of the core) and combustibility.

The results are shown in Tables 1 to 3.
<Measurement method>
(1) Hardness of polyurethane foam (referred to as “25% ILD” in the table below)
In accordance with Method A described in JIS K-6400 (1997), the hardness of a polyurethane foam having a thickness of 100 mm was measured.
(2) Elongation of polyurethane foam Elongation was measured according to the method described in JIS K-6400 (1997).
(3) Tear strength of polyurethane foam Tear strength was measured according to the method described in JIS K-6400 (1997).
(4) Thermal compression set of polyurethane foam (referred to as “Dryset” in the table below)
In accordance with the method described in JIS K-6400 (1997), the thermal compression set was measured.

  In the measurement, the core portion of the polyurethane foam was cut into 50 mm × 50 mm × 25 mm and used as a test piece.

The test piece was compressed to a thickness of 50%, sandwiched between parallel flat plates, and allowed to stand at 70 ° C. for 22 hours. Thereafter, the test piece was taken out, its thickness was measured after 30 minutes, and the distortion rate was measured in comparison with the thickness before the test.
(5) Rebound resilience of the core of the polyurethane foam (referred to as “rebound resilience core” in the table below)
The impact resilience was measured according to the method described in JIS K-6400 (1997).
(6) Combustion test (referred to as “combustibility” in the table below)
In accordance with the method described in FMVSS-302 (2005), a combustion test was conducted by a horizontal method.

  That is, the polyurethane foam was cut into a length of 350 mm, a width of 100 mm, and a thickness of 12.7 mm to obtain a test piece. Moreover, the A marked line was provided at a position 40 mm from the free end of the test piece. In addition, when the center of the free end of the test piece was used as a fire source and combustion did not reach the A mark, it was evaluated as nonflammable, and although it reached the A mark, it reached the A mark. When the burned length of the later test piece was 50 mm or less from the A marked line, it was evaluated as self-extinguishing.

  If the result of the combustion test is nonflammable, it is 0 points, and if it is self-extinguishing, it is 1 point, and it is combustible (in cases other than nonflammable and self-extinguishing) Is scored according to the burned distance (2 points for 51 mm to 149 mm from the A mark, 3 points for 150 mm to 249 mm from the A mark, and 250 points from the A mark for 250 mm. Was 4 points), and the combustion test was conducted a total of 4 times, and the total value was evaluated. The smaller the total value, the better the flame retardancy.

<Explanation of abbreviations in the table>
EP: Polyoxyalkylene polyol (polyether polyol)
POP: Polymer polyol The description of what is described in the description of the raw materials is omitted.

In the following discussion, the flame retardant content in the polyurethane foam is compared with the amount of the flame retardant in the resin premix. That is, in all examples and all comparative examples, since the isocyanate index is 100, the content of the flame retardant in the polyurethane foam of each example and each comparative example is used as a raw material in each example and comparative example. It can be compared by the flame retardant content in the existing resin premix.
<Discussion>
When the polyurethane foam of Example 14 containing 458 ppm of flame retardant and the polyurethane foam of Comparative Example 1 containing no flame retardant were compared in a resin premix having the same composition as the other components, Example 14 In the polyurethane foam, compared with the polyurethane foam of Comparative Example 1, its hardness, elongation and thermal compression set are improved, its tear strength and impact resilience are maintained, and its flame retardancy is also improved. You can see that

  In addition, with respect to the polyurethane foams of Examples 1 to 5 in which the prescription other than the flame retardant is changed with respect to Example 14, each physical property is substantially maintained as compared with the polyurethane foam of Comparative Example 1. Nevertheless, the flame retardancy is improved.

  Further, in the polyurethane foams of Example 17 and Example 18 in which the content ratio of the polyoxyalkylene polyol in the polyol component was increased and the content ratio of the polymer polyol was decreased, the same flame retardant was included in the Examples Compared with Comparative Example 2 and Comparative Example 3 in which other components have the same composition and no flame retardant is contained, the hardness and impact resilience thereof are not sufficient. It can be seen that the flame retardancy is also improved.

  Further, in the polyurethane foams of Examples 6 to 16, the flame retardant content in the resin premix was changed from 9 ppm to 2469 ppm. However, increasing the flame retardant content improves the hardness of the polyurethane foam. It can be seen that the flame retardancy of the polyurethane foam is improved even if the content of the flame retardant is reduced to about 9 ppm.

  On the other hand, in the polyurethane foams of Comparative Examples 7 to 9, when 18005 ppm of TCPP is included as a flame retardant, the flame resistance is improved to some extent, but the hardness is reduced. On the other hand, when the content of TCPP is reduced, it is understood that although the hardness is improved, the improvement in flame retardancy becomes insufficient.

  In the polyurethane foams of Comparative Examples 4 to 6, the cyclic phosphazene compound Ravitor FP-110 (2,2,4,4,6,6-hexa) having a chemical structure similar to that of the flame retardant of the present invention is used as the flame retardant. When phenoxycyclotriphosphazene) is included in 18005 ppm, the flame retardancy is slightly improved, but the hardness is reduced. On the other hand, when the content of Ravitor FP-110 is decreased, it is understood that although the hardness is improved, the improvement in flame retardancy becomes insufficient.

  Therefore, if a polyurethane foam is produced using a polyol composition containing a specific flame retardant (compound represented by the above formula (1)), the resulting polyurethane foam can maintain physical properties such as hardness. The flame retardancy can be improved.

Claims (6)

A polyol component containing at least one selected from the group consisting of a polyoxyalkylene polyol and a polymer polyol;
Including flame retardants,
The polyol composition, wherein the flame retardant is a compound represented by the following formula (1).

(In the formula, R ^{1 s} are the same or different from each other and represent a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and X ⁻ represents an anion. However, R ^{1 s} are bonded to each other to form a ring. A structure may be formed.)   The polyol composition according to claim 1, wherein the content of the flame retardant is 5 ppm or more and 20000 ppm or less.   The polyol composition according to claim 1, wherein the polyol component has a hydroxyl value of 10 mgKOH / g or more and 80 mgKOH / g or less. The polyol composition according to any one of claims 1 to 3,
A catalyst,
A resin premix comprising a foaming agent.   The resin premix according to claim 4, wherein the content of the flame retardant is 5 ppm or more and 20000 ppm or less. The resin premix according to claim 4 or 5,
A polyurethane foam obtained by reacting with a polyisocyanate component.