Composition for polyurethane foam, preparation for polyurethane foam, polymer polyol preparation for polyurethane foam, production processes therefor, and polyurethane foam

Abstract

This invention relates to a preparation for a polyurethane foam and a polymer polyol preparation for a polyurethane foam, each of which exhibits high coloration and discoloration inhibition properties over a long period of time when stored, and to a composition for a polyurethane foam, which is excellent in storage stability and is preferable as a resin premix. The composition comprises (i) at least one polyol, (ii) a compound having a PN bond, (iii) an antioxidant having a hydroxyphenyl group, (iv) at least an acid and/or its salt, (v) a catalyst for polyurethane foam production and (vi) a blowing agent.

Claims

1. A composition for a polyurethane foam, comprising: (i) at least one polyol selected from a polyoxyalkylene polyol (p) obtained by addition polymerization of an alkylene oxide compound onto an active hydrogen compound using (ii) a compound having a PN bond as a catalyst and a polymer polyol wherein polymer fine particles obtained by polymerizing a compound having an unsaturated bond are dispersed in the polyoxyalkylene polyol (p), (ii) the compound having a PN bond, (iii) an antioxidant having a hydroxyphenyl group, (iv) an acid other than phosphoric acid, a salt of the acid other than phosphoric acid, or combinations thereof; the acid other than phosphoric acid being at least one acid selected from the group consisting of a sulfonic acid and an acid having a sulfuric acid ester group, (v) a catalyst for polyurethane foam production, and (vi) a blowing agent, wherein the molar ratio (a/b) of (a) the compound (iv) to (b) the compound (ii) is not less than 0.5 but not more than 4.0, and a content ratio of the compound (ii) to the polyoxyalkylene polyol (p) is 200 ppm or more and 5000 ppm or less.

2. The composition for a polyurethane foam as claimed in claim 1, wherein the compound (ii) is represented by the following formula (2) or represented by the following formula (4): ##STR00006## wherein a, b, c and d are each a positive number of 0 to 3 but there is no case where all of a, b, c and d become 0 at the same time, each R is the same or different hydrocarbon group of 1 to 10 carbon atoms and two R on the same nitrogen atom may be bonded to each other to form a cyclic structure, and Q.sup. represents a hydroxyl anion, an alkoxy anion, an aryloxy anion or a carboxy anion, ##STR00007## wherein each R is the same or different hydrocarbon group of 1 to 10 carbon atoms, and x is 0 to 5.

3. The composition for a polyurethane foam as claimed in claim 1, which comprises a preparation (c) for a polyurethane foam, the catalyst (v) and the blowing agent (vi), wherein: the preparation (c) comprises the polyol (i), the compound (ii) having a PN bond and having been used for the production of the polyol (p), the antioxidant (iii) and the acid other than phosphoric acid, salt, or combinations thereof (iv), and the preparation (c) is obtained by adding the acid other than phosphoric acid, salt, or combinations thereof (iv) and the antioxidant (iii) to the polyol (i).

4. The composition for a polyurethane foam as claimed in claim 1, wherein the content ratio of the compound (ii) to the polyol (p) is 300 to 5000 ppm.

5. The composition for a polyurethane foam as claimed in claim 1, wherein the content ratio of the antioxidant (iii) in the composition for a polyurethane foam is 100 to 15000 ppm.

6. The composition for a polyurethane foam as claimed in claim 1, wherein the hydroxyl value of the polyoxyalkylene polyol is 10 to 80 mgKOH/g, the hydroxyl value of the polyoxyalkylene polyol of the polymer polyol is 10 to 80 mgKOH/g, and the hydroxyl value of the polymer polyol is 10 to 80 mgKOH/g.

7. A polyurethane foam obtained by reacting the composition for a polyurethane foam as claimed in claim 1 with polyisocyanate.

8. A polyurethane foam obtained by reacting the composition for a polyurethane foam as claimed in claim 3 with polyisocyanate.

9. A production process for a composition for a polyurethane foam, comprising a step which comprises adding, to a polyol (i) containing a polyoxyalkylene polyol (p) obtained by addition polymerization of an alkylene oxide compound onto an active hydrogen compound using a compound (ii) having a PN bond as a catalyst, and the compound (ii) having been used for the production of the polyol (p), an antioxidant (iii) having a hydroxyphenyl group and an acid, a salt of the acid, or combinations thereof (iv) wherein component (iv) is present in such an amount that the molar ratio (a/b) of (a) the acid, salt, or combinations thereof (iv) to (b) the compound (ii) having a PN bond is not less than 0.5 but not more than 4.0, to obtain a preparation (c) for a polyurethane foam and then adding a catalyst (v) for polyurethane foam production and a blowing agent (vi) to the preparation (c), wherein: the acid is at least one acid selected from the group consisting of a sulfonic acid and an acid having a sulfuric acid ester group, and a content ratio of the compound (ii) to the polyoxyalkylene polyol (p) is 200 ppm or more and 5000 ppm or less.

10. The production process for a composition for a polyurethane foam as claimed in claim 9, which comprises a step of preparing a polymer polyol in the preparation (c), wherein: the polymer polyol is obtained by dispersing polymer fine particles obtained by polymerizing a compound having an unsaturated bond in the preparation (c).

11. The production process for a composition for a polyurethane foam as claimed in claim 9, wherein the compound (ii) is represented by the following formula (2) or represented by the following formula (4): ##STR00008## wherein a, b, c and d are each a positive number of 0 to 3 but there is no case where all of a, b, c and d become 0 at the same time, each R is the same or different hydrocarbon group of 1 to 10 carbon atoms and two R on the same nitrogen atom may be bonded to each other to form a cyclic structure, and Q.sup. represents a hydroxyl anion, an alkoxy anion, an aryloxy anion or a carboxy anion, ##STR00009## wherein each R is the same or different hydrocarbon group of 1 to 10 carbon atoms, and x is 0 to 5.

Description

EXAMPLES

(1) The present invention is described below in more detail with reference to the following examples, but it should be construed that the present invention is in no way limited to those examples. In the examples, part (s) and % mean part (s) by mass and % by mass, respectively.

(2) Analysis and measurement in the examples and the comparative examples were carried out in accordance with the following methods.

(3) [Measurement and Evaluation Method]

(4) (1) Hydroxyl Value (OHV)

(5) Measurement was carried out in accordance with the method described in the B method of JIS K-1557-1 (2007).

(6) (2) Total Degree of Unsaturation

(7) Measurement was carried out in accordance with the method described in JIS K-1557-3 (2007).

(8) (3) Content Ratio (% by Mass) of Oxyethylene End Group

(9) The content ratio (% by mass) of an oxyethylene end group in a polyol was calculated from the charge of each component using the following calculation formula.
(Amount of ethylene oxide)/(amount of active hydrogen compound+amount of alkylene oxide+amounts of other components)100

(10) The content ratio (% by mass) can be measured also by the use of 1H-NMR.

(11) (4) Content Ratio (ppm) of Compound Having PN Bond

(12) In the examples, the content ratio of the compound having a PN bond in a polyol was calculated from the charge of each component. The calculation formula is shown below.
(Amount of compound having PN bond)/(amount of compound having PN bond+amount of active hydrogen compound+amount of alkylene oxide+amounts of other components)1000000

(13) Measurement of the content ratio of the compound having a PN bond in a polyol was carried out by the use of a capillary electrophoresis method using a fully automatic CIA system manufactured by Waters Corporation. To a polyol, a hydrochloric acid aqueous solution was added, and using a shaker, extraction of the compound having a PN bond from the hydrochloric acid aqueous solution was carried out. Thereafter, standstill liquid separation was carried out to separate an aqueous layer, and using a capillary electrophoresis analyzer, determination of phosphazenium cation was carried out.

(14) On the other hand, when the solubility of the polyol was high, nitrogen atoms remaining in the polyol were determined, whereby the content ratio of phosphazenium cation was calculated back. For the analysis of nitrogen contained in the polyol, a trace total nitrogen analyzer (model: TN-100) manufactured by Mitsubishi Chemical Corporation and an element analyzer (model: PE2400) manufactured by Perkin Elmer, Inc. were used.

(15) The content ratio of the compound having a PN bond can be determined also by carrying out .sup.1H-NMR measurement using a nuclear magnetic resonance apparatus AL-400 manufactured by JOEL Ltd., referring to the method of Japanese Patent Laid-Open Publication No. 2000-344881.

(16) For example, the chemical shift of proton of a methyl group of tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium is in the vicinity of 2.7 ppm, and the content ratio can be also calculated by comparing it with tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium of a known concentration.

(17) (5) Molar Ratio (a/b) of Acid/Compound Having PN Bond

(18) With respect to the acid having a sulfuric acid ester group, titration was carried out using sodium hydroxide, and from the titration value obtained, the molar ratio was calculated.

(19) With respect to other acids, the number of moles was calculated from the molecular weight, and the molar ratio was calculated.

(20) (6) Coloring Property Test of Composition (Resin Premix) for Polyurethane Foam.

(21) The composition for a polyurethane foam was portioned in a glass bottle containing nitrogen, and stored for 7 days at room temperature. After the storage, the composition was placed in a colorless and transparent cell having an optical path length of 2 cm, and the appearance (degree of discoloration) was visually observed.

(22) (7) Evaluation of Storage Stability of Composition for Polyurethane Foam

(23) When polyurethane foams were prepared using the composition for a polyurethane foam given immediately after preparation and the composition stored for 7 days at room temperature after preparation, a rise time (RT, second(s)) was measured. A difference (RT.sub.bRT.sub.a) between the rise time after 7 days (RT.sub.b) and the rise time immediately after preparation (RT.sub.a) was calculated, and the resulting value was compared with a value (RT.sub.bRT.sub.a: 40 seconds) obtained in Reference Example 1 in which no acid was added, whereby storage stability of the resulting composition for a polyurethane foam was evaluated.

(24) The rise time indicates a time taken for a foamed reaction mixture to reach a maximum height from the beginning of mixing of a resin premix with a polyisocyanate. A smaller difference (RT.sub.bRT.sub.a) indicates that the urethanation reaction is more stable without a change with time, so that the reactivity can be properly controlled, and a urethane foam can be stably obtained.

(25) (8) Coloring Property Test of Preparation for Polyurethane Foam

(26) The resulting preparation for a polyurethane foam was portioned in a glass bottle containing nitrogen and stored for 28 days at 50 C. or 24 hours at 100 C. After the preparation or after the storage, the preparation was placed in a colorless and transparent cell having an optical path length of 2 cm, and the appearance (degree of discoloration) was visually observed.

(27) [Raw Materials]

(28) <Polyols>

(29) (Polyol a)

(30) In an autoclave equipped with a stirring device, a thermometer and a manometer, glycerol and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide (PZN) in an amount of 0.18 mol %/molOH based on the hydroxyl group of glycerol, as a compound having a PN bond, were placed, then vacuum dehydration was carried out at 100 C. for 6 hours, and thereafter, propylene oxide was continuously fed at a reaction temperature of 80 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization. Subsequently, ethylene oxide was continuously fed at a reaction temperature of 100 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization, whereby a polyol a was obtained.

(31) The total degree of unsaturation of this polyol was 0.018 meq/g, the hydroxyl value thereof was 34 mgKOH/g, and the content ratio of the oxyethylene end group was 15% by mass. The content ratio of the compound having a PN bond to the polyol a was calculated to be 800 ppm from the charge of the compound.

(32) (Polyol b)

(33) In an autoclave equipped with a stirring device, a thermometer and a manometer, glycerol and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide in an amount of 0.18 mol %/molOH based on the hydroxyl group of glycerol, as a compound having a PN bond, were placed, then vacuum dehydration was carried out at 100 C. for 6 hours, and thereafter, propylene oxide was continuously fed at a reaction temperature of 80 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization. Subsequently, ethylene oxide was continuously fed at a reaction temperature of 100 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization, whereby a polyol b was obtained.

(34) The total degree of unsaturation of this polyol was 0.025 meq/g, the hydroxyl value thereof was 24 mgKOH/g, and the content ratio of the oxyethylene end group was 14.5% by mass. The content ratio of the compound having a PN bond to the polyol b was calculated from the charge of the compound, similarly to the polyol (a), and as a result, it was 580 ppm.

(35) (Polyol c)

(36) In an autoclave equipped with a stirring device, a thermometer and a manometer, 1 mol of pentaerythritol, 0.03 mol of glycerol and tetrakis[tris(dimethylamino)phosphoranylideneamino]phosphonium hydroxide in an amount of 0.07 mol %/molOH based on the total amount of the hydroxyl groups of pentaerythritol and glycerol, as a compound having a PN bond, were placed, and thereafter, propylene oxide was continuously fed at a reaction temperature of 107 C. and a maximum reaction pressure of 2.9 kg/cm.sup.2 to perform addition polymerization. Subsequently, ethylene oxide was continuously fed at a reaction temperature of 120 C. and a maximum reaction pressure of 2.9 kg/cm.sup.2 to perform addition polymerization, whereby a polyol c was obtained.

(37) The total degree of unsaturation of this polyol was 0.025 meq/g, the hydroxyl value thereof was 34 mgKOH/g, and the content ratio of the oxyethylene end group was 15% by mass. The content ratio of the compound having a PN bond to the polyol c was calculated from the charge of the compound, similarly to the polyol (a), and as a result, it was 300 ppm.

(38) (Polyol d)

(39) In an autoclave, the polyol a was placed, then the system was set in a nitrogen atmosphere, and thereafter, the temperature was raised to 80 C. Subsequently, to 100 parts by weight of the polyol a, 4 parts by weight of ion-exchanged water were added, then BHT in an amount of 300 ppm based on the polyol a was introduced, and thereafter, 0.5 part by weight of an adsorbent KW-700 (available from Kyowa Chemical Industry Co., Ltd.) was introduced. After stirring at 100 C. for 3 hours, dehydration was carried out under reduced pressure, and finally, with passing nitrogen into the liquid phase, nitrogen bubbling under reduced pressure was carried out for 4 hours under the conditions of 110 C. and 30 mm Hgabs. (3990 Pa). After the pressure was returned to atmospheric pressure from reduced pressure using nitrogen, vacuum filtration was carried out through a 5C filter paper (retention particle diameter: 1 m) manufactured by ADVANTEC Toyo Kaisha, Ltd. to perform purification of the polyol.

(40) After the purification operation, the hydroxyl value of the polyol d was 34 mgKOH/g, and the total degree of unsaturation thereof was 0.018 meq./g. The content ratio of the compound having a PN bond to the polyol d was measured to be 17 ppm by the use of .sup.1H-NMR.

(41) (Polyol e)

(42) In an autoclave equipped with a stirring device, a thermometer and a manometer, glycerol and tris[tris(dimethylamino)phosphoranylideneamino]phosphine oxide (PZO) in an amount of 0.18 mol %/molOH based on the hydroxyl group of glycerol, as a compound having a PN bond, were placed, then vacuum dehydration was carried out at 100 C. for 6 hours, and thereafter, propylene oxide was continuously fed at a reaction temperature of 80 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization. Subsequently, ethylene oxide was continuously fed at a reaction temperature of 100 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization, whereby a polyol e was obtained.

(43) The total degree of unsaturation of this polyol was 0.018 meq/g, the hydroxyl value thereof was 34 mgKOH/g, and the content ratio of the oxyethylene end group was 15% by mass. The content ratio of the compound having a PN bond to the polyol e was calculated to be 612 ppm from the charge of the compound. The appearance was slightly white opaque.

(44) (Polymer Polyol a)

(45) In an autoclave equipped with a stirring device, a thermometer and a manometer, glycerol and potassium hydroxide were placed, then vacuum dehydration was carried out at 100 C. for 6 hours, and thereafter, propylene oxide was continuously fed at a reaction temperature of 120 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization. Subsequently, ethylene oxide was continuously fed at a reaction temperature of 110 C. and a maximum reaction pressure of 3.8 kg/cm.sup.2 to perform addition polymerization, whereby a polyol f was obtained.

(46) Subsequently, to the polyol f, water and one equivalent of phosphoric acid based on KOH were added, and they were stirred for 30 minutes. Further, an adsorbent (available from Tomita Pharmaceutical Co., Ltd., trade name: AD-600) and 300 ppm of BHT were added, and dehydration drying was carried out for 3 hours under the conditions of 100 C. and 1330 Pa. Thereafter, solids were removed by filtration to obtain a polyol g. The hydroxyl value of this polyol g was 34 mgKOH/g, and the content ratio of the oxyethylene end group was 15% by mass.

(47) In an autoclave equipped with a stirring device, a thermometer, a manometer and a liquid feeding device, the polyol g was introduced to a full liquid level, and the temperature was raised to 120 C. with stirring. To the autoclave, a mixture of the polyol g, 2,2-azobis(isobutyronitrile), acrylonitrile and styrene was continuously introduced. The initial reaction solution continuously obtained through a discharge port was discarded, and the subsequent reaction solution was used in the next step. The reaction was carried out under the reaction conditions of a reaction temperature of 120 C. and a reaction pressure of 440 kPa, and the residence time was 50 minutes. To the resulting reaction solution, BHT in an amount of 300 ppm based on the reaction solution was added, and thereafter, a reduced pressure heating treatment was carried out for 3 hours under the conditions of 120 C. and not more than 655 Pa to remove an unreacted ethylenically unsaturated monomer and a decomposed product of the polymerization initiator, whereby a polymer polyol a was obtained.

(48) The hydroxyl value of this polymer polyol a was 21 mgKOH/g, the content ratio of a component derived from the polyol g was 61.5% by mass, the content ratio of a polymer component derived from acrylonitrile was 30.8% by mass, and the content ratio of a polymer component derived from styrene was 7.7% by mass. These content ratios were calculated from the charges of the components and the amount of the unreacted monomer determined by gas chromatography. Since the compound having a PN bond was not used in the preparation of the polymer polyol a, the content ratio of the compound was 0 ppm.

(49) (Polymer Polyol b)

(50) In a four-neck flask equipped with a stirring device, a nitrogen feed pipe and a thermometer, to the polyol b was added DBSA-L in such an amount that the molar ratio (acid (a)/compound (b)) became 4.0, and they were heated at 100 C. for 2 hours. Thereafter, an antioxidant (BHT) was added in an amount of 300 ppm based on the polyol b, and the mixture was heated at 100 C. for 1 hour to obtain a polyol h. The mixing was entirely carried out in a closed state. On the assumption that the compound having a PN bond was derived from the polyol b and was not eliminated during the preparation, the content ratio of the compound having a PN bond to the polyol h was taken to be 580 ppm. Further, on the assumption that DBSA-L and BHT were not eliminated either during the preparation, the content ratios of them to the polyol h were calculated to be 1000 ppm and 300 ppm, respectively.

(51) A polymer polyol b was obtained by carrying out the same operations as those of the production of the polymer polyol a, except that the solution of the polyol h was used instead of the polyol g, and acrylonitrile was used while changing the amounts of acrylonitrile and styrene.

(52) The hydroxyl value of this polymer polyol b was 19 mgKOH/g, the content ratio of a component derived from the polyol h was 80% by mass, and the content ratio of a polymer component derived from acrylonitrile was 20% by mass. On the assumption that the compound having a PN bond was derived from the polyol h and was not eliminated during the step of dispersing the polymer, the content ratio of the compound having a PN bond to the polymer polyol b was calculated to be 464 ppm.

(53) (Polymer Polyol d)

(54) A polymer polyol c was obtained by carrying out the same operations as those of the production of the polymer polyol a, except that the amounts of acrylonitrile and styrene were changed, and the polyol g was replaced with the polyol c.

(55) The hydroxyl value of this polymer polyol c was 22.3 mgKOH/g, the content ratio of a component derived from the polyol c was 60% by mass, the content ratio of a polymer component derived from acrylonitrile was 12.3% by mass, and the content ratio of a polymer component derived from styrene was 27.7% by mass.

(56) In a four-neck flask equipped with a stirring device, a nitrogen feed pipe and a thermometer, to the polymer polyol c was added DBSA-L in such an amount that the molar ratio (acid (a)/compound (b)) became 4.0, and they were heated at 100 C. for 2 hours. Thereafter, an antioxidant (BHT) was added in an amount of 300 ppm based on the polymer polyol c, and the mixture was heated at 100 C. for 1 hour to obtain a polymer polyol d. The mixing was entirely carried out in a closed state. On the assumption that the compound having a PN bond was derived from the polyol c and was not eliminated during the preparation, the content ratio of the compound having a PN bond to the polymer polyol d was taken to be 180 ppm. Further, on the assumption that DBSA-L and BHT were not eliminated either during the preparation, the content ratios of them to the polymer polyol d were calculated to be 310 ppm and 300 ppm, respectively.

(57) (Polymer Polyol e)

(58) In a four-neck flask equipped with a stirring device, a nitrogen feed pipe and a thermometer, to the polyol a was added DBSA-L in such an amount that the molar ratio (acid (a)/compound (b)) became 2.3, and they were heated at 100 C. for 2 hours. Thereafter, an antioxidant (BHT) was added in an amount of 300 ppm based on the polyol a, and the mixture was heated at 100 C. for 1 hour to obtain a polyol i. The mixing was entirely carried out in a closed state. On the assumption that the compound having a PN bond was derived from the polyol a and was not eliminated during the preparation, the content ratio of the compound having a PN bond to the polyol i was taken to be 800 ppm. Further, on the assumption that DBSA-L and BHT were not eliminated either during the preparation, the content ratios of them to the polyol were calculated to be 800 ppm and 300 ppm, respectively.

(59) A polymer polyol e was obtained by carrying out the same operations as those of the production of the polymer polyol a, except that the solution of the polyol i was used instead of the polyol g, and acrylonitrile and styrene were used while changing the amounts of acrylonitrile and styrene.

(60) The hydroxyl value of this polymer polyol e was 19.9 mgKOH/g, the content ratio of a component derived from the polyol i was 61% by mass, the content ratio of a polymer component derived from acrylonitrile was 15.6% by mass, and the content ratio of a polymer component derived from styrene was 23.4% by mass. On the assumption that the compound having a PN bond was derived from the polyol i and was not eliminated during the step of dispersing the polymer, the content ratio of the compound having a PN bond to the polymer polyol e was calculated to be 488 ppm.

(61) (Polymer Polyol f)

(62) A polyol j was obtained by carrying out the same operations as those of the preparation of the polyol g, except that BHT was not added. Thereafter, a polymer polyol f was obtained by carrying out the same operations as those of the production of the polymer polyol a, except that the polyol j was used and BHT was not used.

(63) The hydroxyl value of this polymer polyol f was 21 mgKOH/g, the content ratio of a component derived from the polyol j was 61.5% by mass, the content ratio of a polymer component derived from acrylonitrile was 30.8% by mass, and the content ratio of a polymer component derived from styrene was 7.7% by mass. These content ratios were calculated from the charges of the components and the amount of the unreacted monomer determined by gas chromatography. Since the compound having a PN bond was not used in the preparation of the polymer polyol f, the content ratio of the compound was 0 ppm.

(64) <Antioxidants Having Hydroxyphenyl Group>

(65) (Antioxidant a) BHT (available from Junsei Chemical Co., Ltd.)

(66) (Antioxidant b) Irganox 1010 (available from BASF Japan Ltd.)

(67) (Antioxidant c) Irganox 1076 (available from BASF Japan Ltd.)

(68) (Antioxidant d) Irganox 1135 (available from BASF Japan Ltd.)

(69) <Antioxidant Having No Hydroxyl Group>

(70) (Antioxidant e) Tris(2-ethylhexyl phosphite) (JP-308E available from Johoku Chemical Co., Ltd.)

(71) (Antioxidant f) Bis(tridecyl)pentaerythritol diphosphite (JPP-13R available from Johoku Chemical Co., Ltd.)

(72) <Acids and their Salts>

(73) (Acyclic aliphatic monocarboxylic acid of 2 to 25 carbon atoms or its salt> Acetic acid (available from Wako Pure Chemical Industries, Ltd.) Heptanoic acid (available from Wako Pure Chemical Industries, Ltd.) Palmitic acid (available from Wako Pure Chemical Industries, Ltd.)

(74) (Hydroxycarboxylic Acid of 2 to 25 Carbon Atoms or its Salt) Lactic acid (available from Wako Pure Chemical Industries, Ltd.)

(75) (Polycarboxylic Acid of 20 to 60 Carbon Atoms or its Salt) Dimer acid (Pripol 1009 available from Croda Japan K.K.)

(76) (Aromatic Monocarboxylic Acid Represented by the Formula (1) or its Salt) Decylbenzoic acid (DCA available from Wako Pure Chemical Industries, Ltd.) Benzoic acid (available from Wako Pure Chemical Industries, Ltd.)

(77) (Sulfonic Acid or its Salt) p-Toluenesulfonic acid (PTSA available from Wako Pure Chemical Industries, Ltd.) Camphorsulfonic acid (CSA available from Wako Pure Chemical Industries, Ltd.) Dodecylbenzenesulfonic acid (DBSA-L (straight-chain type): NEOPELEX GS available from Kao Corporation) Dodecylbenzenesulfonic acid (DBSA-B (branched type): Lipon LH-900 available from Lion Corporation)

(78) (Acid Having Sulfuric Acid Ester Group or its Salt) Polyoxyethylene styrenated phenyl ether ammonium sulfate (Latemul E-1000A available from Kao Corporation) Polyoxyalkylene alkenyl ether ammonium sulfate (Latemul PD-105 available from Kao Corporation)

(79) (Others) Oxalic acid (available from Wako Pure Chemical Industries, Ltd.) Suberic acid (available from Wako Pure Chemical Industries, Ltd.) Phosphoric acid (available from Wako Pure Chemical Industries, Ltd.)

(80) <Catalysts for Polyurethane Foam>

(81) (Catalyst a) Amine catalyst of Minico L-1020 (trade name, 33% diethylene glycol solution of triethylenediamine) available from Katsuzai-Chemical Corporation

(82) (Catalyst b) Amine catalyst of bis(2-dimethylaminoethyl)ether (trade name: Minico TMDA) available from Katsuzai-Chemical Corporation

(83) <Blowing Agent> Water

(84) <Other Additives>

(85) (Interconnecting Agent a) Polyether polyol of ACTOCOL EP-505S (trade name, hydroxyl value: 52 mgKOH/g) available from Mitsui Chemicals, Inc.

(86) (Crosslinking Agent a) Amine-based crosslinking agent of ACTOCOL KL-210 (trade name, hydroxyl value: 840 mgKOH/g) available from Mitsui Chemicals, Inc.

(87) (Crosslinking Agent b) Purified glycerol (hydroxyl value: 1830 mgKOH/g)

(88) (Foam Stabilizer a) Silicone foam stabilizer of DC-6070 (trade name) available from Air Products Japan, Inc.

(89) (Foam Stabilizer b) Silicone foam stabilizer of DC-2525 (trade name) available from Air Products Japan, Inc.

Preparation of Composition for Polyurethane Foam and Polyurethane Foam

Example 1

(90) In a four-neck flask equipped with a stirring device, a nitrogen feed pipe and a thermometer, to the polyol a was added acetic acid in such an amount that the molar ratio (a/b) became 20.5, and they were heated at 100 C. for 2 hours. Thereafter, an antioxidant (BHT) was added in an amount of 300 ppm based on the polyol a, and the mixture was heated at 100 C. for 1 hour to prepare a preparation for a polyurethane foam. The mixing was entirely carried out in a closed state. On the assumption that the compound having a PN bond was derived from the polyol a and was not eliminated during the preparation, the content ratio of the compound having a PN bond to the polyol a was taken to be 800 ppm. Further, on the assumption that acetic acid and BHT were not eliminated either during the preparation, the content ratios of them to the polyol a were calculated to be 1300 ppm and 300 ppm, respectively.

(91) 60 Parts of the preparation for a polyurethane foam, 40 parts of the polymer polyol (a), 0.4 part of the catalyst (a), 0.1 part of the catalyst (b), 4.0 parts of water, 1.5 parts of the interconnecting agent (a), 2.5 parts of the crosslinking agent (a), 0.2 part of the crosslinking agent (b), 0.3 part of the foam stabilizer (a) and 0.7 part of the foam stabilizer (b) were mixed to prepare a composition (resin premix) for a polyurethane foam. As the compound having a PN bond (catalyst), the compound contained in the preparation for a polyurethane foam was used as it was, and therefore, the content ratio of the compound having a PN bond in the resin premix was calculated to be 438 ppm. The content ratios of acetic acid and BHT in the resin premix were calculated to be 711 ppm and 273 ppm, respectively. Using the resulting resin premix, a coloring property evaluation test was carried out. The results are set forth in Table 1. The resin premix was not discolored even after storage for 7 days.

(92) Subsequently, 100 parts by mass of the resin premix were temperature-controlled to 221 C. in advance, then to the resin premix, 46 parts of a polyisocyanate (COSMONATE (trademark) TM-20 available from Mitsui Chemicals, Inc.) (NCO index: 1.00) having been temperature-controlled to 221 C. were added, and they were immediately vigorously stirred at 5000 rpm for 5 seconds using a homogenizer. Thereafter, the mixed liquid was introduced into a polypropylene container of 150 mm (diameter)300 mm (height) to obtain apolyurethane foam. During foaming, a rise time (RT.sub.a) was measured in an environment of 221 C. by the use of a laser sensor manufactured by Keyence Corporation, and the foam height was also recorded for 5 minutes.

(93) Using the composition after storage for 7 days at room temperature, a rise time (RT.sub.b) was measured in the same manner as that for the composition immediately after preparation, and storage stability of the resin premix was evaluated. The results are set forth in Table 1.

(94) Each of the urethane foams obtained by the use of the composition immediately after preparation and the composition after storage for 7 days was not yellowed and had proper impact resilience, moldability and durability.

Examples 2 to 24 and 27, Comparative Examples 1 to 5

(95) Resin premixes and polyurethane foams (Examples 2 to 24 and 27, Comparative Examples 1 to 5) were obtained in the same manner as in Example 1, except that the charges of the polyols (a to e), the polymer polyols (a, b, e and f), the antioxidants (a to f), the acid or its salt, the catalysts (a and b), water, the interconnecting agent (a), the crosslinking agents (a and b) and the foam stabilizers (a and b) were changed in accordance with Tables 1 to 4. The results are set forth in Tables 1 to 4.

Example 25

(96) 40 Parts of the polymer polyol (b) as the preparation (c) for a polyurethane foam, 60 parts of the polyol (d), 0.4 part of the catalyst (a), 0.1 part of the catalyst (b), 3.9 parts of water, 1.0 part of the interconnecting agent (a), 1.5 parts of the crosslinking agent (a), 0.2 part of the crosslinking agent (b) and 1.0 part of the foam stabilizer (b) were mixed to prepare a composition (resin premix) for a polyurethane foam. The compound having a PN bond (catalyst) was contained in the polyol (d) and the polymer polyol (b), and therefore, the content ratio of the compound having a PN bond in the resin premix was calculated to be 222 ppm. The content ratios of DBSA-L and BHT in the resin premix were calculated to be 370 ppm and 278 ppm, respectively. Using the resulting resin premix, a coloring property evaluation test was carried out.

(97) Further, the same operations as in Example 1 were carried out to obtain a polyurethane foam, and storage stability of the resin premix was evaluated. The results are set forth in Table 3.

(98) The urethane foams obtained by the use of the composition immediately after preparation and the composition after storage for 7 days were evaluated, and as a result, each of them was not yellowed and had proper impact resilience, moldability and durability.

Example 26

(99) A resin premix and a polyurethane foam were obtained by carrying out the same operations as in Example 25, except that the amount of the polyol (d) mixed was changed and the polymer polyol (b) was replaced with the polymer polyol (e). The results are set forth in Table 3.

(100) The urethane foams obtained by the use of the composition immediately after preparation and the composition after storage for 7 days were evaluated, and as a result, each of them was not yellowed and had proper impact resilience, moldability and durability.

Reference Example 1

(101) In a four-neck flask equipped with a stirring device, a nitrogen feed pipe and a thermometer, to the polyol a was added an antioxidant (BHT) in an amount of 300 ppm based on the polyol a, and they were heated at 100 C. for 1 hour. The mixing was entirely carried out in a closed state. On the assumption that the compound having a PN bond was derived from the polyol a and was not eliminated during the preparation, the content ratio of the compound having a PN bond to the polyol a was taken to be 800 ppm. Further, on the assumption that BHT was not eliminated either during the preparation, the content ratio of BHT to the polyol a was calculated to be 300 ppm.

(102) Using 60 parts of the preparation for a polyurethane foam, 40 parts of the polymer polyol (a), 0.4 part of the catalyst (a), 0.1 part of the catalyst (b), 3.9 parts of water, 1.0 part of the interconnecting agent (a), 1.5 parts of the crosslinking agent (a), 0.2 part of the crosslinking agent (b) and 1.0 part of the foam stabilizer (b), the same operations as in Example 1 were carried out, whereby a resin premix and a polyurethane foam were obtained, and they were evaluated.

(103) The results are set forth in Table 4.

Reference Examples 2 and 3

(104) Resin premixes and polyurethane foams (Reference Examples 2 and 3) were obtained in the same manner as in Reference Example 1, except that the polyol (a or d), water, the interconnecting agent (a), the crosslinking agent (a) and the foam stabilizers (a and b) were changed in accordance with Table 4. Then, they were evaluated.

(105) The results are set forth in Table 4.

(106) TABLE-US-00001 TABLE 1 Example Resin premix 1 2 3 4 5 6 7 8 9 10 Content in resin premix (part(s) by mass) Polyol a 60 60 60 45 60 60 60 60 60 Polyol b 60 Polyol d 15 Polymer polyol a 40 40 40 40 40 40 40 40 40 40 Content ratio (10.sup.6) of compound having PN 800 800 800 604 800 800 800 800 800 580 bond to polyol in preparation (c) Content ratio (10.sup.6) of compound having PN 438 438 438 330 438 438 438 438 438 322 bond to resin premix Content ratio (10.sup.6) of antioxidant a to 300 300 300 300 300 300 300 300 300 300 polyol in preparation (c) Content ratio (10.sup.6) of antioxidant a to 273 273 273 273 273 273 273 273 273 278 resin premix Acid species acetic heptanoic palmitic dimer DCA PTSA CSA lactic benzoic DBSA-L acid acid acid acid acid acid Content ratio (10.sup.6) of acid to polyol in 1300 2000 3000 1200 1100 250 370 300 700 1000 preparation (c) Content ratio (10.sup.6) of acid to resin premix 711 1094 1641 656 602 137 202 164 383 555 Catalyst a 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Catalyst b 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 4.0 3.9 Interconnecting agent a 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.5 1.0 Crosslinking agent a 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 2.5 1.5 Crosslinking agent b 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Foam stabilizer a 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Foam stabilizer b 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 1.0 Acid/compound having PN bond (mol/mol) 20.5 14.5 11.1 2.7 4.0 1.2 1.5 3.2 5.4 4.0 Polyisocyanate TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 Coloring property test Immediately after preparation cream cream color cream cream cream cream cream cream cream cream color color color color color color color color color 7 days after preparation cream cream color cream cream cream cream cream cream cream cream color color color color color color color color color Evaluation of storage stability Immediately after preparation 133 119 119 104 108 107 113 113 106 113 RT.sub.a (sec) 7 days after preparation 136 123 117 115 115 116 120 125 127 117 RT.sub.b (sec) RT.sub.b RT.sub.a 3 4 2 11 7 9 7 12 21 4 (1) Each content ratio was calculated from the charge.

(107) TABLE-US-00002 TABLE 2 Example Resin premix 11 12 13 14 15 16 17 18 19 20 21 Content in resin premix (part(s) by mass) Polyol a 60 60 60 60 60 60 60 60 Polyol b 60 60 60 Polymer polyol a 40 40 40 40 40 40 40 40 40 40 40 Content ratio (10.sup.6) of compound 580 800 800 800 800 800 580 800 800 800 580 having PN bond to polyol in preparation (c) Content ratio (10.sup.6) of compound 322 438 438 438 438 438 322 438 438 438 322 having PN bond to resin premix Content ratio (10.sup.6) of antioxidant 300 300 10,000 300 300 300 300 300 a to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant 278 273 109 109 109 5,579 278 273 273 273 278 a to resin premix Content ratio (10.sup.6) of antioxidant 300 b to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant 164 b to resin premix Content ratio (10.sup.6) of antioxidant 300 c to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant 164 c to resin premix Content ratio (10.sup.6) of antioxidant 300 d to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant 164 d to resin premix Acid species DBSA- DBSA- DBSA- DBSA- DBSA- DBSA-L Latemul Latemul DBSA-L DBSA- DBSA-L B L L L L E-1000A PD-105 L Content ratio (10.sup.6) of acid to 500 100 1030 1030 1030 1030 3000 2000 10300 70 1375 polyol in preparation (c) Content ratio (10.sup.6) of acid 278 55 563 563 563 563 1665 1094 5634 38 763 to resin premix Catalyst a 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Catalyst b 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water 3.9 4.0 4.0 4.0 4.0 4.0 3.9 4.0 4.0 4.0 3.9 Interconnecting agent a 1.0 1.5 1.5 1.5 1.5 1.5 1.0 1.5 1.5 1.5 1.0 Crosslinking agent a 1.5 2.5 2.5 2.5 2.5 2.5 1.5 2.5 2.5 2.5 1.5 Crosslinking agent b 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Foam stabilizer a 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Foam stabilizer b 1.0 0.7 0.7 0.7 0.7 0.7 1.0 0.7 0.7 0.7 1.0 Acid/compound having PN 2.0 0.3 3.0 3.0 3.0 3.0 1.3 1.5 29.8 0.2 5.5 bond (mol/mol) Polyisocyanate TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 Coloring property test Immediately after preparation cream cream cream cream cream cream cream cream cream cream cream color color color color color color color color color color color 7 days after preparation cream cream cream cream cream cream cream cream cream orange cream color color color color color color color color color color color Evaluation of storage stability Immediately after preparation 102 96 102 112 114 110 110 104 No foam 96 135 RT.sub.a (sec) obtained 7 days after preparation 108 107 108 118 123 119 114 110 107 141 RT.sub.b (sec) RT.sub.b RT.sub.a 6 11 6 6 9 9 4 6 11 6 (1) Each content ratio was calculated from the charge.

(108) TABLE-US-00003 TABLE 3 Example Resin premix 22 23 24 25 26 27 Content in resin premix (part(s) by mass) Polyol a 60 60 60 Polyol d 50 60 Polyol e 60 Polymer polyol a 40 40 40 40 Polymer polyol b 50 Polymer polyol e 40 Content ratio (10.sup.6) of compound having PN bond to polyol in 800 800 800 17 17 612 preparation (c) Content ratio (10.sup.6) of compound having PN bond to polymer 464 488 polyol in preparation (c) Content ratio (10.sup.6) of compound having PN bond to 444 444 444 222 190 340 resin premix Content ratio (10.sup.6) of antioxidant a to polyol in preparation (c) 300 300 300 300 300 300 Content ratio (10.sup.6) of antioxidant a to resin premix 249 249 249 278 278 278 Acid species DBSA-L DBSA-L DBSA-L DBSA-L DBSA-L DBSA-L Content ratio (10.sup.6) of acid to polyol in preparation (c) 3106 4142 5176 400 Content ratio (10.sup.6) of acid to polymer polyol in preparation (c) 800 488 Content ratio (10.sup.6) of acid to resin premix 1724 2299 2873 370 181 148 Catalyst a 0.4 0.4 0.4 0.4 0.4 0.4 Catalyst b 0.1 0.1 0.1 0.1 0.1 0.1 Water 3.9 3.9 3.9 3.9 3.9 3.9 Interconnecting agent a 1.0 1.0 1.0 1.0 1.0 1.0 Crosslinking agent a 1.5 1.5 1.5 1.5 1.5 1.5 Crosslinking agent b 0.2 0.2 0.2 0.2 0.2 0.2 Foam stabilizer a Foam stabilizer b 1.0 1.0 1.0 1.0 1.0 1.0 Acid/compound having PN bond (mol/mol) 9.0 12.0 15.0 4.0 2.3 1.2 Polyisocyanate TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 Coloring property test Immediately after preparation cream cream cream cream white cream color color color color color color 7 days after preparation cream cream cream cream white cream color color color color color color Evaluation of storage stability Immediately after preparation 156 184 237 127 117 113 RT.sub.a (sec) 7 days after preparation 156 188 241 123 118 119 RT.sub.b (sec) RT.sub.b RT.sub.a 0 4 4 4 1 6 (1) Each content ratio was calculated from the charge.

(109) TABLE-US-00004 TABLE 4 Comparative Example Reference Example Resin premix 1 2 3 4 5 1 2 3 Content in resin premix (part(s) by mass) Polyol a 37.5 22.5 60 60 60 60 Polyol c 60 Polyol d 22.5 37.5 60 Polymer polyol a 40 40 40 40 40 40 Polymer polyol f 40 40 Content ratio (10.sup.6) of compound 506 311 300 800 800 800 800 17 having PN bond to polyol in preparation (c) Content ratio (10.sup.6) of compound 277 170 164 438 438 444 438 9 having PN bond to resin premix Content ratio (10.sup.6) of antioxidant a 300 300 300 300 0 300 to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant a 273 273 273 278 109 273 to resin premix Content ratio (10.sup.6) of antioxidant e 10,000 to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant e 5,469 to resin premix Content ratio (10.sup.6) of antioxidant f 10,000 to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant f 5,469 to resin premix Acid species oxalic acid suberic acid phosphoric DBSA-L DBSA-L acid Content ratio (10.sup.6) of acid to 120 210 100 1030 1030 0 0 0 polyol in preparation (c) Content ratio (10.sup.6) of acid to resin 66 115 55 563 563 0 0 0 premix Catalyst a 0.4 0.4 0.4 0.4 0.4 0.4 0.4 0.4 Catalyst b 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water 4.0 4.0 4.0 4.0 4.0 3.9 4.0 4.0 Interconnecting agent a 1.5 1.5 1.5 1.5 1.5 1.0 1.5 1.5 Crosslinking agent a 2.5 2.5 2.5 2.5 2.5 1.5 2.5 2.5 Crosslinking agent b 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 Foam stabilizer a 0.3 0.3 0.3 0.3 0.3 0.3 0.3 Foam stabilizer b 0.7 0.7 0.7 0.7 0.7 1.0 0.7 0.7 Acid/compound having PN bond 2.0 2.9 2.6 3.0 3.0 (mol/mol) Polyisocyanate TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 TM-20 Coloring property test Immediately after preparation cream color cream color cream color cream color cream color pink color cream color cream color 7 days after preparation cream color cream color cream color cream color cream color pink color orange color cream color Evaluation of storage stability Immediately after preparation 104 105 109 107 119 100 91 105 RT.sub.a (sec) 7 days after preparation 174 199 184 147 165 140 125 113 RT.sub.b (sec) RT.sub.b RT.sub.a 70 94 75 40 46 40 34 8 (1) Each content ratio was calculated from the charge.

(110) (Observation of Change of Polyurethane Foam with Time)

(111) Appearances of the polyurethane foams obtained in Examples 10, 11, 17, and 22 to 27 were visually observed. The appearance 5 minutes after foaming and the appearance 10 minutes after foaming were compared, and a polyurethane foam whose appearance shrinkage had been observed was evaluated as X. Likewise, a polyurethane foam whose appearance shrinkage had been observed one hour after foaming was evaluated as , and a polyurethane foam whose appearance shrinkage had not been observed even one hour after foaming was evaluated as .

(112) The results are set forth in Table 5.

(113) TABLE-US-00005 TABLE 5 Example 10 11 17 22 23 24 25 26 27 Acid species DBSA-L DBSA-B Latemul E-1000A DBSA-L DBSA-L DBSA-L DBSA-L DBSA-L DBSA-L Compound having PN bond PZN PZN PZN PZN PZN PZN PZN PZN PZO Acid/compound having PN bond 4.0 2.0 1.3 9.0 12.0 15.0 4.0 2.3 1.2 (mol/mol) Appearance X

(114) (Properties of Soft Polyurethane Foam)

(115) The resin premixes obtained in Examples 10 and 11 were temperature-controlled to 221 C. in advance, then to each of the resin premixes, a polyisocyanate (COSMONATE (trademark) TM-20 available from Mitsui Chemicals, Inc.) (NCO index: 1.00) having been temperature-controlled to 221C was added, and they were immediately vigorously stirred at 5000 rpm for 5 seconds by the use of a homogenizer. The mixtures were each injected into an aluminum test mold (internal size: 300300100 mm) of 65 C. having been coated with a commercially available release agent in advance, and thereafter, the mold was covered with a lid and closed with a clamp to perform foaming/curing. Five minutes after the beginning of stirring, the clamp of the test mold was removed, then the cured soft polyurethane foam was released from the mold, and subsequently, the thickness of the polyurethane foam was compressed by 80% using a roller to completely interconnect bubbles (crushing operation). Various properties of the soft polyurethane foam obtained 24 hours after foaming were measured by the methods described in JIS K-6400. The results are set forth in Table 6.

(116) TABLE-US-00006 TABLE 6 Example 10 11 Immediately Immediately after 7 days after after 7 days after preparation preparation preparation preparation Hardness 25% 188 185 175 177 ILD (kgf/314 cm.sup.2) Overall density 42.7 41.4 42.3 40.9 (kg/m.sup.3) Wet heat 11.6 11.5 12.7 11.5 durability Wet set (%)

Example 100

(117) In a four-neck flask equipped with a stirring device, a nitrogen feed pipe and a thermometer, to 100 parts by weight of the polyol a was added PTSA in such an amount that the molar ratio (a/b) became 1.2, and they were heated at 100 C. for 2 hours. Thereafter, an antioxidant (BHT) was added in an amount of 300 ppm based on the polyol a, and the mixture was heated at 100 C. for 1 hour to obtain a preparation for a polyurethane foam. The mixing was entirely carried out in a closed state. On the assumption that the compound having a PN bond was derived from the polyol a and was not eliminated during the preparation, the content ratio of the compound having a PN bond to the polyol a was taken to be 800 ppm. Further, on the assumption that PTSA and BHT were not eliminated either during the preparation, the content ratios of them to the polyol a were calculated to be 250 ppm and 300 ppm, respectively.

(118) The resulting preparation was subjected to a coloring property test. The results are set forth in Table 7. The preparation for a polyurethane foam was not discolored after the passage of 24 hours at 100 C. and even after storage for 28 days at 50 C.

Examples 101 to 106, Comparative Examples 100 and 101, Reference Examples 100 and 101

(119) Preparations for polyurethane foam (Examples 101 to 106, Comparative Examples 100 and 101, Reference Examples 100 and 101) were obtained in the same manner as in Example 100, except that the charges of the polyols (a, c, d), the antioxidants (a to c) and the acid or its salt were changed in accordance with Table 7 or 8.

(120) Evaluation results of the preparations obtained are set forth in Tables 7 and 8.

Examples 107 and 108

(121) Using the polymer polyol b or d as the preparation (c) for a polyurethane foam, evaluation was carried out. The results are set forth in Table 7.

(122) TABLE-US-00007 TABLE 7 Example Polyol 100 101 102 103 104 105 106 107 108 Blending quantity (part(s) by mass) Polyol a 100 100 100 100 100 100 100 Polymer polyol b 100 Polymer polyol d 100 Content ratio (10.sup.6) of 800 800 800 800 800 800 800 compound having PN bond to polyol in preparation (c) Content ratio (10.sup.6) of 464 180 compound having PN bond to polymer polyol in preparation (c) Content ratio (10.sup.6) of 300 300 300 300 300 antioxidant a to polyol in preparation (c) Content ratio (10.sup.6) of 300 300 antioxidant a to polymer polyol in preparation (c) Content ratio (10.sup.6) of 300 antioxidant b to polymer polyol in preparation (c) Content ratio (10.sup.6) of 300 antioxidant c to polymer polyol in preparation (c) Acid species PTSA CSA lactic acid benzoic acid DBSA-L DBSA-L DBSA-L DBSA-L DBSA- L Content ratio (10.sup.6) of acid 250 370 300 700 100 1030 1030 to polyol in preparation (c) Content ratio (10.sup.6) of acid 800 310 to polymer polyol in preparation (c) Acid/compound having 1.2 1.5 3.2 5.4 0.3 3.0 3.0 4.0 4.0 PN bond (mol/mol) Coloring property test First day of preparation colorless and colorless and colorless and colorless and colorless and colorless and colorless and cream cream transparent transparent transparent transparent transparent transparent transparent color color 24 hours after preparation colorless and colorless and colorless and colorless and colorless and colorless and colorless and cream cream (storage at 100 C.) transparent transparent transparent transparent transparent transparent transparent color color 28 days after preparation colorless and colorless and colorless and colorless and colorless and colorless and colorless and cream cream (storage at 50 C.) transparent transparent transparent transparent transparent transparent transparent color color (1) Each content ratio was calculated from the charge.

(123) TABLE-US-00008 TABLE 8 Comparative Example Reference Example Polyol 100 101 100 101 Blending quantity (part(s) by mass) Polyol a 100 100 Polyol c 100 Polyol d 100 Content ratio (10.sup.6) of compound having 580 300 800 17 PN bond to polyol in preparation (c) Content ratio (10.sup.6) of antioxidant a to 300 300 300 300 polyol in preparation (c) Acid species DBSA-L oxalic acid Content ratio (10.sup.6) of acid to polyol 70 50 in preparation (c) Acid/compound having PN bond 0.2 1.4 (mol/mol) Coloring property test First day of preparation colorless and transparent colorless and transparent colorless and transparent colorless and transparent 24 hours after preparation purple color and purple color and parple color and colorless and transparent (storage at 100 C.) transparent transparent transparent 28 days after preparation purple color and purple color and purple color and colorless and transparent (storage at 50 C.) transparent transparent transparent (1) Each content ratio was calculated from the charge.