Low-resilience polyurethane foam and production method thereof

Abstract

A low-resilience polyurethane foam is produced by allowing a low-resilience polyurethane foam composition containing polyisocyanate (a), polyol (b), catalyst (c), and blowing agent (d) to react. The polyisocyanate (a) contains bis(isocyanatomethyl)cyclohexane, and the polyol (b) contains 5 to 30 mass % of polyol (b-1) having an average functionality of 1.5 to 4.5 and a hydroxyl number of 20 to 70 mgKOH/g, and 70 to 95 mass % of polyol (b-2) having an average functionality of 1.5 to 4.5 and a hydroxyl number of 140 to 300 mgKOH/g.

Claims

1. A low-resilience polyurethane foam produced by allowing a low-resilience polyurethane foam composition containing polyisocyanate (a), polyol (b), catalyst (c), blowing agent (d) and cross-linking agent (e) to react, wherein the polyisocyanate (a) comprises bis(isocyanatomethyl)cyclohexane, and the polyol (b) comprises, 5 to 30 mass % of polyoxypropylenepolyol (b-1) having an average functionality of 1.5 to 4.5 and a hydroxyl number of 20 to 70 mgKOH/g, and 70 to 95 mass % of polyol (b-2) having an average functionality of 1.5 to 4.5 and a hydroxyl number of 140 to 300 mgKOH/g, the bis(isocyanatomethyl)cyclohexane contains cis-1,4-bis(isocyanatomethyl)cyclohexane and trans-1,4-bis(isocyanatomethyl)cyclohexane, the bis(isocyanatomethyl)cyclohexane contains 80 mol % or more and 93 mol % or less of trans-1,4-bis(isocyanatomethyl)cyclohexane, and an impact resilience determined in conformity with JIS K 6400 (2004) is 14% or less.

2. The low-resilience polyurethane foam according to claim 1, wherein the polyol (b-2) is polyoxyalkylene polyol comprising 10 mass % or more of oxyethylene unit and 90 mass % or less of oxypropylene unit.

3. The low-resilience polyurethane foam according to claim 1, wherein the cross-linking agent (e) comprises alkanolamine.

4. The low-resilience polyurethane foam according to claim 3, wherein the alkanolamine comprises triisopropanolamine.

5. A method for producing a low-resilience polyurethane foam, the method comprising: allowing a low-resilience polyurethane foam composition containing polyisocyanate (a), polyol (b), catalyst (c), blowing agent (d) and cross-linking agent (e) to react and foam, thereby producing a low-resilience polyurethane foam, wherein the polyisocyanate (a) comprises bis(isocyanatomethyl)cyclohexane, and the polyol (b) comprises, 5 to 30 mass % of polyoxypropylenepolyol (b-1) having an average functionality of 1.5 to 4.5 and a hydroxyl number of 20 to 70 mgKOH/g, and 70 to 95 mass % of polyol (b-2) having an average functionality of 1.5 to 4.5 and a hydroxyl number of 140 to 300 mgKOH/g, the bis(isocyanatomethyl)cyclohexane contains 80 mol % or more and 93 mol % or less of trans-1,4-bis(isocyanatomethyl)cyclohexane, and an impact resilience determined in conformity with JIS K 6400 (2004) is 14% or less.

Description

EXAMPLES

(1) In the following, the present invention is described in detail based on Synthesis Examples, Examples, and Comparative Examples. However, the present invention is not limited to these.

(2) 1) Materials

(3) Materials are prepared in accordance with Synthesis Examples below and as shown in Table 1 to Table 4.

Synthesis Example 1-1

Synthesis of Polyisocyanate (a)(1-1)

(4) 1,4-BIC was synthesized as polyisocyanate (a)(1-1) in accordance with Production Example 3 of WO2009-51114.

(5) The produced 1,4-BIC bad a purity measured by gas chromatography of 99.9%, and a trans/cis ratio measured by .sup.13C-NMR based on mol of 86/14.

Synthesis Example 1-2

Synthesis of Polyisocyanate (a)(1-2)

(6) 1,4-BIC was synthesized as polyisocyanate (a)(1-2) in accordance with Production Example 4 of Japanese Unexamined Patent Publication No. 2011-140618.

(7) The produced 1,4-BIC had a purity measured by gas chromatography of 99.9%, and a trans/cis ratio measured by .sup.13C-NMR based on mol of 70/30.

Synthesis Example 1-3

Synthesis of Polyisocyanate (a)(1-3)

(8) 1,4-BIC was synthesized as polyisocyanate (a)(1-4) in accordance with Production Example 1 of Japanese Unexamined Patent Publication No. 2011-140618.

(9) The produced 1,4-BIC had a purity measured by gas chromatography of 99.9%, and a trans/cis ratio measured by .sup.13C-NMR based on mol of 93/7.

Synthesis Example 1-4

Synthesis of polyisocyanate (a)(1-4)

(10) A reactor equipped with a stirrer, a gas inlet tube, a thermometer, a gas purge line, and a condenser was charged with 286.6 parts by mass of 1,4-cyclohexanedicarboxylic acid, 55.7 parts by mass of N,N-dimethylimidazolidinone, and 3.6 parts by mass of tin (II) oxide. Ammonia gas and nitrogen were allowed to pass through in mixture at 90 mL/min (0.14 mol equivalent/1,4-cyclohexanedicarboxylic acid/hr) and at 10 mL/min, respectively while stirring, and the temperature was increased to 280 C. Thereafter, the temperature was kept constant, thereby allowing the mixture to react. The reaction was terminated at that temperature after 48 hours, and the mixture was cooled to 90 C.

(11) 520 parts by mass of 1-butanol was added to the product, and the mixture was stirred. The liquid was subjected to hot filtration, thereby removing the catalyst. The filtrate was analyzed by gas chromatography, and it was found that the yield of 1,4-dicyanocyclohexane was 86%.

(12) Next, the filtrate produced as described above was cooled to room temperature while stirring, and precipitation occurred. The suspension was filtered, and 230 parts by mass of 1-butanol was added to the residue. The mixture was stirred at 90 C. for 1 hour, and thereafter, cooled to room temperature while stirring, and again, precipitation occurred. The suspension was filtered, and washed with 1-butanol twice, and thereafter, the filtrate was dried, thereby producing 100 parts by mass of white solid (yield 45%).

(13) Analysis by gas chromatography revealed that the solid was 1,4-dicyanocyclohexane with a purity of 99.5% or more, and the result of .sup.13C-NMR analysis showed that its trans isomer/cis isomer ratio was 99/1.

(14) Next, a pressure-resistant reactor equipped with a stirrer was charged with 550 parts by mass of the above-described 1,4-dicyanocyclohexane having a trans isomer/cis isomer ratio of 99/1, 30 parts by mass of a catalyst (Raney nickel manufactured by Kawaken Fine Chemicals Co., Ltd.), 560 parts by mass of 28 wt % ammonia water, and 1050 parts by mass of 1-butanol. Replacement was conducted three times by introducing nitrogen from the nozzle of the reactor at 5 MPa, and the mixture was heated under normal pressure while stirring at 400 rpm to 80 C.

(15) When the temperature reached 80 C., hydrogen feeding was started so that the pressure was 4.5 MPa, and reaction was conducted until there is no hydrogen absorption. The reaction time was 3 hours.

(16) After the completion of reaction, the reaction product liquid was cooled to room temperature. The reaction product liquid was taken out, and then filtered to remove the catalyst.

(17) The filtrate was analyzed by gas chromatography, and it was found that 1,4-dicyanocyclohexane conversion rate was 100%, the 1,4-bis(aminomethyl)cyclohexane yield was 98%, and the trans/cis ratio analyzed by .sup.13C-NMR was 98/2 based on mol.

(18) The reaction solution was subjected to reduced-pressure distillation at 10 mmHg, thereby producing 1,4-bis(aminomethyl)cyclohexane (1,4-BAC) having a purity of 99.5% or more and a trans isomer/cis isomer ratio of 98/2 with a yield of 93%.

(19) Using this 1,4-BAC, 1,4-BIC was synthesized by hot/cold two-stage phosgene method. The produced 1,4-BIC had a purity measured by gas chromatography of 99.9%, an APHA color of 5, and a trans isomer/cis isomer ratio measured by .sup.13C-NMR of 98/2.

Synthesis Example 2

Synthesis of Polyol (b-1)(1)

(20) Glycerine was subjected to addition polymerization of propyleneoxide in the presence of potassium hydroxide (polymerization catalyst), thereby synthesizing polyoxypropylenetriol having an average functionality of 3 and a hydroxyl number of 34.0 mgKOH/g as polyol (b-1)(1).

Synthesis Example 3

Synthesis of Polyol (b-1)(2)

(21) Glycerine was subjected to addition polymerization of propylene oxide. The produced polyoxypropylenetriol (manufactured by Mitsui Chemicals, trade name: T1000) in which glycerine was subjected to polymerization catalyst of propylene oxide was subjected to further addition polymerization of propylene oxide in accordance with the method described in Comparative Example 6 of U.S. Pat. No. 3,905,638 using the composite metal cyanide complex (Zn.sub.3[Co(CN).sub.6].sub.2.2.48DME.4.65H.sub.2O.0.94ZnCl.sub.2. DME is an abbrebiation of 1,2-dimethoxyethane.) prepared in accordance with U.S. Pat. No. 4,477,589 as a polymerization catalyst, thereby synthesizing polyoxypropylenetriol having an average functionality of 3 and a hydroxyl number of 33.8 mgKOH/g as polyol (b-1)(2).

Synthesis Example 4

Synthesis of Polyol (b-2)

(22) Glycerine was subjected to addition polymerization of propyleneoxide and ethyleneoxide in the presence of potassium hydroxide (polymerization catalyst), thereby synthesizing polyoxyalkylenetriol having an average functionality of 3, a hydroxyl number of 180.2 mgKOH/g, and an oxyethylene unit content of 18 mass % as polyol (b-2).

Synthesis Example 5

Synthesis of Open-Cell Blowing Agent (f)(1)

(23) Glycerine was subjected to addition polymerization of ethylene oxide in the presence of potassium hydroxide (polymerization catalyst), and thereafter, subjected to addition polymerization of propylene oxide and ethylene oxide randomly, thereby synthesizing polyoxyalkylenetriol having an average functionality of 3, a hydroxyl number of 49.9 mgKOH/g, and an oxyethylene unit content of 75 mass % as polyol (f)(1).

Synthesis Example 6

Synthesis of Open-Cell Blowing Agent (f)(2)

(24) Dipropylene glycol was subjected to addition polymerization of ethylene oxide in the presence of potassium hydroxide (polymerization catalyst), thereby synthesizing polyoxyethylenediol having an average functionality of 2, a hydroxyl number of 125.0 mgKOH/g, and an oxyethylene unit content of 85 mass % as polyol (f)(2).

Synthesis Example 7

Synthesis of Open-Cell Blowing Agent (f)(3)

(25) Diglycerol was subjected to addition polymerization of ethyleneoxide in the presence of potassium hydroxide (polymerization catalyst), thereby producing polyoxyethylenepolyol having an average functionality of 4, an oxyethylene unit content of 91 mass %, and a hydroxyl number of 125.1 mgKOH/g as polyol (f)(3).

(26) The materials shown in Table 1 to Table 4 are listed below.

(27) <Polyisocyanate (a)>

(28) Polyisocyanate (a)(1-1): 1,4-BIC, synthesized in Synthesis Example 1-1, trans/cis ratio=86/14

(29) Polyisocyanate (a)(1-2): 1,4-BIC, synthesized in Synthesis Example 1-2, trans/cis ratio=70/30

(30) Polyisocyanate (a)(1-3): 1,4-BIC, synthesized in Synthesis Example 1-3, trans/cis ratio=93/7

(31) Polyisocyanate (a)(1-4): 1,4-BIC, synthesized in Synthesis Example 1-4, synthesized in Synthesis Example 1-3, trans/cis ratio=98/2

(32) Polyisocyanate (a)(2): 1,3-BIC, manufactured by Mitsui Chemicals, trade name: TAKENATE 600

(33) Polyisocyanate (a)(3): 60/40 (mass ratio) mixture of 1,4-BIC and XDI (manufactured by Mitsui Chemicals, trade name: TAKENATE 500). 1,4-BIC was the one synthesized in Synthesis Example 1-1, trans/cis ratio=86/14.

(34) Polyisocyanate (a)(4): 60/40 (mass ratio) mixture of 1,4-BIC and 1,3-BIC. 1,4-BIC was the one synthesized in Synthesis Example 1-1, trans/cis ratio=86/14.

(35) Polyisocyanate (a)(5): 60/40 (mass ratio) mixture of 1,4-BIC and IPDI (manufactured by Evonik Degussa Japan Co., Ltd., trade name: VESTANAT IPDI). 1,4-BIC was the one synthesized in Synthesis Example 1-1, trans/cis ratio=86/14.

(36) Polyisocyanate (a)(6): TDI (isomer mixture of 2,4- and 2,6-toluenediisocyanate: 2,4/2,6 isomer mixing ratio 80:20, manufactured by Mitsui Chemicals, trade name: Cosmonate T-80)

(37) Polyisocyanate (a)(7): 85/15 (mass ratio) mixture of HDI-1 (allophanate-modified HDI, manufactured by Mitsui Chemicals, trade name: TAKENATE D-178N, NCO %=19.3%) and HDI-2 (nurete-modified HDI, manufactured by Mitsui Chemicals, trade name: TAKENATE D-170N, NCO %=20.7%).

(38) <Polyol (b)>

(39) Polyol (b-1)(1): polyoxypropylenetriol, hydroxyl number 34.0 mgKOH/g, synthesized in Synthesis Example 2

(40) Polyol (b-1)(2): polyoxypropylenetriol, hydroxyl number 33.8 mgKOH/g, synthesized in Synthesis Example 3 (composite metal cyanide complex used as polymerization catalyst)

(41) Polyol (b-2): polyoxyalkylenetriol, hydroxyl number 180.2 mgKOH/g, oxyethylene unit content 18 mass %, synthesized in Synthesis Example 4

(42) <Catalyst c>

(43) Amine catalyst 1: manufactured by Air Products and Chemicals, Inc., trade name: DABCO 33LV, 33% solution of triethylenediamine in dipropylene glycol

(44) Amine catalyst 2: manufactured by Tosoh Corporation, trade name: TOYOCAT ET, 70 mass % solution of bis(dimethylaminoethyl) ether in dipropylene glycol

(45) Organic metal catalyst 1: manufactured by Momentive Performance Materials Inc., organic lead compound, trade name: FOMREZ UL-28

(46) Organic metal catalyst 2 (manufactured by Air Products and Chemicals, Inc., organic lead compound, trade name: Dabco T-9

(47) <Open-Cell Blowing Agent (f)>

(48) Open-cell blowing agent (f)(1): polyoxyalkylenetriol, hydroxyl number of 49.9 mgKOH/g, oxyethylene unit content 75 mass %, synthesized in Synthesis Example 5

(49) Open-cell blowing agent (f)(2): polyoxyethylenediol, hydroxyl number of 125.0 mgKOH/g, oxyethylene unit content 85 mass %, synthesized in Synthesis Example 6

(50) Open-cell blowing agent (f)(3): polyoxyethylenepolyol, hydroxyl number of 125.1 mgKOH/g, oxyethylene unit content 91 mass %, synthesized in Synthesis Example 7

(51) <Auxiliary Agent>

(52) Silicone-based foam stabilizer 1: manufactured by Air Products and Chemicals, Inc., trade name: DC5906

(53) Silicone-based foam stabilizer 2: manufactured by Shin-Etsu Chemical Co., Ltd., trade name: F-242T

(54) Antioxidant 1: manufactured by BASF, hindered phenol compound, trade name: IRGANOX 1135

(55) Antioxidant 2: manufactured by Johoku Chemical Co. Ltd., organic phosphorus compound, trade name: JP-308E

(56) Ultraviolet absorber: manufactured by BASF, benzotriazole compound, trade name: TINUVIN 571

(57) Light stabilizer: manufactured by BASF, hindered amine compound, trade name: TINUVIN 765

(58) 2) Production of Low-Resilience Polyurethane Foam

(59) Of the components (material) shown in Table 1 to Table 4 below, the components other than the polyisocyanate (b) were weighed; they were blended in accordance with the mixing formulation of Table 1 to Table 4 in a laboratory having a temperature of 23 C. and a relative humidity of 55%; and they are stirred and mixed so that they are homogeneous, thereby preparing a premix.

(60) Separately prepared polyisocyanate (b) was weighed in accordance with the mixing formulation shown in Table 1 to Table 4, and the temperature was adjusted to 23 C.

(61) Thereafter, the polyisocyanate (b) was added to the premix, and the mixture was stirred with a hand-mixer (number of revolution 5000 rpm) for 15 seconds to prepare a low-resilience polyurethane foam composition, and immediately after the preparation, the low-resilience polyurethane foam composition was introduced quickly into a wooden box to foam. A low-resilience polyurethane foam was produced in this manner.

(62) 3) Evaluation on Low-Resilience Polyurethane Foam

(63) (i) Shrinkage

(64) The produced low-resilience polyurethane foam was allowed to stand in a laboratory having a temperature of 23 C. and a relative humidity of 55% for 2 days, and presence or absence of shrinkage of the low-resilience polyurethane foam thereafter was visually observed. The results are shown in Tables 1 to 4.

(65) (ii) Apparent Core Density (Unit: kg/m.sup.3)

(66) (i) A rectangular solid having a size of 10105 cm was cut out from the central portion (core) of the low-resilience polyurethane foam after the shrinkage evaluation to prepare a measurement sample, and thereafter, apparent density of the measurement sample was measured in accordance with JIS K7222 (2005). Apparent core density of the low-resilience polyurethane foam was evaluated in this manner. The results are shown in Tables 1 to 4.

(67) (iii) Resilience by Ball Rebound (Impact Resilience) (Unit: %)

(68) (i) A rectangular solid having a size of 10105 cm was cut out from the central portion of the low-resilience polyurethane foam after the shrinkage evaluation to prepare a measurement sample, and thereafter, resilience by ball rebound (impact resilience) of the measurement sample was measured in accordance with JIS K6400-3 (2004). The results are shown in Tables 1 to 4.

(69) (iv) Air Flow Value (Unit: Ml/cm.sup.2/sec)

(70) (i) The low-resilience polyurethane foam after the shrinkage evaluation was cut into a sheet having a thickness of 10 mm, and thereafter subjected to crushing (crushing conditions: low-resilience polyurethane foam passes between two rollers (interval 0.2 mm)) to prepare an air flow value measurement sample, and thereafter, the air flow value of the air flow value measurement sample was measured in accordance with method B of JIS K6400-7 (2004). The results are shown in Tables 1 to 4.

(71) (v) Resistance to UV Discoloration

(72) (i) A rectangular solid having a size of 304010 mm was cut out from the low-resilience polyurethane foam after the shrinkage evaluation to prepare a measurement sample, and thereafter, using a QUV weathering tester equipped with an ultraviolet ray fluorescent lamp, the measurement sample was irradiated with ultraviolet ray of a short wavelength (wavelength 270 to 720 nm) for 24 hours.

(73) The b (change amount in value b) of the low-resilience polyurethane foam before and after the irradiation was measured using a color difference meter (manufactured by Tokyo Denshoku CO., LTD., COLOR ACE MODEL TC-1). The results are shown in Tables 1 to 4.

(74) The b is an index of resistance to UV discoloration of a low-resilience polyurethane foam.

(75) (vi) The Number of the Cells Per Unit Area (1 cm.sup.2) (Unit: Number/cm.sup.2)

(76) The number of cells per unit area was measured based on the following method.

(77) That is, first, black ink was applied thinly on a smooth cut surface of the low-resilience polyurethane foam after evaluation of (i). Then, the applied surface was magnified to 20 times using a CCD camera (manufactured by Keyence Corporation, microscope VHX-900) and was shown on a display. A region corresponding to 1 cm.sup.2 of the low-resilience polyurethane foam is shown on the same display in overlapping manner, and the number of the cells included in the region was counted visually, regarding it as the number of the cells per unit area (1 cm.sup.2). The results are shown in Tables 1 to 4.

(78) TABLE-US-00001 TABLE 1 Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5 Ex. 6 Polyisocyanate Polyisocyanate (a)(1-1) 1,4-BIC,trans/cis ratio = 86/14 54.67 52.16 50.63 (a) Polyisocyanate (a)(1-2) 1,4-BIC,trans/cis ratio = 70/30 Polyisocyanate (a)(1-3) 1,4-BIC,trans/cis ratio = 93/7 Polyisocyanate (a)(1-4) 1,4-BIC,trans/cis ratio = 98/2 Polyisocyanate (a)(2) 1,3-BIC 54.81 52.30 50.63 Polyisocyanate (a)(3) 1,4-BIC*.sup.1/XDI(60/40) Polyisocyanate (a)(4) 1,4-BIC*.sup.1/1,3-BIC(60/40) Polyisocyanate (a)(5) 1,4-BIC*.sup.1/IPDI(60/40) Polyisocyanate (a)(6) TDI Polyisocyanate (a)(7) HDI-1/HDI-2(85/15) Isocyanate index (NCO concentration/OH 70 70 70 70 70 70 concentration) 100 Polyol Polyol (b-1)(1) Hydroxyl number 34.0(mgKOH/g) 6.01 20.01 29.03 6.03 20.07 28.97 (b) Oxyethylene unit content 0(%) Polyol (b-1)(2) Hydroxyl number 33.8(mgKOH/g) Oxyethylene unit content 0(%) Polyol (b-2) Hydroxyl number 180.2(mgKOH/g) 93.99 79.99 71.07 93.97 79.97 71.03 oxyethylene unit content 18(%) Catalyst Amine catalyst 1 33LV 0.52 0.50 0.50 0.49 0.50 0.50 (c) Amine catalyst 2 ET 0.50 0.49 0.50 0.50 0.50 0.50 Organic metal catalyst 1 UL-28 0.15 0.15 0.15 0.15 0.15 0.15 Organic metal catalyst 2 T-9 Blowing agent Ion exchange water 3.00 2.99 3.00 3.02 3.00 3.00 (d) Cross-linking Alkanolamine Triethanol amine 7.99 8.01 8.00 8.00 8.03 8.00 agent (e) Triisopropanolamine Diethanolamine Low molecular-weight Glycerine alcohol Open-cell Open-cell blowing Average functionality 3 blowing agent(f)(1) Hydroxyl number 49.9(mgKOH/g) agent(f) oxyethylene unit content 75(%) Open-cell blowing Average functionality 2 agent(f)(2) Hydroxyl number 125.0(mgKOH/g) oxyethlene unit content 85(%) Open-cell blowing Average functionality 4 agent(f)(3) Hydroxyl number 125.1(mgKOH/g) oxyethylene unit content 91(%) Silicone foam stabilizer 1 DC5609 1.00 1.00 1.01 1.00 0.98 1.00 Silicone foam stabilizer 2 F-242T Antioxidant 1 IRGANOX1135 0.31 0.32 0.30 0.30 0.30 0.30 Antioxidant 2 JP-308E 1.00 0.99 1.00 1.01 1.00 0.99 Ultraviolet absorber TINUVIN 571 0.60 0.60 0.60 0.60 0.60 0.60 Light stabilizer TINUVIN 765 0.60 0.60 0.60 0.61 0.60 0.60 Evaluation {circle around (1)}Presence of Absence Absent Absent Absent Absent Absent Absent of Shrinkage {circle around (2)}Apparent core density (kg/m.sup.3) 52.1 54.2 55.3 53.2 55.2 56.2 {circle around (3)}Resilience by ball (%) 7 6 6 6 5 5 rebound {circle around (4)}Air flow value (ml/cm.sup.2/sec) 84 130 109 75 105 98 {circle around (5)}Resistance to UV b before and after UV 10.2 10.5 10.7 10.3 10.5 10.7 discoloration irradiation {circle around (6)}Number of the cells (Number/cm.sup.2) 234 256 248 246 265 264

(79) TABLE-US-00002 TABLE 2 Ex. 7 Ex. 8 Ex. 9 Polyisocyanate Polyisocyanate 1,4-BIC, trans/cis (a) (a)(1-1) ratio = 86/14 Polyisocyanate 1,4-BIC, trans/cis (a)(1-2) radio = 70/30 Polyisocyanate 1,4-BIC, trans/cis (a)(1-3) ratio = 93/7 Polyisocyanate 1,4-BIC, trans/cis (a)(1-4) ratio = 98/2 Polyisocyanate 1,3-BIC (a)(2) Polyisocyanate 1,4-BIC*.sup.1/XDI(60/40) 51.58 (a)(3) Polyisocyanate 1,4-BIC*.sup.1/1,3-BIC(60/40) 52.13 (a)(4) Polyisocyanate 1,4-BIC*.sup.1/IPDI(60/40) 55.28 (a)(5) Polyisocyanate TDI (a)(6) Polyisocyanate HDI-1/HDI-2(85/15) (a)(7) Isocyanate index (NCO concentration/OH 70 70 70 concentration) 100 Polyol (b) Polyol (b-1)(1) Hydroxyl number 20.01 20.01 20.02 34.0(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-1)(2) Hydroxyl number 33.8(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-2) Hydroxyl number 80.01 80.03 80.10 180.2(mgKOH/g) oxyethylene unit content 18(%) Catalyst Amine catalyst 1 33LV 0.50 0.50 0.50 (c) Amine catalyst 2 ET 0.50 0.50 0.51 Organic metal UL-28 0.15 0.15 0.15 catalyst 1 Organic metal T-9 catalyst 2 Blowing Ion exchange 3.00 2.98 3.00 agent(d) water Cross- Alkanolamine Triethanol amine 8.00 8.02 8.01 linking Triisopropanolamine agent(c) Diethanolamine Low Glycerine molecular- weight alcohol Open-cell Open-cell Average functionality3 blowing blowing Hydroxyl number agent(f) agent(f)(1) 49.9(mgKOH/g) oxyethylene unit content 75(%) Open-cell Average functionality2 blowing Hydroxyl number agent(f)(2) 125.0(mgKOH/g) oxyethylene unit content 85(%) Open-cell Average functionality4 blowing Hydroxyl number agent(f)(3) 125.1(mgKOH/g) oxyethylene unit content 91(%) Silicone foam stabilizer 1 DC5609 1.00 1.00 0.99 Silicone foam stabilizer 2 F-242T Antioxidant 1 IRGANOX1135 0.31 0.30 0.30 Antioxidant 2 JP-308E 1.00 1.00 1.00 Ultraviolet absorber TINUVIN 571 0.60 0.60 0.60 Light stabilizer TINUVIN 765 0.61 0.60 0.60 Evaluation {circle around (1)}Presence of Absent Absent Absent Absence of Shrinkage {circle around (2)}Apparent (kg/m.sup.3) 54.2 53.2 52.8 core density {circle around (3)}Resilience (%) 6 6 6 by ball rebound {circle around (4)}Air flow (ml/cm.sup.2/sec) 88 92 72 value {circle around (5)}Resistance to b before and after UV 13.2 10.3 10.5 UV irradiation discoloration {circle around (6)}Number of (Number/cm.sup.2) 251 245 229 the cells Ex. 10 Ex. 11 Ex. 12 Polyisocyanate Polyisocyanate 1,4-BIC, trans/cis 46.7 52.27 (a) (a)(1-1) ratio = 86/14 Polyisocyanate 1,4-BIC, trans/cis (a)(1-2) radio = 70/30 Polyisocyanate 1,4-BIC, trans/cis (a)(1-3) ratio = 93/7 Polyisocyanate 1,4-BIC, trans/cis (a)(1-4) ratio = 98/2 Polyisocyanate 1,3-BIC (a)(2) Polyisocyanate 1,4-BIC*.sup.1/XDI(60/40) 51.56 (a)(3) Polyisocyanate 1,4-BIC*.sup.1/1,3-BIC(60/40) (a)(4) Polyisocyanate 1,4-BIC*.sup.1/IPDI(60/40) (a)(5) Polyisocyanate TDI (a)(6) Polyisocyanate HDI-1/HDI-2(85/15) (a)(7) Isocyanate index (NCO concentration/OH 70 70 70 concentration) 100 Polyol (b) Polyol (b-1)(1) Hydroxyl number 20.00 34.0(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-1)(2) Hydroxyl number 20.00 20.00 33.8(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-2) Hydroxyl number 80.00 79.98 80.04 180.2(mgKOH/g) oxyethylene unit content 18(%) Catalyst Amine catalyst 1 33LV 0.51 0.50 0.48 (c) Amine catalyst 2 ET 0.49 0.49 0.50 Organic metal UL-28 0.15 0.15 0.15 catalyst 1 Organic metal T-9 catalyst 2 Blowing Ion exchange 2.99 3.01 3.00 agent(d) water Cross- Alkanolamine Triethanol amine 4.00 7.99 8.00 linking Triisopropanolamine agent(c) Diethanolamine Low Glycerine molecular- weight alcohol Open-cell Open-cell Average functionality3 blowing blowing Hydroxyl number agent(f) agent(f)(1) 49.9(mgKOH/g) oxyethylene unit content 75(%) Open-cell Average functionality2 blowing Hydroxyl number agent(f)(2) 125.0(mgKOH/g) oxyethylene unit content 85(%) Open-cell Average functionality4 blowing Hydroxyl number agent(f)(3) 125.1(mgKOH/g) oxyethylene unit content 91(%) Silicone foam stabilizer 1 DC5609 1.00 1.01 1.00 Silicone foam stabilizer 2 F-242T Antioxidant 1 IRGANOX1135 0.32 0.32 0.30 Antioxidant 2 JP-308E 0.99 1.00 1.00 Ultraviolet absorber TINUVIN 571 0.60 0.60 0.60 Light stabilizer TINUVIN 765 0.60 0.61 0.60 Evaluation {circle around (1)}Presence of Absent Absent Absent Absence of Shrinkage {circle around (2)}Apparent (kg/m.sup.3) 53.8 67.2 68.4 core density {circle around (3)}Resilience (%) 10 8 8 by ball rebound {circle around (4)}Air flow (ml/cm.sup.2/sec) 95 55 45 value {circle around (5)}Resistance to b before and after UV 9.7 10.4 13.3 UV irradiation discoloration {circle around (6)}Number of (Number/cm.sup.2) 259 194 216 the cells *.sup.1trans/cis ratio = 86/14

(80) TABLE-US-00003 TABLE 3 Comp. Comp. Comp. Comp. Ex. 1 Ex. 2 Ex. 3 Ex. 4 Polyisocyanate Polyisocyanate (a)(1-1) 1,4-BIC,trans/cis ratio = 86/14 55.31 48.75 (a) Polyisocyanate (a)(1-2) 1,4-BIC,trans/cis ratio = 70/30 Polyisocyanate (a)(1-3) 1,4-BIC,trans/cis ratio = 93/7 Polyisocyanate (a)(1-4) 1,4-BIC,trans/cis ratio = 98/2 Polyisocyanate (a)(2) 1,3-BIC Polyisocyanate (a)(3) 1,4-BIC*.sup.1/XDI(60/40) Polyisocyanate (a)(4) 1,4-BIC*.sup.1/1,3-BIC(60/40) Polyisocyanate (a)(5) 1,4-BIC*.sup.1/TPDI(60/40) Polyisocyanate (a)(6) TDI 30.00 Polyisocyanate (a)(7) HDI-1/HDI-2(85/15) 115.92 Isocyanate index (NCO concentration/OH 70 70 70 70 concentration) 100 Polyol Polyol (b-1)(1) Hydroxyl number 34.0(mgKOH/g) 2.98 40.01 20.03 20.04 (b) oxyethylene unit content 0(%) Polyol (b-1)(2) Hydroxyl number 33.8(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-2) Hydroxyl number 180.2(mgKOH/g) 96.98 59.99 80.03 80.01 oxyethylene unit content 18(%) Catalyst Amine catalyst 1 33LV 0.51 0.49 0.50 (c) Amine catalyst 2 ET 0.50 0.50 0.30 0.50 Organic metal catalyst 1 UL-28 0.15 0.15 0.15 Organic metal catalyst 2 T-9 0.10 Blowing Ion exchange water 3.01 3.01 1.50 3.00 agent(d) Cross-linking Alkanolamine Triethanol amine 8.00 8.01 2.00 8.00 agent(e) Triisopropanolamine Diethanolamine Low molecular-weight Glycerine alcohol Open-cell Open-cell blowing Average functionality3 blowing agent(f)(1) Hydroxyl number 49.9(mgKOH/g) agent(f) oxyethylene unit content 75(%) Open-cell blowing Average functionality2 agent(f)(2) Hydroxyl number 125.0(mgKOH/g) oxyethylene unit content 85(%) Open-cell blowing Average functionality4 agent(f)(3) Hydroxyl number 125.1(mgKOH/g) oxyethylene unit content 91(%) Silicone foam stabilizer 1 DC5609 1.02 1.00 1.00 Silicone foam stabilizer 2 F-242T 1.00 Antioxidant1 IRGANOX1135 0.30 0.32 0.30 0.30 Antioxidant2 JP-308E 1.00 1.01 1.01 1.00 Ultraviolet absorber TINUVIN 571 0.60 0.60 0.60 0.60 Light stabilizer TINUVIN 765 0.60 0.60 0.60 0.60 Evaluation {circle around (1)}Presence or Absence Absent Present Absent Absent of Shrinkage {circle around (2)}Apparent core density (kg/m.sup.3) 53.8 54.8 52.2 55.0 {circle around (3)}Resilience by ball (%) 9 15 5 7 rebound {circle around (4)}Air flow value (ml/cm.sup.2/sec) 35 68 32 35 {circle around (5)}Resistance to UV b before and after UV 10.1 11.2 19.6 10.4 discoloration irradiation {circle around (6)}Number of the cells (Number/cm.sup.2) 63 296 260 185 *.sup.1trans/cis ratio = 86/14

(81) TABLE-US-00004 TABLE 4 Ex. 13 Ex. 14 Ex. 15 Ex. 16 Ex. 17 Ex. 18 Ex. 19 Polyisocyanate Polyisocyanate (a)(1-1) 1,4-BIC,trans/cis ratio = 85/14 54.12 52.06 48.72 45.77 43.32 (a) Polyisocyanate (a)(1-2) 1,4-BIC,trans/cis ratio = 70/30 52.06 Polyisocyanate (a)(1-3) 1,4-BIC,trans/cis ratio = 93/7 52.24 Polyisocyanate (a)(1-4) 1,4-BIC,trans/cis ratio = 98/2 Polyisocyanate (a)(2) 1,3-BIC Polyisocyanate (a)(3) 1,4-BIC*.sup.1/XDI(60/40) Polyisocyanate (a)(4) 1,4-BIC*.sup.1/1,3-BIC(60/40) Polyisocyanate (a)(5) 1,4-BIC*.sup.1/TPDI(60/40) Polyisocyanate (a)(6) TDI Polyisocyanate (a)(7) HDI-1/HDI-2(85/15) Isocyanate index (NCO concentration/OH 70 70 70 70 70 70 70 concentration) 100 Polyol Polyol (b-1)(1) Hydroxyl number 34.0(mgKOH/g) 20.00 20.02 20.01 20.00 20.03 20.01 20.02 (b) oxyethylene unit content 0(%) Polyol (b-1)(2) Hydroxyl number 33.8(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-2) Hydroxyl number 180.2(mgKOH/g) 80.03 80.01 80.03 80.10 80.05 80.03 80.00 Oxyethylene unit content 18(%) Catalyst Amine catalyst 1 33LV 0.51 0.50 0.50 0.50 0.49 0.50 0.49 (c) Amine catalyst 2 ET 0.50 0.50 0.51 0.51 0.50 0.50 0.50 Organic metal catalyst 1 UL-28 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Organic metal catalyst 2 T-9 Blowing Ion exchange water 3.00 3.01 2.99 3.00 3.00 3.01 3.00 agent(d) Cross-linking Alkanolamine Triethanol amine 8.00 8.01 agent(e) Triisopropanolamine 12.01 10.00 7.01 4.01 2.00 Diethanolamine Low molecular-weight Glycerine alcohol Open-cell Open-cell blowing Average functionality blowing agent(f)(1) Hydroxyl number 49.9(MgKOH/g) agent(f) oxyethylene unit content 75(%) Open-cell blowing Average functionality2 agent(f)(2) Hydroxyl number 125.0(mgKOH/g) oxyethylene unit content 85(%) Open-cell blowing Average functionality4 agent(f)(3) Hydroxyl number 125.1(mgKOH/g) oxyethylene unit content 91(%) Silicone foam stabilizer 1 DC5609 1.01 0.99 1.00 1.01 1.00 1.00 1.00 Silicone foam stabilizer 2 F-242T Antioxidant 1 IRGANOX1135 0.30 0.31 0.30 0.30 0.30 0.29 0.29 Antioxidant 2 JP-308E 1.00 1.00 1.00 1.00 1.01 1.00 1.00 Ultraviolet absorber TINUVIN 571 0.61 0.60 0.60 0.60 0.61 0.60 0.60 Light stabilizer TINUVIN 765 0.59 0.61 0.60 0.60 0.59 0.60 0.60 Evaluation {circle around (1)}Presence or Absence Absent Absent Absent Absent Absent Absent Absent of Shrinkage {circle around (2)}Apparent core density (kg/m.sup.3) 52.8 54.1 55.1 56.2 60.2 51.0 55.0 {circle around (3)}Resilience by ball (%) 5 6 8 10 1.1 8 6 rebound {circle around (4)}Air flow value (ml/cm.sup.2/sec) 135 128 105 90 75 55 140 {circle around (5)}Resistaisce to UV b before and before and after UV 14.8 9.5 6.8 3.5 2.0 10.1 10.3 discoloration irradiation {circle around (6)}Number of the cells (Number/cm.sup.2) 256 242 247 252 265 273 250 Ex. 20 Ex. 21 Ex. 22 Ex. 23 Ex. 24 Ex. 25 Ex. 26 Polyisocyanate Polyisocyanate (a)(1-1) 1,4-BIC,trans/cis ratio = 86/14 50.91 53.62 47.94 52.31 52.60 52.67 (a) Polyisocyanate (a)(1-2) 1,4-BIC,trans/cis ratio = 70/30 Polyisocyanate (a)(1-3) 1,4-BIC,trans/cis ratio = 93/7 Polyisocyanate (a)(1-4) 1,4-BIC,trans/cis ratio = 98/2 52.23 Polyisocyanate (a)(2) 1,3-BIC Polyisocyanate (a)(3) 1,4-BIC*.sup.1/XDI(60/40) Polyisocyanate (a)(4) 1,4-BIC*.sup.1/1,3-BIC(60/40) Polyisocyanate (a)(5) 1,4-BIC*.sup.1/TPDI(60/40) Polyisocyanate (a)(6) TDI Polyisocyanate (a)(7) HDI-1/HDI-2(85/15) Isocyanate index (NCO concentration/OH 70 70 70 70 70 70 70 concentration) 100 Polyol Polyol (b-1)(1) Hydroxyl number 34.0(mgKOH/g) 20.00 20.01 20.00 20.03 20.01 20.03 20.01 (b) oxyethylene unit content 0(%) Polyol (b-1)(2) Hydroxyl number 33.8(mgKOH/g) oxyethylene unit content 0(%) Polyol (b-2) Hydroxyl number 180.2(mgKOH/g) 80.01 80.03 80.10 80.05 79.99 79.99 80.00 oxyethylene unit content 18(%) Catalyst Amine catalyst 1 33LV 0.50 0.50 0.50 0.49 0.50 0.50 0.50 (c) Amine catalyst 2 ET 0.51 0.51 0.51 0.50 0.49 0.51 0.49 Organic metal catalyst 1 UL-28 0.15 0.15 0.15 0.15 0.15 0.15 0.15 Organic metal catalyst 2 T-9 Blowing Ion exchange water 2.99 2.99 3.00 3.00 2.99 2.99 2.99 agent(d) Cross-linking Alkanolamine Triethanol amine 7.99 8.01 8.01 8.00 agent(e) Triisopropanolamine 7.01 4.01 Diethanolamine 3.00 Low molecular-weight Glycerine 1.00 1.00 3.00 alcohol Open-cell Open-cell blowing Average functionality3 3.00 blowing agent(f)(1) Hydroxyl number 49.9(mgKOK/g) agent(f) oxyethylene unit content 75(%) Open-cell blowing Average functionality2 3.00 agent(f)(2) Hydroxyl number 125.0(mgKOH/g) oxyethylene unit content 85(%) Open-cell blowing Average functionality4 3.00 agent(f)(3) Hydroxyl number 125.1(mgKOH/g) oxyethylene unit content 91(%) Silicone foam stabilizer 1 DC5609 1.00 1.00 1.01 1.00 1.00 1.00 1.01 Silicone foam stabilizer 2 F-242T Antioxidant 1 IRGANOX1135 0.30 0.31 0.30 0.30 0.32 0.30 0.31 Antioxidant 2 JP-308E 1.00 1.00 1.00 1.03 0.99 1.00 0.99 Ultraviolet absorber TINUVIN 571 0.60 0.60 0.59 0.61 0.60 0.60 0.61 Light stabilizer TINUVIN 765 0.59 0.60 0.60 0.59 0.60 0.60 0.60 Evaluation {circle around (1)}Presence or Absence Absent Absent Absent Absent Absent Absent Absent of Shrinkage {circle around (2)}Apparent core density (kg/m.sup.3) 55.8 49.0 52.0 68.0 56.2 56.1 57.6 {circle around (3)}Resilience by ball (%) 5 7 9 12 6 6 6 rebound {circle around (4)}Air flow value (ml/cm.sup.2/sec) 150 135 130 45 155 160 162 {circle around (5)}Resistance to UV b before and before and after UV 10.5 5.7 2.5 1.7 10.6 10.2 10.3 discoloration irradiation {circle around (6)}Number of the cells (Number/cm.sup.2) 218 237 227 155 227 235 223 *.sup.1trans/cis ratio = 86/14

(82) While the illustrative embodiments of the present invention are provided in the above description, such is for illustrative purpose only and it is not to be construed as limiting in any manner. Modification and variation of the present invention that will be obvious to those skilled in the art is to be covered by the following claims.

INDUSTRIAL APPLICABILITY

(83) A low-resilience polyurethane foam is used as a low-resilience elastomer for, for example, a shock absorbing material, a sound absorbing material, a vibration absorbing material, and a body pressure relieving material.