POLYOL-CONTAINING COMPOSITION, FOAMABLE POLYURETHANE COMPOSITION, AND POLYURETHANE FOAM

Abstract

Provided is a polyol-containing composition capable of preventing a polyurethane foam from hydrolyzing and having a good foaming property, a foamable polyurethane composition, and a polyurethane foam. The polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, the polyol-containing composition comprising a polyol, a catalyst, a foaming agent, and a filler, a content of the filler in the polyol-containing composition being 8 mass % or more, the catalyst comprising a metal catalyst containing at least one selected from the group consisting of bismuth and tin.

Claims

1. A polyol-containing composition for obtaining a polyurethane foam by reacting with a polyisocyanate, the polyol-containing composition comprising a polyol, a catalyst, a foaming agent, and a filler, a content of the filler in the polyol-containing composition being 8 mass % or more, the catalyst comprising a metal catalyst containing at least one selected from the group consisting of bismuth and tin.

2. The polyol-containing composition according to claim 1, wherein the metal catalyst contains bismuth.

3. The polyol-containing composition according to claim 1, wherein the catalyst further comprises an imidazole derivative.

4. The polyol-containing composition according to claim 3, wherein the imidazole derivative is imidazole substituted on the 1.sup.st position and the 2.sup.nd position each independently with an alkyl group having 4 or less carbon atoms.

5. The polyol-containing composition according to claim 3, wherein the imidazole derivative is at least one selected from the group consisting of 1,2-dimethylimidazole and 1-isobutyl-2-methylimidazole.

6. A foamable polyurethane composition comprising the polyol-containing composition according to claim 1 and a polyisocyanate.

7. The foamable polyurethane composition according to claim 6, wherein a content of the filler in the foamable polyurethane composition is 4 parts by mass or more per 100 parts by mass of a urethane resin.

8. The foamable polyurethane composition according to claim 6, wherein a water absorption rate of a polyurethane foam obtained by reacting and foaming the foamable polyurethane composition is 1.5 g/100 cm.sup.2 or less.

9. The foamable polyurethane composition according to claim 6, wherein the foamable polyurethane composition has an isocyanate index of 250 or more.

10. A polyurethane foam obtained by reacting and foaming the foamable polyurethane composition according to claim 6.

Description

EXAMPLES

[0113] Hereinafter, the present invention will be more specifically described in reference with examples but is not limited thereto.

1. Production of Polyurethane Foams

[0114] Polyol-containing compositions and polyisocyanates were separately prepared according to the formulations shown in Table 1 to obtain the polyurethane foams of Examples and Comparative Examples. Details of the components in the table are as follows.

(1) Polyol-Containing Composition

Polyols

[0115] p-Phthalic acid polyester polyol (manufactured by KAWASAKI KASEI CHEMICALS LTD., product name: MAXIMOL RLK-087, hydroxy value=200 mg KOH/g)
p-Phthalic acid polyester polyol (manufactured by KAWASAKI KASEI CHEMICALS LTD., product name: MAXIMOL RLK-505, hydroxy value=250 mg KOH/g)

Catalysts

[0116] Amine catalyst for resinification, 1,2-dimethylimidazole (manufactured by Tosoh Corporation, product name: TOYOCAT (registered trademark)-DM70), concentration 65 to 75 mass %
Amine catalyst for resinification, 1-isobutyl-2-methylimidazole (manufactured by Air Products and Chemicals, Inc., product name: DABCO NC-IM), concentration about 98 mass %
Metal catalyst for resinification, bismuth trioctate (manufactured by NITTO KASEI CO., LTD., product name: Neostann U-600), concentration 55 to 58 mass %
Metal catalyst for resinification, dioctyitin versatate (manufactured by NITTO KASEI CO., LTD., product name: Neostann U-830), concentration about 99 mass %
Metal catalyst (trimerization catalyst), potassium 2-ethylhexanoate (manufactured by Air Products and Chemicals, Inc., product name: DABCO K-15), concentration 70 to 80 mass %

Foaming Agents

[0117] Hydrofluoroolefin (HFO, manufactured by Honeywell Japan Ltd, product name: Solstice LBA, trans-1-chloro-3,3,3-trifluoropropene)

Water

Flame Retardant

[0118] Tris(β-chloropropyl)phosphate (manufactured by Daihachi Chemical Industry Co., Ltd., product name: TMCPP)

Fillers

[0119] Red phosphorus (manufactured by PIN KAGAKU KOGYO Co., Ltd., product name: Nova Excel 140)
Zinc borate (manufactured by HAYAKAWA & CO., LTD., product name: Firebrake ZB)
Wollastonite (SiO.sub.2.CaO) (manufactured by KINSEI MATEC CO., LTD., product name: SH-1250)
Antimony trioxide (manufactured by NIHON SEIKO CO., LTD., product name: PATOX-C)
Aluminum hydroxide (manufactured by ALMORIX LTD., product name: B-325)

(2) Polyisocyanate

[0120] 4,4′-Diphenylmethane diisocyanate (4,4′-MDI) (manufactured by Wanhua Chemical Japan Co., Ltd., product name: PM200)

[0121] The polyurethane foam in each of Examples and Comparative Examples was formed by following the procedure below.

[0122] The polyisocyanate was added in the blending ratio shown in Table 1 to 100 g of a kneaded product of the components of the polyol-containing composition shown in the formulation of Table 1. The resultant was stirred until homogeneously mixed at an outside temperature of 20° C. and a solution temperature of 15±1° C. using a hand mixer (high-speed disperser HOMOGENIZING MIXER Model 2.5, manufactured by PRIMIX Corporation) at a rotation speed of 8,000 rpm to make a foamable polyurethane resin composition. The obtained foamable polyurethane resin composition lost the fluidity in the course of time, thereby obtaining a foam of the foamable polyurethane resin composition (polyurethane foam).

2. Evaluation

[0123] Evaluations were made according to the following criteria.

Filler Content

[0124] The filler content of the polyurethane foam was calculated by the following method.

(1) The weight (g) of the polyol-containing composition used for forming the polyurethane foam, weight A, was measured.
(2) A Kiriyama funnel filter paper (manufactured by NIPPON RIKAGAKU KIKAI CO., LTD., acid and alkali resistant, No. 2) was provided to use for separating the filler in the polyol-containing composition, and the weight (g) of the Kiriyama funnel filter paper, weight B, was measured.
(3) The polyol-containing composition was filtered through the Kiriyama funnel. Then, the Kiriyama funnel filter paper used for the filtration was rinsed with acetone to wash off surpluses attached to the Kiriyama funnel filter paper and the filler. The filtration with the Kiriyama funnel filter paper and the following washing were carried out under the room temperature (23° C.) environment.

[0125] The rinsed Kiriyama funnel filter paper was dried in an oven at 40° C. for 30 minutes and the weight (g) of the dried Kiriyama funnel filter paper, weight C, was measured.

(4) The filler content was calculated by the following formula. The results are shown in Table 1.

Filler content (mass %)=100×(C−B)/A

Water Absorption Rate

[0126] The water absorption rate of the polyurethane foam made by the above method was calculated by the following method.

(1) A test piece having a size of width 100 mm×length 1.00 mm×thickness 20 mm was cut out from the obtained polyurethane foam.
(2) The test piece was immersed in water for 24 hours under an atmosphere of a temperature of 22.5° C. and a humidity of 55% and then taken out from water. The weight (g) of the test piece after the water was removed from the surface, weight X, was measured.
(3) The test piece was immersed in water for 10 seconds under an atmosphere of a temperature of 22.5° C. and a humidity of 55% and then taken out from water. The weight (g) of the test piece after the water was removed from the surface, weight Y, was measured.
(4) A water absorption rate of the polyurethane foam was calculated by the following formula. The results are shown in Table 1.

Water absorption rate (g/100 cm.sup.2)=(X−Y)/(surface area of test piece)/100

[0127] Test pieces having a water absorption rate of 1.5 or less were rated as “A”, and those with over 1.5 were “B”.

Foaming Property

[0128] The polyurethane foam made by the above method was cut out, and the cross section was observed using a microscope. As a result of the observation, the polyurethane foams showing fine homogeneous foamed cells were rated as “A”, those with rather large and/or rather nonhomogeneous cell diameters of foamed cells were “B”, and those with large and/or nonhomogeneous cell diameters of broken foamed cells were “C”. The results are shown in Table 1.

TABLE-US-00001 TABLE 1 Examples 1 2 3 4 5 6 7 8 Polyisocyanate (parts by mass) PM200 75.5 76.1 75.5 75.5 75.5 75.5 75.5 75.5 Polyol-containing Polyol RLK-087 14.7 9.6 14.7 14.7 14.7 14.7 14.7 14.7 composition (parts by mass) RFK-505 9.8 14.3 9.8 9.8 9.8 9.8 9.8 9.8 Catalyst TOYOCAT DM70 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 DABCO NCIM Neostann U-600 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Neostann U-830 0.05 DABCO K-15 0.37 0.38 0.37 0.37 0.37 0.37 0.37 0.37 Foaming HFO 5.9 7.6 5.9 5.9 5.9 5.9 5.9 5.9 agent Water 0.61 0.62 0.61 0.61 0.61 0.61 0.61 0.61 Flame TMCPP 9.8 7.3 9.8 9.8 9.8 9.8 9.8 9.8 retardant Filler Nova Excel 140 7.3 9.3 7.3 7.3 7.3 7.3 7 Firebrake ZB 2.0 9.0 2.0 2.0 2.0 2.0 SH-1250 7.3 9.3 9.0 7.3 Antimony trioxide 7.3 Aluminum hydroxide 7.3 Properties•Evaluation Filler content (mass %) 29 32 30 29 29 29 18 14 Isocyanate index 343 339 343 343 343 343 343 343 Water absorption rate (g/100 cm.sup.2) 0.87 0.86 0.88 0.95 1.02 0.98 1.26 1.32 Water absorption rate (evaluation) A A A A A A A A Foaming property A A A B A A A A Examples 9 10 11 12 13 14 15 16 Polyisocyanate (parts by mass) PM200 75.5 75.5 75.5 75.5 75.5 76.1 70.8 78.7 Polyol-containing Polyol RLK-087 14.7 14.7 14.7 14.7 14.7 9.6 29.2 composition (parts by mass) RFK-505 9.8 9.8 9.8 9.8 9.8 14.3 21.3 Catalyst TOYOCAT DM70 0.10 0.08 0.12 0.10 0.12 0.09 DABCO NCIM 0.10 Neostann U-600 0.05 0.1 0.04 0.06 0.05 0.05 0.06 0.04 Neostann U-830 DABCO K-15 0.37 0.42 0.3 0.41 0.37 0.38 0.44 0.33 Foaming HFO 5.9 5.9 5.9 5.9 5.9 7.6 7.0 5.1 agent Water 0.61 0.61 0.61 0.61 0.61 0.62 0.74 0.53 Flame TMCPP 9.8 9.8 9.8 9.8 9.8 11.7 8.5 retardant Filler Nova Excel 140 5 7.3 7.3 7.3 7.3 7.3 8.7 6.3 Firebrake ZB 2.0 2.0 2.0 2.0 1.7 SH-1250 7.3 7.3 7.3 7.3 7.3 8.7 6.3 Antimony trioxide Aluminum hydroxide Properties•Evaluation Filler content (mass %) 11 29 29 29 29 31 26 29 Isocyanate index 343 343 343 343 343 334 254 448 Water absorption rate (g/100 cm.sup.2) 1.40 0.93 0.95 0.91 0.89 0.90 1.13 1.18 Water absorption rate (evaluation) A A A A A A A A Foaming property A B 8 B B B A A Comparative Examples 1 2 3 4 5 6 Polyisocyanate (parts by mass) PM200 75.5 75.5 75.5 75.5 75.5 76.1 Polyol-containing Polyol RLK-087 14.7 14.7 14.7 14.7 14.7 9.6 composition (parts by mass) RFK-505 9.8 9.8 9.8 9.8 9.8 14.3 Catalyst TOYOCAT DM70 0.10 0.10 0.10 0.10 0.10 0.10 DABCO NCIM Neostann U-600 0.05 0.05 0.05 0.05 Neostann U-830 DABCO K-15 0.37 0.37 0.37 0.37 0.37 0.38 Foaming HFO 5.9 5.9 5.9 5.9 5.9 7.6 agent Water 0.61 0.61 0.61 0.61 0.61 0.62 Flame TMCPP 9.8 9.8 9.8 9.8 9.8 7.3 retardant Filler Nova Excel 140 3 7.3 9.3 Firebrake ZB 3 2.0 SH-1250 3 7.3 9.3 Antimony trioxide Aluminum hydroxide Properties•Evaluation Filler content (mass %) 7 7 7 0 29 32 Isocyanate index 343 343 343 343 343 339 Water absorption rate (g/100 cm.sup.2) 1.55 1.53 1.57 1.93 0.89 0.88 Water absorption rate (evaluation) B B B B A A Foaming property A A A A C C

[0129] As evident from the above results of the examples, when the content of the filler in the polyol-containing composition is a specific value or more, the water absorption rates of the polyurethane foams were decreased, thereby preventing the polyurethane foams from hydrolyzing. Further, when specific catalysts were contained in the polyol-containing compositions, the foaming property was enhanced.