US007825166B2
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`(12) United States Patent
`Sasaki et al.
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`(10) Patent No.:
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`(45) Date of Patent:
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`US 7,825,166 B2
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`Nov. 2, 2010
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`JP
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`W0
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`(54) FLEXIBLE POLYURETHANE FOAM,
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`PROCESS FOR ITS PRODUCTION, AND SEAT
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`FOR AUTOMOBILE USING THE FLEXIBLE
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`POLYURETHANE FOAM
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`(75)
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`Inventors: Takayuki Sasaki, Kamisu (JP); Takashi
`Ito, Kamisu (JP); Yoshinori Toyota,
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`Kamisu (JP); Naohiro Kumagai,
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`Kamisu (JP)
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`(73) Assignee: Asahi Glass Company, Limited, Tokyo
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`(JP)
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`Subject to any disclaimer, the term of this
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`patent is extended or adjusted under 35
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`U.S.C. 154(b) by 0 days.
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`( * ) Notice:
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`(21) Appl.No.: 11/944,730
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`(22)
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`Filed:
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`Nov. 26, 2007
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`(65)
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`Prior Publication Data
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`US 2008/0081847 A1
`Apr. 3, 2008
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`Related U.S. Application Data
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`(63) Continuation of application No. PCT/JP2006/310393,
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`filed on May 24, 2006.
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`(30)
`May 25, 2005
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`Foreign Application Priority Data
`(JP)
`........................... .. 2005-153106
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`7/2006 Sasaki et al.
`2006/0160913 A1
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`9/2006 Sasaki et al.
`2006/0205834 A1
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`9/2007 Kimura et al.
`2007/0213420 A1
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`9/2007 Sasaki et al.
`2007/0219284 A1
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`FOREIGN PATENT DOCUMENTS
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`56-151715
`11/1981
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`7/1982
`57-117524
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`2/1985
`60-35017
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`1/1988
`63-6025
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`5-320304
`12/1993
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`3/1994
`6-87945
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`7-330843
`12/1995
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`8/1998
`10-218957
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`3/1999
`11-60676
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`11-322875
`11/1999
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`2002-187929
`7/2002
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`2004-75700
`3/2004
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`WO 2005/052020 A1
`6/2005
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`OTHER PUBLICATIONS
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`U.S. Appl. No. 11/876,237, filed Oct. 22, 2007, Sasaki, et al.
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`U.S. Appl. No. 11/944,002, filed Nov. 21, 2007, Sasaki, et al.
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`U.S. Appl. No. 11/944,665, filed Nov. 26, 2007, Sasaki, et al.
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`U.S. Appl. No. 11/994,779, filed Nov. 26, 2007, Sasaki, et al.
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`U.S. Appl. No. 12/200,145, filed Aug. 28, 2008, Sasaki, et al.
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`U.S. Appl. No. 12/210,509, filed Sep. 15, 2008, Sasaki, et al.
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`U.S. Appl. No. 12/429,762, filed Apr. 24, 2009, Sasaki, et al.
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`U.S. Appl. No. 12/412,416, filed Mar. 27, 2009, Sasaki, et al.
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`U.S. Appl. No. 12/486,790, filed Jun. 18,2009, Sasaki, et al.
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`U.S. Appl. No. 12/719,930, filed Mar. 9, 2010, Sasaki, et al.
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`U.S. Appl. No. 12/732,778, filed Mar. 26, 2010, Sasaki, et al.
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`* cited by examiner
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`Primary Exami/1er—John Cooney
`(74) Attorney, Agent, or Firm—Oblon, Spivak, McClelland,
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`Maier & Neustadt, L.L.P.
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`(51)
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`(56)
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`Int.Cl.
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`(2006.01)
`C08G 18/28
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`..................... .. 521/111;521/112; 521/128;
`(52) U.S.Cl.
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`521/129; 521/130; 521/131; 521/133; 521/137;
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`521/163; 521/170; 521/174
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`(58) Field of Classification Search ............... .. 521/111,
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`521/112,130,131,133,137,170,174,163,
`521/128, 129
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`See application file for complete search history.
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`References Cited
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`U.S. PATENT DOCUMENTS
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`4,350,777 A *
`9/1982 Henrichs et al.
`.......... .. 521/110
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`5,177,116 A *
`1/1993 Genz et al.
`................ .. 521/110
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`6,653,362 B2
`11/2003 Toyota et al.
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`6,734,219 B2
`5/2004 Wada et 211.
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`6,756,415 B2
`6/2004 Kimura et al.
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`2002/0091170 A1
`7/2002 Sakata et al.
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`2004/0152797 A1
`8/2004 Wada et al.
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`2004/0229970 A1
`11/2004 Sasaki et al.
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`2006/0160912 A1
`7/2006 Sasaki et al.
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`(57)
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`ABSTRACT
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`To provide a flexible polyurethane foam having good vibra-
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`tion characteristics and suitable particularly for a seat for an
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`automobile.
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`A flexible polyurethane foam obtained by reacting a high
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`molecular weight polyoxyalkylene polyol or a polymer-dis-
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`persed polyol containing fine polymer particles in the high
`molecular weight polyoxyalkylene polyol, with a polyisocy-
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`anate compound, in the presence of a catalyst, a blowing
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`agent and a foam stabilizer, characterized in that an amino-
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`modified silicone (F) having a silicon atom and a nitrogen
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`atom in its molecule is used in an amount of from 0.00001 to
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`1 part by mass per 100 parts by mass of all active hydrogen
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`compounds.
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`14 Claims, No Drawings
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`PAGE 1 OF 11
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`BOREALIS EXHIBIT 1024
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`BOREALIS EXHIBIT 1024
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`PAGE 1 OF 11
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`

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`US 7,825,166 B2
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`1
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`FLEXIBLE POLYURETHANE FOAM,
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`PROCESS FOR ITS PRODUCTION, AND SEAT
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`FOR AUTOMOBILE USING THE FLEXIBLE
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`POLYURETHANE FOAM
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`TECHNICAL FIELD
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`The present invention relates to a novel flexible polyure-
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`thane foam, suitable as a urethane cushion material providing
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`good riding comfort, particularly for a seat for an automobile.
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`BACKGROUND ART
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`In recent years, in the field of polyurethane foams useful
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`for various applications, various researches and develop-
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`ments have been made in order to improve the characteristics
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`suitable for the respective applications. For example, along
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`with upgrading of automobile seats in order to improve the
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`riding comfort of seat cushion, it is targeted to improve the
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`rebound resilience, vibration characteristics, durability, etc.
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`With respect to the vibration characteristics, the influence of
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`car body vibration over a human body varies depending upon
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`the vibration frequency. However, it is considered effective
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`for improvement of the riding comfort to take damping of
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`vibration particularly large in a frequency range (for example
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`from 4 to 8 Hz or from 6 to 20 Hz) to which a human is
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`sensitive. Further, it is considered that in order to improve
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`these characteristics, a seat cushion is effective which
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`employs a polyoxyalkylene polyol having a higher molecular
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`weight than one heretofore produced.
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`On the other hand, as a seat cushion, a combination of a
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`metal spring with a pad material made of a flexible polyure-
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`thane foam (hereinafter referred to simply as a flexible foam)
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`has been used in many cases. However, in recent years, there
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`has been a trend of employing an automobile seat so-called a
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`deep foam type whereby a metal spring is abolished by
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`imparting spring characteristics to the flexible foam itself to
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`meet the demand for e. g. cost down, reduction of weight, etc.
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`The deep foam type seat has become thick, since no metal
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`spring is used in combination.
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`Further,
`the characteristics of the flexible foam have
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`become a factor substantially influential over the sitting com-
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`fort and riding comfort of the seat. Namely, the static charac-
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`teristics and dynamic characteristics as indices for the sitting
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`comfort and riding comfort, have been regarded as important
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`in the development of flexible foams. Among the static char-
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`acteristics, it is particularly important to control the supported
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`feeling at the initial stage of sitting and the bottom-hitting
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`feeling at the final stage of sitting.
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`When a person actually sits on a seat provided with a pad
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`material of flexible foam, the flexible foam will be com-
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`pressed and deflected, and the position ofe.g. the hip will sink
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`to a certain height. As a method for measuring this static
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`characteristic (the static sitting feeling), a test method may be
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`employed wherein the deflection is measured in a load test in
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`accordance with a performance test method for a pad material
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`for an automobile seat according to JASO automobile stan-
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`dard B408-89 (1989), to obtain a load-deflection curve, or the
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`deflection under a load of 500N (Newton Load) may be used
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`which is obtained from a load-deflection curve obtained by
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`the measurement employing a pressure plate in accordance
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`with JIS E7104 (2002). This pressure plate is oval with a long
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`diameterA of 300 mm, a short diameter B of 250 mm and a
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`thickness C of at least 35 mm and is so-called Tekken Plate.
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`On the other hand, the polyoxyalkylene polyol to be used
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`as a material for the flexible foam, is usually produced by ring
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`opening polymerization of an alkylene oxide such as propy-
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`lene oxide, using a sodium/potassium catalyst such as sodium
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`hydroxide or potassium hydroxide and an initiator such as a
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`polyhydric alcohol. By this production method, an unsatur-
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`ated monool having an unsaturated bond (hereinafter referred
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`to simply as a monool) will be formed as a by-product, and the
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`amount of such a monool produced, will increase with an
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`increase of the molecular weight of the polyoxyalkylene
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`polyol (a decrease of the hydroxyl value).
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`In the case of a polyoxyalkylene polyol having a hydroxyl
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`value of about 56 mgKOH/g which is commonly used as a
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`material for resilient polyurethane foams, the amount of such
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`a monool produced, is not so large as to bring about a prob-
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`lem. However, in the case of a polyoxyalkylene polyol having
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`the
`a high molecular weight and a low hydroxyl value,
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`amount of such a monool produced, will be problematic.
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`Namely, in a case where a resilient polyurethane foam is
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`produced by using a polyoxyalkylene polyol having a high
`monool content (a high total unsaturation value), there will be
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`a problem such as a decrease in hardness or a worse in com-
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`pression set of the produced foam, or a worse in curing
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`property at the time of production of the foam. Further, even
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`if it is attempted to produce a polyoxyalkylene polyol having
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`a low hydroxyl value by using a sodium/potassium catalyst,
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`the amount of the monool produced will be so large that such
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`production will be practically diflicult.
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`Under the circumstances, a method has been proposed
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`wherein in order to improve the characteristics such as the
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`riding comfort, durability, etc. for an automobile seat, a poly-
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`oxyalkylene polyol having a low monool content is used for
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`the production of a resilient polyurethane foam (Patent Docu-
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`ment 1).
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`However, it has been found that a resilient polyurethane
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`foam represented by a deep foam type produced by using a
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`polyoxyalkylene polyol having a low monool content, has an
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`extremely high rebound resilience (rebound resilience of core
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`portion: 71 to 74%), whereby the riding comfort is inadequate
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`from the viewpoint of the occupant posture-stability perfor-
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`mance or supporting performance during traveling. In order
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`to solve such problems, an invention has been proposed to
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`suppress the rebound resilience by a combined use of a poly-
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`oxyalkylene polyol having a low unsaturation value and a
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`polyoxyalkylene polyol having a low molecular weight with
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`a hydroxyl value of from 90 to 300 mgKOH/g (Patent Docu-
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`ment 2), but the hysteresis loss has been relatively large at a
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`level of from 25 to 33%, such being disadvantageous from the
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`viewpoint of the durability.
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`Further, with a seat ofthe above-mentioned deep foam type
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`structure, the load-deflection characteristics are substantially
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`influenced by the flexible foam itself, and it will be a seat
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`having a relatively small difference in deflection on pressure
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`side of from 500 N to 900 N, when the deflection under load
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`is measured when it is pressed by the above-mentioned pres-
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`sure plate from above. A seat having a small difference in
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`deflection presents a bottom-hitting feeling and thus showed
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`a tendency that the evaluation of the riding comfort was poor.
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`Therefore, with a seat of deep foam type, in order to increase
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`the difference in deflection, the thickness of the foam was
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`increased. As a technique to increase the difference in deflec-
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`tion without increasing the thickness of the foam, it was
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`proposed to use a fluorinated surfactant having a perfluoro-
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`alkyl group structure (Patent Document 3). However, a prob-
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`lem has been pointed out such that the effects tend to be
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`different depending upon the structure of the fluorinated sur-
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`factant.
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`On the other hand, in a method for producing a polyure-
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`thane foam by reacting a polyol component comprising a
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`polyol, a catalyst, a blowing agent and other additives with a
`
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`
`PAGE 2 OF 11
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`PAGE 2 OF 11
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`

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`
`
`US 7,825,166 B2
`
`4
`
`
`
`-continued
`
`
`
`formula (2)
`
`
`
`
`CH3
`
`I
`R3—Ti—o
`CH3
`
`
`
`
`
`
`CH3
`
`I
`Ti—o
`CH3
`
`
`
`
`
`
`CH3
`
`I
`Ti—o
`R4
`
`
`
`
`
`
`CH3
`I
`Ti—R5
`CH3
`
`
`
`
`
`
`
`provided that in the formula (1), R1 is a C 1_ 10 alkylene group,
`
`
`
`
`
`
`R2 is a CH0 alkyl group, andk is an integer offrom 1 to 2,000,
`
`
`
`
`
`
`
`
`and
`
`in the formula (2), m is an integer offrom 0 to 100; n is an
`
`
`
`
`
`
`
`integer of from 1 to 2,000; each of R3, R4 and R5 which may
`
`
`
`
`
`
`
`
`
`be the same or different, is a group selected from the group
`
`
`
`
`
`
`
`
`
`consisting of a C1_ 10 alkyl group, a CH0 alkoxy group and a
`
`
`
`
`
`
`
`
`C1_ 10 alkyl group having a nitrogen atom (provided that when
`
`
`
`
`
`
`
`
`
`m is 0, at least one of R3 and R5 is an alkyl group having a
`
`
`
`
`
`
`
`
`
`
`nitrogen atom, and when m is from 1 to 100, at least one ofR3 ,
`
`
`
`
`
`
`
`
`
`R5 and a “m” number of R4’s is an alkyl group having a
`
`
`
`
`
`
`
`
`
`
`
`nitrogen atom).
`The above flexible polyurethane foam, characterized in
`
`
`
`
`
`
`that with respect to a foam obtained by foaming into a thick-
`
`
`
`
`
`
`
`
`ness of 100 mm, the 25% hardness (ILD) X (N/314 cmz)
`
`
`
`
`
`
`
`
`
`measured in accordance with IIS K6400 (1997) andY (mm)
`
`
`
`
`
`
`
`the value (difference in deflection on pressure side)
`i.e.
`
`
`
`
`
`
`
`
`
`obtained by subtracting the deflection on 500 N pressure side
`
`
`
`
`
`
`
`from the deflection on 900 N pressure side obtained from a
`
`
`
`
`
`
`
`
`load-deflection curve as measured by means of a pressure
`
`
`
`
`
`plate (Tekken Plate) in accordance with JIS E7104 (2002),
`
`
`
`
`
`
`
`
`satisfy a relation formula represented by the following for-
`
`
`
`
`
`
`
`mula (3):
`
`
`YZ—0.000370842X2+0.225401X—10.5013
`
`
`
`(3)
`
`
`
`
`
`A seat for an automobile, which is made of the above
`
`
`
`
`
`
`
`flexible polyurethane foam.
`
`
`
`A process for producing a flexible polyurethane foam,
`
`
`
`
`
`
`
`which comprises reacting a high molecular weight polyoxy-
`
`
`
`
`
`
`
`alkylene polyol or a polymer-dispersed polyol containing fine
`
`
`
`
`
`
`
`
`
`
`
`
`
`polymer particles in the high molecular weight polyoxyalky-
`lene polyol, with a polyisocyanate compound, in the presence
`
`
`
`
`
`
`
`of a catalyst, a blowing agent and a foam stabilizer, charac-
`
`
`
`
`
`
`
`
`terized in that an amino-modified silicone (F) having a silicon
`
`
`
`
`
`
`
`atom and a nitrogen atom in its molecule is used in an amount
`
`
`
`
`
`
`
`offrom 0.00001 to 1 part by mass per 100 parts by mass ofall
`
`
`
`
`
`
`
`
`
`
`
`
`active hydrogen compounds.
`The above process for producing a flexible polyurethane
`
`
`
`
`
`
`foam, wherein the amino equivalent of the amino-modified
`
`
`
`
`
`
`silicone (F) is from 100 to 100,000 g/mol.
`
`
`
`
`
`
`The above process for producing a flexible polyurethane
`
`
`
`
`
`
`foam, wherein the amino-modified silicone (F) is a compound
`
`
`
`
`
`represented by the above formula (1) or (2).
`
`
`
`
`
`
`
`
`
`
`
`
`
`Effects of the Invention
`
`
`
`
`The present invention provides a novel flexible polyure-
`
`
`
`
`
`
`
`thane foam having good vibration characteristics and excel-
`
`
`
`
`
`
`
`
`lent in occupant posture-stability performance, by using a
`
`
`
`
`
`
`
`specific amino-modified silicone.
`
`
`
`
`10
`
`15
`
`20
`
`
`
`25
`
`
`30
`
`
`
`35
`
`
`40
`
`
`
`45
`
`
`50
`
`
`
`55
`
`
`60
`
`
`
`65
`
`3
`
`polyisocyanate component, it has been proposed to add a
`
`
`
`
`
`
`certain specific bifunctional secondary amine in order to pro-
`
`
`
`
`
`
`
`duce a foam having a reduced inclination of the curve on
`
`
`
`
`
`
`
`
`pressure side at a deflection of 75% as an index for evaluating
`
`
`
`
`
`
`
`the bottom-hitting feeling, which has no bottom-hitting feel-
`
`
`
`
`
`
`
`ing, and has all of the flexibility, the sinking degree and the
`
`
`
`
`
`
`
`
`
`
`
`vibration characteristics well balanced. However, the sup-
`
`
`
`
`
`
`
`ported feeling was insuflicient, and the durability particularly
`
`
`
`
`
`
`
`wet set was inadequate (Patent Document 4).
`
`
`
`
`
`Furthermore, a technique to increase the density of a sur-
`
`
`
`
`
`
`face skin layer of the foam by using a known defoaming
`
`
`
`
`
`
`
`
`agent, has been known (Patent Document 5). This technique
`
`
`
`
`
`
`
`
`is particularly applied to an integral skin foam and is substan-
`
`
`
`
`
`
`
`
`tially different from the present invention.
`
`
`
`
`
`
`Further, a technique to increase the distribution of the size
`
`
`
`
`
`
`of cell by using an amino-modified silicone, has been known
`
`
`
`
`
`
`
`
`(Patent Document 6). This technique relates to a polyurethane
`
`
`
`
`
`
`foam for a polishing sheet, provides a foam having a specific
`
`
`
`
`
`
`
`gravity of 0.87, and is different from the present invention.
`
`
`
`
`
`
`
`
`
`
`
`JP-A-7-330843
`JP-A-11-60676
`JP-A-11-322875
`JP-A-5-320304
`
`.TP-A- 6-87945
`
`JP-A-2004-75700
`
`
`
`
`
`Patent Document 1:
`Patent Document 2:
`
`
`Patent Document 3:
`
`
`Patent Document 4:
`
`
`Patent Document 5:
`
`
`Patent Document 6:
`
`
`
`
`
`DISCLOSURE OF THE INVENTION
`
`
`
`
`Object to be Accomplished by the Invention
`
`
`
`
`
`The present invention provides a novel flexible polyure-
`
`
`
`
`
`
`
`thane foam having good vibration characteristics and excel-
`
`
`
`
`
`
`
`
`lent in the occupant posture-stability performance.
`
`
`
`
`
`
`Means to Accomplish the Object
`
`
`
`
`
`The present invention provides the following.
`
`
`
`
`
`
`A flexible polyurethane foam obtained by reacting a high
`
`
`
`
`
`
`
`molecular weight polyoxyalkylene polyol or a polymer-dis-
`
`
`
`
`
`
`
`
`
`
`
`
`
`persed polyol containing fine polymer particles in the high
`molecular weight polyoxyalkylene polyol, with a polyisocy-
`
`
`
`
`
`
`anate compound, in the presence of a catalyst, a blowing
`
`
`
`
`
`
`
`agent and a foam stabilizer, characterized in that an amino-
`
`
`
`
`
`
`
`modified silicone (F) having a silicon atom and a nitrogen
`
`
`
`
`
`
`
`
`atom in its molecule is used in an amount of from 0.00001 to
`
`
`
`
`
`
`
`1 part by mass per 100 parts by mass of all active hydrogen
`
`
`
`
`
`
`
`
`
`
`compounds.
`The above flexible polyurethane foam, wherein the amino
`
`
`
`
`
`
`
`
`equivalent of the amino-modified silicone (F) is from 100 to
`
`
`
`
`
`
`100,000 g/mol.
`
`
`The above flexible polyurethane foam, wherein the amino-
`
`
`
`
`
`
`
`
`modified silicone (F) is a compound represented by the fol-
`
`
`
`
`
`
`
`lowing formula (1) or (2):
`
`
`
`
`
`formula (1)
`
`
`H3N—R1—si
`
`TH3
`O—Ti
`CH3
`
`’“
`
`OR2
`
`3
`
`PAGE 3 OF 11
`
`PAGE 3 OF 11
`
`

`
`
`
`US 7,825,166 B2
`
`5
`
`BEST MODE FOR CARRYING OUT THE
`
`
`
`
`
`
`INVENTION
`
`
`
`
`
`
`
`(High Molecular Weight Polyoxyalkylene Polyol)
`The high molecular weight polyoxyalkylene polyol to be
`
`
`
`
`
`
`used for producing the flexible polyurethane foam of the
`
`
`
`
`
`
`
`
`present invention, is preferably one obtained by ring opening
`
`
`
`
`
`
`
`polymerization of a cyclic ether using, as an initiator, an
`
`
`
`
`
`
`
`
`active hydrogen compound having an average number of
`
`
`
`
`
`
`
`hydroxyl groups of from 2 to 6, in the presence of a polymer-
`
`
`
`
`
`
`ization catalyst. The molecular weight per hydroxyl group is
`
`
`
`
`
`
`
`
`preferably at least 500, more preferably from 1,000 to 5,000.
`
`
`
`
`
`
`
`
`The molecular weight per hydroxyl group is particularly pref-
`
`
`
`
`
`
`
`
`erably from 1,500 to 2,500.
`
`
`
`
`The average number of hydroxyl groups in the high
`
`
`
`
`
`
`
`
`molecular weight polyoxyalkylene polyol
`is the average
`
`
`
`
`
`
`number of hydroxyl groups in the initiator used. Further, the
`
`
`
`
`
`
`
`
`high molecular weight polyoxyalkylene polyol is regarded as
`
`
`
`
`
`
`having a molecular weight calculated by the following for-
`
`
`
`
`
`
`
`mula based on the hydroxyl value measured in accordance
`
`
`
`
`
`
`
`with JIS K-1557 (1970):
`
`
`
`
`Molecular weight:(56,100><the average number of
`
`
`
`
`hydroxyl groups in the polyol)/hydroxyl value
`
`
`
`
`
`
`The polymerization catalyst may, for example, be an alkali
`
`
`
`
`
`
`
`metal compound or an alkali metal hydroxide such as a potas-
`
`
`
`
`
`
`
`sium compound, e.g. potassium hydroxide or potassium
`
`
`
`
`
`
`
`methoxide, a cesium compound, e.g. cesium metal, cesium
`
`
`
`
`
`
`hydroxide, cesium carbonate or cesium methoxide, a cationic
`
`
`
`
`
`
`polymerization catalyst such as boron trifluoride, a double
`
`
`
`
`
`
`metal cyanide complex, or a phosphazenium compound.
`
`
`
`
`
`
`Among these catalysts, a usual alkali catalyst such as potas-
`
`
`
`
`
`
`
`
`sium hydroxide, a cesium compound or a double metal cya-
`
`
`
`
`
`
`
`nide complex is preferred, and in order to obtain a polymer
`
`
`
`
`
`
`
`having a high molecular weight, a double metal cyanide com-
`
`
`
`
`
`
`
`
`
`
`
`plex is particularly preferred.
`The double metal cyanide complex catalyst may, for
`
`
`
`
`
`
`
`
`example be one disclosed in JP-B-46-27250. Specifically, it
`
`
`
`
`
`may, for example, be a complex containing zinc hexacyano-
`
`
`
`
`
`
`
`cobaltate as the main component, preferably an ether and/or
`
`
`
`
`
`
`
`an alcohol complex thereof. As the ether, ethylene glycol
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`dimethyl ether (glyme), diethylene glycol dimethyl ether
`
`
`
`
`
`
`(diglyme), ethylene glycol mono-tert-butyl ether (METB),
`
`
`
`
`
`
`ethylene glycol mono-tert-pentyl ether (METP), diethylene
`
`
`
`
`
`
`glycol mono-tert-butyl ether (DETB), tripropylene glycol
`monomethyl ether (TPME) or the like is preferred. As the
`
`
`
`
`
`
`
`alcohol, tert-butyl alcohol or the like is preferred.
`
`
`
`
`
`
`The cyclic ether is preferably an alkylene oxide having at
`
`
`
`
`
`
`
`least 2 carbon atoms, and specifically, it may, for example, be
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-
`butylene oxide or styrene oxide. Among them, a combination
`
`
`
`
`
`
`
`of ethylene oxide and at least one member selected from
`
`
`
`
`
`
`
`
`
`propylene oxide, 1,2-butylene oxide and 2,3-butylene oxide
`
`
`
`
`
`
`
`
`
`
`is particularly preferred.
`
`
`
`
`
`
`
`Further, the high molecular weight polyoxyalkylene polyol
`preferably has oxyethylene groups, particularly preferably
`
`
`
`
`
`
`has oxyethylene groups at its terminals. Further, it may be a
`
`
`
`
`
`
`
`polyoxyalkylene polyol having oxyethylene groups in its
`
`
`
`
`
`
`
`
`
`
`
`
`inside. The polyoxyalkylene polyol having oxyethylene
`groups in its inside may be obtained, for example, by sequen-
`
`
`
`
`
`
`
`tially mixing an alkylene oxide having at least 3 carbon atoms
`
`
`
`
`
`
`
`
`and ethylene oxide, using an initiator, to carry out ring open-
`
`
`
`
`
`
`
`
`
`
`
`ing polymerization.
`The polyoxyalkylene polyol having oxyethylene groups at
`
`
`
`
`
`
`its terminals may be obtained, for example, by subjecting an
`
`
`
`
`
`
`
`alkylene oxide having at least 3 carbon atoms to ring opening
`
`
`
`
`
`
`
`
`
`10
`
`15
`
`20
`
`
`
`25
`
`
`30
`
`
`
`35
`
`
`40
`
`
`
`45
`
`50
`
`
`
`55
`
`
`60
`
`
`
`65
`
`
`PAGE 4 OF 11
`
`
`
`6
`
`polymerization using an initiator, and then subjecting ethyl-
`
`
`
`
`
`
`
`ene oxide to ring opening polymerization. Otherwise, it may
`
`
`
`
`
`
`
`be obtained by sequentially mixing an alkylene oxide having
`
`
`
`
`
`
`
`at least 3 carbon atoms and ethylene oxide to carry out ring
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`opening polymerization using the above-described initiator,
`and then subjecting ethylene oxide to ring opening polymer-
`
`
`
`
`
`
`
`
`ization.
`
`The lower limit of the content of the terminal oxyethylene
`
`
`
`
`
`
`groups in the polyoxyalkylene polyol is preferably 3 mass %,
`
`
`
`
`
`
`particularly preferably 5 mass %. The upper limit is prefer-
`
`
`
`
`
`
`
`ably 25 mass %. If the content of the terminal oxyethylene
`
`
`
`
`
`
`
`groups is less than 3 mass %, collapse of the foam, etc. tends
`
`
`
`
`
`
`
`
`to occur. Further, if it exceeds 25 mass %, closed cells in the
`
`
`
`
`
`
`
`
`foam tend to increase, whereby the foam is likely to break at
`
`
`
`
`
`
`
`
`the time of crushing treatment, or shrinkage or the like is
`
`
`
`
`
`
`
`
`likely to occur after the crushing treatment.
`
`
`
`
`
`
`The content of all oxyethylene groups is preferably at most
`
`
`
`
`
`30 mass %.
`
`
`The initiator may, for example, be ethylene glycol, dieth-
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`ylene glycol, dipropylene glycol, neopentyl glycol, 1,4-bu-
`tanediol, 1,6-hexanediol, glycerol, trimethylolpropane, pen-
`
`
`
`
`
`taerythritol, diglycerol, dextrose, sucrose, bisphenol A or the
`
`
`
`
`
`
`like, or a compound obtained by adding a small amount of an
`
`
`
`
`
`
`alkylene oxide to the above initiators. The initiators may be
`
`
`
`
`
`
`
`
`used preferably alone or in combination of two or more of
`
`
`
`
`
`
`them. Ifthe average number ofhydroxyl groups is less than 2,
`
`
`
`
`
`
`
`
`the durability and the riding comfort of the foam may
`
`
`
`
`
`
`
`
`
`
`decrease in some cases. On the other hand, if the average
`
`
`
`
`
`
`
`
`number of hydroxyl groups is more than 6, the flexible foam
`
`
`
`
`
`
`
`
`to be produced tends to be hard and tends to have impaired
`
`
`
`
`
`
`
`
`mechanical properties such as elongation.
`
`
`
`
`In the present invention, it is preferred to use a polyoxy-
`
`
`
`
`
`
`
`
`alkylene polyol (a) as at least a part of the high molecular
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`
`weight polyoxyalkylene polyol. The polyoxyalkylene polyol
`(a) is a high molecular weight polyoxyalkylene polyol, which
`
`
`
`
`
`
`
`is a polyoxyalkylene polyol having an unsaturation value ofat
`
`
`
`
`
`
`most 0.07 meq/g (hereinafter sometimes referred to as polyol
`
`
`
`
`
`
`
`(a)). Particularly, in the high molecular weight polyoxyalky-
`
`
`
`
`
`
`
`lene polyol, the amount ofthe polyol (a) is preferably from 30
`
`
`
`
`
`
`
`to 100 mass %, particularly preferably from 40 to 100
`
`
`
`
`
`
`
`
`
`mass %. Further, in a case where the high molecular weight
`
`
`
`
`
`
`
`
`polyoxyalkylene polyol contains fine polymer particles as
`
`
`
`
`
`
`
`described hereinafter, the ratio of the high molecular weight
`
`
`
`
`
`
`
`polyoxyalkylene polyol and the polyol (a) is calculated on the
`
`
`
`
`
`
`basis of the mass of the polyols excluding the fine polymer
`
`
`
`
`
`
`
`
`
`
`particles.
`The average molecular weight per hydroxyl group of the
`
`
`
`
`
`
`
`
`polyol (a) is preferably at least 500, more preferably from
`
`
`
`
`
`
`
`
`1,000 to 5,000, particularly preferably from 1,500 to 2,500. If
`
`
`
`
`
`
`
`the average molecular weight per hydroxyl group is lower
`
`
`
`
`
`
`
`
`than 1,500, the durability or the riding comfort of the poly-
`
`
`
`
`
`
`
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`urethane foam may decrease in some cases. On the other
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`hand, if it is higher than 2,500, the viscosity of the polyol
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`tends to be high, whereby the operation efficiency tends to
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`deteriorate.
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`Further, the polyol (a) preferably contains oxyethylene
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`groups at its terminals, and the preferred range of the content
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`is as described with respect to the high molecular weight
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`polyoxyalkylene polyol. The polyol (a) is preferably a polyol
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`having a content of oxypropylene groups of at least 70
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`mass %, particularly preferably at least 75 mass %.
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`The polyol (a) has an unsaturation value of at most 0.07
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`meq/g, particularly preferably at most 0.05 meq/g. If the
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`unsaturation value of the polyol (a) is larger than 0.07 meq/g,
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`the durability or riding comfort ofthe polyurethane foam may
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`sometimes decrease.
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`PAGE 4 OF 11
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`US 7,825,166 B2
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`7
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`In the present invention, a polymer-dispersed polyol con-
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`taining fine polymer particles in the high molecular weight
`polyoxyalkylene polyol is used. Such a polymer-dispersed
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`polyol contains fine polymer particles in a polyoxyalkylene
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`polyol matrix, and the fine polymer particles are preferably
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`contained as dispersed. Such fine polymer particles are pref-
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`erably fine particles of an addition polymerization type poly-
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`mer or a condensation polymerization type polymer.
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`for
`The addition polymerization type polymer may,
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`example, be a homopolymer or copolymer of a vinyl mono-
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`mer such as acrylonitrile, styrene, a methacrylate or an acry-
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`late. The condensation polymerization type polymer may, for
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`example, be a polyester, a polyurea, a polyurethane or a
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`melamine resin. By the presence of such fine polymer par-
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`ticles, the hydroxyl value of the entire polymer-dispersed
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`polyol may usually be made lower than the hydroxyl value of
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`the matrix polyol.
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`The content of the fine polymer particles contained in the
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`high molecular weight polyoxyalkylene polyol is preferably
`at most 50 mass %. Ifthe content ofthe fine polymer particles
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`is higher than 50 mass %, the viscosity tends to be high, such
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`being troublesome. The fine polymer particles are preferably
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`contained in an amount of from 1 to 35 mass % in the high
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`molecular weight polyoxyalkylene polyol.
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`(Amino-Modified Silicone (F))
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`In the present invention, an amino-modified silicone (F)
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`having a silicone atom and a nitrogen atom in its molecule is
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`used.
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`The amino equivalent ofthe amino-modified silicone (F) is
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`preferably from 100 to 100,000 g/mol. The amino equivalent
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`can be determined by a common neutralization titration
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`method. For example, it can be calculated by the neutraliza-
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`tion titration method as specified in JIS K7245 (2000). When
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`the amino equivalent is from 100 to 100,000 g/mol, the