(12) United States Patent
`Haseyama et al.
`
`USOO684.9667B2
`US 6,849,667 B2
`Feb. 1, 2005
`
`(10) Patent No.:
`(45) Date of Patent:
`
`(54) FOAM OF THERMOPLASTICURETHANE
`ELASTOMER COMPOSITION AND
`PROCESS FOR PRODUCING THE FOAM
`(75) Inventors: Ryuuji Haseyama, Sodegaura (JP);
`Masahiko Hashiba, Sodegaura (JP);
`Kaoru Yorita, Sodegaura (JP); Shigeo
`Nishikawa, Sodegaura (JP); Yoko
`Shimada, Kodaira (JP)
`(73) Assignee: Mitsui Chemicals, Inc., Tokyo (JP)
`* Y Not
`Subj
`y disclai
`h
`f thi
`Otice:
`ubject to any disclaimer, the term of this
`patent is extended or adjusted under 35
`U.S.C. 154(b) by 0 days.
`(21) Appl. No.:
`10/148,998
`(22) PCT Filed:
`Oct. 11, 2001
`(86) PCT No.:
`PCT/JP01/08942
`S371 (c)(1),
`(2), (4) Date: Jun. 6, 2002
`(87) PCT Pub. No.: WO02/32986
`PCT Pub. Date: Apr. 25, 2002
`Prior Publication Data
`US 2002/0193459 A1 Dec. 19, 2002
`Foreign Application Priority Data
`(30)
`Oct. 18, 2000 (JP) ....................................... 2OOO-318307
`(51) Int. Cl. ................................................ C08G 18/28
`(52) U.S. Cl. ....................... 521/170; 521/130,521/131;
`521/174
`(58) Field of Search ................................. 521/130, 131,
`521/170, 174
`
`(65)
`
`
`
`(56)
`
`References Cited
`U.S. PATENT DOCUMENTS
`
`2/2002 Calabrese et al. .......... 521/130
`6,348,514 B1
`FOREIGN PATENT DOCUMENTS
`
`EP
`JP
`JP
`JP
`
`3/2002
`1, 186 392 A1
`6/1995
`T-157588
`1/1996
`O8-O11190
`8-157635. A 6/1996
`
`* cited by examiner
`
`Primary Examiner John M. Cooney, Jr.
`(74) Attorney, Agent, or Firm-Birch, Stewart, Kolasch &
`Birch, LLP
`ABSTRACT
`(57)
`The method of the present invention for producing a
`urethane-based thermoplastic elastomer composition foam
`comprises the Steps of:
`adding and mixing 0.1 to 30 parts by weight of carbon
`dioxide (B) to 100 parts by weight of a urethane-based
`thermoplastic elastomer composition (A) in a molten
`State, wherein Said urethane-based thermoplastic elas
`tomer composition (A) comprises a urethane-based
`thermoplastic elastomer (A-1) and other thermoplastic
`elastomer (A-2) in an (A-1)/(A-2) ratio of 20/80 to 99/1
`by weight, to form a molten urethane-based thermo
`plastic elastomer composition (C) which is in a State of
`a mixture of the urethane-based thermoplastic elas
`tomer composition (A) and the carbon dioxide (B) (gas
`dissolving step); and
`lowering a temperature of said molten urethane-based
`thermoplastic elastomer composition (C) (cooling
`Step).
`
`The present invention can produce the urethane-based ther
`moplastic elastomer foam of Stable quality over a range from
`low foamed product to highly foamed product by adding a
`given quantity of carbon dioxide in the molten urethane
`based thermoplastic elastomer quantitatively and Stably. It
`can also produce the foam excellent in flexibility, thermal
`insulation and Surface appearances. It is also excellent in
`Safety, because of use of carbon dioxide in place of the
`common foaming agent of fluorochlorohydrocarbon or
`butane, thus causing no air pollution or destruction of the
`oZone layer.
`
`EP
`
`O 610 953 A1
`
`8/1994
`
`16 Claims, 7 Drawing Sheets
`
`EX1068
`Yita v. MacNeil
`IPR2020-01139
`
`

`

`U.S. Patent
`U.S. Patent
`
`Feb. 1, 2005
`Feb. 1, 2005
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`Feb. 1, 2005
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`Feb. 1, 2005
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`US 6,849,667 B2
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`

`1
`1
`FOAM OF THERMOPLASTIC URETHANE
`FOAM OF THERMOPLASTIC URETHANE
`ELASTOMER COMPOSITION AND
`ELASTOMER COMPOSITION AND
`PROCESS FOR PRODUCING THE FOAM
`PROCESS FOR PRODUCING THE FOAM
`
`This application is the national phase under 35 U.S.C. S.
`This application is the national phase under 35 U.S.C. §
`371 of PCT International Application No. PCT/JP01/08942
`371 of PCT International Application No. PCT/JP01/08942
`which has an International filing date of Oct. 11, 2001,
`which has an International filing date of Oct. 11, 2001,
`which designated the United States of America.
`which designated the United States of America.
`TECHNICAL FIELD
`TECHNICAL FIELD
`This invention relates to a urethane-based thermoplastic
`This invention relates to a urethane-based thermoplastic
`elastomer composition foam, method for producing the
`elastomer composition foam, method for producing the
`Same, and molded article or laminate thereof, more particu
`same, and moldedarticle or laminate thereof, more particu-
`larly a urethane-based thermoplastic elastomer composition
`larly a urethane-based thermoplastic elastomer composition
`foam of Stable quality obtained from a Specific urethane
`foam of stable quality obtained from a specific urethane-
`based thermoplastic elastomer, optionally another thermo
`based thermoplastic elastomer, optionally another thermo-
`plastic elastomer, and carbon dioxide as a foaming agent,
`plastic elastomer, and carbon dioxide as a foaming agent,
`method for producing the Same, and molded article or
`method for producing the same, and molded article or
`laminate thereof.
`laminate thereof.
`
`BACKGROUNDART
`BACKGROUND ART
`Foams composed of polyurethane, polyvinyl chloride or
`Foams composed of polyurethane, polyvinyl chloride or
`the like have been used as a foam excellent in its flexibility
`the like have been used as a foam excellent in its flexibility
`and cushioning characteristics, and foams composed of
`and cushioning characteristics, and foams composed of
`polystyrene, polyethylene, polypropylene or the like have
`polystyrene, polyethylene, polypropylene or the like have
`been used as a foam excellent in its thermoformability.
`been used as a foam excellent in its thermoformability.
`Methods for producing polyethylene foams are disclosed
`Methods for producing polyethylene foamsare disclosed
`in, e.g., Japanese Patent Publication No. 41-6278. There is,
`in, e.g., Japanese Patent Publication No. 41-6278. Thereis,
`however, a problem that the foam produced by this method
`however, a problem that the foam produced by this method
`does not provide Soft cushioning characteristics, although it
`does not provide soft cushioning characteristics, althoughit
`is excellent in thermoformability Such as vacuum molding.
`is excellent in thermoformability such as vacuum molding.
`As a method of producing thermoplastic polyurethane
`As a method of producing thermoplastic polyurethane
`foams, a chemical foaming method using a thermally
`foams, a chemical
`foaming method using a thermally
`decomposable foaming agent, Such as azodicarbon amide, is
`decomposable foaming agent, such as azodicarbon amide,is
`known which is disclosed in Japanese Patent Laid-Open No.
`known whichis disclosed in Japanese Patent Laid-Open No.
`7-157588.
`7-157588.
`In the chemical foaming method, however, thermoplastic
`In the chemical foaming method, however, thermoplastic
`polyurethane is partly decomposed and foamed to deterio
`polyurethane is partly decomposed and foamed to deterio-
`rate the cells, and it is difficult to produce foams with a high
`rate the cells, and it is difficult to produce foams with a high
`molecular weight.
`molecular weight.
`Therefore, foams excellent in all of elongation Set,
`Therefore,
`foams excellent
`in all of elongation set,
`hysteresis, cell uniformity and heat resistance are desired.
`hysteresis, cell uniformity and heat resistance are desired.
`Simple methods of producing Such foams, and molded
`Simple methods of producing such foams, and molded
`articles and laminates thereof are also demanded.
`articles and laminates thereof are also demanded.
`It is an object of the present invention to provide a foam
`It is an object of the present invention to provide a foam
`excellent in elongation Set, hysteresis, cell uniformity and
`excellent in elongation set, hysteresis, cell uniformity and
`heat resistance, more particularly a foam obtained from a
`heat resistance, more particularly a foam obtained from a
`composition containing a thermoplastic polyurethane
`composition containing a thermoplastic polyurethane
`(including a composition composed of a 100% thermoplastic
`(including a composition composed of a 100% thermoplastic
`polyurethane, hereinafter referred to as a thermoplastic
`polyurethane, hereinafter referred to as a thermoplastic
`polyurethane composition, unless otherwise Stated). It is
`polyurethane composition, unless otherwise stated). It is
`another object of the present invention to provide a method
`another object of the present invention to provide a method
`for producing the above-described foam. It is still another
`for producing the above-described foam. It is still another
`object of the present invention to provide a molded article or
`object of the present invention to provide a moldedarticle or
`laminate of the above-described foam.
`laminate of the above-described foam.
`The present invention also provides a method of easily
`The present invention also provides a method of easily
`foaming the thermoplastic polyurethane composition.
`foaming the thermoplastic polyurethane composition.
`DISCLOSURE OF THE INVENTION
`DISCLOSURE OF THE INVENTION
`The inventors of the present invention have found, after
`The inventors of the present invention have found,after
`having Studied to Solve the above problems, a foam obtained
`having studied to solve the above problems, a foam obtained
`from a thehermoplastic polyurethane composition, excellent
`from a thehermoplastic polyurethane composition, excellent
`in elongation Set, hysteresis, cell uniformity and heat resis
`in elongation set, hysteresis, cell uniformity and heat resis-
`tance. The inventors have also found that thermoplastic
`tance. The inventors have also found that
`thermoplastic
`polyurethane foams of varying expansion ratio can be
`polyurethane foams of varying expansion ratio can be
`
`5
`
`10
`
`15
`15
`
`20
`
`25
`25
`
`30
`
`35
`35
`
`40
`40
`
`45
`45
`
`50
`50
`
`55
`55
`
`60
`60
`
`65
`65
`
`US 6,849,667 B2
`US 6,849,667 B2
`
`2
`2
`obtained with ease, when a urethane-based thermoplastic
`obtained with ease, when a urethane-based thermoplastic
`elastomer composition composed of a specific urethane
`elastomer composition composed of a specific urethane-
`based thermoplastic elastomer and other thermoplastic elas
`based thermoplastic elastomer and other thermoplastic elas-
`tomer mixed in an arbitrary composition ratio is foamed
`tomer mixed in an arbitrary composition ratio is foamed
`with carbon dioxide as a foaming agent.
`with carbon dioxide as a foaming agent.
`The present invention is as follows.
`The present invention is as follows.
`A urethane-based thermoplastic elastomer composition
`A urethane-based thermoplastic elastomer composition
`foam of the present invention comprises thermoplastic poly
`foam of the present invention comprises thermoplastic poly-
`urethane resin-containing composition containing a thermo
`urethane resin-containing composition containing a thermo-
`plastic polyurethane resin at 20% by weight or more,
`plastic polyurethane resin at 20% by weight or more,
`wherein the form has
`wherein the form has
`an average cell diameter of 0.1 to 1,000 um,
`an average cell diameter of 0.1 to 1,000 um,
`an average cell number of 10 to 10/cm,
`an average cell number of 10° to 107°/cm3,
`an elongation set of 1 to 100%, and
`an elongation set of 1 to 100%, and
`a bulk density of 0.03 to 1.10 g/cm.
`a bulk density of 0.03 to 1.10 g/cm’.
`It is preferable that a melting point of the urethane-based
`It is preferable that a melting point of the urethane-based
`thermoplastic elastomer composition foam (T) and the
`thermoplastic elastomer composition foam (T,,,,) and the
`non-foamed resin (T) Satisfies the following formula (1):
`non-foamedresin (T,,,.) satisfies the following formula (1):
`T-T225 C.
`(1)
`@
`TnTm225° C.
`It is also preferable that the chloroform-insolubles is
`It
`is also preferable that
`the chloroform-insolubles is
`contained at 10% by weight or more in the urethane-based
`contained at 10% by weight or more in the urethane-based
`thermoplastic elastomer composition foam.
`thermoplastic elastomer composition foam.
`It is still also preferable that a residue after chloroform
`It is still also preferable that a residue after chloroform
`extraction of the urethane-based thermoplastic elastomer
`extraction of the urethane-based thermoplastic elastomer
`composition foam is at 20% by weight or more, and a
`composition foam is at 20% by weight or more, and a
`temperature in losing 5% by weight of the residue after
`temperature in losing 5 % by weight of the residue after
`chloroform extraction is 180° C. or higher.
`chloroform extraction is 180° C. or higher.
`The first method for producing a urethane-based thermo
`The first method for producing a urethane-based thermo-
`plastic elastomer composition foam comprises the Steps of:
`plastic elastomer composition foam comprises the steps of:
`adding and mixing 0.1 to 30 parts by weight of carbon
`adding and mixing 0.1 to 30 parts by weight of carbon
`dioxide (B) to 100 parts by weight of a urethane-based
`dioxide (B) to 100 parts by weight of a urethane-based
`thermoplastic elastomer composition (A) in a molten
`thermoplastic elastomer composition (A) in a molten
`State, wherein Said urethane-based thermoplastic elas
`state, wherein said urethane-based thermoplastic elas-
`tomer composition (A) comprises a urethane-based
`tomer composition (A) comprises a urethane-based
`thermoplastic elastomer (A-1) and other thermoplastic
`thermoplastic elastomer (A-1) and other thermoplastic
`elastomer (A-2) in an (A-1)/(A-2) ratio of 20/80 to 99/1
`elastomer (A-2) in an (A-1)/(A-2) ratio of 20/80 to 99/1
`by weight, to form a molten urethane-based thermo
`by weight, to form a molten urethane-based thermo-
`plastic elastomer composition (C) which is in a State of
`plastic elastomer composition (C) which is in a state of
`a mixture of the urethane-based thermoplastic elas
`a mixture of the urethane-based thermoplastic elas-
`tomer composition (A) and the carbon dioxide (B) (gas
`tomer composition (A) and the carbon dioxide (B) (gas
`dissolving step); and
`dissolving step); and
`lowering a temperature of Said molten urethane-based
`lowering a temperature of said molten urethane-based
`thermoplastic elastomer composition (C) (cooling
`thermoplastic elastomer composition (C)
`(cooling
`Step).
`step).
`The Second method for producing a urethane-based ther
`The second method for producing a urethane-based ther-
`moplastic elastomer composition foam comprises the Steps
`moplastic elastomer composition foam comprises the steps
`of:
`of:
`adding and mixing 0.1 to 30 parts by weight of carbon
`adding and mixing 0.1 to 30 parts by weight of carbon
`dioxide (B) to 100 parts by weight of a urethane-based
`dioxide (B) to 100 parts by weight of a urethane-based
`thermoplastic elastomer composition (A) in a molten
`thermoplastic elastomer composition (A) in a molten
`State to form a molten urethane-based thermoplastic
`state to form a molten urethane-based thermoplastic
`elastomer composition (C) which is in a state of a
`elastomer composition (C) which is in a state of a
`mixture of the urethane-based thermoplastic elastomer
`mixture of the urethane-based thermoplastic elastomer
`composition (A) and the carbon dioxide (B) (gas dis
`composition (A) and the carbon dioxide (B) (gas dis-
`Solving Step); and
`solving step); and
`charging or transferring the molten urethane-based ther
`charging or transferring the molten urethane-based ther-
`moplastic elastomer composition (C), which is
`moplastic elastomer composition (C), which is
`obtained through the cooling step (the Step of lowering
`obtained through the cooling step (the step of lowering
`a temperature of the molten urethane-based thermo
`a temperature of the molten urethane-based thermo-
`plastic elastomer composition (C)) in or to a space
`plastic elastomer composition (C)) in or to a space
`controlled at a lower pressure than that of in the cooling
`controlled at a lower pressure than that of in the cooling
`Step to produce cell nuclei in the molten urethane-based
`step to producecell nuclei in the molten urethane-based
`thermoplastic elastomer composition (C), and then
`thermoplastic elastomer composition (C), and then
`foaming while controlling an expansion ratio (foaming
`foaming while controlling an expansion ratio (foaming
`controlling step).
`controlling step).
`
`

`

`3
`3
`It is preferable that the method for producing a urethane
`It is preferable that the method for producing a urethane-
`based thermoplastic elastomer composition (A) has a melt
`based thermoplastic elastomer composition (A) has a melt
`flow rate (determined in accordance with ASTM D-1238
`flow rate (determined in accordance with ASTM D-1238-
`65T) of 0.5 to 50 g/10 minutes.
`65T) of 0.5 to 50 g/10 minutes.
`It is also preferable that the urethane-based thermoplastic
`It is also preferable that the urethane-based thermoplastic
`elastomer composition (A) comprises the urethane-based
`elastomer composition (A) comprises the urethane-based
`thermoplastic elastomer (A-1) and the other thermoplastic
`thermoplastic elastomer (A-1) and the other thermoplastic
`elastomer (A-2) having a melt flow rate (determined in
`elastomer (A-2) having a melt flow rate (determined in
`accordance with ASTM D-1238-65T) of 0.01 g/10 minutes
`accordance with ASTM D-1238-65T) of 0.01 g/10 minutes
`or more and less than 50 g/10 minutes, said other thermo
`or more and less than 50 g/10 minutes, said other thermo-
`plastic elastomer (A-2) being contained in 5 to 60 parts by
`plastic elastomer (A-2) being contained in 5 to 60 parts by
`weight per 100 parts by weight of said urethane-based
`weight per 100 parts by weight of said urethane-based
`thermoplastic elastomer composition (A).
`thermoplastic elastomer composition (A).
`It is preferable that a temperature of the molten urethane
`It is preferable that a temperature of the molten urethane-
`based thermoplastic elastomer composition in the gas dis
`based thermoplastic elastomer composition in the gas dis-
`Solving step is in the range of 100 to 240° C. and a
`solving step is in the range of 100 to 240° C. and a
`temperature of Said molten urethane-based thermoplastic
`temperature of said molten urethane-based thermoplastic
`elastomer composition in the cooling step is 10 to 100° C.
`elastomer composition in the cooling step is 10 to 100° C.
`lower than that in the gas dissolving step.
`lower than that in the gas dissolving step.
`It is preferable that an amount of the carbon dioxide (B)
`It is preferable that an amount of the carbon dioxide (B)
`added is in the range of 0.1 to 20 parts by weight per 100
`added is in the range of 0.1 to 20 parts by weight per 100
`parts by Weight of Said urethane-based thermoplastic elas
`parts by weight of said urethane-based thermoplastic elas-
`tomer composition (A).
`tomer composition (A).
`It is preferable that the carbon dioxide (B) is a supercriti
`It is preferable that the carbon dioxide (B) is a supercriti-
`cal carbon dioxide (B-1).
`cal carbon dioxide (B-1).
`It is preferable that a method for adding carbon dioxide in
`It is preferable that a method for adding carbon dioxide in
`the gas dissolving step is the one that carbon dioxide in a
`the gas dissolving step is the one that carbon dioxide in a
`liquified form is added to a pump or like to charge while
`liquified form is added to a pump orlike to charge while
`keeping in a liquified form,
`keeping in a liquified form,
`and under the charging pressure of carbon dioxide by the
`and underthe charging pressure of carbon dioxide by the
`pump being kept in a constant pressure of critical
`pump being kept
`in a constant pressure of critical
`pressure of carbon dioxide (7.4 MPa) to 40 Mpa, the
`pressure of carbon dioxide (7.4 MPa) to 40 Mpa,the
`carbon dioxide is charged by the pump, and the carbon
`carbon dioxide is charged by the pump,and the carbon
`dioxide charged from the pump is heated to a critical
`dioxide charged from the pump is heated to a critical
`temperature of carbon dioxide (31° C) or higher, to be
`temperature of carbon dioxide (31° C.) or higher, to be
`a Supercritical carbon dioxide, and then the Supercriti
`a supercritical carbon dioxide, and then the supercriti-
`cal carbon dioxide is added to said urethane-based
`cal carbon dioxide is added to said urethane-based
`thermoplastic elastomer compound of a molten state.
`thermoplastic elastomer compound of a molten state.
`It is preferable that the urethane-based thermoplastic
`is preferable that
`the urethane-based thermoplastic
`It
`elastomer (A-1) is selected from the group consisting of an
`elastomer (A-1) is selected from the group consisting of an
`amorphous polymer, Semi-crystalline polymer, liquid
`amorphous polymer, semi-crystalline polymer,
`liquid-
`crystalline polymer, thermoplastic polymer and elastomer,
`crystalline polymer, thermoplastic polymer and elastomer,
`each containing at least one kind of bond selected from the
`each containing at least one kind of bond selected from the
`group consisting of urethane bond, urea bond, thiourethane
`group consisting of urethane bond, urea bond, thiourethane
`bond and thiourea bond.
`bond and thiourea bond.
`A urethane-based thermoplastic elastomer composition
`A urethane-based thermoplastic elastomer composition
`foam of the present invention has:
`foam of the present invention has:
`an average cell diameter of 0.1 to 1,000 um,
`an average cell diameter of 0.1 to 1,000 um,
`an average cell number of 10 to 10°/cm,
`an average cell number of 10° to 10°/cm®,
`an elongation set of 1 to 100%, and
`an elongation set of 1 to 100%, and
`a bulk density of 0.03 to 1.10 g/cm,
`a bulk density of 0.03 to 1.10 g/cm?,
`and is obtainable through steps that; a gas dissolving step in
`and is obtainable through steps that; a gas dissolving step in
`which 0.1 to 30 parts by weight of carbon dioxide (B) is
`which 0.1 to 30 parts by weight of carbon dioxide (B) is
`added to 100 parts by weight of a urethane-based thermo
`added to 100 parts by weight of a urethane-based thermo-
`plastic elastomer composition (A) of a molten state, wherein
`plastic elastomer composition (A) of a molten state, wherein
`Said urethane-based thermoplastic elastomer composition
`said urethane-based thermoplastic elastomer composition
`(A) comprises a urethane-based thermoplastic elastomer
`(A) comprises a urethane-based thermoplastic elastomer
`(A-1) and other thermoplastic elastomer (A-2) in an (A-1)/
`(A-1) and other thermoplastic elastomer (A-2) in an (A-1)/
`(A-2) ratio of 20/80 to 99/1 by weight to form a molten
`(A-2) ratio of 20/80 to 99/1 by weight to form a molten
`urethane-based thermoplastic elastomer composition (C)
`urethane-based thermoplastic elastomer composition (C)
`which is in a state of a mixture of the urethane-based
`which is in a state of a mixture of the urethane-based
`thermoplastic elastomer composition (A) and the carbon
`thermoplastic elastomer composition (A) and the carbon
`dioxide (B), and a cooling step in which a temperature of the
`dioxide (B); and a cooling step in which a temperature ofthe
`molten urethane-based thermoplastic elastomer composition
`molten urethane-based thermoplastic elastomer composition
`(C) is lowered.
`(C) is lowered.
`
`5
`5
`
`10
`
`15
`15
`
`20
`
`25
`25
`
`30
`
`35
`35
`
`40
`40
`
`45
`45
`
`50
`50
`
`55
`55
`
`60
`60
`
`65
`65
`
`US 6,849,667 B2
`US 6,849,667 B2
`
`4
`4
`A urethane-based thermoplastic elastomer composition
`A urethane-based thermoplastic elastomer composition
`foam of the present invention has:
`foam of the present invention has:
`an average cell diameter of 0.1 to 1,000 um,
`an average cell diameter of 0.1 to 1,000 um,
`an average cell number of 10 to 10'/cm,
`an aver age cell number of 10° to 10*°/cm’,
`an elongation set of 1 to 100%, and
`an elongation set of 1 to 100%, and
`a bulk density of 0.03 to 1.10 g/cm.
`a bulk density of 0.03 to 1.10 g/cm’.
`and is obtainable through steps that:
`and is obtainable through steps that:
`a gas dissolving step in which 0.1 to 30 parts by weight
`a gas dissolving step in which 0.1 to 30 parts by weight
`of carbon dioxide (B) is added to 100 parts by weight
`of carbon dioxide (B) is added to 100 parts by weight
`of a urethane-based thermoplastic elastomer composi
`of a urethane-based thermoplastic elastomer composi-
`tion (A) of a molten state to form a molten urethane
`tion (A) of a molten state to form a molten urethane-
`based thermoplastic elastomer composition (C) which
`based thermoplastic elastomer composition (C) which
`is in a state of a mixture of urethane-based thermoplas
`is in a state of a mixture of urethane-based thermoplas-
`tic elastomer composition (A) and the carbon dioxide
`tic elastomer composition (A) and the carbon dioxide
`(B);
`(B);
`a cooling step in which a temperature of said molten
`a cooling step in which a temperature of said molten
`urethane-based thermoplastic elastomer composition
`urethane-based thermoplastic elastomer composition
`(C) is lowered; and
`(C) is lowered; and
`a foaming controlling step in which said molten urethane
`a foaming controlling step in which said molten urethane-
`based thermoplastic elastomer composition (C)
`based thermoplastic elastomer composition (C)
`obtained through the gas dissolving step and the cool
`obtained through the gas dissolving step and the cool-
`ing step, is charged in or transferred to a space con
`ing step, is charged in or transferred to a space con-
`trolled at a lower pressure than that of the cooling step
`trolled at a lower pressure than that of the cooling step
`to produce cell nuclei in said molten urethane-based
`to produce cell nuclei in said molten urethane-based
`thermoplastic elastomer composition (C), and foamed
`thermoplastic elastomer composition (C), and foamed
`while controlling an expansion ratio.
`while controlling an expansionratio.
`Alaminate of the present invention includes the urethane
`A laminate of the present invention includes the urethane-
`based thermoplastic elastomer composition foam.
`based thermoplastic elastomer composition foam.
`A molded article of the present invention comprises the
`A moldedarticle of the present invention comprises the
`urethane-based thermoplastic elastomer composition foam.
`urethane-based thermoplastic elastomer composition foam.
`The present invention provides a high-quality
`The present
`invention provides a high-quality
`polyurethane-based foam having fine bubbles of uniform
`polyurethane-based foam having fine bubbles of uniform
`Size distributed uniformly throughout the foam, excellent in
`size distributed uniformly throughout the foam, excellent in
`Surface conditions and outer appearances, and also excellent
`surface conditions and outer appearances,and also excellent
`in flexibility and mechanical properties. Particularly, use of
`in flexibility and mechanical properties. Particularly, use of
`carbon dioxide allows for forming the composition
`carbon dioxide allows for
`forming the composition
`Smoothly in high productivity without the use of a fluoro
`smoothly in high productivity without the use of a fluoro-
`chlorohydrocarbon and organic Solvent, and hence is desir
`chlorohydrocarbon and organic solvent, and hence is desir-
`able in terms of environmental considerations and safety.
`able in terms of environmental considerations and safety.
`Moreover, the present invention, using a thermoplastic
`Moreover, the present invention, using a thermoplastic
`resin (e.g., TPU) as the starting material, provides a
`resin (e.g., TPU) as the starting material, provides a
`urethane-based thermoplastic resin material excellent in
`urethane-based thermoplastic resin material excellent
`in
`recyclability and low in environmental burden.
`recyclability and low in environmental burden.
`The molded article or the like made of the foam of the
`The molded article or the like made of the foam of the
`urethane-based thermoplastic elastomer composition of the
`urethane-based thermoplastic elastomer composition of the
`present invention is excellent in lightness, flexibility, ther
`present invention is excellent in lightness, flexibility, ther-
`mal insulation and Surface appearances, and can be suitably
`mal insulation and surface appearances, and can be suitably
`used for various areas, e.g., interiors for automobiles, other
`used for various areas, e.g., interiors for automobiles, other
`Vehicles and ships, cushioning materials, insulators, and
`vehicles and ships, cushioning materials,
`insulators, and
`interiors for constructed Structures, e.g., houses. The foam of
`interiors for constructed structures, e.g., houses. The foam of
`the polyurethane-based thermoplastic elastomer composi
`the polyurethane-based thermoplastic elastomer composi-
`tion of the present invention can also be suitably used for
`tion of the present invention can also be suitably used for
`laminates.
`laminates.
`BRIEF DESCRIPTION OF THE DRAWINGS
`BRIEF DESCRIPTION OF THE DRAWINGS
`FIG. 1 Schematically shows the structure of one example
`FIG. 1 schematically showsthe structure of one example
`of the method of the present invention for producing a
`of the method of the present
`invention for producing a
`urethane-based thermoplastic elastomer foam;
`urethane-based thermoplastic elastomer foam;
`FIG. 2 schematically shows the structure of another
`FIG. 2 schematically shows the structure of another
`example of the method of the present invention for produc
`example of the method of the present invention for produc-
`ing a urethane-based thermoplastic elastomer foam;
`ing a urethane-based thermoplastic elastomer foam;
`FIG. 3 schematically shows the structure of still another
`FIG. 3 schematically showsthe structure of still another
`example of the method of the present invention for produc
`example of the method of the present invention for produc-
`ing a urethane-based thermoplastic elastomer foam;
`ing a urethane-based thermoplastic elastomer foam;
`FIG. 4 schematically shows the structure of still another
`FIG. 4 schematically showsthe structure of still another
`example of the method of the present invention for produc
`example of the method of the present invention for produc-
`ing a urethane-based thermoplastic elastomer foam;
`ing a urethane-based thermoplastic elastomer foam;
`
`

`

`US 6,849,667 B2
`US 6,849,667 B2
`
`S
`5
`FIG. 5 schematically shows the structure of still another
`FIG. 5 schematically showsthe structure of still another
`example of the method of the present invention for produc
`example of the method of the present in