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`INFORMATION DISCLOSURE
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`STATEMENT BY APPLICANT
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`(Not for submission under 37 CFR 1.99)
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`Application Number
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`13491327
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`Filing Date
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`2012-06-07
`Chris K. Leser
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`Art Unit
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`Examiner Name
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`Michael C. Miggins
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`5723-221135
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`2012-06-07
`Chris K. Leser
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`| Michael C. Miggins
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`200905-13
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`Shanghai Secco
`Petrochemical Co., Ltd.
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`1980-01-24
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`Maschinenfabrik Rissen
`GmbH
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`5723-221 135
`Attorney Docket Number
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`1666530
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`0659647
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`Nihon Dixie Company
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`2001310429
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`2001-11-06
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`JSP Corp
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`2006130814
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`2006-05-25
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`Kaneka Corp
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`3140847
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`0132758
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`0309991 3
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`1994-01-11
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`2001-05-10
`
`Exxon Chemical Patents
`Inc.
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`2003-12-04
`
`Dow Global
`Technologies, Inc.
`
`2004104075
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`2004-12-02
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`2007020074
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`2007-02-22
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`Borealis Technology Oy
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`Application Number
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`03076497
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`2003-09-18
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`Sentinel Products Corp.
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`58029618
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`1983-02-21
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`Dainippon Printing Co.
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`

`
`(19) 0
`
`)
`
`European Patent Office
`Office européen des brevets
`
`(11)
`
`lllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllllll
`
`1
`
`6
`
`(12)
`
`EUROPEAN PATENT APPLICATION
`
`(43) Date ofr>ub|ication=
`24.11.2004 Bulletin 2004/48
`
`(51)
`
`|ntC|.7: C08J 9/00, C08J 9/14
`
`(21) Application number: 03101486.3
`
`(22) Date of filing: 22.05.2003
`
`(84) Designated Contracting States:
`AT BE BG CH CY CZ DE DK EE ES FI FR GB GR
`HU IE IT LI LU MC NL PT RO SE SI SK TR
`
`(72)
`
`Inventor: Job, Denis
`4031 Angleur (BE)
`
`Designated Extension States:
`AL LT LV MK
`
`(71) Applicant: NMC S.A.
`B-4731 Raeren (BE)
`
`(74) Representative: Kihn, Pierre Emile Joseph et al
`Office Ernest T. Freylinger S.A.
`234, route d'Ar|on
`B.P. 48
`3001 Strassen (LU)
`
`(54)
`
`High temperature resistant, flexible, low density polypropylene foams
`
`High temperature resistant, high flexibility and
`(57)
`low density foam comprising from:
`
`ymer is between 90/10 and 30/70 and
`
`-
`
`a permeability modifier.
`
`-
`
`about 5 to about 95 weight percent of a High Melt
`strength polypropylene,
`
`about 95 to about 5 weight percent of a polypropyl-
`ene modified with ethylene/C3-C1 2 a|pha—olefin co-
`polymers, where the weight ratio between polypro-
`pylene and the ethylene/C3-C1 2 a|pha—o|efin copo|—
`
`EP1479716A1
`
`Printed by Jouve, 75001 PAFllS (FFl)
`
`PAGE 10 OF 30
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`

`
`Description
`
`EP 1 479 716 A1
`
`[0001] The present invention relates to polypropylenefoams with highertemperature resistance, betterflexibility and
`with an improved dimensional stability.
`[0002]
`Polypropylene is the most versatile commodity plastic, remaining thefastest growing major polymer. It is used
`in various industries for its wide range of mechanical, thermal and optical properties. Due to the numerous processes
`and catalysts available to synthesize polypropylene and its copolymers, this ‘polymer family‘ offers some decisive
`advantages over other resins, among which one can highlight:
`
`commodity thermoplastic;
`ease of processability;
`high temperature resistance;
`high rigidity;
`low density (900 to 917 kg/m3, depending on comonomer content);
`extended range of flow properties;
`hydrolytical stability;
`recyclability.
`
`Foams can benefit from the properties of the polypropylenes. Higher temperature resistance, higher rigidity
`[0003]
`for a given density of the foam, can be obtained as compared to a conventional foamable low melting point polyolefins
`such as low-density polyethylene.
`[0004] A typical direct gassing loaming process proceeds as follows: polymers and optional additives are led in the
`entrance zone of the cylinder of an extruder, having single or double screws (co— or cou nter—rotatives). The components
`are molten in the cylinder, then gas is injected at a certain point of the cylinder, the whole mixture is homogeneously
`cooled down, and finally flows through a die in which foaming begins due to pressure drop, causing insolubility of the
`gas in the melt and bubble formation. During the free expansion of the polypropylene foam to the outside atmosphere,
`cells are growing and the cell walls are highly stretched. They remain in a partially molten state for a while, and the
`viscosity build up at that moment is crucial for the cell stability and the integrity of the finished foam
`[0005] The linear structure of most of the polypropylene types is leading to poor cell integrity, open cells structure
`and a lack of foamability. This is partly due to the non—branched structure causing the molecular chains to easily slipping
`over each other, without any other constraint than chain—to—chain friction. Moreover, the gap between melting point and
`crystallization point is wide (crystallization temperature often leads at i 100°C for non-nucleated PP, while melting
`point can be from 140°Cto 170°C). As during the foaming, the inner center of the foam remains hotterthan the exterior
`because ofthe inherent thermal insulating properties of cellular materials, cells at the middle of the foams are opening
`easily. Mechanical properties of the resulting foams are poor.
`if a foam density as low as 15 to 20 kg/m3 is
`[0006]
`In the particular case of direct gassing foaming processes,
`desired, having a majority of closed cells, it is necessary to use a special kind of polypropylene, the so—called « High
`Me|t—strength » (referred to hereafter as « HMS PP ») grades. These grades possess long—chain branched structure,
`which leads to entanglements of the molecular chains. In the molten state, if such HMS PP ar e stretched, the disen-
`tanglement step of the molecular chains leads to an increase of the shear & elongational Viscosity, which is favorable
`to maintain cell wall integrity during expansion in the still molten state. Furthermore, branches are believed to induce
`crystal nucleation, so that the temperature gap between melting point and crystallization point is reduced: the crystal-
`lization temperature rises to 120—125°C while the melting point is unaffected. This is definitely promoting c|osed—ce|ls
`structure of the foam.
`[0007] BASELL Pro-Fax PF 814, BOREALIS DAPLOY 130D have both the aforementioned long—chain branching
`structure, introduced by a post—reactor step, either by irradiation (BASELL) or by reactive extrusion (BOREALIS), and
`are up to now the main materials successfully used to produce very low density foams.
`[0008] The foams obtained by using HMS PP can have a very low density, provided a maximum of HMS PP is used.
`The counterpart polymer may be another conventional linear polypropylene homopolymer or copolymer, having a melt-
`ing point range from 140°C to 170°C, as measured by Differential Scanning Calorimetw (DSC). Foams made from
`polypropylene are reported in the prior art to be more rigid than LD PE foams for example, influenced by the higher E-
`modulus of conventional homopolymer or copolymer (random or bloc) polypropylenes compared to LDPE.
`[0009]
`International patent application WO 01/94092 FFHERMAFLEX INTERNATIONAL HOLDING] discloses a proc-
`ess for producing a polyolefin foam having higher temperature resistance and comprising a polypropylene and/or pol-
`yethylene. The process comprises first mixing and melting one or more polyolefins having a melting range, measured
`by means of differential scanning calorimetry at a heating rate of 10°C/min, within the range of 95°C to 170°C, with
`optionally other polyolefins and/or additives, so as to form a homogeneous mixture having a melt temperature within
`the range of 120 to 160°C, melting said homogeneous mixture in an extruder, mixing said molten mixture with a physical
`
`PAGE 11 OF 30
`
`

`
`EP1 479 716 A1
`
`foaming agent and cooling it to produce a foam at atmosphere. The polyolefins having a melting range from 95 to
`170°C are constituted from polypropylene having melting temperature range within 140 to 170°C, and PROFAX 814
`HMS-PP from BASELL is cited as representative of the polypropylene used. The other polyoiefin can be a polyethylene
`having a melting range from 95 to 135°C. for example low density polyethylene, high density polyethylene, or EVA.
`[0010]
`Further in this patent application, it is pointed out that foams having a high polypropylene content have the
`best temperature resistance BUT are somewhat less flexible than the foams having a lower polypropylene content.
`The flexibility of foams containing from 40 to 95% by weight of polypropylene having a melting range within the range
`of 140 to 170°C are said to have in general aflexibility of 0.10 N/mm? at 20% impression, measured according to DIN
`53577, while the foams containing from 0 to 40% by weight of polypropylene having a melting range within the range
`of 140 to 170°C in general have a flexibility of 0.060 N/mm2 at 20% impression, measured according to DIN 53577.
`[0011]
`Finally, WO 01/94092 teaches the advantage of compounding the polymers and additives priorto the extrusion
`of the foam, so that one single DSC melting peak is obtained.
`[0012] However, there are end uses that require both higher temperature resistance and improved flexibility.
`[0013] The present invention addresses the request for foams having improved flexibility while possessing a high
`thermal resistance, higherthan existing flexible foams made, for example, from LDPE, orthe aforementioned combi-
`nation of polypropylene and polyethylene disclosed in WO 01/94092.
`[0014] The foams of the present invention comprise from about 5 to about 95 weight percent of a High Melt Strength
`polypropylene. The remaining 95 to 5 weight percent will comprise from 95 to 5 weight percent of a polypropylene
`modified with ethylene/C3-C12 alpha-olefin copolymers, where the weight ration between polypropylene and the eth-
`ylene/C3-C12 alpha-olefin copolymer is between 90/10 and 30/70. These materials are commercially available with
`thetradenames Moplen or TPO HIFAX (Basell), FINAPRO (Fina) and the like. These products, having aflexural mod-
`ulus equal or interior to 200 MPa and a melting point between 140°C and 170°C, may eventually be complemented
`by a polypropylene resin having a melting point between 140°C and 170°C, like a polypropylene homopolymer AND/'
`OR a polypropylene bloc (heterophasic) copolymer AND/OR a polypropylene random copolymer.
`[0015]
`Surprisingly, when associating HMS PP with such flexible polypropylene copolymers, the mechanical prop-
`erties of the resulting foams are greatly improved. The resulting foam is much more flexible than PP foams, while the
`meltingtemperature is still much higherthanfor LDPE foams and higherthanthe prior art combination of polypropylenes
`with polyethylenes.
`[0016] An advantage of the foams according to the invention is that the dimensional stability problem arising during
`extrusion of such flexible polypropylene foams is solved.
`[0017] HIFAX resins which are manufactured under CATALLOY BASELL proprietary synthesis may be sued in the
`present invention. They are elastomeric thermoplastic olefins, bloc copolymers of polypropylene, with a peculiarly high
`rubber content. In the following table, key properties are listed in order to compare conventional polypropylene types
`with some of the HIFAX grades used in the frame ofthe present invention; these resins will be identified as « TPO PP » :
`
`Producer
`
`BAS ELL
`
`BASELL
`
`DSM
`
`BAS ELL
`
`DSM
`
`BASELL
`
`PRO FAX PF—
`814
`
`MOPLEN
`HP5OON
`
`STAMYLAN
`P 11E10
`
`HOSTALEN
`PP H 1022
`
`STAMYLAN
`P HA1 E10
`
`HIFAX CA 60
`A
`
`BAS ELL
`
`HIFAX 7320
`
`BAS ELL
`
`HIFAX CA
`020
`
`Flexural
`MFI
`230°C/2.16kg Modulus
`(g/10min.)
`(MPa)
`ISO 1133
`ISO 178
`
`Tensile
`Modulus
`(MPa)
`ISO 527-2
`
`Melting point
`(°C)
`ISO 3146
`
`3
`
`12
`
`0.3
`
`0.3
`
`0.3
`
`HPP
`
`Bloc Copo PP
`
`1700
`
`800
`
`80
`
`200
`
`20
`
`163°C
`
`165°C
`
`143.5°C
`
`142°
`
`C
`
`162°C
`
`141°
`
`C
`
`PAGE 12 OF 30
`
`

`
`[0018]
`
`For comparison, here is the same set of property for a low-density polyethylene:
`
`EP1 479 716 A1
`
`MFI 230°C]
`2.16kg (gl
`10min.) ISO
`1133
`
`Density Kgl
`m3
`
`Tensile
`Modulus (MPa)
`ISO 527-2
`
`Melting point
`(°C) ISO 3146
`
`Producer
`
`DSM
`
`BASELL
`
`STAMYLAN LD
`2601TX‘l 7
`
`LUPOLEN
`1800 H
`
`[0019] One clearly sees that the cited HIFAX grades potentially combine an exceptional flexibility with a high melting
`point, more comparable to those of the conventional polypropylene homo and copolymers.
`[0020]
`It is however necessary to combine the HIFAX TPO with HMS PP in orderto reach low density foams. HIFAX
`by themselves are not foaming well at all, a minimum of 5 % HMS PP (PROFAX PF-814 from BASELL for example)
`is therefore necessary to help foaming of the composition of the present invention.
`[0021] Optionally, one can add to the above composition ethylenic polymers having a melting point from 95°C to
`135°C, such as a high pressure copolymer of ethylene (for example: ethylene ethyl acrylate [EEA], ethylene acrylic
`acid (EAA), ethylene methacrylic acid [EMAA], ethylene vinyl acetate [EVA], ethylene butyl acrylate [EBA]) AND/OR
`a low density polyethylene AND/OR a medium density polyethylene AND/OR a high density polyethylene, provided
`the required combination of flexibility and temperature resistance of the foamed blend is achieved.
`[0022] Gas for foaming are chosen among following products: short chain alkanes from C2 to C8, C02, l-lFC (134,
`134a, 152a) andtheirblends. Preferred blowing agentformaking very low density are butane and propane and mixtures
`thereof, especially recommended is the use of isobutane.
`[0023]
`All kind of additives known to the skilled man in the art can be used to improve processability and properties
`of thefoams ofthe present invention: flame retardant, antistatics, processing aids, nucleating agents, pigments, infrared
`reflector/absorber, anti-UV agents, antioxidants, etc.
`[0024] The dimensional stability of polypropylene foams is governed by the relative permeation of the foaming gas
`compared to the outside air through the polymer membrane of each cell wall.
`It is also known that physical blowing
`agents having a molar volume somewhat bigger than atmospheric gases (nitrogen, oxygen and CO2), permeate at a
`different rate than air components through polypropylene. This is the case for HCFC 142b, which permeates at one
`fifth of the rate of air in a PP resin. For an approximately sterically similar molecule, isobutane, it is verified in practice
`to permeate also more slowly than air in polypropylene: foam is blowing further after the day of extrusion. This phe-
`nomenon induces a variation in the dimensions and density, which is more or less acceptable.
`[0025] Despite the use of permeability modifiers known in the art, like GMS or a saturated fatty acid derivative (stear-
`amide for example) commonly used for volume stabilization of LDPE foams, a collapse of the foam occurs after some
`meter on the cooling line. Despite thatthe next day the foam has blown back to a lower density, the foam has never-
`theless a bad aspect surface.
`[0026]
`Surprisingly, it has been discovered that by adding a permeability modifier like stearamide or glycerol mono-
`stearate to the composition of the present invention, and by applying a rapid cooling on the foam surface immediately
`after the die exit, the collapse during extrusion is unexpectedly reduced and the surface aspect is improved. Cooling
`is ideally made by air blowing ring having the external shape of the foam profile to be made in order to maintain an
`equal cooling efficiency overthe entire external surface of the foam. Care must be taken to avoid a cooling of the die,
`which would freezethe foam. An insulating Teflon plate with a small aperture can be used, for example, placed against
`the die, letting the foam expand after passing through the aperture in the Teflon plate.
`[0027]
`Preferably, a direct gassing extrusion process is used for making the foams of the present invention. The
`process comprises the following steps
`
`feeding the polymers and optional additives into an extruder and heating the blend in the cylinder of the extruder
`so as to melt and blend the polymers and the optional additives;
`injecting a blowing agent which is liquid under injection pressure but gaseous at ambient conditions, mixing of the
`gas and molten polymers and the optional additives in the last part of the cylinder;
`cooling and further homogenizing through a heat exchanger section, followed by a static mixer element;
`extruding the cooled mixture through a die, the mixture is expanding by evaporation of the dissolved gas due to
`pressure drop and insolubility limit, so as to form afoam;
`cooling the foam immediately afterthe die;
`
`PAGE 13 OF 30
`
`

`
`EP1 479 716 A1
`
`-
`
`further cooling the foam to the atmosphere conditions and while drawing the foam slightly.
`
`[0028] Another advantage brought by the use of these HIFAX with high rubber content and low E-modulus, is the
`improvement of impact at low temperature. Foams in some automotive use have to maintain their flexibility event at
`deep freeze temperature such as -40°C. Without the use of impact modifier, it is impossible to avoid break of the foam.
`The combination of high melt strength polypropylene and CATALLOY rubber modified polypropylene allows to pass
`this test, without affecting the upper side of temperature resistance of the foams.
`[0029] Applications for such new foams are numerous. Their combined high flexibility and high temperature resist-
`ance allows to outperform flexible LDPE foams where higher service temperature are requested, in thermal insulation
`of pressurized steam water for example. Automotive industry is very pleased to replace non-thermoplastics parts, like
`PUR, or PVC components; lightweight, recyclable, higher temperature resistance and flexible new PP foams of the
`present invention are adequate candidates. Furthermore, << All PP car » is a wish in automotive industry, and the per-
`centage of PP in automotive plastic parts is more and more increasing. Any shape can be made with the new formu-
`lationz tube, rectangles, hollow shapes, sheets, irregular convex or concave shapes ...in any thickness, density and
`cell size according to the final use request.
`[0030] Care must betaken about the long-term stability of polypropylene, especially if in contact with metal, peculiarly
`copper. Antioxidant packages, including metal deactivator, are available and can help to satisfy the automotive stand-
`ards. Maximum temperature for long-term exposure must be determined carefully, in the most severe condition. Peak
`temperatures have also to be tested. It is however clear that the new polypropylene foams of the present invention
`can withstand a higher long-term service temperature than LDPE foams.
`[0031]
`Finally, the «flexibility» of the resulting new foams, measured for example by compression stress at 20%
`deformation according to D|N53577, is superior to prior art foams like those described in WO 01/94092, that is, a lower
`value of the force is required to compress foam of 20% (remains 80% of initial height). Dimensional stability during
`extrusion is improved.
`
`Comparative example 1 , not representing the present invention
`
`[0032] A foam is prepared by introducing in a twin screw co—rotative extruder a blend made from 40 weight parts of
`HMS polypropylene PHOFAX PF—814 (BASELL) and 60 weight parts of a random copolymer STAMYLAN P RA1 E10
`(DSM, flexural Modulus = 800 MPa), adding 5 weight parts of a PP based masterbatch containing 40% wt talcum, 1
`weight part of glycerol monostearate ATM ER 129, 5 parts of a PE based 5% fluoroelastomer masterbatch and 6 parts
`of a 25% antioxidant PP based masterbatch. The mixture is extruded at 20 kg/h, using 1,86 kg isobutane per hour as
`blowing agent. The melt is cooled through a heat exchanger section, then passes a static mixer and finally is extruded
`through a rectangular shape die. Melt temperature beforethe die is 153.7°C. No air is blown on the foam surface. The
`resulting foams expands to the atmosphere, has a fresh density of 30.5 kg/m3, with 870 cells/cm2.
`It seems rather
`stable in dimensions in the cooling bath. Size of the rectangular foam is 26 x 17.5mm. Foam is moderatly flexible,
`compression at 20% deformation (DIN 53577) in the direction of extrusion is 0.063 N/mmz. Next day, density has fallen
`to 26 kg/m3.
`
`Comparative example 2, not representative of the invention
`
`[0033] A foam is prepared by introducing in a twin screw co—rotative extruder a blend made from 60 weight parts of
`HMS polypropylene PROFAX PF—814 (BAS ELL) and 40 weight parts of TPO PP HIFAX CA020 (BASELL), adding 0.5
`weight parts of a PP based masterbatch containing 60% wt talcum, 5 weight pans of an EVA based masterbatch
`containing 90wt% stearamide ARMID HT (AKZO NOBEL). The mixture is extruded at 15 kg/h, using 1,5 kg isobutane
`per hour as blowing agent. The melt is cooled through a heat exchanger section, then passes a static mixe