(19)
(11)EP 2 185 334 B1

(12)EUROPEAN PATENT SPECIFICATION

(45)Mention of the grant of the patent:
29.04.2020 Bulletin 2020/18

(21)Application number: 08828401.3

(22)Date of filing:  26.08.2008
(51)International Patent Classification (IPC): 
B29C 44/56(2006.01)
B29C 44/34(2006.01)
(86)International application number:
PCT/US2008/074318
(87)International publication number:
WO 2009/029619 (05.03.2009 Gazette  2009/10)

(54)

IMPROVED METHOD OF FORMING EXTRUDED POLYSTYRENE FOAMS AND THE PRODUCTS MADE THEREFORM

VERBESSERTES VERFAHREN ZUR FORMUNG EXTRUDIERTER POLYSTYROLSCHAUMSTOFFE UND DARAUS HERGESTELLTE PRODUKTE

PROCÉDÉ AMÉLIORÉ DE FORMATION DE MOUSSES DE POLYSTYRÈNE EXTRUDÉ ET PRODUITS AINSI OBTENUS


(84)Designated Contracting States:
AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK TR

(30)Priority: 27.08.2007 US 966285 P

(43)Date of publication of application:
19.05.2010 Bulletin 2010/20

(73)Proprietor: DDP Specialty Electronic Materials US, Inc.
Wilmington, DE 19805 (US)

(72)Inventors:
  • MAURER, Myron, J.
    Midland, MI 48675 (US)
  • SAGNARD, Alain, Michel, André
    Midland, MI 48675 (US)
  • BINDELS, Dominicus, L.
    NL-6136 Aw Sittard (NL)
  • BOVEN, Michelle, L.
    Midland, MI 48675 (US)
  • CHOI, Byoung-Ho
    Uijeongbu-Si Kyounggi-do 480-917 (KR)
  • CLEEREMAN, Robert, J.
    Midland, MI (UY)
  • GASTON, Ryan, S.
    Midland, MI 48642 (US)
  • LANGMAIND, Joseph, A.
    Caro, MI 48723 (US)

(74)Representative: Beck Greener LLP 
Fulwood House 12 Fulwood Place
London WC1V 6HR
London WC1V 6HR (GB)


(56)References cited: : 
WO-A-03/061938
DE-C1- 19 542 717
JP-A- 6 218 860
US-A- 4 863 791
US-A1- 2006 148 919
WO-A-2006/128656
GB-A- 834 956
JP-A- 10 250 205
US-A- 6 062 624
  
      
    Note: Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned statement. It shall not be deemed to have been filed until the opposition fee has been paid. (Art. 99(1) European Patent Convention).


    Description

    CROSS-REFERENCE TO RELATED APPLICATION



    [0001] This application claims the benefit of US Provisional Application Serial No. 60/966,285, filed August 27, 2007.

    Field of the Invention



    [0002] The invention relates to an improved method of forming extruded polystyrene foams into useful shapes.

    Background of the Invention



    [0003] Extruded polystyrene (XPS) foams have been used for some time in sound and insulation applications. The foams are formed by extruding continuously a heated plastic resin containing a blowing agent through a die, which upon exiting the die expands under, for example, steam or vacuum. Generally, these foams have been limited to applications only requiring simple shapes or complex shapes with a thin thickness. For example, simple shapes include toys that are die cut out of a board that are essentially flat including puzzles and imitation badges. Other more complex shapes, generally, have been made by thermoforming. Thermoforming, however, commercially has been limited to shapes using thin XPS sheets such as milk crates. This is due to the long times necessary to heat and cool the foam to enable molding the foam.

    [0004] More complex shapes of polystyrene have, generally, been formed using partially foamed beads of polystyrene that still contain a blowing agent and air diffused therein as a result of aging of the foam from ½ to 6 days. The beads are then placed in a mold and heated sufficiently to expand the beads further such that they fill in the mold and weld to each other. Polystyrenes made this way are typically referred to as expanded polystyrene (EPS). Examples of EPS shapes include, coffee cups, cushioned packaging shapes (e.g., shapes that provide cushioning to shipped articles), and bike helmets. This method of forming polystyrene shapes suffers from a complex method involving multiple heating and cooling steps and costly molds that need to be heated and cooled.

    [0005] Other 3-dimensional shapes of polystyrene foams have been made by dye cutting flat shapes and laminating them together as described in U.S. Pat. No. 6,129,969. This method suffers from multiple steps to fashion the shaped article.

    [0006] Finally, polystyrenes foam properties have been modified by uniformly crushing the foam one or more times. This elasticizing/flexibilization allows for the foam to bounce back after being impacted or bent further without being broken. For extruded foams, the crushing is typically done by roll presses. Examples of such crushing are described in U.S. Pat. Nos. 3,445,406; 4,510,268; 5,114,656; 5,520,873; and 5,718,968.

    [0007] WO 03/061938 A discloses a method for producing decorative strips, in particular decorative corner strips consisting of extruded polystyrene foam. According to said method, at least one surface of the decorative corner strip is moulded under pressure and thermal action using a heated die, which has an anti-adhesion coating and a separation agent is used. Extruded polystyrene panels, each of which is cut into strip-shaped blanks, are used as the material in said method. Once the surface of the blank has been moulded by the die, at least one thermally softened, fused softened zone is formed along the length of the blank with the help of at least one resistance heating element and at least one controllable angle bending tool, said zone cooling and hardening after completion of the thermal treatment, whereby a bending point with a reinforcing material crust is formed, which divides the blank into a central strut and at least one limb that is positioned at a predefined angle to said central strut.

    [0008] Accordingly, it would be desirable to provide a forming method for extruded polystyrene that is able to quickly shape complex extruded polystyrene shaped articles and in particular thicker shaped foam articles (e.g., greater than about a couple of millimeters thick).

    Summary of the Invention



    [0009] Surprisingly, a method has been discovered to quickly form complex, thick shaped styrenic polymer foam shapes.

    [0010] A first aspect of the invention is a method to form a foam styrenic polymer comprising,
    1. (a) extruding a styrenic polymer with a blowing agent to form a styrenic polymer foam plank, the plank having a top and bottom surface in which said surfaces lie in the plane defined by the direction of extrusion and width of the plank,
    2. (b) creating a pressing surface by
      1. (i) removing a layer of foam from (a) the top surface, (b) bottom surface, (c) both the top and bottom surface or
      2. (ii) cutting the foam plank between the top and bottom surface creating two pressing surfaces opposite the top and bottom surface,
    3. (c) pressing the foam plank with the pressing surface such that the shaped styrenic polymer foam is formed.


    [0011] A second aspect of the invention is a method of forming a styrenic polymer foam shape comprising
    1. (a) providing a styrenic foam having a higher concentration of open cells at a surface of the foam than the concentration of open cells within the foam,
    2. (b) contacting the surface with the higher concentration of open cells with a forming tool, and
    3. (c) pressing the foam such that the complex foam shape is formed.


    [0012] Surprisingly, the methods of the invention allow for the fast production of shaped foam parts having complex curvatures on one or both faces of the plank and is of varying thickness without need for expensive thermal molding techniques.

    [0013] The method may be used to form styrenic polymer foam shapes having at lease some portion where the thickness is greater than a few millimeters. Examples of such applications include automobile energy absorbing countermeasures, automobile sun visors, automobile head rests, automobile bumpers, automobile door panels, bicycle helmet foam padding, floral and craft foam articles, interior partition panels, concrete floor thermal insulation incorporating recessed grooves for continuous hydronic floor heat tubing, insulation boards with integral water drainage channels, interior and exterior decorative cornices, cushion packaging articles and exterior building façade panels.

    Brief Description of the Drawings



    [0014] 
    Fig. 1
    is an illustration of the step change in the pressed foam of this invention.
    Fig. 2
    is a photograph of a forming tool used to form pressed foams of this invention.
    Fig. 3
    is a photograph of a foam made not using a method of this invention.
    Fig. 4
    is a photograph of a pressed foam made using a method of this invention.
    Fig. 5
    is a photograph of the open cell concentration of a foam blank as shown by a penetrated dye.
    Fig. 6
    is a photograph of the open cell concentration of a foam blank as shown by a penetrated dye.
    Fig. 7
    is a photograph of another forming tool used to form pressed foams of this invention.
    Fig. 8
    is a photograph of a foam made not using a method of this invention.
    Fig. 9
    is a photograph of a foam made using a method of this invention.

    Detailed Description of the Invention



    [0015] The invention is a method of quickly forming complex shapes from styrenic polymer foams. In the first aspect of the invention a styrenic polymer is extruded with a blowing agent to form a styrenic polymer foam plank. The use of plank, herein, is merely used for convenience with the understanding that other shapes than a flat board having a rectangular cross-section may be extruded.

    [0016] Any suitable method of extruding to form the foam plank may be used such as mixing the styrenic polymer and blowing agent and extruding by a method known in the art. For example, a method for extruding styrenic foams such as described in U.S. Pat. Nos.3,231,524; 3,482,006, 4,420,448 and 5,340,844 may be used.

    [0017] As per convention, but not limited by, the extrusion of the plank is taken to be horizontally extruded (the direction of extrusion is orthogonal to the direction of gravity). Using such convention, the plank's top surface is that farthest from the ground and the plank's bottom surface is that closest to the ground, with the height of the foam (thickness) being orthogonal to the ground when being extruded.

    [0018] In making the foam by extrusion, a blowing agent is used. The blowing agent may be any suitable blowing agent, such as a volatile aliphatic hydrocarbon, chlorinated hydrocarbon, fluorinated hydrocarbon, chlorofluorinated hydrocarbon, gas present in the atmosphere (oxygen, nitrogen, carbon dioxide, hydrogen, helium and the like) or combination thereof.

    [0019] Examples of a volatile hydrocarbon include ethane, ethylene, propane, propylene, butane, butylenes, isobutene, pentane, cyclopentane, isopentane, hexane, heptane, or mixture thereof. Examples of chlorinated hydrocarbons, fluorinated hydrocarbons and chlorofluorinated hydrocarbons include methyl chloride, Dichlorodifluoromethane, Octafluorocyclobutane, Chlorodifluoromethane, 1,2-Dichlorotetrafluoroethane, 1,1-Dichlorotetrafluoroethane, Pentafluoroethane, 2-Chloro-1,1-difluoroethane, 2-Chloro-1,1,1-trifluoroethane, 1,1,1,2-Tetrafluoroethane, 1,1,1-Trifluoroethane, 1,1,1-Trifluoropropane, Trichlorotrifluoroethane, Difluoromethane, 2-Chloro-1,1,1,2-tetrafluoroethane, 2,2-Difluoropropane, Ethyl chloride or a mixture thereof.

    [0020] Illustratively, styrenic polymer foams typically have employed chlorofluoro hydrocarbons as the gas blowing agent. These have tended, because of their slow diffusion rate, to form closed cell foams where the average gas pressure is greater than 1 atmosphere even after the foam has been aged for a long period of time. When the foam is closed or has substantial closed cells (i.e., generally greater than about 25% by number of the cells) it is preferred that at least one blowing agent or one component of the mixture of blowing agents has a substantially faster diffusion rate through the foam than air to facilitate the formation of a foam having a gas pressure of 1 atmosphere or less after aging the foam, for example, for a day or more. Substantially faster in this context means that the diffusion rate of the blowing agent is at least about 2 times faster than the diffusion rate of air. Diffusion of air is taken as the average diffusion rate of oxygen and nitrogen weighted by the presence of each in air. Preferably, the diffusion rate of the blowing agent is at least about 3 times, more preferably at least 4 times, even more preferably at least 5 times and most preferably at least 10 times faster than the diffusion rate of air.

    [0021] Because, of environmental concerns, the blowing agent desirably is or is comprised of carbon dioxide, water or both.

    [0022] To facilitate the shape retention and appearance after pressing, particularly of closed cell foams, the average gas pressure of the closed cells generally should be at most about 1.4 atmospheres. It is desirable that the gas pressure of the cells is less than atmospheric pressure to minimize the potential for spring back of the foam after pressing causing a less than desirable shape retention, for example, squeaking or dislodging of the foam from the structural member. Preferably, the average gas pressure of the closed cells is at most about 1.0 atmosphere, more preferably at most about 0.95, and even more preferably at most about 0.9 atmosphere and most preferably less than about 0.8 atmosphere.

    [0023] The average gas pressure of the closed cells may be, using gas diffusion rates, calculated by estimating the gas content in a cellular material at differing times if the initial time that the foam is made is known (e.g., ASTM D7132-05). However, because the initial time of the foam is not always known, the cell pressure may be determined empirically as described in co-pending U.S. Patent Application No. 11/391804 (page 15 of the application as filed).

    [0024] The styrenic polymer is understood to mean a synthetic organic polymer of a styrenic monomer or styrenic monomer and a comonomer that is not a styrenic monomer. Styrenic monomer means a styrene monomer, derivative of a styrene monomer (e.g., a substituted styrene) or combination thereof. Examples of substituted styrenes are o-methylstyrene, m-methylstyrene, p-methylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, p-tert-butylstyrene, p-chlorostyrene. Preferably, the styrenic polymer is polystyrene.

    [0025] A copolymer of a styrenic monomer (styrene and derivative of a styrene monomer) described above and a comonomer that is not a styrenic monomer, which is also referred to herein as a "polystyrenic copolymer". Exemplary comonomers include acrylonitrile, poly(2,6-dimethyl-1,4-phenylene ether), methyl acrylate, butyl acrylate, methacrylonitrile, maleimide, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride or combination thereof. The comonomer is preferably acrylonitrile, maleic anhydride or combination thereof. More preferably, the comonomer is acrylonitrile.

    [0026] Generally, the amount of styrenic monomer in the polystyrenic copolymer is at least about 50% by mole of the copolymer. Typically, the amount of comonomer is about 1% to 50% by mole of the polystyrenic copolymer. Preferably the amount of comonomer is at least 5%, more preferably at least about 10%, even more preferably at least about 20% and most preferably at least about 25% by mole of the polystyrenic copolymer.

    [0027] A preferred polystyrenic copolymer is a styrene-acrylonitrile copolymer (SAN). The SAN copolymer may have 1% to 50% by weight of acrylonitrile. Preferably, the acrylonitrile is present in an amount of at least about 5%, more preferably at least 10%, and most preferably at least about 15% to preferably at most 45%, more preferably at most about 40% and most preferably at most about 35% by weight of the SAN copolymer.

    [0028] The styrenic polymer may be of any useful weight average molecular weight (MW). Illustratively, the MW of a polystyrenic or polystyrenic copolymer may be from 10,000 to 1,000,000. The polymer may be of any useful weight average molecular weight (MW). Illustratively, the MW of the styrenic polymer may be from 10,000 to 1,000,000. The MW of a styrenic polymer is desirably less than about 200,000, which surprisingly aids in forming a shaped foam part retaining excellent surface finish and dimensional control. In ascending further preference, the MW of a polystyrenic or polystyrenic copolymer is less than about 190,000, 180,000, 175,000, 170,000, 165,000, 160,000, 155,000, 150,000, 145,000, 140,000, 135,000, 130,000, 125,000, 120,000, 115,000, 110,000, 105,000, 100,000, 95,000, and 90,000. For clarity, molecular weight (MW) herein is reported as weight average molecular weight unless explicitly stated otherwise. The MW may be determined by any suitable method such as those known in the art.

    [0029] In addition the styrenic polymer may also contain other additives such as those commonly used in extruded polystyrenic foams. Examples of other additives include small amounts of cross-linking agents (e.g., divinyl benzene), colorants, UV-protectants, antioxidants, fillers, flame retardants, stabilizers, for example of the flame retardants, antistats, cell nucleation control agents and the like.

    [0030] The styrenic polymer after extruding is a foam, that is, it is cellular. Cellular (foam) has the meaning commonly understood in the art in which a polymer has a substantially lowered apparent density comprised of cells that are closed or open. Closed cell means that the gas within that cell is isolated from another cell by the polymer walls forming the cell. Open cell means that the gas in that cell is not so restricted and is able to flow without passing through any polymer cell walls to the atmosphere.

    [0031] The foam may have any amount of open or closed cells. Even so, for some applications a portion of the cells may be advantageously closed, for example, when absorption of water is deleterious to the function of the final product. Even though open or closed foams may be used, when the application desired benefits from lack of water absorption, the foam is preferably closed cell. For such applications, it is preferred, that at least about 55%, more preferably at least about 60%, even more preferably at least about 75% and most preferably at least about 90% of the cells of the foam are closed cells.

    [0032] Generally, the foam may have a density from about 16 kg/m3 to about 100 kg/m3 or more. The foam density, typically, is selected depending on the particular application, for example, for an exterior building façade panel, the density is typically is at least about 24 kg/m3 to about 64 kg/m3.

    [0033] The cells of the foam may have an average size (largest dimension) of from about 0.05 to about 5.0 mm, especially from about 0.1 to about 3.0 mm, as measured by ASTM D-3576-98. Foams having larger average cell sizes, of especially about 1.0 to about 3.0 mm or about 1.0 to about 2.0 mm in the largest dimension, are of particular use when the foam fails to have a compressive ratio of at least 0.4 as described in the following few paragraphs.

    [0034] The forming of the complex foam shapes are surprisingly enhanced by having foams that have at least one direction where at least one of CE/CT, CV/CT and CH/CT is at least 0.4 said one of CE/CT, CV/CT and CH/CT (compressive ratio), CE, CV and CH being the compressive strength of the cellular polymer in each of three orthogonal directions E, V and H where one of these directions is the direction of maximum compressive strength in the foam and CT equals the sum of CE, CV and CH.

    [0035] The compressive strength is established when the compressive strength of the foam is evaluated in three orthogonal directions, E, V and H, where E is the direction of extrusion, V is the direction of vertical expansion after it exits the extrusion die and H is the direction of horizontal expansion of the foam after it exits the extrusion die. These measured compressive strengths, CE, CV and CH, respectively, are related to the sum of these compressive strengths, CT, such that at least one of CE/CT, CV/CT and CH/CT, has a value of at least 0.40, preferably at least two have a value of at least 0.4 and most preferably. Preferably, at least one value is at least 0.45. When using such a foam, the pressing direction is desirably parallel to the maximum value in the foam.

    [0036] After the foam plank is formed, the first aspect's method requires creating a pressing surface, by removing a layer from the top or bottom surface or cutting the foam plank between the top and bottom surface to create two pressing surfaces opposite the top and bottom surface. Examples of methods that may be useful are cutting using equipment such as band saws, computer numeric controlled (CNC) abrasive wire cutting machines, CNC hot wire cutting equipment and the like. When removing a layer, the same cutting methods just described may be used and other methods such as planing, grinding or sanding may be used.

    [0037] Typically, after the removing or cutting, the plank is at least about several millimeters thick to at most about a 60 centimeters thick. Generally, when removing a layer, the amount of material is at least about a millimeter and may be any amount useful to perform the method such as 1.2, 1.4, 1.6, 1.8, 2, 2.5, 3, 3.5, 4, 5 millimeters or any subsequent amount determined to be useful such as an amount to remove any skin that is formed as a result of extruding the styrenic polymer foam, but is typically no more than 10 millimeters. In another embodiment, the foam is cut and a layer is removed from the top or bottom surface opposite the cut surface to form two pressing surfaces.

    [0038] In a particular embodiment, the foam plank having a pressing surface, has a density gradient from the pressing surface to the opposite surface of the foam plank. Generally, it is desirable to have a density gradient of at least 5%, 10%, 15%, 25%, 30% or even 35% from the pressing surface to the opposing surface of the foam plank. To illustrate the density gradient, if the density of the foam at the surface (i.e., within a millimeter or two of the surface) is 48.0 kg/m3 (3.0 pounds per cubic foot, pcf), the density would be for a 10% gradient either 2.7 or 3.3 pcf at the center of the foam. Even though the density of the foam at the pressing surface may be less or greater than the density at the center of the foam, the density of the foam at the pressing surface is preferably less than the density at the center of said foam plank. Likewise, if the foam plank has two pressing surfaces, both desirably have the aforementioned density gradient.

    [0039] The plank prior to contacting with a forming tool may be cut to fit into a tool, or may be cut simultaneously, such as in die cutting where the die cutting apparatus is set up such that during the cutting, the shape is simultaneously pressed into the pressing surface. Lastly, the final shape maybe cut from the pressed part, for example, the foam plank may be roll pressed to form the shape into the pressing surface and subsequently cut. When cutting the foam, any suitable method may be used, such as those known in the art and those described previously for cutting the foam to form the pressing surfaces. In addition, methods that involve heat may also be used to cut the foam since the pressed shape has already been formed in the pressing surface.

    [0040] The pressing surface(s) of the plank is contacted with a forming tool such as a die face. Herein die face means any tool having an impressed shape that when pressed into the foam plank will cause the foam to take the shape of the die face. That is, the material making up the die face is such that it does not deform when pressed against the foam plank, but the foam plank deforms to form and retain the desired shape of the die face.

    [0041] Typically when pressing, at least a portion of the foam is pressed such that the foam is compressed to a thickness of 95% or less of the to be pressed foam thickness 15 as shown in Fig. 1, which typically corresponds to just exceeding the yield stress of the foam. Likewise, when pressing the part, the maximum deformation of the foam (elastically deforming the foam) is typically no more than about 20% of the original thickness 15 of the foam ready to be pressed.

    [0042] The forming tool such as a die face, because a shape is most often desired, typically has contours that create an impression (step change) in height 30 of at least a millimeter in the foam 10 having thickness 15 as shown in Fig. 1. The height/depth 30 of an impression may be measured using any suitable technique such as contact measurement techniques (e.g., coordinate measuring machines, dial gauges, contour templates) and non-contact techniques such as optical methods including laser methods. The height of the step change 30 may be greater than 1 millimeter such as 1.5, 2, 2.5, 3, 3.5, 4, 5, 6, 7, 8, 9 and 10 to a height that is to a point where there are no more foam cells to collapse such that pressing further starts to elastically deform the plastic (polymer) of the foam.

    [0043] The step change, surprisingly, may be formed where the foam undergoes shear. For example, the foam may have a shear angle 20 of about 45° to about 90° from the press surface 40 of the foam 10 in a step change 30. It is understood that the shear angle may not be linear, but may have some curvature, with the angle in these cases being an average over the curvature. The angle surprisingly may be greater than 60°, 75° or even by 90° while still maintaining an excellent finish and appearance.

    [0044] In another aspect of the invention, a styrenic foam having a higher concentration of open cells at a surface of the foam than the concentration of open cells within the foam is contacted and pressed to form the shape. In this aspect of the invention the foam may be any styrenic foam such as the extruded styrenic polymer foam described above. It may also be any other styrenic polymeric foam such as those known in the art including, for example, where the blowing agent is added to polymer beads, typically under pressure, as described by U.S. Pat. No. 4,485,193 and each of the U.S. patents this patent cites at col. 3, lines 6-13.

    [0045] With respect to this open cell gradient, the gradient is as described above for the density gradient where the concentration of open cells if determined microscopically and is the number of open cells per total cells at the surface.

    [0046] Generally, the amount of open cells in this aspect of the invention at the surface is at least 5% to completely open cell. Desirably, the open cells at the surface is at least in ascending order of 6%, 7%, 8%, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% and completely open cell at the surface.

    [0047] The foam may have the open cells formed at the surface by mechanical means such as those described above (e.g., planing/machining or cutting) or may be induced chemically, for example, by use of suitable surfactants to burst closed cells at the surface.

    [0048] The foam surface with the higher concentration of open cells is contacted with a die face and pressed as described above. In a preferred embodiment for such foams, the die faces are heated, but the foam is not (ambient 15-30°C) and the foam is pressed. Surprisingly, the heated die faces being heated results in superior surface contour and appearance, whereas when doing the same with a foam without such open cells at the surface, the appearance of the foam is degraded.

    [0049] When pressing with a heated forming tool such as a die face, the contact time with the foam is typically from about 0.1 second to about 60 seconds. Preferably, the dwell time is at least about 1 second to at most about 45 seconds.

    [0050] When pressing with a heated forming tool such as a die face, the temperature of the die face is not so hot or held for too long a time such that the foam is degraded. Typcically, the temperature of the die face is about 50°C to about 200°C. Preferably, the temperature is at least about 60°, more preferably at least about 70°C, even more preferably at least about 80°C and most preferably at least about 90°C to preferably at most about 190°, more preferably at most about 180°, even more preferably at most about 170°C and most preferably at most about 160°C.

    TEST METHODS



    [0051] The density profile through the thickness of each foam blank was tested using a QMS Density Profiler, model QDP-O1X, from Quintek Measurement Systems, Inc. Knoxville, TN. The High Voltage kV Control was set to 90%, the High Voltage Current Control was set to 23% and the Detector Voltage was approximately 8v. Data points were collected every 0.06 mm throughout the thickness of the foam. Approximate thickness of the foam samples in the plane of the x-ray path was 2 inches. Mass absorption coefficients were calculated for each sample individually, based on the measured linear density of the foam part being tested. The skin density, ρskin, was reported as a maximum value whereas the core density, ρcore, was averaged within an approximate 5 mm range. The density gradient, in units of percentage, was then computed in accordance with the following equation:



    [0052] The compressive response of each material was measured using a Materials Test System equipped with a 5.0 displacement card and a 17.793 kN (4,000 lbf) load card. Cubical samples measuring the approximate thickness of each plank were compressed at a compressive strain rate of 0.065 s-1. Thus, the crosshead velocity of the MTS, in units of inches per minute, was programmed in accordance with the following equation:

    where the thickness of the foam specimen is measured in units of inches. The compressive strength of each foam specimen is calculated in accordance with ASTM D1621 while the total compressive strength, CST, is computed as follows:

    where CSV, CSE and CSH correspond to the compressive strength in the vertical, extrusion and horizontal direction respectively. Thus, the compressive balance, R, in each direction can be computed as shown below:







    [0053] Open cell content was measured by using an Archimedes method on 25mm x 25mm x 50mm samples.

    EXAMPLES


    Forming Procedure Examples 1-5 & Comp. Ex 1



    [0054] The foam specimens of each Example 1-5 and Comparative Example 1 were formed against the surface of a 1.77 inch thick prototype cedar-shake aluminum casting tool shown in Figure 2 using the following general procedure with the foam's pertinent characteristics, the surface temperature of the cedar shake tool and results shown for each in Table 1. The surface of the tool had previously been Teflon coated by Sun Coatings in Plymouth, MI to eliminate the foam from sticking to the surface upon heating.

    [0055] Examples 1 and 4 and Comparative Example 1 used IMPAXX™ 700, available from The Dow Chemical Co., Midland, MI. This foam is an extruded polystyrene foam with plank dimensions measuring 100x600x2200 millimeters in the vertical (i.e. thickness), horizontal (i.e. width) and extrusion (i.e. length) directions respectively. The polystyrene had a MW of about 146,000 and was blown using carbon dioxide and a minor amount (i.e. 0.35 pph) of isobutane.

    [0056] Examples 3, 5 and 6 used IMPAXX TM 300, available from The Dow Chemical Co., Midland, MI, was tested as described above with the results shown in Table 1. This foam is an extruded polystyrene foam with plank dimensions measuring 110x600x2200 millimeters in the vertical (i.e. thickness), horizontal (i.e. width) and extrusion (i.e. length) directions respectively. The polystyrene had a MW of about 146,000 and was blown using carbon dioxide.

    [0057] The tool thickness was laid flat on the moving platen surface of a 15-ton Carver compression molding machine (Model No. 3893). In addition, a series of metal stop blocks approximately 2.50 inches thick were measured using Mitutoyo digital calipers (Model No. CD-8" CS) and laid on the moving platen surface to prevent the upper platen from making direct contact with the tool surface. For those parts produced with a heated tool, the platen temperature was digitally programmed and the actual surface temperature of the tool was measured using a Tegam 871A Digital Thermometer. An extruded polystyrene (XPS) foam "blank" approximately 2.0 inches thick was cut from a XPS foam plank using a Rockwell band saw (Model 14 Band Saw). The thickness of each foam plank prior to forming was measured using the digital calipers described previously. Finally, the foam blank was then double-sided taped to the surface of the stationary platen and parts were formed by bottoming the stationary platen against the stop blocks. After being pressed, the platens were opened and the part was removed from the tool and the part examined, for example, for cracks and shape retention, which is shown in Table 1.

    [0058] In Tables 1 and 2, when the pressing surface is referred to as "skin", this is the surface that is pressed against the tooling of Figure 2 and "skin" means the foam plank was used as is without planing (removing) any material from the plank surface. "Planing" means that about 5-7 mm of material was removed from the board surface by planing and this planed surface was placed against the tooling of Fig. 2. "Cut" means that the foam plank was cut in the middle of the thickness of the plank and this cut surface was placed against the tooling of Figure 2.

    [0059] Example 1 and Comparative Example 1 are shown in Figures 3 and 4. The only difference in making these pressed foam parts was that for Example 1, the "cut" surface was placed against the cedar shake tool and pressed, whereas for Comp. Ex. 1 the as formed surface of the foam was placed against the cedar shake tool. Surprisingly, by doing this, the cedar shake of Example 1 has excellent shape retention and no visible surface cracks whereas Comp. Ex. 1 has multiple surface cracks and poor grain retention in the pressed foam.

    [0060] Examples 2 and 3 show the desirability to have an open cell gradient where there are more open cells at the pressing surface when the tool is heated above ambient temperatures as shown by Example 2 having superior pressing results than Example 3.

    [0061] Example 4 shows that for a differing foam, excellent aesthetics can be obtained when pressing against the "cut" surface. Likewise, Example 5 shows that using a "planed" surface improves the foam compared to using a "skin" surface to press against.

    Forming Procedure Examples 6-9 & Comp. Ex. 2-5



    [0062] The foam specimens of each Example 6-9 and Comparative Example 2-5 were formed against the surface of a 1.01 inch thick corrugated aluminum casting tool shown in Figure 7 using the following general procedure with the foam's pertinent characteristics, the surface temperature of the corrugated tool and results shown for each in Table 2. The surface of the tool had previously been Teflon coated by Sun Coatings in Plymouth, MI to eliminate the foam from sticking to the surface of a heated tool.

    [0063] The tool thickness was laid flat on the moving platen surface of a 15-ton Carver compression molding machine (Model No. 3893). In addition, a series of metal stop blocks approximately 1.50 inches thick were measured using Mitutoyo digital calipers (Model No. CD-8" CS) and laid on the moving platen surface to prevent the upper platen from making direct contact with the tool surface. An extruded polystyrene (XPS) foam "blank" approximately 1.0 inches thick was cut from a XPS foam plank using a Rockwell band saw (Model 14 Band Saw). The thickness of each foam plank prior to forming was measured using the digital calipers described previously. Finally, the foam blank was then double-sided taped to the surface of the stationary platen and parts were formed by bottoming the stationary platen against the stop blocks. After pressing, the platens were opened and the part was removed from the tool.

    [0064] Example 6 and Comparative Ex. 2 were formed from A 2" x 48" x 96" plank of R-10 STYROFOAM™ SCOREBOARD extruded polystyrene (XPS) sheathing foam, produced by The Dow Chemical Company, Midland, MI, which was purchased from Lowe's Home Center, Inc. in Midland, MI (Item No. 14541). The surface of the plank contained a skin from the manufacturing process. This foam was made from a polystyrene having a MW of about 168,000 and blown using HCFC 142B (1-chloro-1,1-difluoroethane).

    [0065] Example 7 and Comp. Ex. 3 were formed from STYROFOAM™ DECKMATE™ Plus brand insulation, available from The Dow Chemical Co., Midland, MI. This foam is an extruded polystyrene foam with plank dimensions measuring 4X48X96 in. in the vertical (i.e. thickness), horizontal (i.e. width) and extrusion (i.e. length) directions respectively. The surface of the plank contained a skin from the manufacturing process. The polystyrene had a MW of about 168,000 and was blown using HCFC 142B (1-chloro-1,1-difluoroethane).

    [0066] Example 8 and Comp. Ex. 4 were formed from SOLIMATE™ 400, available from The Dow Chemical Co., Midland, MI. This foam is an extruded polystyrene foam with plank dimensions measuring 100x570x2385 millimeters in the vertical (i.e. thickness), horizontal (i.e. width) and extrusion (i.e. length) directions respectively. The surface of the plank contained a skin from the manufacturing process. The polystyrene had a MW of about 146,000 and was blown using carbon dioxide.

    [0067] Example 9 and Comp. Ex. 5 were from FLOORMATE™ 500 SL-A, available from The Dow Chemical Co., Midland, MI. This foam is an extruded polystyrene foam with plank dimensions measuring 100X600X1250 millimeters in the vertical (i.e. thickness), horizontal (i.e. width) and extrusion (i.e. length) directions respectively. The surface of the plank contained a skin from the manufacturing process. The polystyrene had a MW of about 146,000 and was blown using carbon dioxide.

    [0068] These Examples and Comp. Exs. demonstrate the method where there is severe topography introduced by the tool for multiple different foams. Every foam part was substantially improved by the method of this invention (e.g., Comp. Ex. 2 v Ex. 6 etc.). Illustratively, the difference is shown by Comp. Ex. 3 versus Example 7 in Figures 8 and 9 respectively.
    Table 1. Cedar Shake Examples and Comparative Example 1.
    ExampleTool Surface T(°C)Pressing SurfaceRvAverage Open Cell. (%)Density (Kg/m3)Density* Gradient (%)Open cell gradient#Pressing Results
    Comp. 1 23 skin 0.62 2.2 41 -53.3   Multiple surface cracks. Poor grain retention. Crack propagation beyond shear plane depth. Lack of depth between adjacent shakes.
    1 23 cut 0.62 2.2 41 -53.3   No visible surface cracks. Excellent grain retention. No visible crack beyond shear plane. Good depth between adjacent shakes
    2 111 cut 0.59 4.9 36 18.6 substantial No visible surface cracks. Good grain retention. No visible crack propagation beyond shear plane. Good depth between adjacent shakes.
    3 111 cut 0.62 2.2 41 -53.3 negligible No visible surface cracks. Swollen cedar shakes. Poor grain retention. No visible crack propagation beyond shear plane. Lack of depth between adjacent shakes.
    4 23 cut 0.59 4.9 36 18.6   No visible surface cracks. Exceptional grain retention. No visible crack propagation beyond shear plane. Good depth between adjacent shakes.
    5 23 planed 0.59 4.9 36 18.6   Few visible surface cracks. Poor grain retention. Crack propagation extending beyond shear plane depth. Lack of depth between adjacent shakes.
    Rv is the compressive balance in the direction of the applied pressing force.
    * Density Gradient is the gradient of the foam blank to be pressed.
    # Thin samples through the thickness of the plank were penetrated with a a soapy red dye under vacuum for about two minutes and the gradient observed visually from penetration of dye after being lightly blotted by a paper towel (see Fig. 5 for Ex. 2 and Fig. 6 for Ex. 3).
    Table 2. Corrugated Examples and Comparative Example 1.
    ExampleTool Surface Temperat ure (°C)Pressing SurfaceRvAverage Open Cell (%)Density (Kg/m3)Density* Gradient (%)Pressing Results
    Comp 2 23 skin 0.33 3.6 26 -28.4 Little or no depth of corrugations. Jagged shear edges
    6 23 cut 0.33 3.6 26 -28.4 Some depth of corrugations. Visible cracks along shear edges
    Comp 3 23 skin 0.48 3.1 37 -47.2 Poor depth of corrugations. Jagged shear edge.
    7 23 cut 0.48 3.1 37 -47.2 Good depth of corrugations. Clean Shear edges. Visible crack formation at base of part.
    Comp 4 23 skin 0.45 2.9 34 -18.2 Poor depth of corrugations. Jagged shear edges. Visible crack propagation beyond base of part.
    8 23 cut 0.45 2.9 34 -18.2 Excellent depth of corrugations. Clean shear edges. No visible crack propagation beyond base of part.
    Comp 5 23 skin 0.58 4.6 39 -45.5 Excellent depth of corrugations. Rounded shear edge. Crack at base of part
    9 23 cut 0.58 4.6 39 -45.5 Excellent depth of corrugations. Clean shear edge. No visible crack propagation at base of part.



    Claims

    1. A method to form a foam styrenic polymer comprising,

    (a) extruding a styrenic polymer with a blowing agent to form a styrenic polymer foam plank, the plank having a top and bottom surface in which said surfaces lie in the plane defined by the direction of extrusion and width of the plank,

    (b) creating a pressing surface by

    (i) removing a layer of foam from (A) the top surface, (B) the bottom surface, or (C) both the top and bottom surface or

    (ii) cutting the foam plank between the top and bottom surface creating two pressing surfaces opposite the top and bottom surface,

    (c) contacting the pressing surface of the foam plank with a die face, and

    (d) pressing the foam plank such that the shaped styrenic polymer foam is formed;

    further comprising after the extruding to form the styrenic foam plank, the plank having at least a portion of the cells being closed, aging said plank for at least one day such that the average gas pressure of the closed cells is less than 1 bar (atmospheres).
     
    2. The method of Claim 1, wherein the styrenic polymer foam is polystyrene.
     
    3. The method of Claim 1, wherein the styrenic polymer is a copolymer of styrenic monomer and a comonomer selected from the group consisting of acrylonitrile, poly(2,6-dimethyl-1,4-phenylene ether), methyl acrylate, methacrylonitrile, maleimide, acrylic acid, methacrylic acid, maleic anhydride, itaconic anhydride and combination thereof.
     
    4. The method of Claim 3, wherein the comonomer is acrylonitrile.
     
    5. The method of Claim 1, wherein the extruding of the foam plank employs a blowing agent that is a volatile aliphatic hydrocarbon, carbon dioxide, water or combination thereof.
     


    Ansprüche

    1. Verfahren zum Bilden eines styrolischen Schaumstoffpolymers umfassend,

    (a) Extrudieren eines Styrolpolymers mit einem Treibmittel, um ein Brett aus styrolischem Polymerschaumstoff zu bilden, wobei das Brett eine obere und untere Oberfläche aufweist, wobei die Oberflächen in der Ebene liegen, die durch die Extrusionsrichtung und die Breite des Brettes definiert wird,

    (b) Erzeugen einer Pressfläche durch

    (i) Entfernen einer Schicht Schaumstoff von (A) der oberen Oberfläche, (B) der unteren Oberfläche oder (C) sowohl der oberen als auch der unteren Oberfläche oder

    (ii) Schneiden des Schaumstoffbrettes zwischen der oberen und unteren Oberfläche, um zwei Pressflächen der oberen und unteren Oberfläche entgegengesetzt zu erzeugen

    (c) Kontaktieren der Pressfläche des Schaumstoffbrettes mit einer Matrizenfläche und

    (d) Pressen des Schaumstoffbrettes, derart, dass der geformte styrolische Polymerschaumstoff gebildet wird;

    ferner nach Extrudieren zum Bilden der styrolischen Schaumstoffbohle, wobei bei dem Brett mindestens ein Teil der Zellen geschlossen ist, Altern des Brettes mindestens einen Tag lang umfassend, derart, dass der durchschnittliche Gasdruck der geschlossenen Zellen weniger als 1 bar (Atmosphären) beträgt.
     
    2. Verfahren nach Anspruch 1, wobei der styrolische Polymerschaumstoff Polystyrol ist.
     
    3. Verfahren nach Anspruch 1, wobei das styrolische Polymer ein Copolymer von styrolischem Monomer und einem Comonomer ausgewählt aus der Gruppe bestehend aus Acrylnitril, Poly(2,6-dimethyl-1,4-phenylenether), Methylacrylat, Methacrylnitril, Maleimid, Acrylsäure, Methacrylsäure, Maleinsäureanhydrid, Itaconsäureanhydrid und Kombinationen davon ist.
     
    4. Verfahren nach Anspruch 3, wobei das Comonomer Acrylnitril ist.
     
    5. Verfahren nach Anspruch 1, wobei bei dem Extrudieren des Schaumstoffbrettes ein Treibmittel verwendet wird, das ein flüchtiger aliphatischer Kohlenwasserstoff, Kohlendioxid, Wasser oder eine Kombination davon ist.
     


    Revendications

    1. Procédé de formation d'un polymère styrénique en mousse comprenant,

    (a) l'extrusion d'un polymère styrénique avec un agent d'expansion pour former une planche de mousse de polymère styrénique, la planche ayant une surface supérieure et inférieure dans laquelle lesdites surfaces reposent dans le plan défini par le sens d'extrusion et la largeur de la planche,

    (b) la création d'une surface de compression en

    (i) retirant une couche de mousse de (A) la surface supérieure, (B) la surface inférieure, ou (C) à la fois la surface supérieure et inférieure ou

    (ii) la découpe de la planche de mousse entre les surfaces supérieure et inférieure créant deux surfaces de compression opposées aux surfaces supérieure et inférieure,

    (c) la mise en contact de la surface de compression de la planche de mousse avec une face de matrice, et

    (d) la compression de la planche de mousse de sorte que la mousse de polymère styrénique mise en forme est formée;

    comprenant en outre après l'extrusion pour former la planche de mousse styrénique, la planche ayant au moins une partie des alvéoles qui sont fermées, la maturation de ladite planche durant au moins une journée, de sorte que la pression moyenne du gaz des alvéoles fermées est inférieure à 1 bar (atmosphère).
     
    2. Procédé selon la revendication 1, la mousse de polymère styrénique étant le polystyrène.
     
    3. Procédé selon la revendication 1, le polymère styrénique étant un copolymère de monomère styrénique et d'un comonomère sélectionné dans le groupe constitué de l'acrylonitrile, du poly(2,6-diméthyl-1,4-phénylène éther), de l'acrylate de méthyle, du méthacrylonitrile, du maléimide, de l'acide acrylique, de l'acide méthacrylique, de l'anhydride maléique, de l'anhydride itaconique et de leurs combinaisons.
     
    4. Procédé selon la revendication 3, le comonomère étant l'acrylonitrile.
     
    5. Procédé selon la revendication 1, l'extrusion de la planche de mousse utilisant un agent d'expansion qui est un hydrocarbure aliphatique volatil, du dioxyde de carbone, de l'eau ou une combinaison de ceux-ci.
     




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    Cited references

    REFERENCES CITED IN THE DESCRIPTION



    This list of references cited by the applicant is for the reader's convenience only. It does not form part of the European patent document. Even though great care has been taken in compiling the references, errors or omissions cannot be excluded and the EPO disclaims all liability in this regard.

    Patent documents cited in the description