Source: http://www.google.com/patents/US4911978?dq=6188988
Timestamp: 2014-03-10 06:49:49
Document Index: 87811173

Matched Legal Cases: ['art)               12', 'art         1', 'art        1', 'art)               12', 'art         2', 'art        1', 'art)       70', 'art)        0', 'art  3', 'art 2']

Patent US4911978 - Polyolefin resin foamed laminate sheet and double-side vacuum forming of the ... - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsA foamed laminate sheet suitable for thermoforming and a double-side vacuum forming process using the same are disclosed, said foamed laminate sheet being composed of a foamed interlayer comprising a polyolefin resin as a main resinous component and from 0.5 to 35 parts by weight of an inorganic filler...http://www.google.com/patents/US4911978?utm_source=gb-gplus-sharePatent US4911978 - Polyolefin resin foamed laminate sheet and double-side vacuum forming of the sameAdvanced Patent SearchPublication numberUS4911978 APublication typeGrantApplication numberUS 07/358,110Publication dateMar 27, 1990Filing dateMay 30, 1989Priority dateMay 30, 1988Fee statusLapsedAlso published asCA1293913C, DE68918159D1, DE68918159T2, EP0344726A2, EP0344726A3, EP0344726B1Publication number07358110, 358110, US 4911978 A, US 4911978A, US-A-4911978, US4911978 A, US4911978AInventorsYoshinori Kajimoto, Masahiro Tsubone, Toru YoshimiOriginal AssigneeSekisui Kaseihin Kogyo Kabushiki KaishaExport CitationBiBTeX, EndNote, RefManPatent Citations (3), Referenced by (24), Classifications (21), Legal Events (6) External Links: USPTO, USPTO Assignment, EspacenetPolyolefin resin foamed laminate sheet and double-side vacuum forming of the sameUS 4911978 AAbstract A foamed laminate sheet suitable for thermoforming and a double-side vacuum forming process using the same are disclosed, said foamed laminate sheet being composed of a foamed interlayer comprising a polyolefin resin as a main resinous component and from 0.5 to 35 parts by weight of an inorganic filler per 100 parts by weight of the polyolefin resin, said foamed interlayer having a density of from 0.18 to 0.98 g/cm.sup.3, and a polyolefin film laminated on both sides of said foamed interlayer. The foamed laminate sheet exhibits excellent formability, and formings obtained therefrom have excellent heat resistance, oil resistance, heat insulating properties, and strength, with outstanding use in a microwave oven or as a retort food container.
What is claimed is: 1. A foamed laminate sheet suitable for thermoforming, which is composed of a foamed interlayer comprising a polyolefin resin as a main resinous component and from 0.5 to 35 parts by weight of an inorganic filler per 100 parts by weight of the polyolefin resin, said foamed interlayer having a density of from 0.18 to 0.98 g/cm.sup.3, and a polyolefin film laminated on both sides of said foamed interlayer.
7. A process of double-side vacuum forming of a polyolefin resin foamed laminate sheet by using male and female molds, in which a foamed laminate sheet composed of a polyolefin resin foamed interlayer having a density of from 0.18 to 0.98 g/cm.sup.3 and a polyolefin film laminated on both sides of said interlayer is vacuum-formed between the male and female molds having a gap therebetween, said gap being from 1.0 to 2.5 times the thickness of the foamed laminate sheet heated and softened.
9. A process of double-side vacuum forming as claimed in claim 7, wherein said male and female molds are set at a temperature of 50 lower.
10. A formed article obtained by double-side vacuum forming of a polyolefin resin foamed laminate sheet by using male and female molds, in which a foamed laminate sheet composed of a polyolefin resin foamed interlayer having a density of from 0.18 to 0.98 g/cm.sup.3 and a polyolefin film laminated on both sides of said interlayer is vacuum-formed between the male and female molds having a gap therebetween, said gap being from 1.0 to 2.5 times the thickness of the foamed laminate sheet heated and softened.
A blowing agent which can be used in the resin composition for the foamed interlayer includes those decomposable on heating to liberate N.sub.2 or CO.sub.2 and those which are gaseous or liquid at room temperature, e.g., N.sub.2, CO.sub.2, air, water, alcohols, propane, butane, pentane, trichloromonofluoromethane, dichlorodifluoromethane, monochlorodifluoromethane, 1,2-dichlorotetrafluoro-ethane, 1-chloro-1,1-difluoroethane, methyl chloride, and ethyl chloride. The heat-decomposable blowing agent is mixed with raw materials in advance, and the blowing agent which is gaseous or liquid at room temperature is supplied to the middle of an extruder.
The density of the foamed layer ranges from 0.18 to 0.98 g/cm.sup.3. If it is less than 0.18 g/cm.sup.3, a pattern of wavy lines is formed on extrusion foaming, and formings obtained from such foamed sheet suffer from poor appearance, deformation and poor stretchability. If it exceeds 0.98 g/cm.sup.3, the foamed layer exhibits low post-expandability and is therefore of no use.
It is desirable that the foamed laminate sheet of the present invention has a percent heat shrinkage as small as possible so as to have high retention of dimension after heat shrinkage. It is also desirable that the shrinkage in the machine direction and that in the cross direction are substantially equal. For example, the foamed laminate sheet preferably has a percent retention of at least 50% and a residual dimension ratio of at least 0.7. The terminology "percent retention" as used herein means a percentage of the dimension after shrinkage to the original dimension in the machine or cross direction when the sheet is heated at 190 If the percent retention is less than 50%, the percent shrinkage on heating and softening becomes too great to make it difficult to form the sheet to shape. The terminology "residual dimension ratio" as used herein means a ratio of the shorter dimension after heat shrinkage in either the machine direction or the cross direction to the longer dimension in the other direction. If the residual dimension ratio is less than 0.7, the sheets tends to have poor stretchability on forming and the resulting formings tend to have defective appearance. These criteria can be adjusted by controlling the amount of the inorganic filler or the ratio of polyolefin to polystyrene in the foamed layer, the size of a mold, and the like.
The double-side vacuum forming in accordance with the present invention is illustrated below. The gap between the female and male molds is preferably set at 1.0 to 2.5 times, more preferably 2.0 times, the thickness of the heated and softened foamed laminate sheet. The foamed laminate sheet is clamped at the four corners and previously heated and softened at a temperature between 160 the open space between the molds. At this time, the gap between the molds is desirably 1.0 to 2.5 times, more desirably 2.0 times, the thickness of the heated and softened laminate sheet as stated above. This gap has an influence on strength of the resulting post-expanded and formed article. If it exceeds 2.5 times the thickness of the sheet, the degree of expansion becomes too high, resulting in extremely reduced bending strength. If it is less than 1.0 time, no contribution to improvement of bending strength can be obtained. The mold temperature is preferably 50 forming of polystyrene resin sheets, the mold temperature is set at 50 post-expansion and cooling. To the contrary, in the present invention in which the formable sheet is composed of a foamed sheet of polyolefin resins, e.g., polypropylene, laminated on both sides thereof a polyolefin film, since polypropylene resins have a large specific heat and poor cooling efficiency, mold temperatures of 50 increase of cycle speed but deformation of the laminate sheet. However, too a low mold temperature functions to cool the heated and softened sheet to lose plasticity, thus failing to achieve sufficient vacuum forming. From all these considerations, a suitable mold temperature ranges from about 35 usually 500 mmHg vac. or more.
The process of the vacuum forming according to the present invention will be explained with reference to FIG. 2. Foamed laminate sheet 1 composed of a polypropylene resin foamed interlayer having adhered a polypropylene film to both sides thereof is heated and softened at 300 to 50 seconds by means of a far infrared heater. The heated foamed sheet is transferred to the open space between a pair of molds 2, 3 (FIG. 2-a). The molds used here are matching male and female molds. Female mold 2 is connected to a suction apparatus to perform straight vacuum forming (FIG. 2-b). The peripheries of the both molds are then matched (FIG. 2-c), and the cavity is evacuated from male mold 3 to cause expansion-in-mold to obtain a formed article 11 (FIG. 2-d). During the forming the mold temperature is kept at 50 After complete expansion, the pressure of the cavity is returned to atmospheric pressure, and the formed article 11 is removed from the molds.
TABLE 1__________________________________________________________________________                              MIDesig-                             Value Measurementnation    Kind of Polymer       Trade Name               Grade                    Manufacturer                              (g/10 min)                                    Method__________________________________________________________________________A   Polypropylene       Sumitomo               D-501                    Sumitomo  0.4   JIS K-6758       Noblen                     Co., Ltd.B   Polypropylene       Sumitomo               FH-1015                    Sumitomo  0.5   JIS K-6758       Noblen                     Co., Ltd.C   Styrene-maleic       More Max                UG-830                    Idemitsu  1.8   JIS K-7210    anhydride            Petrochemical   230    copolymer            Co., Ltd.D   Styrene-       AX Polymer               AX-T Asahi Chemical                              3.7   JIS K-7210    methacrylic     100  Industry Co., Ltd.                                    230    acid copolymerE   Polystyrene       Styron                8703 Asahi Chemical                              1.6   JIS K-6870                                    200                                    -    Industry Co.,                                    Ltd.  200F   &#945;-Methyl-       HS Polymer               HS-400                    Denki Kagaku                              2.1   Denka Method    styrene              Kogyo K.K.      250G   Saturated       Taftic                H-1011                    Asahi Chemical                              13.9  JIS K-7210    thermoplastic        Industry Co., Ltd.                                    230    elastomerH   Polypropylene       Sumitomo               FS-2011                    Sumitomo Chemical                              2.5   JIS K-6758       Noblen I   Polypropylene       Sumitomo               AD-571                    Sumitomo Chemical                              0.6   JIS K-6758       Noblen J   Polyethylene       Yukalon                HE-30                    Mitsubishi                              0.27  ASTM D1238                    Petrochemical   190                    Co., Ltd.K   Polyethylene       Petrothene                172J Tosoh     0.38  ASTM D1238                    Corporation     190L   Polyethylene       Lumirror                F 86 Toray Industries,                              --    --    terephthalate        Inc.    filmM   Polypropylene/       Barielon                &#956; Asahi Chemical                              --    --    polyvinylidene       Industry Co., Ltd.    chloride/poly-    propylene__________________________________________________________________________
EXAMPLE 1 A polymer mixture consisting of 40 parts of a polypropylene resin A, 30 parts of a polypropylene resin B, 25 parts of a polystyrene resin C, and 5 parts of a saturated thermoplastic elastomer G was uniformly mixed with 12.5 parts of talc as an inorganic filler in an extruder. To the resin composition was added 0.6% by weight of butane (hereinafter abbreviated as "C.sub.4") as a blowing agent and the resulting foaming compound was supplied to an extruder. Separately, 55 parts of a polypropylene resin H and 45 parts of a block polypropylene resin I were uniformly mixed in an extruder to prepare a film-forming resin. The above-prepared foaming compound and the film-forming resin were co-extruded to obtain a foamed laminate sheet. The extrusion of the foaming compound was carried out at a resin temperature of 203 The resulting foamed laminate sheet had a thickness of 1290 μm [50 μm/1185 μm (foamed interlayer)/55 μm] and a basis weight of 608 g/m.sup.2 [46/512 (foamed interlayer)/50 g/m.sup.2 ], and the foamed interlayer had a density of 0.41 g/cm.sup.3 and an open cell ratio of 52%.
A 100 mm-square piece was cut out of the foamed laminate sheet and heated in an oven at 190 56 mm in the machine direction (MD) and 58 mm in the transverse direction (TD), giving a residual dimension ratio MD/TD of 0.97. The foamed laminate sheet had a smooth surface with no bubbles due to gas entrapment.
The foamed laminate sheet as above produced was clamped at the four corners and heated and softened at 300 a far infrared heater. The sheet heated and softened had a thickness of about 1.2 mm. The sheet heated and softened was double-side vacuum formed into a container by using matched male and female molds. The female mold had a cavity size of 157 without clamping of the sheet between the male and female molds was 1.5 mm at the bottom part and 1.0 mm at the upright part. The sheet was first subjected to straight vacuum forming using the female mold set at 40 periphery of the male mold also set at 40 evacuated from the vacuum ports provided in both molds to a reduced pressure of 550 mmHg vac. for a matching time of 10 seconds to effect double-side vacuum forming. The sheet exhibited satisfactory formability.
The tray had a density of 0.33 g/cm.sup.3. When it was heated in a Geer oven set at 130 within 2%, proving of excellent heat resistance of the tray. These results are shown in Table 2.
In Example 15, polyethylene terephthalate films were coated on the both sides of a foamed layer in a separate step; in Example 16, a polypropylene/polyvinylidene chloride/polypropylene laminate film was laminated on one side of a film/foamed layer/film foamed laminate sheet in a separate step; and in Example 14, forming was carried out by use of a far infrared heater of 180
The abbreviate "H.C" for the blowing agent used in Examples 9 and 10 signifies Hydrocellol acid, made by Beringer AG).
TABLE 2-(1)__________________________________________________________________________               Example 1                      Example 2                             Example 3                                    Example 4                                           Example__________________________________________________________________________                                           5Resin Composition:Foamed Interlayer (part)               A/B/C/G =                      B/C/G =                             B/C = 75/25                                    A/B/C/G =                                           A/B/C/G =               40/30/25/5                      70/25/5       40/45/10/5                                           40/5/50/5External Film Layer (part)               H/I = 55/45                      H/I = 55/45                             H/I = 55/45                                    H/I = 55/45                                           H/I = 55/45Amount of Talc (part)               12.5   0.5    0.5    12.5   12.5Blowing Agent (% by wt.)               C.sub.4 0.6                      C.sub.4 0.8                             C.sub.4 0.1                                    C.sub.4 0.5                                           C.sub.4 0.7Temp. of Foaming Resin (               203    202    202    201    200Extrusion Output (kg/hr)               90     90     91     89     92Total Thickness (&#956;m)               1290   2954   2428   1161   2659(Film/Foamed Layer/Film)               50/1185/55                      51/2847/55                             50/2326/52                                    49/1059/53                                           50/2555/54Total Basis Weight (g/cm.sup.3)               608    608    602    601    605(Film/Foamed Layer/Film)               46/512/50                      46/512/50                             45/510/47                                    44/509/48                                           45/511/49Density of Foamed Layer (g/cm.sup.3)               0.41   0.18   0.22   0.48   0.20Open Cell Ratio (%) 52     30     35     56     48Residual Dimension (190MD                  56     52     55     62     60TD                  58     74     71     63     72MD/TD               0.97   0.70   0.77   0.98   0.83Dimensional Change (130               within 2%                      within 2%                             within 2%                                    within 2%                                           within 2%Appearance of Sheet excellent                      good   good   excellent                                           excellentBubble              good   good   good   good   goodThickness of Formed Article (mm)bottom part         1.8    4.4    3.2    1.6    4.1upright part        1.2    2.9    2.2    1.1    2.7Density of Foamed Layer of               0.33   0.14   0.19   0.38   0.15Formed Article (g/cm.sup.3)Appearance of Formed Article               excellent                      good   good   excellent                                           excellent__________________________________________________________________________
TABLE 2-(2)__________________________________________________________________________               Example 6                      Example 7                             Example 8                                    Example 9                                           Example__________________________________________________________________________                                           10Resin Composition:Foamed Interlayer (part)               A/B/D/G =                      A/B/F/G =                             A/B/E/G =                                    B/C/G =                                           B/C/G =               40/30/25/5                      40/30/25/5                             40/30/25/5                                    70/25/5                                           70/25/5External Film Layer (part)               H/I = 55/45                      H/I = 55/45                             H/I = 55/45                                    H/I = 55/45                                           H/I = 55/45Amount of Talc (part)               12.5   12.5   12.5   0.5    0.5Blowing Agent (% by wt.)               C.sub.4 0.6                      C.sub.4 0.7                             C.sub.4 0.8                                    (H.C) 0.3                                           C.sub.4 0.6 + H.C 0.3Temp. of Foaming Resin (               202    202    201    208    201Extrusion Output (kg/hr)               91     90     92     89     90Total Thickness (&#956;m)               1442   1316   1263   1064   2783(Film/Foamed Layer/Film)               52/1336/54                      50/1214/52                             50/1160/53                                    48/964/52                                           52/2674/57Total Basis Weight (g/cm.sup.3)               604    603    604    601    606(Film/Foamed Layer/Film)               47/508/49                      46/510/47                             45/511/48                                    43/511/47                                           47/508/51Density of Foamed Layer (g/cm.sup.3)               0.38   0.42   0.44   0.53   0.19Open Cell Ratio (%) 54     58     61     31     53Residual Dimension (190MD                  54     56     57     61     54TD                  57     58     60     64     73MD/TD               0.95   0.97   0.95   0.95   0.74Dimensional Change (130               within 2%                      within 2%                             within 2%                                    within 2%                                           within 2%Appearance of Sheet excellent                      excellent                             good   excellent                                           excellentBubble              good   good   good   good   goodThickness of Formed Article (mm)bottom part         2.0    1.8    1.7    1.5    3.8upright part        1.3    1.2    1.1    1.0    2.5Density of Foamed Layer of               0.31   0.34   0.36   0.41   0.16Formed Article (g/cm.sup.3)Appearance of Foamed Article               excellent                      excellent                             good   excellent                                           excellent__________________________________________________________________________
TABLE 2-(3)__________________________________________________________________________                                              Compara-                                                    Compara-                                              tive  tive        Example 11              Example 12                    Example 13                          Example 14                                Example 15                                       Example 16                                              Example                                                    Example__________________________________________________________________________                                                    2Resin Composition:Foamed Interlayer        B/C/G =              A/B/C =                    A/B/C =                          J = 100                                B/C/G =                                       A/B/C/G =                                              B/C/G                                                    A = 100(part)       70/25/5              40/35/25                    40/35/25                          70/25/5                                70/25/5                                       40/30/25/5External Film layer        H/I=55/45              H/I=55/45                    H/I=55/45                          K = 100                                L      H/I=55/45                                              H/I=55/45                                                    H/I=55/45(part)                                      M = 5Amount of Talc (part)        0.5   35    30    5     5      12.5   0.2   40Blowing Agent        C.sub.4 0.8              C.sub.4 0.5                    C.sub.4 0.6                          C.sub.4 0.5                                C.sub.4 0.8                                       C.sub.4 0.6                                              C.sub.4                                                    C.sub.4 0.5(% by wt.)Temp. of Foaming Resin        198   203   202   120   203    202    202   204(Extrusion Output (kg/hr)        93    90    91    91    91     90     90    89Total Thickness (&#956;m)        2414  626   1120  2235  2913   1355   2642  617(Film/Foamed Layer/        51/2305/58              52/514/60                    51/1010/59                          49/2126/60                                *25/2863/25                                       55/1185/                                              53/2530/59                                                    51/513/53Film)                                       55/60Total Basis Weight        605   605   604   605   585    666    607   602(g/cm.sup.3) (Film/Foamed        46/507/52              47/504/54                    46/505/53                          45/505/55                                35/515/35                                       50/512/                                              48/506/53                                                    46/508/48Layer/Film)                                 50/54Density of Foamed Layer        0.22  0.98  0.5   0.31  0.36   0.41   0.20  0.99(g/cm.sup.3)Open Cell Ratio (%)        35    95    91    33    30     52     22    98Residual Dimension(190MD           38    85    60    54    56     55     41    91                          (120                                (200                          30 min.)                                30 min.)TD           76    87    65    76    75     76     74    92MD/TD        0.50  0.98  0.92  0.71  0.75   0.72   0.55  0.99Dimensional Change        within 2%              within 2%                    within 2%                          within 2%                                within 2%                                       within 2%                                              within                                                    within 2%(130                          (80                                (135                          30 min.)                                30 min.)Appearance of Sheet        good  good  excellent                          good  good   excellent                                              poor  poorBubble       good  good  good  good  good   good   good  poorThickness of FormedArticle (mm)bottom part  3.4   0.9   1.5   3.4   4.4    1.8    3.6   0.9upright part 2.3   0.6   1.0   2.3   2.9    1.2    2.4   0.6Density of Foamed        0.18  0.67  0.39  0.23  0.28   0.32   0.17  0.70Layer of FormedArticle (g/cm.sup.3)Appearance of Foamed        fair  good  excellent                          good  good   excellent                                              poor  poorArticle__________________________________________________________________________
In order to solve the problems associated with single-side vacuum forming, double-side vacuum forming of thermoplastic resin foamed sheets has been developed as disclosed in JP-B-59-1184 and JP-A-60-192615 (the term "JP-B" as used herein means an "examined published Japanese patent application" and the term "JP-A" means an "unexamined published Japanese patent application"), in which a pair of forming molds with a prescribed gap therebetween and having a clamping frame at the periphery thereof are used, the male mold being set at 50 plasticized thermoplastic resin foamed sheet is clamped between the male and female molds, the gap is evacuated from the both molds to thereby adibatically expand the sheet to the full of the gap to give a prescribed shape, the formed sheet is cooled, a gas is introduced into the mold cavity to raise the pressure to atmospheric pressure, the molds are opened, and the formed article is removed. The above-cited references describe that the double-side vacuum forming technique produces formings from a foamed sheet of a thermoplastic resin, such as polystyrene and polymers mainly comprising styrene, or a foamed laminate sheet composed of such a foamed sheet and a thermoplastic resin film.
It has now been found that the above objects of this invention can be accomplished by a polyolefin resin foamed laminate sheet suitable for thermoforming, which is composed of a foamed interlayer comprising 100 parts by weight of a polyolefin resin and from 0.5 to 35 parts by weight of an inorganic filler, said foamed interlayer having a density of from 0.18 to 0.98 g/cm.sup.3, and a polyolefin film laminated on both sides of said foamed interlayer.
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