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WO1997038049A1 - Melanges et procedes de melange de copolymeres olefine/ester qui possedent une plus grande resistance aux contraintes de fissuration et a la fatigue en exterieur, articles faits de ces polymers et procedes de moulage de ces articles - Google Patents

Melanges et procedes de melange de copolymeres olefine/ester qui possedent une plus grande resistance aux contraintes de fissuration et a la fatigue en exterieur, articles faits de ces polymers et procedes de moulage de ces articles Download PDF

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Publication number
WO1997038049A1
WO1997038049A1 PCT/US1997/005617 US9705617W WO9738049A1 WO 1997038049 A1 WO1997038049 A1 WO 1997038049A1 US 9705617 W US9705617 W US 9705617W WO 9738049 A1 WO9738049 A1 WO 9738049A1
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WO
WIPO (PCT)
Prior art keywords
copolymer
ester monomer
weight percent
ethylenically unsaturated
olefin
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/US1997/005617
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English (en)
Inventor
Hugh Joseph O'donnell
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Procter and Gamble Co
Original Assignee
Procter and Gamble Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Procter and Gamble Co filed Critical Procter and Gamble Co
Priority to EP97920130A priority Critical patent/EP0891392A1/fr
Priority to JP53634997A priority patent/JP3379068B2/ja
Priority to BR9708527A priority patent/BR9708527A/pt
Publication of WO1997038049A1 publication Critical patent/WO1997038049A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing atoms other than carbon or hydrogen
    • C08L23/0853—Ethene vinyl acetate copolymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms
    • C08L23/0815—Copolymers of ethene with unsaturated hydrocarbons only containing four or more carbon atoms with aliphatic 1-olefins containing one carbon-to-carbon double bond

Definitions

  • the present invention relates to blends of copolymers of olefins/and ethylenically unsaturated carboxylic ester monomers having improved environmental stress cracking or environmental fatigue resistance, to methods of making such blends, to products made therefrom, and to methods of molding such products.
  • Stress cracking or environmental stress cracking is the brittle failure of plastic parts when simultaneously subjected to mechanical stress and chemical exposure.
  • Environmental fatigue is the failure or cracking or a part when simultaneously subjected to dynamic mechanical stress and chemical exposure. Insufficient environmental stress cracking or environmental fatigue resistance leads to greatly shortened service life of a part.
  • Ethylene/vinyl acetate copolymers are commonly injection molded into products utilized in applications requiring good environmental stress cracking or environmental fatigue resistance.
  • An ethylene/vinyl acetate copolymer with good environmental stress cracking or environmental fatigue resistance is obtained by selecting a high molecular weight viscous resin especially a resin with a narrow molecular weight distribution.
  • a viscous resin cannot be molded into a product.
  • the difference between the copolymer monomer contents are less than about 6 weight percent, and the difference between the copolymer melt flow indexes is greater than about 8.
  • the difference between the copolymer ester monomer contents is at least 6 weight percent, and the ratio of the melt flow index of the copolymer having a higher ester monomer content to the melt flow index of the other copolymer, is about 2 or less.
  • a blend composition of a first copolymer and a second copolymer of an olefin and an ethylenically unsaturated carboxylic ester monomer with each copolymer comprising greater than about 10 weight percent of the blend.
  • the difference between the copolymer ester monomer contents is less than about 6 weight percent, and the difference between the copolymer melt flow indexes is greater than about 8.
  • the difference between the copolymer ester monomer content is at least 6 weight percent, and the ratio of the melt flow index of the copolymer having a higher ester monomer content to the melt flow index of the other copolymer, is about 2 or less.
  • Another embodiment provides a method of making a polymer blend by generally contacting together, the first and second copolymers as described above. Even another embodiment provides a product having a body with a flexible portion made ofthe blend of the first and second copolymer as described above.
  • Still another embodiment provides a method of forming a product which includes forming a softened or molten blend of first and second copolymers as described above, forming the molten blend into a desired shape, cooling the formed shape to stabilize the product.
  • FIG. 1 is an illustration of a sprayer bellows 60 of Example 2.
  • FIG. 2 is a side view of lotion pump bellows 30 of Example 2.
  • the blends of the present invention include a first and second copolymer of an a- olefin and an ethylenically unsaturated carboxylic ester monomer. While preferred, it is not necessary that the copolymers have similar monomers.
  • the first copolymer is selected to provide the blend with suitable resistance to cracking, while not deterring its use for molding. Therefore, the first copolymer must have a molecular weight low enough to provide suitable flowability for the type of mold utilized. For example, the molding of fine or thin walled parts requires lower molecular weight than the molding of other parts. However, the molecular weight of the first copolymer must also be high enough to provide the desired resistance to cracking. Generally, the first copolymer utilized in the present invention will generally have a melt flow index in the range of about 0.5 to about 35, preferably from about 1 to about 20, more preferably from about 1.2 to about 15, and most preferably from about 1.5 to about 10.
  • the first copolymer utilized in the present invention will generally have an ester monomer content greater than 6 weight percent, preferably from about 8 to about 40, more preferably from about 10 to about 40, even more preferably from about 12 to about 40, still more preferably from about 20 to about 35,and yet more preferably from about 25 to about 28 weight percent.
  • the second copolymer utilized in the present invention is selected to provide flowability to the blend, and will generally have a lower molecular weight then the first copolymer.
  • the second copolymer will generally have a melt flow index in the range of about 3 to about 50. preferably from about 5 to about 40, and most preferably from about 7 to about 35 weight percent.
  • the second copolymer utilized in the present invention will generally have an ester monomer content greater than about 6, preferably from about 8 to about 22, more preferably from about 10 to about 22, even more preferably from about 12 to about 22, still more preferably from about 15 to about 22, and yet more preferably from about 15 to about 19 weight percent.
  • the first and second copolymers are generally selected to provide a blend having a desired resistance to environmental stress cracking and environmental fatigue. As these properties will vary depending upon the particular chemical environment, the selection ofthe copolymers must be tailored to each environment.
  • the copolymers can be selected by one of two general embodiments, depending upon whether the comonomer contents of the two copolymers is similar or dissimilar.
  • copolymer contents are considered similar if the arithmetic difference (i.e., upon subtraction) in their weight percent ester comonomer contents is generally less than about 6, preferably less than about 4, and most preferably less than about 3 weight percent.
  • the first and second copolymers are chosen such that their melt flow indexes are different.
  • the arithmetic difference between the melt flow indexes of the two copolymers is greater than about 8, more preferably greater than about 15, and most preferably greater than about 20.
  • the second embodiment consists of choosing two copolymers such that the numerical difference (i.e. upon substraction) between their weight percent comonomer contents is at least 6, more preferably at least about 8, and most preferably at least about 9 weight percent.
  • the copolymers utilized with this method comprise in the range of about 5 to about 40, more prefrably from about 9 to about 35, and most preferably from about 15 to about 28 weight percent monomer.
  • the resins are chosen so that the ratio of the melt flow index of the copolymer with the higher ester monomer content to the melt flow index of the copolymer with the low ester monomer content is about 2 or less, more preferably about 1.5 or less, and most preferably less than about 1.
  • the a-olefin utilized in the copolymers of the present invention generally comprises at least 2 carbon atoms, preferably from about 2 to about 8, more preferably from about 2 to about 4, and most preferably from about 2 to about 3 carbon atoms.
  • suitable a-olefins include ethylene, propylene, butylene, most preferably ethylene.
  • the ethylenically unsaturated carboxylic ester monomers utilized in the copolymers of the present invention are selected from the group of vinyl esters of saturated carboxylic acids and alkyl esters of an a,b-ethylenically unsaturated carboxylic acids. Suitable examples include methyl acrylate, ethyl acrylate, butyl acrylate. isobutyl acrylate, methyl methacrylate, diethyl maleate, dimethyl fumarate, vinyl acetate, vinyl propionate and the like.
  • the copolymer contains at least one of the following ester monomers: methyl acrylate, ethyl acrylate and vinyl acetate. Most preferably, the copolymer ethylene vinyl acetate.
  • the blends of the present invention can include any suitable amount of first and second copolymer which provide the desired properties.
  • the first and second copolymers will each comprise greater than about 10 weight percent of the blend, preferably in the range of greater than about 10 to less than about 90, more preferably from about 12 to about 88, even more preferably from about 15 to about 85, still more preferably from about 20 to about 80, and still even more preferably in the range of about 30 to 70 weight percent ofthe blend.
  • the blends of the present invention can be obtained utilizing any suitable blending method and apparatus, for example, Banbury mixers, steam heated two roll mill mixers, screw type extruders, and the like. Any conventional method which provides a homogeneous mixture can be employed.
  • the selected polymers can be fluxed along with any desired additives in a Banbury mixer for a four or five minute cycle and then to work the material on a two-roll mill before transferring it into the rolls of a calender mill. It is also possible to have the mixing accomplished in a mixing extruder prior to forming the composition.
  • the blends can also be formed in one or more reactors in situ.
  • the blends of the present invention will find utility in the making of products subject to static or cyclic loading conditions in a harsh chemical environment, for example, bellows, diaphragms, and boots.
  • Such products have a flexible, resilient, spring -like portion, which can be subject to static or cyclic loading.
  • a spring-like portion may comprise one or more folds, pleats or the like, to form an accordion-shaped section which functions as a spring, for example as with a bellows.
  • Products can be made from the blends of the present invention utilizing any suitable method, including for example, a broad range of polymer fabrication processes such as, injection molding, stamp molding, extrusion, pultrusion, pressing, blow molding, and the like.
  • the blends of the present invention are heated above the melting point, formed into a desired shape, and cooled to stabilize the blend into the • desired shape.
  • Methods of copolymerizing an olefin and an ethylenically unsaturated carboxylic ester monomer are well known, and any suitable method may be utilized.
  • the typical method utilizes a high pressure free radical reaction where ethylene and liquid comonomer are admixed in the presence of catalyst to create copolymer.
  • Such reaction may be conducted in a stirred tank reactor as described in U.S. Patent No. 2,220,429, or conducted in a continuous tubular reactor as described in U.S. Patent No. 3,988,509, both herein inco ⁇ orated by reference.
  • antioxidants there may be utilized, as desired and/or necessary, antioxidants, antiblock agents, slip agents, cross linking agents, stabilizers, ultraviolet ray absorbers, lubricants, foaming agents, antistatic agents, organic and inorganic flame retardants, plasticizers, dyes, pigments, talc, calcium carbonate, carbon black, mica, glass fibers, carbon fibers, aramid resin, asbestos, as well as other fillers as are known in the art.
  • the blends of the present invention may be further blended with or inco ⁇ orated into one or more thermoplastics.
  • the first and second copolymers can first be blended and then blended with the one or more thermoplastics, or the one or more thermoplastics can be included during the blending of the first and second copolymers.
  • Suitable thermoplastics include polyolefins, especially polyethylenes and polypropylenes, polyesters, polyacrylamides, polyamides, polycarbonates, polyurethanes, polyacrylonitriles, and butadiene styrenes.
  • Preferred polyethylenes include linear low density polyethylenes.
  • Blends of commercially available resins were prepared as follows. Desired portions of resins were dry blended to obtain a dispersion. Dry blending was performed in a Kelly Duplex mixer sold by Duplex Mill & Manufacturing Company, Springfield OH 45501. The resin was blended for 10 to 20 minutes. Next, the dry blended resins were feed to the hopper of an extruder for melt blending. The extrusion was performed in a 30 mm Werner Pfleiderer ZSK-30 corotating twin screw extruder, made in Austria, configured with one kneading section. The temperatures in the feeding zone were approximately 130°C, and the temperatures in the plasticizing and mixing zones of the barrel were approximately 170°C, with melt temperature measured at the die at about 175°C. Sccrew speed was about 250 ⁇ m, and the throughput was between 20 and 50 pounds per hour. A two hole die plate which created dual strands of molten plastic was utilized. Strands were quenched in 50 to 70°F water and pelletized.
  • Ethylene vinyl acetate resins used in the blends were either Ultrathene (UE) obtained from Quantum Chemical Co., Cincinnati OH or Elvax (EL) obtained from E.I. DuPont, Wilmingtion DE. Blends made from resins with a range of vinyl acetate contents between 9 and 28 percent and MFI between 1.8 and 43 were evaluated. The estimated VA, MFI, and MFI ratio are listed in the last three columns of Table 1.
  • Method A The bellows 60 illustrated in Figure 1 (sprayer bellows) was made in a hand-mold lacking temperature control or cooling circuits. Because of manual handling, the cooling time of the part and residence time in the injection molder were variable.
  • the injection molder used for manufacture of this style bellow was an Arburg Allrounder 220-75-250, made in Germany. The melt temperature measured in these runs was between 195 and 225°C. An injection time between 0.2 and 0.6 seconds was used to fill the part. A pressure of about 12,000 psi was used to pack the part and this pressure was held for about 2 seconds. Bellows were removed from the core side of the mold by inflating the bellows with an air pressure of about 25 psi while simultaneously pulling the bellow off the core.
  • Method B The bellows 30 illustrated in Figure 2 (lotion pump bellows) were made in an automatic unit cavity mold.
  • the injection molding machine was a Engel 200 ton tie-barless machine, model EC88, made in Canada. Manufacturing conditions are specified in Table 2-B, and are similar to the conditions used to manufacture the bellows described in Method A. Producing a bellow in the automatic mold with the Engel injection molding machine allowed for a more uniform and reproducible operation, in particular control of time, pressure, and temperature.
  • Blend 5 of Table 1 was compared to a ternary blend of Material C and D from Table 2-A and a linear low density polyethylene, GA564, sold by Quantum Chemical Company. These three materials were blended as described in Example 1 in ratios of 55:37:8 percent. The ratio of Material C to D was equal to that of Blend 5. These materials were molded into bellows as described in Method A of Example 2 and tested for ESCR in the mariner described in Example 5.
  • the chemical environment for these tests consisted of cleaning solutions sold commercially as Comet Pine Bathroom Cleaner, Comet Mildew Stain Remover, and Spic and Span Cinch Glass & Surface Cleaner (Cinch) by Procter & Gamble Co.
  • the Comet Pine is an acidic aqueous solution of pH 4, in part, containing dipropylene glycol butyl ether, citric acid and perfume.
  • the Comet Mildew Stain Remover is an aqueous cleaning solution of pH 13, in part containing sodium hypochlorite or bleach.
  • the Cinch is an alkaline aqueous cleaning solution of pH 11, in part, containing isopropanol and perfumes.
  • Example 2 Materials listed in Table 2 -A individually or in blends prepared as described in Example 1 were made into bellows as described in Method B of Example 2. The environmental fatigue of these materials was tested as described in Example 3 with the exception that the stroke length was 14". These materials cover a vinyl acetate range from 18 (low) to 28% (high). Blends were prepared by mixing low and high vinyl acetate containing resins. These materials were tested in Pantene Shampoo as sold in Japan. This shampoo was found to be representative of other shampoos in terms of the aggressiveness of the formula as a stress cracking agent. The bellows were tested within a four week period of manufacture. The results are shown in Figure 3. The ordinate measures the degree of failure on a scale from 1 to 6.
  • a minor amount of cracking (less than 15 small cracks) is indicated by a crack index of 2.
  • the other crack indices are repressed by the following conditions: 1- no cracking; 3 - more than 15 small cracks without any deep cracks; 4 - deep cracks potentially leading to a hole; 5 - one or more isolated holes; 6 - coalescence of two or more holes typically forming a slit.
  • the absisca measures the amount of either Material B or Material C in the blend (i.e. the low vinyl acetate resin): the remainder of the blend being composed of Materials D, E, or F (containing a high amount of vinyl acetate) as indicated in the key of Figure 3.
  • the MFI for each material is also shown in the key of Figure 3.
  • the MFI for the five blends of Figure 3 at a 60% composition are shown in Table 6-A. Resistance to cracking increases with either a decrease in MFI or a decrease in MFI ratio.
  • Example 6 The blends of Example 6 were tested for environmental fatigue resistance in a commercial cleaning product, Comet Pine Cleaner made by the Procter & Gamble Co. This product was described in Example 5. The environmental fatigue resistance was graded on a scale from 1 to 6 as described in Example 6. This scale shown on the ordinate and absisca of Figure 4 are as described in Example 6. The MFI for each material is also shown in the key of Figure 4.
  • the MFI for the five blends presented in Figure 4 at a 60% composition are shown in Table 7-A.
  • the resistance to cracking increases with either a decrease in MFI or a decrease in MFI ratio.
  • Table 7-A MFI for Blends in Figure 4 Having a 60% Composition.
  • Example 6 The blends prepared in Example 6 were tested for environmental fatigue resistance in a commercial cleaning product, Tide made by the Procter & Gamble Co. This product was, in part, comprised of anionic and nonionic surfactants, enzymes, and fragrances.
  • the environmental fatigue resistance was graded on a scale from 1 to 6 as described in Example 6. This scale shown on the ordinate and absisca of Figure 5 are as described in Example 6.
  • the MFI for each material is also shown in the key of Figure 5.
  • the MFI for the five blends of Figure 5 at a 60% composition are shown in Table 8-A.
  • the resistance to cracking increases with either a decrease in MFI or a decrease in MFI ratio.
  • Blend 1 and 5 were molded into bellows as described in Method A of Example 2. These materials are 5:95 and 40:60 ratios of Materials D and C, respectively. Material C was also molded into bellows as described in Method A of Example 2. The environmental fatigue resistance of these three bellows was tested as described in Example 3. The results for testing in Comet Bathroom Cleaner are shown in Table 9.
  • Comet Bathroom Cleaner has a pH of 3, and is partially composed of dipropylene glycol butyl ether, citric acid, and perfume.
  • Blends 6 and 7, containing 85% of either Material E or Material F, were molded into bellows as described in Method B of Example 2. Materials E and F were also molded into bellows as described in Method B of Example 2. The environmental fatigue resistance of these four bellows was tested as described in Example 3, with results shown in Table 10.
  • Blend 7 1.5 1 1.0
  • Blend 3 1.0 1.0 1.5
  • Blend 3 which conforms to the preferred embodiment, has superior environmental fatigue.
  • Blend 2 contains 20% vinyl acetate and has a MFI of 29. This blend is compared to Material C of Table 2-A which has similar properties. These resins were made into bellows by Method B of Example 2, and were tested for environmental fatigue as by Example 3.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Vibration Dampers (AREA)

Abstract

Cette invention concerne un mélange et un article flexible se composant de deux copolymères d'un oléfine et d'un monomère d'ester carboxylique non saturé en éthylène. Ces copolymères sont choisis de manière à ce que chacun d'entre eux comprenne plus de 6 % en poids d'un monomère d'ester carboxylique non saturé en éthylène ou, encore, de manière à ce qu'ils représentent plus de 10 % en poids du mélange. Dans le cas où ils possèdent des contenus en ester similaires ou, plus préciséement, qui diffèrent de moins de 6 % en poids, les copolymères sont choisis de manière à ce qu'ils présentent une différence, entre leurs flux à l'état fondu, qui soit supérieure à 8 environ. Dans le cas où ils possèdent des contenus en ester non similaires ou, plus précisément, qui diffèrent de plus de 6 % en poids, ces copolymères sont choisis de manière à ce que le rapport entre leurs flux à l'état fondu soit inférieur ou égal à 2 environ.
PCT/US1997/005617 1996-04-04 1997-04-03 Melanges et procedes de melange de copolymeres olefine/ester qui possedent une plus grande resistance aux contraintes de fissuration et a la fatigue en exterieur, articles faits de ces polymers et procedes de moulage de ces articles Ceased WO1997038049A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
EP97920130A EP0891392A1 (fr) 1996-04-04 1997-04-03 Melanges et procedes de melange de copolymeres olefine/ester qui possedent une plus grande resistance aux contraintes de fissuration et a la fatigue en exterieur, articles faits de ces polymers et procedes de moulage de ces articles
JP53634997A JP3379068B2 (ja) 1996-04-04 1997-04-03 改善された環境応力亀裂または環境疲労耐性を有するオレフィン／エステルコポリマーブレンド、ブレンド方法、これから製造される製造物および前記製造物の成形方法
BR9708527A BR9708527A (pt) 1996-04-04 1997-04-03 Homogeneizações e métodos de homogeneizar copolímeros de olefina/éster tendo resistência aperfeiçoada contra craqueamento

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US1462296P 1996-04-04 1996-04-04
US60/014,622 1996-04-04

Publications (1)

Publication Number Publication Date
WO1997038049A1 true WO1997038049A1 (fr) 1997-10-16

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PCT/US1997/005617 Ceased WO1997038049A1 (fr) 1996-04-04 1997-04-03 Melanges et procedes de melange de copolymeres olefine/ester qui possedent une plus grande resistance aux contraintes de fissuration et a la fatigue en exterieur, articles faits de ces polymers et procedes de moulage de ces articles

Country Status (7)

Country Link
EP (1) EP0891392A1 (fr)
JP (1) JP3379068B2 (fr)
CN (1) CN1220681A (fr)
BR (1) BR9708527A (fr)
CA (1) CA2250910A1 (fr)
TW (1) TW440587B (fr)
WO (1) WO1997038049A1 (fr)

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3744214A1 (de) * 1987-12-24 1989-07-06 Ruhrchemie Ag Ethylen-vinylacetat-zusammensetzung
EP0424724A2 (fr) * 1989-10-10 1991-05-02 Viskase Corporation Film thermoplastique contenant des résines à indice de fusion élevé
WO1995026377A1 (fr) * 1994-03-29 1995-10-05 Norton Performance Plastics Corporation Melanges d'acrylates et stratifies obtenus avec ces melanges d'acrylates

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3744214A1 (de) * 1987-12-24 1989-07-06 Ruhrchemie Ag Ethylen-vinylacetat-zusammensetzung
EP0424724A2 (fr) * 1989-10-10 1991-05-02 Viskase Corporation Film thermoplastique contenant des résines à indice de fusion élevé
WO1995026377A1 (fr) * 1994-03-29 1995-10-05 Norton Performance Plastics Corporation Melanges d'acrylates et stratifies obtenus avec ces melanges d'acrylates

Also Published As

Publication number Publication date
JP2000507637A (ja) 2000-06-20
TW440587B (en) 2001-06-16
BR9708527A (pt) 1999-08-03
EP0891392A1 (fr) 1999-01-20
JP3379068B2 (ja) 2003-02-17
CA2250910A1 (fr) 1997-10-16
CN1220681A (zh) 1999-06-23

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