Connect public, paid and private patent data with Google Patents Public Datasets

Polyethelene films exhibiting low blocking force

Info

Publication number
CA2120729A1
CA2120729A1 CA 2120729 CA2120729A CA2120729A1 CA 2120729 A1 CA2120729 A1 CA 2120729A1 CA 2120729 CA2120729 CA 2120729 CA 2120729 A CA2120729 A CA 2120729A CA 2120729 A1 CA2120729 A1 CA 2120729A1
Authority
CA
Grant status
Application
Patent type
Prior art keywords
interpolymer
film
resin
weight
product
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.)
Abandoned
Application number
CA 2120729
Other languages
French (fr)
Inventor
Lonnie G. Hazlitt
Pak-Wing S. Chum
Seema V. Karande
John E. Lastovica, Iii
Ian M. Munro
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.)
Dow Chemical Co
Original Assignee
Lonnie G. Hazlitt
Pak-Wing S. Chum
Seema V. Karande
John E. Lastovica, Iii
Ian M. Munro
The Dow Chemical Company
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
Family has litigation

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18Manufacture of films or sheets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08FMACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/06Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type
    • C08F297/08Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the coordination type polymerising mono-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G
    • C08J2323/00Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04Homopolymers or copolymers of ethene
    • C08J2323/08Copolymers of ethene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00Polymer mixtures characterised by other features
    • C08L2205/02Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/13Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1334Nonself-supporting tubular film or bag [e.g., pouch, envelope, packet, etc.]
    • Y10T428/1345Single layer [continuous layer]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/31504Composite [nonstructural laminate]
    • Y10T428/31855Of addition polymer from unsaturated monomers
    • Y10T428/31909Next to second addition polymer from unsaturated monomers
    • Y10T428/31913Monoolefin polymer

Abstract

2120729 9307210 PCTABS00021 Film having good blocking properties and low coefficient of friction is prepared without the presence of antiblock additives from certain thermoplastic ethylene interpolymer products. The thermoplastic ethylene interpolymer products have a density of about 0.935 g/ml or less, a melt flow ratio, I10/I2, of at least about 8, and at least about 0.5 percent by weight of the interpolymer product has a weight average molecular weight of at least about 1,000,000 grams/mole. The interpolymer products are a blend or composite of ethylene polymers or copolymers and comprise at least a first interpolymer of ethylene with at least one alpha-olefin monomer. Preferably, the interpolymer products have a melt index, I2, of from 0.1 to 4 grams/10 minutes. The interpolymer products can be made using discrete polymer blends, or preferably, in a multiple reactor sequence. Blown film made from the interpolymer products is especially useful in grocery sack applications.

Description

~ 3/072l0 212~2~ PCT~US92/0853~

_ 1 , Polyethylene Films Exhibiting Low 8lockin~ Force Films made from broad molecular weight distribution ethylene/alpha-olefin interpolymers are disclosed. The films exhibit low blocking force and low coefficient of friction and are especially useful in making grocery sacks.

Films fabricated from linear low density polyethylene (LL~PE) typically have higher coefficients o~ frî tion (COF) and exhibit higher blocking force than many resin converters and consumers find acceptable.
Blocking force ti.e., unwanted adhesion3 is usually measured according to ASTM D 3354, where the film-to-film adhesion is.expressed a5 grams of blocking load which causes two layers of film ~o separate. Resin converters al~o often require low COF for their fa~rication processes 9 while consumers desire products exhibiting low block because the sacks, bags, etc. are easier to open. The blocking property of film is generally considered to be unsatisfactory when the blocking force is about 20 grams or more. Resin manufacturers can incorporate additives into their LLDPE
polymers to decrease the COF and the block, but this increases their production costs and the additives can adversely affect mechanical film properties such as .
..

tensile strength, dart impact, tear, etc. of the film. In addition, the additives can exude to the surface of the film (a phenomena referred to as "bloom"~
and thereby cause more pr~blems, such as odor and poor adhesion to inks used to print on the surface of the finished product.
In an attempt to improve the physical properties of the film, some converters are making film from high density polyethylene, which, when converted into film, achieves good blocking force w~thout the use of additives, ~ereby retaining more of the other physical properties. For example, it was reported in Plastics Engineering (August, 1991) that high rnolecular weight high density polyethylene ~HMW-HDPE) is expected to displace LLDPE in trash bag and liner applica~ons, due to the ability of the HMW-HDPE to be made at thinner gauges, while maintaining high film s~ength and good blocking force, without having to use additives. ~ilms~
made from HDPE, howe~er, have other problems ~ssociated with them, including poor dart impact strength, high splittiness, higher film stiffness and di~ficult heat sealing.
USP 4,438,238 (Fukushima et al.) describes èthylene/a-olefin copolymer compositions having a density of 0.910 to 0.940 g/cm3, a melt index of 0.02 to 50 g!10 min. and a melt flow ratio (I2~ of 35~to 250.
The copolymer compositions comprise an ethylene/o~-olefin copolymer A
having a density of O.B95 to 0.935 g/cm3 and an ethylene/a-olefin copolymer B having a density of 0.910 to 0.955 g/cm3. The copolymer composi~ons are said to be useful in making extrusion processed materials such as injection molded materials and film. Film made from the copolymer compositions is said to have superior processability, excellent mechanical strength, transparency and heat seal characteristics. However, Fukushima et al. also state ~at additives such as oxidation inhibitors and an'tiblocking agents can be added to the copolymer compositions.
WO 89/10944 discloses specific linear low density polyethylene. The polyethylene can be used to make films, especially heat SU~3STITUTE SHEET

212072~

-2a-sealable films. WO 89/10944 also compares their novel polyethylene with conventional polyethylene, and in example 3, table VI, compares film made from the improved polyethylene (K) versus conventional polyet~ylene (F). The haze values for sample K is reported as 4.2 percent 5 and for conventional sample F as 7.7 percent. The low percentage haze values reveal that the films made in WO 89/10944 have high blocking properties, since haze correlates with surface features of the film.
Although WO 89/10944 does not discuss blocking property of their films, the 45 degree gloss, haze and clarity data reported therein reveals that such 10 filrns will need antiblock additives in order to achieve satisfactory results in making antiblock film.
In spite of the potential drawbacks of making film from LLDPE, comrnercial producers have introduced additives into their LLDPE
resins in order to reduce bloclc and the COF in films of LLDPE. For 15 instance, silicon dioxide, SiO2, is used as an "antiblock" agent to reduce blocking ~orce and erucamide as a "slip" agent to reduce COF. This is a standard practice in the industry, although various other compounds, blends, etc., may also be used.
The current invention avoids all of the problems associated 20 with the introduction of addi~ives , ~ S~ S~

- -93/07210 2 1 2 0 7 2 9 PCT/~S92/08S3~

into LLDPE, including the additional cost for the additive itself and the necessary equipment to put it into the resin.

A new film and method of making the film has now been discovered. The film has a low blocking force and low COF and doesn't require any additives to achieve such desirable properties. The new films are prepared from a thermoplastic ethylene interpolymer product 0 having:
a) a meltflowratio,I10/I2,of at least abou~ 8, b) a density of about 0.935 g/ml or less, and c3 at least about ~.5 percent by weight of the interpolymer having a weight average molecular weight of 5 at least about 1~000,000 gramsJmole.
The interpolymer product is a composite or blend of ethylene interpolymers, ~ypically copolymers or terpolymers o~ ethylene and one or more alpha-olefin monomers having 3 to 13 carbon atoms.

2~ In another aspect, the invantion is a method of preparing interpolymer product pellets having a melt flow ratio, I1o/I29 of at least about 89 a density of about 0.935 grams/milliliter or less, and at least about 0 5 percent by weight of the interpolymer product pellets having a weight average molecular weight of at least about 1,000,000 grams/mole for use in making a ~ilm having a blocking force o~ about 30 grams or less without adding antiblock agents~ comprising the steps 0 of:
a) polymerizing ethylene in a~ least one high molecular weight zone of a reactor at temperatures and pressures sufficient to produce a first polymer, (b)interpolymerizing ethylene and at least a first alpha-olefin in at least one other zone of a WO93/07210 P~T/US92~08~3 reactor at temperatures and pressures sufficient to produce a first interpolymer having a lower molecular weight than the first polymer, (c)combining from 0.5 percent and up to 50 percent of ~a) with the first interpolymer of (b) to form an interpolymer product, (d)extruding the interpolymer product into pellets.
OThe interpolymer product pellets are subsequently extruded into ~ilm. Preferably, the pellets are extruded into a blown or cast film.
Surprisingly~ in addition to the desirable COF
and low blocking force properties, the new interpolymer products alqo process more easily on current commerciàl film fabrication equipment and the film made from the interpolymer products is print~ble.

Blown film made from the interpolymer product is especially useful in grocery sack applications.

Figure 1 schematically represents a polymerization flow chart for making interpolymer 2~ products of the present invention.
Figure 2 is a micrograph of film made from Example 3 at 500X magnification.
Figure 3 is a micrograph of film made from Fxample 8 at 500X magnification~
3OFigure 4 is a micrograph of film made from Resin A (a comparative example) at 500X magnification.
Figure 5 is a micrograph of film made from Resin B (a comparative example) at 500X magnification.

``93/07210 212~729 PCr/~S92/0853~

Figure 6 is a micrograph of film made from Resin C containing SiO2 (a comparative example~ at 500X
magnification.
Figure 7 graphically depicts the relationship between film blocking force and cumulative percent of the interpolymer product having a weight a~erage molecular weight greater than about 1,000,000. Figure 7 is based on data from Examples 1-11 and comparative Resins A, B, and C set forth below.

The thermoplastic interpolymer products for use in this invention preferably comprise at least ~ first interpolymer of ethylene and at least one alpha-olefin.
The alpha-olefin is a C3-C18 alpha-olefin, particularly a C3-C8 alpha-olefin, and especially C8.
The interpolymer product can further comprise a second interpolymer of ethylene and at least one C3-C1~
alpha-olefin. The fiPst interpolymer can have the same density as the second interpolymer, but preferably has a density high~r than that of the second interpolymer~
The first interpolymer can comprise from 4 to 25 percent by weight of the interpolymer product and the second interpolymer can comprise from 75 to 96 percent by weight of the interpolymer product.
The interpolymer products are preferably produced in a polymerization process u~ing a multiple zone reactor in which at least one higher molecular weight ethylene interpolymer is produced in one zone of the reactor. The higher molecular weight zone of the reactor process produces up to about 50 weight percent of the total interpolymer, preferably from 4 weight percent to 25 weight percent, and at least one other 7one produces the remaining fraction of the total WO93/07210 2 12 0 7 2 ~ PCT/US92/0853~ ;

interpolymer product at a lower molecular weight sufficient to obtain the desired I2 and/or I10/I2.
The weight average molecular weight (Mw) of the fraction of total interpolymer produced in the higher molecular weight zone is greater than about 300,000 grams/mole, preferably greater than about 400,000 grams/mole.
Alternatively, the interpolymer products are produced ~y blendin~ at least two ethylene interpolymers to produce a polymer blend conforming to the above specifications.
There are several ways to manufacture the ~hermoplastic ethylene interpolymer products for use in this invention. U.S. Patent 4,076,698, incorporated herein by reference, involves coordination catalysts of the "Ziegler" type or "Phillips" type and includes variations of the Ziegler type, such as the Natta type.
These catalysts may be used at very high pressures, but may also (and generally are) used at very low or intermediate pressures. The products made by these : coordination catalysts are generally known as "linear"
polymers because of the substantial a~sence of branched chains of polymerized monomer units pendant from the main polymer "backbone." It is these linear polymers to which the present invention primarily pertains~ Linear low density polyethylene (LLDPE) and ultra low d~nsity polyethylene (ULDPE) typically have a density between 0~88 grams~milliliter (g/ml) and 0.94 g~ml. The density of the polyethylene is lowered by copolymerizing ethylene with minor amounts of an alpha, beta-ethylenically unsaturated alkene(s) having from 3 to 18 carbons per alkene molecule (e.g., l-propene, l-butene, l-pentene, 4-methyl-l-pentene, l-hexene, l-octene, l,9-decadiene and 1,7-octadiene), preferably 4 to 8 carbon ~93/07210 21~ PCT/US92/Ot53 atoms (e.g., l-butene, l-hexene and l-octene) and most preferably 8 carbons per alkene molecule (i~e., l-octene). The amount of the alkene comonomer is generally sufficient to cause the density of the linear low density polymer to be substantially in the same density range as low density polye~hylene (LDPE), due to the alkyl side chains on the polymer molecule, yet the polymer remains in the "linear" classification; they are conveniently referred to as "linear low density polyethylene~"
The use ~f coordination-type catalysts for copolymerizing ethylene with higher alkenes to make LI,DPE and ULDPE copolymers having densities between 0.88 g/ml and 0.94 g/ml is disclosed variously in, e.g., U.S.
2,699,457; U.S. 2,846,425; U.S. 2,862,917; U.S.
2,905,645; U.S. 3,058,963; U.S. 4,076,698; and ~.S.
4,668,752, incorporated herein by reference. The density of the interpolymer products used in making the films described herein is about 0.93S g/ml or less, preferably from 0.9~ g/ml to 0.935 g/ml, and especially from 0.925 g/ml to 0.935 g/ml.
The molecular weight of the LLDPE useful in the present invention is indicated and measured by melt index according to ASTM D-1238, Condition (E) (i.e., 190C/2.16 kilograms); also known as I2. The I2 of the thermoplastic ethylene interpolymer products used in the film is preferably from 0.1 gramstlO minutes to 4 grams/10 minutes, especially from 0.1 grams/10 minutes to,2 grams/10 minutes and particularly from 0.1 grams/10 minutes to 0.5~ grams/10 minutes. Generally, the melt index of the interpolymer product is dictated by the type of film to be made. An extrusion coating process, for example, can use an interpolymer product having a melt index of about 10 grams/10 minutes, while a blown WO93/07210 2 12 0 7 ~ 9 PCT/US92/0853~

film process usually utilizes an interpolymer product having a melt index of aboùt 0.5 grams/10 minutes.
The molecular weight distribution is indicated and measured by I10/I2 according to ASTM D-1238, Conditions (N) (190C/10 kilograms) and (E), respectively. The melt flow ratio, I10/I2~ of the thermoplastic interpolymer product useful in making the films is at least about 8, and preferably from 8 to 30.
Molecular weight distribution variation can be achieved by many techniques, încluding varying catalytic conditions or reactor conditions.
Similar interpolymers can also be made by blending two or more polymers of the correct density and molecular weight, a method which would certainly be more expensive than producing the desired product directly in a single reactor or in multiple reactor zones. It is important, however, that the interpolymer(s) be well mixed when using disc~ete interpolymer blends. When combining two or more interpolymers to make the interpolymer product for use in making the films of the pre~ent invention, either in discrete blends or in in~
situ polymerization, it is preferable that the higher molecular weight portion of the interpolymer product have a higher denslty than the remaining portion, as long as the final interpolymer product density is about 0.935 g/ml or less.
Alternatively, variations in many commercially active processes including slurry, gas phase, and autoclave processes may be able to produce interpolymers exhibiting low block and low coefficient of friction, provided that these processes are operated in a manner consistenk to make the interpolymers having the properties described herein.

~v~ 93/07210 21 ~ ~ 7 ~ 3 PCr/US92/0853~
_g_ Other processes for making the LLDPE of the present invention can be separated into specific types such as high pressure, gas phase, slurry, solution process, and multiple catalyst systems. Such processing techniques are known to those skilled in the polymer art 5 for making su~h "blends", ineluding USP 4,438,238, which refers to films made from specifie~ blends of two LLDPE
resins.
USP 4,048,412, USP 4,269t948, USP 4,320,088~
and USP 4,814,377 are process patents for high pressure Ziegler catalyst systems. USP 4,336,352, USP 4,414,369, USP 4,692,501, and USP 4,792,588 disclose slurry polymerization processes. USP 3,491,073, and USP

3,969,470 are solution polymerization process patents.
1~ USP 3,914,342 disclo~es another solution polymerization pro~ess whereby the ethylene and the comonomer(s) is polymerized in multiple reactors. USP 4,792,595, USP

4,874,820, USP 4,935,474, USP 4,937,299, and USP
4,939~217 disclo~e the use of multiple catalysts to polymerize ethylene with various commoners. All of the above United States Patents are incorporated herein by reference.
Antioxidants, pigments, hydrophobic and/or hydrophilic agents, etc., can be incorporated into the thermoplastic interpolymer produets of the present invention, to the extent that they do not interfere with the blocking performance of the film. To this extent, othe~ polymers, e.g., LDPE, can also be incorporated in minor amounts into the interpolymer products, as long as the polymers do not detrimentally affect the film forming ability or the blocking performance of the interpolymer product.

WO93/07210 212 0 7 2 9 PCT/US92/08~3~ ~

The interpolymer products of Examples 1-11 were produced in a solution polymerization process using a series, dual-zone (or dual reactor) configuration. A
representative schematic of the process in shown in Figure 1.
The two reactor æones are designated as Zone A
(1) and Zone B (2) in Figure 1. A solvent mixture (3) of saturated C8-Clo hydrocarbons and 1-octene was fed to each zone via separate feed streams (4 and 5). Ethylene (6) and hydrogen (7) were each added to each feed stream independently. The reaction was initiated by injecting catalyst and cocatalyst (8) into both zones.
Ziegler catalyst can be prepared using a number of different methods. (A detailed description of one such method can be found in USP 4,5475475, incorporated herein by reference, including cocatalyst levels and stoichiometries for various metal loadings.) Each zone is agitated.
The polymer density was controlled by the 1-octene flow, the melt index was controlled by the totalhydrogen flow, the ethylene conversion was controlled by the solvent flow, and Zone A is operated at significantly reduced hydrogen concentration to produee higher molecular weight polymer in this zone. Zone A
was equipped with a sampling pot (also not shown) sueh that the contents of the reactor could be removed for further analysis.
~one A was operated at temperatures of from 140C to 190C. Zone B was operated at temperatures of from 170C to 215C.
The interpolymer stream of Zone A was discharged to Zone B for further reaction, where it was combined with fresh ethylene and hydrogen. The total interpolymer product of Zones A and B exited Zone B t9) ~093/07210 2 ~ 2 ~ 7 2 9 PCT/US92/0853 and well mixed, purified and pelletized using conventional equipment (not shown).

Experimental Eleven different thermoplastic ethylene/1-octene interpolymer products of the present inYention were produced using the multiple reactor zone configuration shown in Figure 1. Table 1 describes the physical properties of each of the example interpolymers, and of comparative resins A, B, and C
made using a single reactor zone.

Molecular Weight Distribution Determination Zone A was designed such that samples of interpolymer could be removed for direct analysis.
Approximately 100 grams of the Zone A sample was removed for each of the Examples 1-11 for analysis (except Example 10 which was not collected because of a technical problem). The whole interpolymer samples and zOn2 A samples were analyzed by gel permeation chromatography (GPC) on a W~ters 150C high temperature chromatographic unit equipped with three mixed porosity columns (Polymer Laboratories 103,104, 105, and 106), operating at a syst m temperature of 140C. The solven~
was 1,2,4-trichlorobenzene, from which 0.3 percent by weight solutions of the samples were prepared for injection. The flow rate was 1.0 milliliter/minute and the injection size was 200 microliters.
3 ! The molecular weight determination was deduced by using narrow molecular weight distribution polystyrene standards (from Polymer Laboratories) in conjunction with their elution volumes. The equivalent polyethylene molecular weights were determined by using appropriate Mark-Houwink coefficients for polyethylene W093/07210 2 12 ~ 7 ~ 9 PC~/US92/OX53~ ~

and polystyrene (as described by Williams and Word in Journal of Polymer $cience, Polymer Letters, Vol. 6, (621) 1968, incorporated herein by reference) to derive the equation:

MpOlyethylene = a (Mpolystyrene) In this equation, a - 0.4316 and b = 1Ø
Weight average molecular weight, Mw, is calculated in the usual manner according to the formula:

Mw = R Wi*Mi where wi and Mi and are the weight ~raction and molecular wei~ht respectively of the ith fraction eluting from tlle GPC column.
Table II contains the gel permeation chromatagraphy data ~or the interpolymer products of the present invention and for the comparative resins. The data include weight average molecular weight (Mw), : number average molecular weight (Mn)~ MW/Mn and the amount of the interpolymer product having Mw of at least about 1 x 1 o6 .
The conditions for Zone A described previously are intended to produce very high molecular weight polymer. Table IIA summarizes the molecular weight of the interpolymer Zone A samples. All of the calculated Mw's ~or the Zone A interpolymer samples are in excess of 300,000 grams/mole. Though the whole polymer Mw's for all the example resins were significantly higher than that of Resin B, the example interpolymer products processed more easily on the film fabrication equipment as shown in the Blown Film Fabrication Section, thus . .

7 ~ ~

demonstrating an additional benefit of the present inventicn.

B1QWn Film Fabrication Conditions The improved processing, broad MWD resins produced via 5 the procedure above~ as well as three comparative resins (Resins A, B, and C) were fabricated on an Egan blown film line using the following fabrication conditions:
- 5.08 cm (2 inch3 extruder - 7.62 cm (3 inch) die - 0.762 mm (30 mil~ die gap - 25 RPM extruder speed - 238C (460F) melt temperature - 0.02032 mm (0.8 mil) gauge 2.7:1 Blow up ratio (31.8 cm (12.5 inches) layflat~
- 31.8 cm (12.5 inches) frost line height The melt temperature was kept constant by changing the extruder temperature profile. Prost line height was maintained at 31.8 cm 20 (12.5 inches) by adjusting the air flow. The extruder output rate, back pressure and amps were monitored and a con plete summary of the f~brica~on data is shown in Table III.
Resins A and ~ are conventional sin~sle reactor polymers included herein for comparison. Resin C is similar to resin B, 25 but wi~ SiO2 added as an anti-blocking agent and e~ucamide added as a s~p agent to reduce the coefficient of friction. For comparison, Table X
summarizes data describing blocking force of commercially available resin made into film containing various le~els of SiO2 (an antiblock agent). For ~he .

-interpolymer product examples contained herein, which do not contain antiblock compounds, the blocking force was as low as about 6.5 grams. For comparative commercially available resins, about 7500 ppm of SiO2 must be added to the resin (in film form) to reach a blocking force of about 6 5 grams. A150 for comparison, Table ~a contains data describing kinetic slip of commercially available resin made into film containing various levels of erucamide (a slip agent). For the interpolymer product examples contained herein, which do not contain slip compounds, the kinetic slip was as low as about 0322. For comparative cQmmeraally available resins, 10 about 500 ppm of erucamide must be added to the resin (in film fvrm) to reach a kinetic slip of about 0.33.
Generally, the block of the film consisting essen~ally of the new interpolymer products was about 30 grams or less, preferably about 20 grams or less, and especially about 10 grams or less.
The improved processability of the new interpolymer products is evident by comparing the amps and back pressure of the eleven examples with those of resins A, B, and C.
Other types of film are within the scope of this invention, including cast film and extrusion coating filmr but the bloclc pro~erty of 20 blown film is especially benefited by the invention. Blown film thickness can be from 0.00254 mm ~0.1 mils) to 0.0254 mm (1 mil) or more, but was preferably between 0.01016 mm (0.4 mils~ and 0.02032 mm (0.8 mils). The film of the present invention can also be used as at least one outer layer of a multilayer film structure, in order to take advantage of the good block 25 proper~es of the interpolymer product in the multilayer structure.

SlJ ST~TE SH~

~93/07210 2 1 2 0 7 ~ 9 PCT/~S92/0853~

Film Performance The films above were analyzed for various properties. Blocking force (measured according to ASTM
D 3354, procedure A) and coefficient of friction (COF) (as measured using ASTM D 1894 procedure A or B) were measured for each film sample. Table IV summarizes block and slip film performance results for film made from each interpolymer and from the comparative polymers. The blown film fabricated from the example interpolymers clearly had lower block and lower COF than the comparative polymers. Generally, the kinetic coefficient of friction ranges from 0.2 to 0.45 for film made from the interpolymers of this invention, without ~ additional additives.
Table V summarizes other film physical properties of the interpolymers and the comparative polymers. The complete film performance data show that the example interpolymers had comparable, if not better mechanical performance as compared to the comparative polymers, especially in the machine direction orientation. The data also show that additives used to enhance slip and block can detrimentally affect physical properties of the film (e.g., compare resin B to resin ~; C ) ~ r The in~e~t~s have performed a detailed study of the surface morphologies of the films from the interpolymer film examples described herein using the optical réflectance technique of Nomarski interference contrast. This technique revealed that increased surface roughness was exhibited by those films comprising the present invention. Thus, the invention can also be perceived as a method of increasing surface roughness of at least one layer of a film.

, ~
, ~ ..
: ` ~

WO93/07210 212 0 7 2 9 PC~/US92/0853~ ~

The interpolymer product films of the present invention are useful as liners (e.g., institutional or consumer), merchandise bags, grocery sacks or "T-shirt"
bags.

1~

W093/07210 PCT/US92/08~3 Table I
Resin Specifications . . ~ , . _ _ Weight fraction of I2 the interpolymer Density Example (g/10 I10/I2 product produced (gtml) min.) in Zone A
. .. ..
1 0.59 10.22 13.2 0.925 . ., _ , , ,, .~
2 0.45 16.27 20.5 0.9292 . , . , ~ ___ . , . _ 3 0.38 13.45 20.4 0.9305 . ..- _ _ . ,_ 4 _ 0.60 9.72 13.2 _ 0.924 0.53 13.53 20.3 _ 0.92~4 6 0.41 12.37 20.2 0~9203 l . = . , _ . --7 0.52 9.27 4.68 0.9205 . .' . .. .. ~... ., .

8 0.7~ 8.87 4.76 0.9~04 ~ , , . _ _ ~ . .. , 9 0.60 9.82 13.07 0.9255 ... , ... , ............................ , . _ .
0.63 8.24 4.96 0.9298 _ . : __ _ ~ ~
11 0.82 8.33 4.86 0.9306 . . _ , _, , Resin A 1.05 8.00 N/A 0.9200 , - . .. . . . . ., ~
Resin B 0.66 7 14 N/A 0.9230 Resin C~ 0 61 7 23 N/A 0.9271 N/A = Not applicable *Resin C is similar to Resin B, but with 5000 ppm SiO2 (anti-block) and 500 ppm Erucamide (slip) added.

10 2 ~ 2 ~ ~ 2 9 PCT/US92/0853~ ~

Table II
GPC Mn, Mw and MWD of the Interpolymer Products _ . Weight percent of Example Mw Mn Mw/Mn Interpolymer ~ . ...... M~> 1 x 1Q6 1 160000 379004.22 2.42 _ , . . .~
2 171000 319005.36 3.89 1 0 . ~
_ 3 193000 33800~.71 3.59 4 167000 333005.02~ 2.29 181000 292006.20 3.4 . __~ _ . , -.
6 189000 324005.83 3.27 . . . ,. ,-- _ i 1~ 7 15100Q 34~004.42 1.12 _ ._ _ _ .
: 8 1~1000 33900 4.16 1 D5 , 9 156000 32000 4.88 1.12 _ _ . _ 144000 37200 3.87 0.9 __ ,. _ ._ 11 135000 38200 3.53 0.78 . l _ . . .
Resin A 114000 32100 3.55 0.39 Resin B 130000 39500 3.29 0.11 : _ _ _ C*~129000 38700 3.33 hM
~';
NM = Not measured *~Resin C is similar to Resin B, but with 5000 ppm SiO2 (anti-block) and 500 ppm Erueamide ~slip) added~

3o -~O 93/07210 2 1 2 0 7 2 9 PCI /US~2/0853~
_19_ Table I IA
GPC Mw and MWD of the Zone A Samples l~la~ p 1 e A l1n Zone 11~ /Mn 1 517000 92800 5.57 2 395000 67800 5.83 570000 ~ 96700_ 5.89 4 ~ 13000 106~00 4.84 ~ 15000 127000 4.06 6 724000 108000 6.70 7 676000 108000 6.26 8 633000 126000 5.02 * * *
11 605000 142000 4 ~ 26 Resin A N/A N/A N/A
Resin B N/A NSA N/A
Resi n N /A N /A N /A
N /A = Not p p 1 i cabl * No Zone A fraction collected ~*Resin C is similar to Resin B, but with 5û00ppm SiO2 (anti-block) and 500 ppm Erucamide (slip) added.

3o 212072!3 Table III
Blown Film Fabrication Processin~ Data Example ou~put Rate Press~lre Amps k,~/hr (lbs~hr) MPa (psi) _ ~ . . ~ . .. __ 1 _ l5.4 (34.0) 27.77 (4027) S0 2 1a~.2 (31.3) 21.24 (3080) 41 . ~ . _ 3 13.3 (29.3) 25.79 (3740) 45 . .. . _ _ _ 4 15.4 (33.9) 27.91 (4048) 53 .. _ ..... .
14.7 (32.5~ 2~.89 (3320) 45 ._ . . -~ _ 6 12.~ (27.4) 25.5~ (3706) 50 , ~ . _ _ .
7 ~4` (30.8) - 28.50 (41~4) 55 . _ ,__ _~__ _ _ .
8 14.5 (31.9) 24.65 (3575) - 52 ._ ._ ___ ,.~ ..
9 14.6 (32.2) 27.23 ~3950) 49 -_ ~ ~ . ~
15 (33.1) 30.64 (4444) 54 ~, , .~ _ .~ _ 11 15.2 (33.4) 26.94 (3908) 50 .. _ ~ ,_ _ Resin A 15.7 (34.7) 24.48 (3550) 54 Resin B 15.6 (34.3) 25.1(3640) 55 . _ ... ~ _ Resin C 15.2 (33.5~ 30.06 (4360~ 56 Note: Resin B was fabricated at 71C (520F) Resin C was fabricated at 260C (500F) .
.
.

"'093/07210 2 1 2 0 7 2 9 PCT/US92~0853~

Table IV
Blown Film Block and Slip . . . . . ,_ Fxample Block (g) Slip (COF) Kinetic , . .
1 8.5 0.444 _0.440 2 7.8 0.364 0.388 _ 8.8 0.304 0.322 4 10.8 0.372 0.438 , 10.8 0.470 0.322 __ 6 16.0 0.468 0.366 7 24.3~ 0.540 -0.348 27.0 0.530 ~0.356 . _ _ _ 9 7.5 0.396 0.416 8.8 0.384 0.390 11 6.5 0.398 0.424 -Resin A 46.3 0.707 0.822 Resin B 66.5 0.704 0 600 Resin C* 7.5 0.290 0.324 ~Resin C i s~similar tc ~esin B, bl t with 5000 ppm SiO2 (anti-block) and 500 ppm Erucamide (slip~ added.

3o '' '~'"''''~

:

,. .:' .;

Table V
Blown Film Pro erties . , P ,.......... .. ~.. .
Example MD 2 percent Cl:) 2 percent MD Yield CD Yield Secant Secant Strength Strength Modulus Modulus MPa (psi) MPa (psi) MPa (psi) MPa (psi) .~ . .. __ .. _ .
1 ~05.7 (29833) 214.2 (3106~)13.1 (1899) 13.7 (1981) . _ . . _ _ .. __ 2 249.5 (361g1) 268.3 (38919) 14.1 (2~40) 14.9 (2160) ~ . , _ _, 3 244.4 (35451) 317.1 (45991) 15.1 (2183) 17 (2469) ,. . ... _ i.. __ . .
4 181 (26252) 225.5 (32709)12.2 (1774) 13.2 (19~0) . . . _ . . __ 163.1 (~3661) 171.3 (24~46) 11 (1602) 11.5 (1664) . _. ~ . .
6 166.4 (~4138) 206 (29880) 11.5 (1667) 11.4 (1557 .... . ",.. _.. _. . _ 7171.8 ~24919) 162 (23497) 10.9 ~1574) 11.6 (1683) . . ~ . , , 8 172.8 (25057) 193 (27997) 12.~ (1779) 12.4 (1794) . _ , _ . . ___ 9 190 (27567) 241.3 (34922) 13.~ 94) 14.1 (2046) 219.2 ~317~9) 310.7 (45064)13.7 (1990~ 15.9 (2306) _ .. . _ .
11 269.5 (39090) 342.~ (49656)16.5 (2398~ 17.5 (2541) . _ .. ~
Resin A 152.4 ~22099) 187.9 (27249) 11.1 (1613) 12.1 (1752) .. _ ~ . ~
Resin B 180.6 (26200) 199.2 (28887) 12.9 (1874) 13 (1881) . . . ~ . . . ,___ Resin C 183.8 (26659) 180.4 (26163) 11.8 (1716) 12.4 (1796) Note: Resin B was fabricated at 271C (52ûF~
Resin C was fabricated at 260C ~500F) MD - Machine Direction CD = Cross DLrec~on .

~9 l ,r~ TI 1~ ~ T

212~729 Table VI
Blown Film Pro erties . . ._ . . P .
Example MD Tensile CD Tensile MD CD
Strength Strength Elongation Elongation MPa (psi) MPa (psi) (percent) (percent) . . . ~ . ~_ 1 59.6 (8638) 36.1 (5234) 514 693 _ . , . , , ._ 2 67.6 (9798) 30.3 (4391) 509 749 . _ _ . ... ~
3 79.6 (11551) 42 ~6092) 476 741 . __ _ . . .. _ . ,. _. .
4 60.1 (8716) 37.7 (5465) 543 703 . . . _ . .. _ S 58.9 (8538) 38.9 (5~49) 5g5 823;
. ................... . ~
6 69.9 (10133) 45.3 (6~73~ 520 770 . . . .
7 57.5 (8343) 47.1 (6835) 543 693 .. .
8 51.5 (7467) 36.6 (5306) 547 642 . . - . _ _ . . . .. ___ 9 58.6 (8496) 36.6 (5307) 543 751 . ~ . _~ , ~
10 49.~ (7140) 40.6 (5884) 590 717 .. . . .... I . , 11 48.2 (6995) 39.4 (5711) 597 724 , . . __ ~ .__ . . _ Resin A 42.3 (6139) 46.2 (6698) _ 573 679 _ Resin B 47.2 (6839) 51.8 (7516) 593 7A4 . ~ ~ ..... , . .
Resin C 42.3 (6133) 33.2 (4810) 538_ 631 Note: Resin B was fabricated at 271C (520F) Resin C was fabricated at 260C ~500F) Table VII
Blown Film Properties . .__ ~ . . .h_ _ ~ ~ _ Example MD CD 45 Degree Clari~ Haze Toughness Toughness Gloss Joules Joules (ft-lbs) __(ft-lbs~
2373 (1750)190i(1402) 44.9 10.35 14.44 ._ .~ ~ . , _ _- .
2 3282 (242~)1900 (1401) ~.7 û.25 64.83 . .. __ .. _ , .
3 3001 (2213)2336 (1723) 12.9_ 0.75 _ 51.10 .
4 23~4 (1758)1961 (1446) 32.5 ~2.40 21.85 . , . . , . . .- ._ __ 2614 (1928) 2206 (1~27) 14.2 2.12 46.44 _ j~.,...... . ~
6 2735 (2017) 2275 (1678) 14.3 1.50 4~.80 . . ~ . . ... _ ..
7 1949 (1437)2092 (15~3) 27.4 8.30 25.40 . ~ _ . - - .,. ._ ~ ~
8 1870 (1379)1734 (1279) 43.8 2g.70 16.40 . . . . .
9 228~ (1683)2064 (1522) ~7.5 17.60 25.10 - .... .. . . ... . .. _ , __ . .. ~ . ~_ 1955 (1442)2194 (1618) 4~.5 30.9~ 15.60 ~ _ .. ._ . ~ .. ~
11 2179 (16~7)2199 (1622) 58.3 46.10 10.72 . . . ~ . . .. . . . ...
~esin A 1646 (1214)2065 (1523) 51.7 53.65 . 10.35 . _ , . .. .
Resin B 1958 (144432464 (1817~ 74.4 80.50 4.19 Resin C 1618 (1193)1679 (1238) 67.8 18.67 lO 08 Note: Resin B was fabricated at 271C (520F) Resin C was fabricated at 260C (500F) 2 12072~ `

Table VIII
Blown Film Properties , . _ . ~ .. _ _ Example MD CD MD PPT CD PPr Elmendorf Elmendorf lcg (lbs)kg (lbs) _Tear (g) Tear (g) _ 1 130 458 2.06 (4.55)3.3 (7.28) ~ , . . ,, . . .
2 85 555 _ 2.35 (5.l7)3.36(7.40) 3 51 432 2.08 (4.59)2.97 (6.54) . .. _ ,~ . _ .
4 301 397 2.62 (S~77)3.19 (7.04) . _ . _ _ .
210 453 2.46 (5.43)3.32 (7.31) . _ .. _. . .
6 237 475 2.5 (5.51)3 (6.~3) . . ~ , .
7 264 330 2.51 (5.54)2.8g (638) .. . _ . _ ~ 25~ 37~ 2.42 (5.34)2.78 (6.13) . . . _ ~ , ,.
9 202 402 2.71 ~5.98)3.26 (7.19) ~ _~ . . _ _ .
147 378 7.5~ (5.62) 3.07 (6.77) ,. __-- . . , . ..
11 102 296 2.36 (5.21) 2.93 (6.47) ._ _ . .. _ . ~. ~
Resin A249 2~6 2.31 (5.10) 2.52 (5.5~) . ~ _ - .. . __ ~
Resin B 275 336 2.40 (5.30)2.51 (5.54) - ~. ... __ _ _ .~_ __ Resin C 221 366 2.69 (5.93) 2.88 (6.36?
Note: Resin B was fabricated at 271C (520F) Resin C was fabricated at 260C ~500F) 2 1~ 7 .? 9 -2~

Table IX
Blown Film Properties . _ .__ _ Example Dart Impact Puncture (~rams) ~/cm3 (ft-lbs/cu. in) ~ _ , 1 11~ 17.7 (214) _ . ~ .
2 69 12.8 (155) - . ... .. ..
3 67 13.7 ~166) 4 133 18.5 (223) . . _ ... ~
131 13.2 (160) .. _ . . ~
6 188 17.9 (217) . ._ 7 _ 608 22 (266) _ 8 212 15.3 (185) ..
9 116 17 (205) , .
110 14.7 (178)_ ~ - 11 78 11.9 (144 " . .
Resin A 266 20.2 (244) . . _. . .
Resin B 431 20.5 (248) . ,~
Resin C 191 l0.l (l22?
.
: - ~, Note: Resin B was abricated at 271C (520F
Resin C was fabricated at 260C (500F) Table X
Induced Block v. SiO2 content ..
SiO2 content Induced Bloc~
, ~ (ppm) (grams) _ . . . .~ .
0 ~5 ~ . _ ..

....

-- . ~

. . __ : ~ 7500 6 : .

~"

`~!0 `93/07210 .2~.~.0~.2.'~ PCI/US92/0~53~

Table Xl Kinetic Slip v. Erucamide content ¦ Erucamlde ¦ Kineti~

~ 0.6 . . __ 100 0.55 _ 230 0.47~
, _ _ . .
400 0.39 . .
1 0 500 0.33 . . - . . . .

. ~

3o

Claims (13)

1. A film having a blocking force of about 30 grams or less consisting essentially of a thermoplastic ethylene interpolymer product, characterized in that the interpolymer product has:
a) a melt flow ratio, I10/I2, of at least about 8, b) a density of about 0.935 grams/milliliter or less, and c) at least about 0.5 percent by weight of the interpolymer product having a weight average molecular weight of at least about 1,000,000 grams/mole, said interpolymer product being further characterized as containing no antiblock additives.
2. The film of Claim 1 wherein the interpolymer product has a melt index, I2, of from about 0.1 to about 4 grams/10 minutes.
3. The film of Claim 1 wherein the interpolymer product comprises at least a first interpolymer of ethylene and at least one alpha-olefin.
4. The film of Claim 3 wherein the alpha-olefin is a C3-C18 alpha-olefin.
5. The film of Claim 4 wherein the interpolymer is an interpolymer of ethylene and 1-octene.
6. The film of Claim 5 wherein the interpolymer product further comprises a second interpolymer of ethylene and at least one C3-C18 alpha-olefin.
7. The film of Claim 6 wherein the first interpolymer comprises from 4 to 25 percent by weight of the interpolymer product and the second interpolymer comprises from 75 to 96 percent by weight of the interpolymer product.
8. The film of Claim 87 wherein the first interpolymer has a density higher than the density of the second interpolymer.
9. The film of Claim 1 wherein the film is a blown film.
10. The film of Claim 1 wherein the film is an outer layer of a multilayer film structure.
11. A multilayer film structure having at least one outer layer which has a blocking force of about 30 grams or less, wherein the outer layer comprises a thermoplastic ethylene interpolymer product, characterized in that the interpolymer product has:
a) a melt flow ratio, I10/I2, of at least about 8, b) a density of about 0.935 grams/milliliter or less, and c) at least about 0.5 percent by weight of the interpolymer product having a weight average molecular weight of at least about 1,000,000 grams/mole, said interpolymer product being further characterized as containing no antiblock additives.
12. A method of preparing interpolymer product pellets of a film resin having a melt flow ratio, I10/I2, of at least about 8, a density of about 0.935 grams/milliliter or less, and at least about 0.5 percent by weight of the interpolymer product pellets having a weight average molecular weight of at least about 1,000,000 grams/mole for use in making a film having a blocking force of about 30 grams or less without adding antiblock agents, comprising the steps of:
a) polymerizing ethylene in at least one higher molecular weight zone-of a reactor at temperatures and pressures sufficient to produce a first polymer, (b) interpolymerizing ethylene and at least a first alpha-olefin in at least one other zone of a reactor at temperatures and pressures sufficient to produce a first interpolymer having a lower molecular weight than the first polymer, (c) combining from 0.5 percent and up to 50 percent of (a) with the first interpolymer of (b) to form an interpolymer product, and (d) extruding the interpolymer product into pellets.
13. A sack produced from the film of Claim 1.
CA 2120729 1991-10-07 1992-10-07 Polyethelene films exhibiting low blocking force Abandoned CA2120729A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
US07773375 US5250612A (en) 1991-10-07 1991-10-07 Polyethylene films exhibiting low blocking force
US773,375 1991-10-07

Publications (1)

Publication Number Publication Date
CA2120729A1 true true CA2120729A1 (en) 1993-04-15

Family

ID=25098059

Family Applications (1)

Application Number Title Priority Date Filing Date
CA 2120729 Abandoned CA2120729A1 (en) 1991-10-07 1992-10-07 Polyethelene films exhibiting low blocking force

Country Status (9)

Country Link
US (2) US5250612A (en)
JP (1) JPH07500131A (en)
KR (1) KR100259312B1 (en)
CA (1) CA2120729A1 (en)
DE (2) DE69227637D1 (en)
EP (1) EP0607342B1 (en)
ES (1) ES2123574T3 (en)
FI (1) FI941577A (en)
WO (1) WO1993007210A1 (en)

Families Citing this family (43)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8914703D0 (en) * 1989-06-27 1989-08-16 Dow Europ Sa Bioriented film
US5562958A (en) * 1991-10-15 1996-10-08 The Dow Chemical Company Packaging and wrapping film
US5567772A (en) * 1994-03-07 1996-10-22 E. I. Du Pont De Nemours And Company High flow ionomer resin compositions useful for golf ball covers
JPH07276587A (en) * 1994-04-07 1995-10-24 Mitsui Petrochem Ind Ltd Packaging bag for heavy article
US5514455A (en) * 1994-07-08 1996-05-07 Union Carbide Chemicals & Plastics Technology Corporation Film extruded from an in situ blend of ethylene copolymers
US5503914A (en) * 1994-07-08 1996-04-02 Union Carbide Chemicals & Plastics Technology Corporation Film extruded from an in situ blend of ethylene copolymers
DE69532821T2 (en) 1994-12-20 2005-01-27 Kimberly-Clark Worldwide, Inc., Neenah Films of low thickness and film / nonwoven laminates
KR100389077B1 (en) 1994-12-20 2004-03-22 킴벌리-클라크 월드와이드, 인크. Low gauge films and film / nonwoven laminates
US5965224A (en) * 1995-11-13 1999-10-12 First Brands Corporation Closure bag with internal tack surfaces
US5858515A (en) * 1995-12-29 1999-01-12 Kimberly-Clark Worldwide, Inc. Pattern-unbonded nonwoven web and process for making the same
US5744551A (en) * 1997-03-28 1998-04-28 Union Carbide Chemicals & Plastics Technology Corporation High strength polyethylene film
US6319989B1 (en) 1997-07-21 2001-11-20 The Dow Chemical Company Broad MWD, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom
WO1999003902A1 (en) * 1997-07-21 1999-01-28 The Dow Chemical Company Broad mwd, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom
US6451916B1 (en) 1997-07-21 2002-09-17 The Dow Chemical Company Midland Broad MWD, compositionally uniform ethylene interpolymer compositions, process for making the same and article made therefrom
US6238767B1 (en) 1997-09-15 2001-05-29 Kimberly-Clark Worldwide, Inc. Laminate having improved barrier properties
US6045900A (en) 1997-09-15 2000-04-04 Kimberly-Clark Worldwide, Inc. Breathable filled film laminate
KR20010024063A (en) * 1997-09-19 2001-03-26 그래햄 이. 테일러 Narrow mwd, compositionally optimized ethylene interpolymer composition, process for making the same and article made therefrom
US6492475B1 (en) 1998-06-19 2002-12-10 Japan Polyolefins Co., Ltd. Ethylene/α-olefin copolymer
US6680265B1 (en) 1999-02-22 2004-01-20 Kimberly-Clark Worldwide, Inc. Laminates of elastomeric and non-elastomeric polyolefin blend materials
US6723398B1 (en) * 1999-11-01 2004-04-20 Dow Global Technologies Inc. Polymer blend and fabricated article made from diverse ethylene interpolymers
US20080281063A9 (en) * 1999-12-30 2008-11-13 Sukhadia Ashish M Ethylene polymers and copolymers with high optical opacity and methods of making the same
US6388017B1 (en) 2000-05-24 2002-05-14 Phillips Petroleum Company Process for producing a polymer composition
US20020107343A1 (en) * 2001-02-08 2002-08-08 Mitsui Chemicals, Inc. Ethylene polymer, preparation process thereof and molded articles of the same
US6606986B2 (en) * 2001-06-04 2003-08-19 The Holland Company, Inc. Of The Carolinas Barbeque grill with retractable ventilation system
GB0217522D0 (en) 2002-07-29 2002-09-04 Borealis Tech Oy Product
US6864195B2 (en) * 2002-08-15 2005-03-08 Bfs Diversified Products, Llc Heat weldable roofing membrane
US7736726B2 (en) 2002-12-17 2010-06-15 Cryovac, Inc. Polymeric film with low blocking and high slip properties
US7226880B2 (en) * 2002-12-31 2007-06-05 Kimberly-Clark Worldwide, Inc. Breathable, extensible films made with two-component single resins
US7932196B2 (en) 2003-08-22 2011-04-26 Kimberly-Clark Worldwide, Inc. Microporous stretch thinned film/nonwoven laminates and limited use or disposable product applications
US7119153B2 (en) 2004-01-21 2006-10-10 Jensen Michael D Dual metallocene catalyst for producing film resins with good machine direction (MD) elmendorf tear strength
US7094857B2 (en) * 2004-03-10 2006-08-22 Chevron Phillips Chemical Company, L.P. Ethylene polymers and copolymers with high optical opacity
US7612134B2 (en) * 2005-02-23 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material
US7612135B2 (en) * 2006-02-17 2009-11-03 Callaway Golf Company Golf ball and thermoplastic material
US20060210741A1 (en) * 2005-03-17 2006-09-21 Cryovac, Inc. Retortable packaging film with having seal/product-contact layer containing blend of polyethylenes and skin layer containing propylene-based polymer blended with polyethylene
US20060210742A1 (en) * 2005-03-17 2006-09-21 Cryovac, Inc. Retortable packaging film with outer layers containing blend of propylene-based polymer and homogeneous polymer
US20060210744A1 (en) * 2005-03-17 2006-09-21 Cryovac, Inc. Retortable packaging film with grease-resistance
JP5371436B2 (en) 2005-11-23 2013-12-18 ダウ グローバル テクノロジーズ エルエルシー Heterogeneity was phase-separated by the composition, ethylene α- olefin interpolymer
EP2076565B1 (en) * 2006-10-23 2010-06-02 Dow Global Technologies Inc. Polyethylene compositions, methods of making the same, and articles prepared therefrom
US20110099945A1 (en) * 2009-10-30 2011-05-05 Munchkin, Inc. System and method for disposing waste packages such as diapers
US8739501B2 (en) * 2009-10-30 2014-06-03 Munchkin, Inc. System for disposing waste packages such as diapers
US8833592B2 (en) * 2009-10-30 2014-09-16 Munchkin, Inc. System and method for disposing waste packages such as diapers
US8635838B2 (en) * 2009-10-30 2014-01-28 Munchkin, Inc. System for disposing waste packages such as diapers
US20120055624A1 (en) * 2010-09-02 2012-03-08 Bailey Robert D System and Method for Manufacturing Co-extruded Plastic Film and Products Using Same

Family Cites Families (38)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2770608A (en) * 1954-10-12 1956-11-13 Du Pont Polyethylene composition
US3205190A (en) * 1957-12-18 1965-09-07 Nat Distillers Chem Corp Plastic compositions of improved slip properties
US3104232A (en) * 1958-06-18 1963-09-17 Spencer Chem Co Polyethylene compositions containing n-allyl fatty acid amides
US3108981A (en) * 1958-06-18 1963-10-29 Spencer Chem Co Polyethylene compositions
US3170889A (en) * 1959-03-09 1965-02-23 Du Pont Polyolefin composition
US3396137A (en) * 1965-03-05 1968-08-06 Dow Chemical Co Composition comprising an ethylene polymer and an nu-substituted unsaturated carboxylic amide
US3491073A (en) * 1965-08-13 1970-01-20 Dow Chemical Co Process for the polymerization of olefins
US3489824A (en) * 1968-03-07 1970-01-13 Gulf Research Development Co Blends comprising an ethylene copolymer and self-supporting film prepared therefrom
US3647738A (en) * 1970-11-03 1972-03-07 Union Carbide Corp Alpha-olefin polymer compositions
US3914342A (en) * 1971-07-13 1975-10-21 Dow Chemical Co Ethylene polymer blend and polymerization process for preparation thereof
US3969470A (en) * 1975-04-21 1976-07-13 E. I. Du Pont De Nemours And Company Process for recycling hydrogen when making blends of olefin copolymers
FR2312511B1 (en) * 1975-05-27 1980-01-11 Naphtachimie Sa
US4136072A (en) * 1977-05-24 1979-01-23 Arco Polymers, Inc. Thermoplastic polyolefin film compositions
US4414369A (en) * 1977-08-17 1983-11-08 Nippon Oil Company, Limited Continuous process for the preparation of polyolefins having widely distributed molecular weights
FR2445344B1 (en) * 1978-12-28 1982-03-19 Charbonnages Ste Chimique
JPS5910724B2 (en) * 1979-08-24 1984-03-10 Asahi Chemical Ind
JPH0134250B2 (en) * 1980-12-23 1989-07-18 Mitsubishi Petrochemical Co
US4438238A (en) * 1981-01-30 1984-03-20 Sumitomo Chemical Company, Limited Low density copolymer composition of two ethylene-α-olefin copolymers
GB8313461D0 (en) * 1982-05-20 1983-06-22 Intercontinental Plastics Inc Plastics film bags & c
DE3373438D1 (en) * 1982-05-20 1987-10-15 Stiksack Sts S A Plastics film and bags and sacks therefrom
CA1205052A (en) * 1982-06-02 1986-05-27 William J. Storms Pouches of ethylene c.sub.6-c.sub.1.sub.0 alpha- olefin copolymer film
JPH0571601B2 (en) * 1982-06-02 1993-10-07 Mitsui Petrochemical Ind
US4935474A (en) * 1983-06-06 1990-06-19 Exxon Research & Engineering Company Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4937299A (en) * 1983-06-06 1990-06-26 Exxon Research & Engineering Company Process and catalyst for producing reactor blend polyolefins
US4530914A (en) * 1983-06-06 1985-07-23 Exxon Research & Engineering Co. Process and catalyst for producing polyethylene having a broad molecular weight distribution
US4792595A (en) * 1983-06-15 1988-12-20 Exxon Research & Engineering Co. Narrow MWD alpha-olefin copolymers
US4540753A (en) * 1983-06-15 1985-09-10 Exxon Research & Engineering Co. Narrow MWD alpha-olefin copolymers
EP0227838B1 (en) * 1985-06-27 1991-08-28 Mitsui Petrochemical Industries, Ltd. Polyethylene composition
US4939217A (en) * 1987-04-03 1990-07-03 Phillips Petroleum Company Process for producing polyolefins and polyolefin catalysts
US4814377A (en) * 1987-09-04 1989-03-21 Union Carbide Corporation Process for incorporating high molecular weight olefin based copolymers into a polymer matrix
CA1335392C (en) * 1987-11-05 1995-04-25 Takeshi Shiraki Olefin resin composition for injection molding
US4814135A (en) * 1987-12-22 1989-03-21 Union Carbide Corporation Process for extrusion
US5026594A (en) * 1988-02-18 1991-06-25 Fuji Photo Film Co., Ltd. Packaging material for photosensitive materials
WO1989010944A1 (en) * 1988-05-06 1989-11-16 The Dow Chemical Company Linear low density polyethylene of ultra low density
EP0389611B1 (en) * 1988-09-30 1997-06-04 Exxon Chemical Patents Inc. Linear ethylene interpolymer blends of interpolymers having narrow molecular weight and composition distributions
US5047468A (en) * 1988-11-16 1991-09-10 Union Carbide Chemicals And Plastics Technology Corporation Process for the in situ blending of polymers
US5089321A (en) * 1991-01-10 1992-02-18 The Dow Chemical Company Multilayer polyolefinic film structures having improved heat seal characteristics
US5210142A (en) * 1992-02-13 1993-05-11 The Dow Chemical Company Reduction of melt fracture in linear polyethylene

Also Published As

Publication number Publication date Type
KR100259312B1 (en) 2000-06-15 grant
FI941577D0 (en) grant
ES2123574T3 (en) 1999-01-16 grant
US5250612A (en) 1993-10-05 grant
US5370940A (en) 1994-12-06 grant
DE69227637D1 (en) 1998-12-24 grant
FI941577A (en) 1994-04-06 application
WO1993007210A1 (en) 1993-04-15 application
DE69227637T2 (en) 1999-04-15 grant
EP0607342A1 (en) 1994-07-27 application
EP0607342B1 (en) 1998-11-18 grant
FI941577A0 (en) 1994-04-06 application
JPH07500131A (en) 1995-01-05 application

Similar Documents

Publication Publication Date Title
US6355733B1 (en) Polyethylene blends and films
US5300365A (en) Olefin polymer films
US5902684A (en) Multilayered Metallocene stretch wrap films
US4678836A (en) Blends of ethylene/acrylic acid copolymers with linear low density polyethylene
US4603174A (en) Stretched polypropylene film
US20080038533A1 (en) Linear polymers, polymer blends, and articles made therefrom
US5358792A (en) Heat sealable blend of very low density polyethylene or plastomer with polypropylene based polymers and heat sealable film and articles made thereof
US5210142A (en) Reduction of melt fracture in linear polyethylene
US8129472B2 (en) Polyolefin compositions, articles made therefrom and methods for preparing the same
US5677383A (en) Fabricated articles made from ethylene polymer blends
US4863769A (en) Puncture resistant, heat-shrinkable films containing very low density polyethylene
US5681523A (en) Medium modulus polyethylene film and fabrication method
US6262174B1 (en) Polymer compositions which exhibit high hot tack
US6969741B2 (en) Polyethylene compositions for rotational molding
US5059481A (en) Biaxially stretched, heat shrinkable VLDPE film
US7094472B2 (en) Radiation treated ethylene polymers and articles made from said polymers
US6932592B2 (en) Metallocene-produced very low density polyethylenes
US6613841B2 (en) Preparation of machine direction oriented polyethylene films
US5989725A (en) Clear high molecular weight film
US4976898A (en) Process for making puncture resistant, heat-shrinkable films containing very low density polyethylene
US20070260016A1 (en) Linear low density polymer blends and articles made therefrom
US5707751A (en) Shrink film and methods relating thereto
US5847053A (en) Ethylene polymer film made from ethylene polymer blends
US5206075A (en) Sealable polyolefin films containing very low density ethylene copolymers
US6225421B1 (en) Process for the manufacture of a composition comprising ethylene polymers

Legal Events

Date Code Title Description
EEER Examination request
FZDE Dead