JP2002517583A - Films with permanent fold properties made from alpha-olefin / vinyl aromatic and / or aliphatic or cycloaliphatic vinyl or vinylidene interpolymers - Google Patents

Abstract

  (57) [Summary] The present invention relates to (A) at least an essentially random copolymer wherein (1) (i) at least one vinyl aromatic monomer, or (ii) at least one aliphatic or cycloaliphatic. Derived from vinyl or vinylidene monomers, or (iii) a combination of at least one aromatic monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, and (2) at least one C2-20α-olefin. And (B) Component A and Component A, optionally comprising (3) a polymer derived from (3) one or more ethylenically unsaturated polymerizable monomers other than (1) and (2); A film or sheet or an extruded profile having at least one layer comprising a mixture with at least one other polymer, Film or sheet or extruded profile is laterally or longitudinally, or about those with 40% or more force relaxation in both directions. The invention further relates to a multilayer film, sheet or extruded profile comprising at least two layers, wherein at least one of the layers is (A) at least an essentially random copolymer, wherein (1) (i A) at least one vinyl aromatic monomer, or (ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (iii) at least one aromatic monomer and at least one aliphatic, or A combination of an alicyclic vinyl or vinylidene monomer, (2) a polymer derived from at least one C2-20 α-olefin, and (3) one or more ethylenically non-olefins other than (1) and (2). A polymer comprising a polymer derived from a saturated polymerizable monomer; or (B) a component A and at least one type of poly Comprising a mixture of the over, lateral, or longitudinal, or film or sheet having 40% or more force relaxation in both directions or on what is an extruded profile.

Description

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to one or more α-containing one or more vinyl aromatic monomers or aliphatic or cycloaliphatic vinyl or vinylidene monomers, or compounds thereof, or blends thereof with other polymers. -A film or sheet or extruded profile synthesized from a polymer composed of at least one substantially random interpolymer composed of polymer units derived from olefin monomers.
Films or sheets or extruded profiles synthesized from such interpolymers have high force relief in either the machine direction or the cross direction, or both.
It shows permanent fold characteristics as judged by ce relaxation (≥40 percent).

The subject of the present invention extends to films, sheets and multilayer laminates. The films according to the invention can be co-extruded and multilayer films, for example single-sided sealing films, double-sided sealing films, surface-treated films, colored films, void-forming films, untreated films, single-sided films , A double-sided treated film and a metallized resin film. The films of the present invention can also be laminated to conventional stretched polypropylene, polyethylene, or polyester films, aluminum foil, paper, foam, etc. to impart permanent fold properties to such multilayer composite structures. .

With the above features or characteristics, the films and sheets of the present invention will generally be successfully used for packaging, especially for packaging small items. Potential applications include, but are not limited to, for example, toothpaste tubes, vinyl ties, candy twist packaging, meat wraps, paper substitutes, tablecloths, and shower curtains.

[0004] Materials that have the ability to retain their new shape when molded are said to exhibit permanent fold characteristics. Permanent fold properties have been identified in several packaging application areas, including consumer food wraps and candy twist packaging for putting food and cooking,
Of particular importance is a sealable and flexible walled container such as a toothpaste tube. Currently, there are three different types of films or foils for such applications: aluminum foil, paper, and synthetic resin films or sheets or extruded profiles.

[0005] Aluminum foil has excellent permanent folds and formability. That is,
Once the foil wraps the item, the foil retains its shape and does not spread. However, aluminum foil is somewhat expensive, opaque, and unsuitable for use in microwave ovens. Paper (including glassine paper and paraffin paper)
Although easy to cut, the combination of strength, engineering properties, operating temperature range, and lack of water resistance has limitations in many packaging applications.

One problem with many synthetic resin films used in packaging applications is that they tend to be unable to maintain the shape of the synthetic resin film when wrapped in a container. In other words, the synthetic resin film returns to its original state even if it is bent,
Or it has a tendency to recover to an expanded state. With the advent of high-speed packaging machines, the use of materials with specific properties has been required, which has led to the use of specific films of rigid amorphous polymers such as polyvinyl chloride (PVC), polystyrene, and acrylic copolymers. Was.

[0007] Synthetic resin films, such as those made from polystyrene, flexible PVC, and acrylic polymers, are commonly used in food packaging because of their transparency and low cost. Also, some synthetic resin wraps based on PVC can be used in microwave ovens. However, flexible PVC requires the incorporation of high concentrations of plasticizers and contains chlorine which is not environmentally safe. In addition, polystyrene, soft P
VC and films made from acrylic polymers are brittle and do not exhibit the toughness required for many packaging applications. On the other hand, polypropylene and polyethylene films, which are advantageous in terms of cost as compared with the above-mentioned materials, cannot be used in a form that does not deform because they cannot maintain a twisted state and the permeability is average. .

[0008] In many cases, attempts to solve these problems have involved making multilayer films containing polymer blends. Also, many such films often required an additional stretching process in the film manufacturing process to obtain the desired combination of permanent crease properties and other properties.

No. 5,128,183 (P. Buzio, Borden, Ind.)
c. The entire content of the present invention relates to a modified polyolefin film having stable torsion-retaining and permanent fold properties, which is generally used for packaging and especially for packaging small items. The film of the present invention is obtained by extrusion and stretching of a ternary mixture composed of (1) isotactic polypropylene, (2) high density polyethylene, and (3) glassy amorphous low molecular weight resin.

Japanese Patent No. 59-68212 (Mitsui Toatsu Chemicals) relates to a polyolefin film having improved stiffness and twist retention obtained by uniaxial longitudinal stretching. However, such films have poor lateral properties and are prone to tearing and parallel cracking, which limits their use to longitudinal twist packaging.

German Patent DE 35 14 398 A1 (Hoechst) describes a biaxially stretched film, which consists of polypropylene, a filler and a polymer such as polyamide or polymethyl methacrylate. However, such films have poor twist retention.

[0012] European Application No. 0288227 (Exxo published on October 26, 1988)
n Chemicals) describes a biaxially oriented film, which comprises a polypropylene compound (or a copolymer of propylene and up to 20 weight percent of another olefin, such as ethylene) with 20 to 30 weight percent of a low molecular weight rosin. Alternatively, it can be obtained by extrusion molding of a two-component blend comprising a resin. The process described therein for obtaining extruded stretched films causes significant problems in the extrusion and stretching steps.

[0013] US Patent No. 4, issued June 27, 1989 to Janocha et al.
No. 842,187 describes an opaque two-time stretched thermoplastic film for candy twist packaging. This film is formed from a polymer mixture comprising 40 to 60% by weight of polypropylene, 35 to 50% by weight of polystyrene and 5 to 15% by weight of inorganic or organic filler.

US Pat. No. 4,7, issued Nov. 22, 1988 to Crass et al.
No. 86,533 teaches the preparation of a twist packaging film made from a polypropylene based layer and a polydialkylsiloxane finish layer. The layer based on polypropylene further contains 10 to 40% by weight of a low molecular weight hydrocarbon resin. The polypropylene contained herein is preferably an isotactic propylene homopolymer or a copolymer of ethylene and propylene with an ethylene content of less than 10% by weight. This is a layer based on two components.

[0015] J. EP 0148567 A1 to Canterino (
(Issued July 7, 1985) describes a film comprising a homogeneous blend of a large amount of polyethylene and a small amount of polystyrene as a material for a permanent fold food wrap with paper tear properties.

US Patent No. 4,965,135 to Im et al., Issued October 23, 1990.
No. (Dow Chemical) discloses a multilayer film having permanent crease properties and torsional stability properties, wherein the properties comprise a layer of a generally ductile first material such as LLDPE and a generally brittle nature such as polystyrene or PVC. This is achieved by alternately stacking the layers of the second material shown.

US Pat. No. 5,560 to Peiffer et al., Issued Oct. 1, 1996.
No. 948 (Hoeschst AG) describes a biaxially oriented multi-layer polypropylene film having twisted wrap properties, wherein the properties include at least one base layer comprising a polypropylene polymer and an alpha olefin polymer of 2 to 10 carbon atoms. At least one outer layer.

L., issued April 10, 1990 U.S. Pat. No. 4,916,025 to Pang-Chia (Mobil Oil Corp) describes a high density polyethylene film having good permanent fold properties and moisture permeability properties, which properties can be up to twice in the machine direction. This is achieved by a film containing a blend of HDPE or microcrystalline wax that has been stretched six or more times in the transverse direction.

Published on April 21, 1987 D. US Patent No. 4 by Redding
No. 6,659,408 (American Can Company) describes a luu multilayer sheet structure having improved permanent fold and strength properties, the properties comprising a plurality of polymer layers, including uniaxially oriented polypropylene or high density polyethylene layers. This is achieved by a sheet having a stretched substructure consisting of a combination of

[0020] E. V. British Patent GB2168362A (BCL Ltd.) by Brennan is formed by stretching a mixture containing a SBS block copolymer, a styrene butadiene copolymer, and polystyrene, which is a flat die or a circular die, and has high transparency and permanent fold characteristics. A packaging film is described.

[0021] J. A. published on August 19, 1997. G. FIG. U.S. Pat. No. 5,658,625 to Bradfute et al. Is composed of one or more layers of a thermoplastic, uniform alpha olefin / vinyl aromatic copolymer and has impact resistance, printability, RF heat sealability, It describes a film with improved shrinkage and optical properties. However, Bradfute does not limit the amount of substantially random interpolymer in the blend as well as the amount of ethylene / vinyl and α-olefin monomer in the ethylene / vinylidene aromatic interpolymer blend,
No mention is made of the permanent fold characteristics of the film composition.

The present invention provides one or more compositions comprising a predetermined amount of one or more vinyl aromatic monomers or aliphatic or cycloaliphatic vinyl or vinylidene monomers, or combinations thereof, or blended compositions thereof with other engineering thermoplastics. A film made from a polymer comprising at least one substantially random interpolymer composed of polymer units derived from the α-olefin monomers of the present invention. Films made from such interpolymers exhibit permanent fold properties in the machine direction or the transverse direction or both, as judged by a force relaxation of 40 percent or more. In applications such as tapes, labels, or laminate films, such high force relief provides conformability to uneven or uneven surfaces, excessive edges, curves, and folds. It is also possible to twist, bend, or otherwise shape extruded profiles such as toy tracks, tubes, gaskets, etc., that would otherwise be retained after removal of the shaping forces.

While the desired properties of the films or sheets or extruded profiles of the present invention are achieved using a single layered film, the present invention extends to sheets, and also to multilayer laminates. Therefore, the film according to the present invention is a co-extruded and multilayer film, such as a single-sided sealing film, a double-sided sealing film, a surface-treated film,
It can also be obtained as a colored film, a void forming film, an untreated film, a single-sided treated film, a double-sided treated film, and a metallized resin film. The film of the present invention,
It can also be laminated to conventional polyester films, styrene polymer films, polyethylene films, stretched polypropylene films, etc. to provide such multi-layer composite structures with permanent fold properties.

Due to the presence of the features or characteristics described above, the films or sheets or extruded profiles of the present invention will generally be successfully used for packaging, especially for packaging small items. Other potential uses include, but are not limited to, meat overlays, paper substitutes, stand-up or flat bottomed bags, tablecloths and shower curtains, folding bottles or containers, toothpastes Tubes, folded structures, boxes, cartons, window boxes, surgical drapes, molded members, toys, tubing and clothing, tapes, laminate films, adhesive tapes.

The present invention relates to a film or sheet or extruded profile, wherein the film or sheet or extruded profile comprises: (A) (1) (i) at least one vinyl aromatic monomer, or

(Ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer;
Or

(Iii) a polymer unit derived from a compound of at least one aromatic vinyl monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer;

(2) a polymer unit derived from at least one C _2-20 α-olefin,

(3) one or more ethylenically unsaturated polymerizable monomers other than the above (1) and (2),

Having at least one layer comprised of at least one substantially random interpolymer comprising: or (B) a blend of at least one polymer other than component (A) and component A; The film or sheet or extruded profile has a force relaxation of 40% or more in the machine direction or the cross direction or both directions.

The present invention also relates to a multilayer film or sheet or extruded profile having at least two layers, wherein at least one of the layers has a force relaxation of 40% or more in the machine direction or the transverse direction or both directions. Or a sheet or extruded profile, wherein the film or sheet or extruded profile comprises: (A) (1) (i) at least one vinyl aromatic monomer, or

(Ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer;
Or

(Iii) a polymer unit derived from a compound of at least one aromatic vinyl monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer;

(2) a polymer unit derived from at least one C _2-20 α-olefin,

(3) one or more ethylenically unsaturated polymerizable monomers other than the above (1) and (2),

Or (B) a blend of component A with at least one polymer other than component (A). Definition

All references to elements or metals belonging to a group are referred to here in CRC Pre.
ss, Inc. The Periodic Table of the Elements, published in 1989 and copyrighted (the Periodic Table of the Element)
ts). Also, any reference to a group or groups is to the group or groups that are reflected in the periodic table of this element using the IUPAC system for numbering the groups.

[0038] All numerical values listed herein are separated by at least two units between any low value and any high value, and all values from low to high with an increment of one unit. included. By way of example, 15 to 85 if, for example, the amounts of the components or the values of the varying process, for example temperature, pressure, time, are specified to be for example 1 to 90, preferably 20 to 80, more preferably 30 to 70. , 22 to 68, 43
It is intended that values such as 乃至 51, 30-32, etc., are explicitly listed in this specification. For values less than one, one unit is properly considered to be 0.0001, 0.001, or 0.1. These are merely examples of what is specifically intended, and all possible combinations of numerical values between the lowest and highest values should be considered in a similar manner as explicitly stated in this application. is there.

The term “hydrocarbyl” is used herein to refer to any aliphatic, cycloaliphatic, aromatic, acryl-substituted aliphatic, allyl-substituted cycloaliphatic, aliphatic-substituted aromatic, or aliphatic-substituted cycloaliphatic Means the group

The term “hydrocarbyloxy”
It means a hydrocarbyl group, which has an oxygen bond between the carbon bonded to the group and this group.

The term “interpolymer” as used herein refers to a polymer in which at least two different monomers that form the interpolymer polymerize. This includes copolymers, terpolymers, and the like.

The term “film” as used herein is defined as having a thickness of 12 mils or less.

The term “sheet” as used herein is defined as having a thickness greater than 12 mils.

As used herein, the term “extruded profile” is defined as a polymer composition that has undergone a profile extrusion process for shape-specific applications.

As used herein, the term “deformation” refers to bending,
Defined as decompression or compression.

As used herein, “dead fold property”
The term ")" is defined as a measure of the film's ability to retain its shape or folds or folds once the film is folded or wrapped, and does not return to its unfolded state. A measure of the degree of such permanent fold action is the magnitude of the film force relaxation in the machine or transverse direction or both.
In order to demonstrate the effect of permanent folds, the film must be longitudinally or transversally or in both directions.
Must have a high strength mitigation of at least percent.

As used herein, “dead fold film”
The term is defined as a film having permanent crease properties.

As used herein, the term “structure” refers to a molding process,
It is defined as a polymer composition that has undergone a film forming step, a sheet forming step, or a foam film forming step, or a foam sheet forming step, or a lamination step on a synthetic resin film or aluminum foil or paper or foam.

As used herein, “fabricated article” is first defined as a polymer composition in the form of a finished product formed from an intermediate comprising one of the films described herein.

As used herein, “substantially random”
ndom) "(substantially having polymer units derived from one or more vinyl aromatic monomers or aliphatic or cycloaliphatic vinyl or vinylidene monomers, or one or more α-olefin monomers having a combination thereof) POLYMER SEQUENCE DETERMIN in a random interpolymer)
ATION, Carbon-13 NMR Method , Academi
c Press New York, 1977, pp. 139-143. 71-78.
C. As described by Randall, the monomer distribution of the interpolymer was determined by a Bemoulli statistical model or by a primary or secondary Ma.
This means that it can be described by the rkovian statistical model.
Preferably, the substantially random interpolymer has no more than 15% of the total amount of vinyl aromatic monomers contained in the block of vinyl aromatic monomers of more than 3 units. More preferably, the interpolymer is not characterized by a high degree of either isotacticity or syndiotacticity. This is due to the carbon- ¹³ NMR of the substantially random interpolymer.
In the spectrum, the peak region corresponding to the main chain methylene and methine carbon representing either the mesodiazo sequence or the racemic diazo sequence does not exceed 75% of the total peak region of the main chain methylene and methine carbon. Substantially random interpolymer

The interpolymer used to make the film or sheet or extruded profile of the present invention has one or more vinyl aromatic monomers or one aliphatic or cycloaliphatic vinyl or vinylidene monomer or a combination thereof. Includes substantially random interpolymers synthesized by polymerizing one or more α-olefins and optionally multiple polymerizable monomers.

Suitable α-olefins include, for example, α-olefins containing 2 to 20, preferably 2 to 12, and more preferably 2 to 8 carbon atoms. Particularly suitable are ethylene, propylene, butene-1, 4-methyl-1-pentene, hexene-1, or octene-1, or one or more of propylene, butene-1,4-methyl-1-pentene, hexene-. 1, or ethylene in combination with octene-1. These α-olefins do not contain an aromatic moiety.

Other optional polymerizable, ethylenically unsaturated monomers include norbornene and C _1-10 or C _6-10 allyl with typical interpolymers of ethylene / styrene / naorbomen And substituted norbornenes.

Suitable vinyl aromatic monomers that can be used in the synthesis of the interpolymer include, for example, those represented by the following formula:

[0055]

Embedded image

Where R¹Is an alkyl containing 1 to 4 carbon atoms, preferably methyl or hydrogen
A group selected from the group consisting of a group consisting of²Are 1 to 4 carbon sources separately
Selected from the group consisting of an alkyl group containing hydrogen, preferably methyl or hydrogen, and a group consisting of hydrogen.
The selected group, Ar is a phenyl group, or halo, C_1-4Alkyl, and C_1-4C
Substituted with 1 to 5 substituents selected from the group consisting of
And n has a value of 0 to 4, preferably 0 to 2, and most preferably 0.
I do. Representative vinyl aromatic monomers include, for example, styrene, vinyl toluene
, Α-methylstyrene, t-butylstyrene, chlorostyrene, and compounds thereof
All isomers of the compound are included. Particularly suitable such monomers are styrene
Rene and its lower alkyl or halogen substituted derivatives are included. Preferred
Examples of suitable monomers include styrene, α-methylstyrene, low alkyl- (C₁
-C₄) Or phenyl ring substituted derivatives of styrene, such as ortho-, meta-, and
Para-methylstyrene, ring halogenated styrene, para-vinyltoluene or it
And mixtures thereof. A more preferred aromatic vinyl monomer is styrene
.

“Aliphatic or cycloaliphatic vinyl or vinylidene compounds (aliphatic or
cycloaliphatic vinyl or vinylidene
The term "compounds" means addition polymerizable vinyl or vinylidene monomers corresponding to the formula:

[0058]

Embedded image

Wherein A ¹ is a stereochemically bulky aliphatic or alicyclic substituent comprising up to 20 carbons and R 1 is an alkyl group containing 1 to 4 carbon atoms, preferably methyl or hydrogen. And R ² is a group selected from the group consisting of hydrogen;
Or a group selected from the group consisting of a carbon atom, preferably an alkyl group containing methyl or hydrogen and a group consisting of hydrogen, or R1 and A1 together form a ring system. Preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are monomers in which one of the carbon atoms having an ethylenically unsaturated one is tertiary or quaternary substituted. Examples of such substituents include cycloaliphatic groups such as cyclohexyl, cyclohexenyl, cyclooctenyl, or cyclic alkyl, or allyl-substituted derivatives thereof, tertiary butyl, norbornyl. The most preferred aliphatic or cycloaliphatic vinyl or vinylidene compounds are cyclohexane and various isomeric vinyl substituted derivatives of substituted cyclohexane and 5-ethylidene-2-norbornene. Particularly suitable are 1-, 3-
And 4-vinylcyclohexene.

[0060] The substantially random interpolymer may be modified by general grafting, hydrogenation, functionalization, or other reactions well known to those skilled in the art. Based on established techniques, polymers may be readily sulfonated or chlorinated to produce functionalized derivatives.

The substantially random interpolymer, or at least one layer consisting of the substantially random interpolymer, can be applied to sheets and films by various chain-extension or cross-linking processes without the need for permanent fold action. May be modified by
Such processes include, but are not limited to, for example, peroxide, silane, sulfur, radiation, or azide based cure systems. A full description of various cross-linking techniques is set forth in co-pending U.S. Patent Nos. 08 / 921,641 and 08 / 921,642, both filed August 27, 1997.

A dual cure system using a combination of heat, moisture cure and radiation steps could be used effectively. Dual cure systems are described in L. Walton and S.M.
V. It is disclosed and claimed in U.S. Patent Application Serial No. 536,022, filed September 29, 1995 in Karande. For example, it may be necessary to use a peroxide crosslinking agent with a silane crosslinking agent, a peroxide crosslinking agent with radiation, a sulfur-containing crosslinking agent with a silane crosslinking agent, and the like.

[0063] Substantially random interpolymers may also be modified by various crosslinking processes. Cross-linking processes include, but are not limited to, incorporating the diene component as a termonomer in the formulation and subsequent cross-linking by the methods described above, and yet another method is to use sulfur as a cross-linking agent, for example, vinyl. Vulcanization via groups is included.

One method of synthesizing substantially random interpolymers is to combine one or more metallocenes or constrained geometry catalysts in combination with various cocatalysts.
And polymerizing a mixture of a plurality of polymerizable monomers in the presence of

A substantially random interpolymer is described in James C.W. Stevens
European Patent Application 0,416,815 and Francis J. et al. Ti
It can be stiff as described in U.S. Pat. Such a method of synthesizing a substantially random interpolymer involves polymerizing a mixture of polymerizable polymers in the presence of one or more metallocenes or a constrained geometry catalyst in combination with various cocatalysts. Including. Preferred operating conditions for such polymerization reactions are pressures from atmospheric to 3000 atmospheres and temperatures from -30C to 200C. Polymerization at temperatures above the autopolymerization temperature of each monomer and removal of unreacted monomers may result in the formation of some homopolymeric polymerization products resulting from free radical polymerization.

Examples of suitable catalysts and methods for synthesizing substantially random interpolymers are described in US Patent Application Serial No. 702,47, filed May 20, 1991.
No. 5,514,828, and also U.S. Pat. , 802,, 5,132,380, 5,189,192, 5321,106, 5,347,024, 5,350,723, 5,374,696. No. 5,399,635, No. 5,470,993
Nos. 5,703,187 and 5,721,185.

A substantially random α-olefin / vinyl aromatic interpolymer can also be synthesized by the method disclosed in Japanese Patent Application Laid-Open No. 07-278230. Is used.

[0068]

Embedded image

In the formula, Cp ¹ and Cp ² are each a cyclopentadienyl group, an indenyl group, a fluorenyl group, or a substituent thereof and are independent of each other, and R ¹ and R ² are a hydrogen atom, a halogen atom, A hydrocarbon group having 1 to 12 carbon atoms, an alkoxyl group, or an allyloxy group which is independent of each other, and M is a metal belonging to Group IV, preferably Zr
Alternatively, Hf, most preferably Zr, and further R ³ is an alkylene group or a silanediyl group used for crosslinking Cp ¹ and Cp ² .

A substantially random α-olefin / vinyl aromatic interpolymer is described by Jo
hn G. hn. International application WO 95/32095 by Bradfute et al. (WR Grace &Co.); B. Pannell (Exxon
Chemical Patents, Inc. International application WO / 94)
/ 50050, and Plastics Technology, p. 25
(September 1992).

Also suitable are substantially random interpolymers containing at least one α-olefin / vinylaromatic / vinylaromatic / α-olefin tetrad, on September 4, 1996. Published U.S. Patent Application No. 08/708.
, 809 and International Application WO 98/09999, both of which are described in Francis J. et al. By Timmers et al. These interpolymers contain multiple additional signals in the carbon-13 NMR spectrum, the intensity of which is a peak three times greater than the peak noise. These signals have a chemical shift range of 43.70-44.25 ppm and 38.0-38.5p.
pm. In particular, the main peaks were 44.1, 43.9, and 38.2p
Observed at pm. According to the proton test NMR experiment, the signal in the chemical shift region 43.70-44.25 ppm is methine carbon and the region 38.0.
The signal at ３８38.5 ppm indicates a methylene carbon.

These new signals are sequences containing two vinyl aromatic monomer insertions that are head-to-tail preceded by at least one α-olefin insertion that follows, eg, It is believed that the four molecule styrene monomer insertion is due to ethylene / styrene / styrene / ethylene four molecules occurring exclusively in a 1,2 (head-to-tail) manner. Those skilled in the art will recognize that vinyl aromatic monomers besides styrene, and α-
For such four molecules containing olefins, it is understood that ethylene / vinyl aromatic monomer / vinyl aromatic monomer / ethylene four molecules will occur as similar carbon 13 NMR peaks but with slightly different chemical shifts.

The interpolymer can be synthesized by performing polymerization at a temperature of −30 ° C. to 250 ° C. in the presence of a catalyst represented by the following formula.

[0074]

Embedded image

Wherein each CP is independently a substituted cyclopentadienyl group π-bonded to each resulting M, E is C or Si, M is a Group IV metal, preferably Zr or Hr, most preferably Zr, Each R is independently H, hydrocarbyl, silahydrocarbyl, or hydrocarbylsilyl, each containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms, each R ′ is H, halo, hydrocarbyl, hydrocarbyloxy, silahydrocarbyl, hydrocarbylsilyl each independently occurring and containing up to 30, preferably 1 to 20, more preferably 1 to 10 carbon or silicon atoms, or 2 one of R _{'C 1-10} hydrocarbyl substituted 1,3-butadiene group taken together, m is 1 or 2, further optionally, teeth Preferably there are activated complement catalyst. In particular, suitable substituted cyclopentadienyl groups include those represented by the following formula:

[0076]

Embedded image

Wherein each R is independently H, hydrocarbyl, silahydrocarbyl,
Or hydrocarbylsilyl containing up to 30, preferably 1 to 20, more preferably 1 to 10, carbon or silicon atoms, or the R groups taken together to form the divalent radical of such a group. To form a derivative of Preferably, each independently occurring R (including all suitable isomers) is hydrogen, methyl, ethyl, propyl, butyl, pentyl, hexyl, benzyl, phenyl, or silyl or (suitably) two such The R groups combine to form a fused ring system such as indenyl, fluorenyl, tetrahydroindenyl, tetrahydrofluorenyl, or octahydrofluorenyl.

Particularly preferred catalysts include, for example, racemic (dimethylsilanediyl) -bis- (
2-methyl-4-phenylindenyl) zirconium dichloride, racemic (dim
(Tylsilanediyl) -bis- (2-methyl-4-phenylindenyl) zirconi
, 1,4-diphenyl-1,3-butadiene, racemic (dimethylsilanediethyl
) -Bis- (2-methyl-4-phenylindenyl) zirconiumdi C_1-4
Alkyl, racemic (dimethylsilanediyl) -bis- (2-methyl-4-phenyl)
Ruindenyl) zirconium di-C1-4 alkoxide, or any set thereof
Combination.

The following titanium based limited geometry catalyst, N- (1,1-dimethylethyl) -1,1-dimethyl-1-[(1,2,3,4,5-η) -1,5
, 6,7-Tetrahydro-s-indacen-1-yl] silaneaminate (2-
) N] titanium dimethyl, (1-indenyl) (tert-butylamido) dimethyl-silanetitanium dimethyl, (3-tert-butyl (1,2,3,4
, 5-η) -1-indenyl) (tert-butylamido) dimethylsilanetitanium dimethyl, and ((3-isopropyl) (1,2,3,4,5-η) -1
-Indenyl (tert-butyl) amido) dimethylsilanetitanium dimethyl, or any combination thereof, can also be used.

Further, methods for synthesizing the interpolymer used in the present invention are described in the literature. Longo and Grassi ( Makromol . Chem ., 191 ) .
Vol. 2387-2396 [1990]) and D'Annello et al. (Jo
styrene copolymers - urnal of Applied Polymer Science, 58, pp. ethylene with 1701 or 1706, pages [1995]) catalyst systems based on methyl (MAO), tetra- and cyclopentadienyl titanium trichloride (CpTiCl ₃₎ It reports that it is synthesized. Xu and Lin ( Polymer Preprints, Am. Chem.
Soc. , Div. Polym, Chem . 35 volumes, 686 and 68
7 [1994]) describes MgCl ₂ / TiCl ₄ / NdCl ₃ / Al (iBu)
It is reported that copolymerization using _three catalysts is performed to provide a random copolymer composed of styrene and propylene. Lu et al. ( Journal of Appl
ied Polymer Science , 53, 1453-1460 [
1994]) described the copolymerization of ethylene and styrene using a TiCl ₄ / NdCl ₃ / MgCl ₂ / Al (Et) ₃ catalyst. Sernetz and Mulha
upt (Macromol. Chem. Phys, 197 , pp. 1071 to 1083 pages, _{1997), Me 2 Si (Me 4 Cp} ) (N-tert- butyl) of ethylene with TiCl ₂ / methylaluminoxane Ziegler-Natta catalyst The effect of polymerization conditions on the copolymerization of styrene was described. Copolymers of ethylene and styrene produced by cross-linked metallocenes are available from Arai.
, Toshiaki and Suzuki ( Polymer Preprints,
Am. Chem. Soc. , Div. Polym, Chem . ) 38
Volumes, 349 and 350 [1997]) and U.S. Patent No. 5,652,315 issued to Mitsui Toatsu Chemicals, Inc. The production of alpha-olefin / vinyl aromatic monomer interpolymers such as propylene / styrene and butene / styrene is described in U.S. Pat. No. 5,244,996 issued to Mitsui Toatsu Chemicals, or similarly Mitsui Toatsu Chemicals, Inc. No. 5,652,315 issued to U.S.A., or DE19711339A1 to Denki Kagaku Kogyo.

While synthesizing a substantially random interpolymer, a certain amount of atactic vinyl aromatic homopolymer may be formed by homopolymerization of the vinyl aromatic monomer at elevated temperatures. The presence of the vinyl aromatic homopolymer is generally not harmful for the purposes of the present invention and can be tolerated. If necessary, the vinyl aromatic homopolymer may be separated from the interpolymer by an extraction method such as selective precipitation from a solution containing a non-solvent for either the interpolymer or the vinyl aromatic homopolymer. . For the purposes of the present invention, 30% by weight, based on the total weight of the active vinyl aromatic homopolymer interpolymer,
Hereinafter, it is preferable that the content is preferably less than 20% by weight. Formulation compositions comprising substantially random interpolymers

The present invention also provides films synthesized from substantially random α-olefin / vinyl or vinylidene interpolymers having one or more other polymer components that cover a wide range of compositions.

Other polymer components of the formulation include, but are not limited to, for example, one or more engineering thermoplastics, α-olefin homopolymers or interpolymers, thermoplastic olefins, styrene block copolymers, styrene homopolymers or Copolymers, elastomers, or vinyl halide polymers. Engineering thermoplastic

[0084] Kirk-Othmer Encyclopedia of Science
The third edition of Technology and Technology (Vol. 9, pp. 118-137) describes engineering thermoplastics with dimensional stability and most mechanical properties of 10
It is defined as a neat or unreinforced or filled thermoplastic that is maintained at a temperature above 0 ° C. and below 0 ° C. The terms "engineering plastic" and "engineering thermoplastic" can be used interchangeably. As engineering thermoplastics, for example, acetal, acrylic resin, polyamide (eg, nylon-6, nylon 6,6)
), Polyimide, polyetherimide, cellulose, polyester, poly (arylate), aromatic polyester, poly (carbonate), poly (butylene) and polybutylene and polyethylene terephthalate, liquid crystal polymers, and selected polyolefins of the above resins, blends Or alloys, as well as some examples from other resin types, including, for example, polyethers, high temperature polyolefins such as polycyclopentane, copolymers thereof, as well as polymethylpentane.

A particularly preferred engineering plastic is methyl methacrylate (MM
A) Acrylic resin derived from free radical polymerization catalyzed by peroxide. H.
Modern Plastic Encyclopedia, by Luke,
As described in 1989, pp. 20-21, MMA is commonly used with four basic polymerization processes, bulk, suspension, emulsion, and solution, with other acrylates such as methyl- or ethyl acrylate. Copolymerize. Acrylic resin (acryl
ics) can also be modified with various components, including butadiene, vinyl, and butyl acrylate. α-homopolymer and interpolymer

The α-olefin homopolymer and interpolymer are composed of polypropylene, propylene / C ₄ -C ₂₀ α-olefin copolymer, polyethylene, and ethylene / C ₃ -C ₂₀ α-olefin copolymer, wherein the interpolymer is heterogeneous. Either ethylene / α-olefin interpolymers or homogeneous ethylene / α-olefin interpolymers include substantially linear ethylene / α-olefin interpolymers. Also included are aliphatic α-olefins having 2 to 20 carbon atoms and having a polar group. Suitable aliphatic α-olefin monomers for introducing a polar group into the polymer include, for example, acrylonitrile,
Ethylenically unsaturated nitriles such as methacrylonitrile and ethacrylonitrile;
Ethylenically unsaturated anhydrides such as maleic anhydride; ethylenically unsaturated amides such as acrylamide and methacrylamide; ethylenically unsaturated carboxylic acids such as acrylic acid and methacrylic acid (mono- and bifunctional Methyl methacrylate, ethyl acrylate, hydroxyethyl acrylate, n-butyl acrylate or methacrylate, 2-ethyl-hexyl acrylate, or ethylene-
Esters of ethylenically unsaturated carboxylic acids such as vinyl acetate copolymers (
Particularly, lower, for example, C ₁ -C ₆ alkyl ester); N-alkyl such as N-phenylmaleimide or ethylenically unsaturated dicarboxylic imide such as N-allylmaleimide. Preferably, such monomers containing polar groups are acrylic acid, vinyl acetate, maleic anhydride, and acrylonitrile.
Halogen groups that can be derived from aliphatic α-olefin monomers into polymers include fluorine, chlorine, and bromine, and preferably such polymers are chlorinated polyethylene (CPE).

In a homogeneous interpolymer, substantially all interpolymer molecules have the same ethylene / comonomer ratio within the interpolymer, while in heterogeneous interpolymers, the interpolymer molecules do not have the same ethylene / comonomer ratio. Heterogeneous interpolymers are those differentiated from homogeneous interpolymers. As used herein, the term "broad composition distribution"
"tributation" describes the comonomer distribution of the heterogeneous interpolymer, with the heterogeneous interpolymer having a "linear" fraction and the heterogeneous interpolymer having multiple melting peaks due to DSC (i.e., at least two different melting peaks). Melting peak). The heterogeneous interpolymer has a degree of branching of 2 methyl / 1000 carbons or less, more than 10% (by weight), preferably more than 15% (by weight), particularly preferably more than 20% (by weight). Heterogeneous interpolymers have a degree of branching of 25 methyl / 1000 carbons or more, not more than 25% (per weight), preferably less than 15% (per weight), and particularly preferably less than 10% (per weight). .

Suitable Ziegler catalysts for the synthesis of the foreign components of the present invention are generally supported Ziegler-type catalysts. Examples of such compositions are compositions derived from organomagnesium compounds, alkyl or aluminum halides or hydrogen chloride, and transition metal compounds. Examples of such catalysts are described in U.S. Pat. No. 4,314,912 (Lowry, Jr et al.), 4,54.
7,475 (Glass et al.) And 4,612,300 (Coleman).
, III).

[0089] Suitable catalyst materials may also be derived from inert oxide carriers and transition metal compounds. Examples of such compounds are described in US Pat. No. 5,420,090 (Spenc).
er et al.).

The foreign polymer component is an α-olefin homopolymer, preferably polyethylene or polypropylene, or preferably at least one C ₃ -C ₂₀ α-
It may be an olefin or C ₄ -C ₁₈ ethylene interpolymer having a diene, or mixtures thereof. Propylene, 1-butene, 1-hexene,
Particularly preferred are heterogeneous copolymers of ethylene with 4-methyl-1-pentene and 1-octene.

The relatively new introduction of metallocene-based catalysts for ethylene / α-olefin polymerization has produced a new ethylene interpolymer known as a homogeneous interpolymer.

[0092] Homogeneous interpolymers useful in forming the compositions described herein include homogenous branching distributions.
ions). That is, the polymer is one in which comonomer is randomly distributed in a given interpolymer molecule, and substantially all interpolymer molecules have the same ethylene / comonomer ratio within the interpolymer. The homogeneity of the polymer is generally determined by SCBDI (Short Chain Branch Di).
(Striation Index) or CDBI (Composition)
Distribution Branch Index) and describes the median total molar comonomer content.
It is defined as the weight percentage of polymer molecules having a comonomer content within 50% of the monomer content. Polymer CDBI can be obtained by techniques well known to those skilled in the art, for example, Wild et al., Journal of Polymer Scie.
nce, Poly, Phys. Ed. , Vol. 20, p. 441
(1982), temperature rising elution fractionation as described in US Pat. No. 4,798,081 (Hazlit et al.).
elution fractionation, abbreviated here as TREF),
Alternatively, it is easily calculated from data obtained as described in US Pat. No. 5,008,204 (Stehling). Techniques for calculating CDBI are described in US Pat. Nos. 5,322,728 (Davey et al.) And 5,246,783 (Spenadel et al.), Or US Pat.
321 (Chum et al.). The SCBDI or CDBI for the homogeneous interpolymer used in the present invention is preferably above 30%, especially 50%.
%.

The homogeneous interpolymer used in the present invention has a measurable “high-density” fraction as measured by the TREF technique (ie, a homogeneous ethylene / α-olefin interpolymer has a degree of branching of 2 methyl / (Without the polymer fraction being less than 1000 carbons). Homogeneous interpolymers are also highly short chain branched fractions (ie, they do not include polymer fractions with a degree of branching of 30 methyl / 1000 carbons or more).

The practically linear ethylene / α-olefin polymers and interpolymers of the present invention are also homogeneous interpolymers, but are further described in US Pat.
272,236 (lai et al.) And U.S. Pat. No. 5,272,872. Such polymers, while unique, are due to their excellent processability and unique rheological properties and high melt elasticity and resistance to melt fracture. These polymers can be successfully synthesized by a continuous polymerization process using a limited geometry metallocene catalyst system.

The term “substantially linear” ethylene / α-olefin interpolymer means that the polymer backbone is effectively 0.01 long-chain branches / 1000 carbons to 3 long-chain branches / 1000 carbon, more preferably 0.01 long chain branch / 1000 carbon to 1 long chain branch / 1000 carbon, especially 0.0
It is meant to be replaced by 5 long chain branches / 1000 carbons to 1 long chain branch / 1000 carbons.

[0096] Long chain branching is defined herein as the chain length of at least one carbon above two carbons less than the total number of carbons in the copolymer, for example, ethylene / octene being a substantially linear ethylene. The long chain of the interpolymer is at least 7 carbons in length (
That is, subtracting 2 carbons from 8 carbons results in 6 carbons, and adding 1 results in a long chain branch length of 7 carbons). The long chain branches can be as long as the length of the polymer backbone. Long chain branching is determined using ¹³ C nuclear magnetic resonance (NMR) spectroscopy,
Also, Randall ( Rev. Macromol. Chem. Phys.
, C29 (2 & 3), p285-297). Of course, long-chain branches are distinguished from short-chain branches obtained solely by incorporation of a comonomer, for example the short-chain branches of a substantially linear polymer of ethylene / octene are 6 carbons in length, while Long chain branches are at least 7 in length for the polymer
Carbon.

[0097] The catalyst used to synthesize the homogeneous interpolymer for use as the formulation of the present invention is a metallocene catalyst. Such metallocene catalysts include, for example, bis (cyclopentadienyl) -catalyst systems and mono (cyclopentadienyl) -limited geometry catalyst systems (substantially linear ethylene / α-olefin polymers).
And the like. Such limited geometry metal complexes and methods for their synthesis are described in European Patent Application No. 416,815, European Patent Application No. 468,651, European Patent Application No. 514,828, as well as U.S. Pat. No. 055,438; U.S. Patent Application No. 5,057,475; U.S. Patent Application No. 5,096,867; U.S. Patent Application No. 5,064,802; U.S. Patent Application No. 5,132,380; No. 5,721,185, US Pat. No. 5,374,696, and US Pat. No. 5,470,993.

[0098] European Patent Application No. 418,044, published March 20, 1991, discloses certain cationic derivatives of the above defined geometry catalysts that are highly useful as olefin polymerization catalysts, And has been claimed. US Patent Application No. 5,45
No. 3,410 discloses a combination of a cationic limited geometry catalyst with an alumoxane as a suitable olefin polymerization catalyst. With respect to the teachings contained therein, the above pending US patent applications, issued US patents, and published European patent applications are hereby incorporated by reference in their entirety.

The homopolymer component must be an α-olefin homopolymer, preferably polyethylene or polypropylene, or preferably an ethylene interpolymer that shakes at least one C ₃ -C ₂₀ α-olefin C ₄ -C ₁₈ diene.
Homopolymers of ethylene and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene are particularly preferred. Thermoplastic olefin

Thermoplastic olefins (TPO) are generally polypropylene homo- or copolymers,
Or a blend of ethylene / propylene / rubber (EPM) or ethylene / propylene diene monomer terpolymer (EPDM) and a stiffer material, such as isotactic polypropylene pyrene. Other materials or components can be added to the formulation as required, including oils, fillers, and crosslinkers. Generally, TPO
Is characterized by a balance of stiffness (modulus) and low temperature impact, good chemical resistance, and a wide range of operating temperatures. Due to such features, TPO is used in many applications, such as automotive fronts and instrument panels, especially also wires and cables.

Although the polypropylene is usually derived from a homopolymer polypropylene polypropylene, generally in an isotactic form, other forms of polypropylene can also be used (eg, syndiotactic or atactic). Polypropylene impacts the copolymer (e.g., by a second polymerization step in which ethylene is reacted with propylene) and in random copolymers (also in modified reactors and 1.5-7 percent ethylene copolymerized usually with propylene). Can also be used in the TPO formulations disclosed herein.
PO can also be used as a compounding component of the present invention. A complete description of the various polypropylene polymers can be found in Modern Plastics Cyclopedia.
/ 89, published in mid-October 1988, Volume 65, pages 11, 86-92. The molecular weight of the polypropylene used in the present invention has a melt flow measurement based on ASTM D-1238, condition 230 ° C./2.16 kg (formerly known as “condition L”, also known as I2). Shown conveniently. The melt flow rate is inversely proportional to the molecular weight of the polymer. Thus, although the correlation is not linear, the higher the molecular weight, the lower the melt flow rate. The melt flow rates of polypropylene useful herein are generally 0.1 grams / 10 minutes (g / 1
0 min) to 35 g / 10 min, preferably 0.5 g / 10 min to 25
g / 10 min, and especially 1 g / 10 min to 20 g / min. Styrene block copolymer

Also included are block copolymers, which have unsaturated natural rubber monomer units, including but not limited to styrene-butadiene (SB), styrene-isoprene ( SI), styrene-butadiene-styrene (SBS), styrene-isoprene-styrene (S
IS), α-methylstyrene-butadiene-α-methylstyrene and α-methylstyrene-isoprene-α-methylstyrene. Preferred stylenics are styrene and α-methylstyrene, with styrene being especially preferred.

The styrene portion of the block copolymer is preferably a polymer or interpolymer of styrene, and analogs and homologs thereof, including α-methylstyrene and ring-substituted styrene, especially ring-methylated styrene. Preferred styrene

The block copolymer having unsaturated rubber monomer units may be composed of a homopolymer of butadiene or isoprene, or may consist of one or both of the two dienes with a small amount of styrene monomer. It may be composed of a copolymer.

Preferred block copolymers having saturated rubber monomer units are composed of at least one segment of a styrene unit and at least one segment of an ethylene-butene or ethylene-propylene copolymer. Preferred examples of such block copolymers having saturated rubber monomer units include styrene / ethylene-butene copolymer, styrene / ethylene-propylene copolymer, styrene / ethylene-butene / styrene (SEBS) copolymer, styrene / ethylene-propylene / styrene ( (SEPS) copolymer. Styrene homo- and copolymers

In addition to block copolymers, there are various styrene homopolymers and copolymers, as well as rubber-modified styrene. Examples of these include polystyrene, high impact polystyrene and acrylonitrile-butadiene (ABS) polymer, styrene-acrylonitrile (SAN). Elastomer

Examples of the elastomer include, but are not limited to, polyisoprene, polybutadiene, natural rubber, ethylene / propylene rubber, ethylene / propylene diene (EPDM) rubber, styrene / butadiene rubber, and thermoplastic polyurethane.

Vinyl halides and copolymers are a class of resins, which are represented by a blocking block, vinyl structure CH ₂ ＣCXY, where X is F, Cl,
A group selected from Br and I, and Y is selected from the group consisting of F, Cl, Br, I, and H.

The vinyl halide component of the formulations of the present invention includes, but is not limited to, copolymers and homopolymers of vinyl halides having copolymerizable monomers, wherein the copolymerizable monomers include Α-olefins, such as ethylene, propylene, vinyl esters of organic acids having 1 to 18 carbon atoms, such as vinyl acetate, vinyl stearate, etc .; vinyl chloride, vinylidene chloride, symmetric dichloroethylene; Acrylonitrile, methacrylonitrile; an alkyl acrylate ester in which the alkyl group has 1 to 8 carbon atoms,
For example, methyl acrylate and butyl acrylate; corresponding alkyl methacrylate esters; dialkyl esters of dibasic organic acids having an alkyl group of 1 to 8 carbon atoms, such as dibutyl fumarate, diethyl maleate and the like.

[0110] Preferably, the vinyl halide polymer is a copolymer or homopolymer of vinyl chloride or vinylidene chloride. Poly (vinyl chloride) polymers (PVC) can be further divided into two main types depending on the degree of rigidity. These are "hard" PVC and "soft" PVC. Soft PVC is distinguished from hard PVC mainly because a plasticizer is contained in the resin. Soft PVC is hard PVC
It generally has better workability, lower tensile strength, and higher elongation as compared to.

Of the vinylidene chloride homopolymers and copolymers (PVDC), those having vinyl chloride, acrylate, or nitrile are commonly used commercially and are most preferred. The choice of comonomer has a great influence on the properties of the resulting polymer. Alternatively, the most prominent properties of various PVDC are low permeability to gas and liquid and barrier property, and chemical resistance.

[0112] Included as a group of vinyl halides used as blend components of the present invention are those generally synthesized by post-chlorination of basic resins,
There is a chlorinated derivative of PVC (CPVC) known as C. CPVC is P
Despite being based on VC and having some of its properties in common, it has a much higher melting temperature range (410-450 ° C) and a much higher glass transition temperature (239-275 ° F) compared to PVC. It is a unique polymer.

A composition comprising at least one substantially random interpolymer used to prepare a film or sheet or an extruded profile of the present invention, and optionally comprising one or more other polymer components. In contrast, one or more fillers can be optionally added.

[0114] Extenders

Various organic and inorganic extenders are also included as possible components of the polymer composition used in the present invention, the nature of which depends on the type of application to the mixture to be utilized. Representative examples of such extenders include organic and inorganic fibers such as asbestos, boron, graphite, ceramic, glass, metal (eg, stainless steel), or polymer (eg, aramid fiber) talc, carbon black, carbon fiber, calcium carbonate. , Alumina trihydrate, glass fiber, marble dust,
Cement dust, clay, feldspar, silica or glass, finely divided silica, alumina, magnesium oxide, magnesium hydroxide, antimony oxide, zinc oxide, barium sulfate, aluminum silicate, calcium silicate, titanium dioxide, titanates, aluminum nitride, B ₂ O _3, including those made from nickel powder or chalk. Other typical organic or inorganic, fiber or mineral extenders include carbonates such as barium carbonate, calcium carbonate or magnesium carbonate; fluorides such as aluminum calcium or sodium fluoride; Hydroxides; metals such as aluminum, bronze, lead or zinc; oxides such as aluminum oxide, antimony oxide, magnesium oxide or zinc oxide; silicates such as asbestos, mica, clay (kaolin or calcined kaolin), silicate Calcium, feldspar, glass (ground or exfoliated glass or hollow glass spheres or microspheres or beads, whiskers or filaments), nepheline, perlite, pyrophyllite, talc or wollastonite; such as barium sulfate or calcium sulfate Sulfate; metal Products; including pulverized plastic like and liquid crystal, or thermoset polymers; in the form of a powder timber or shell cellulose; calcium terephthalate. Mixtures of one or more such extenders can likewise be used. These extenders can be used in amounts of 0 to 90, preferably 0 to 80, more preferably 0 to 70% by weight, based on the weight of the polymer or polymer mixture. Other additives Antioxidants such as tethered phenols such as Irganox® 10
10, and phosphites (esters) such as Irgafos ™ 168 (
Both are registered trademarks of Ciga-Geigy Corporation (NY) and are supplied by the company), u. v. Stabilizer (Tinuvin ™ 3
28 and Chimassorb (TM) 944. Both are Ciga-
A registered trademark of Geigy Corporation (NY), supplied by the company), adhesive additives (eg, polyisobutylene), lubricants (eg, erucamide stearamide), anti-blocking additives, anti-fog agents, colorants, pigments Additives such as can also be included in the interpolymer mixtures used to make the thin films or sheets or extruded profiles according to the present invention to the extent that they do not interfere with the properties of the substantially random interpolymer. . Processing aids, also referred to herein as plasticizers, are optionally used to reduce the viscosity of the composition, but these include phthalates (esters) such as dioctyl phthalate and diisobutyl phthalate, lanolin, And natural oils such as paraffin, naphthenes and aromatic oils obtained from petroleum refining, and liquid resins derived from rosin or petroleum feedstocks. Suitable modifiers that can be used as plasticizers in the present invention include phthalates, trimellitates, benzoic acids, adipic esters, epoxy compounds, phosphates (triaryl, trialkyl, mixed alkylaryl phosphates), glutaric acid It includes at least one plasticizer selected from the group consisting of salts (esters) and oils. Particularly suitable phthalates are, for example, dialkyl C4-C18 phthalates, such as diethyl phthalate, dibutyl, diisobutyl phthalate, 2-ethylhexyl butyl phthalate, dioctyl phthalate, diisooctyl phthalate, dinonyl phthalate, diisononyl phthalate , Didecyl phthalate, diisodecyl phthalate, diundecyl phthalate,
Mixed aliphatic esters such as heptyl nonyl phthalate, di (n-hexyl, n-octyl, n-decyl) phthalate (P610), di (n-octyl, n
-Decyl) (P810), and aromatic phthalates, such as diphenyl phthalate, or mixed aliphatic-aromatic esters, such as benzyl butyl phthalate, or any combination thereof. Examples of classes of oils useful as processing aids include liquid paraffin (eg, Kayd
ol ™ oil (available from Witco) and Shellflex ™
371 naphthenic oil (available from Shell Oil Company) is included. Another suitable oil is Tuflo ™ oil (available from Lyondell). Anti-fogging or antistatic agents can be added to the films and sheets according to the invention to increase the surface conductivity and to prevent the formation of water droplets on the film surface and the attraction of dust and dirt. These anti-fog agents include glycerol monostearate, glycerol monooleate, diphthalamide laurate, ethoxylated amines, ethoxylated esters, and other additives known in the art. Tackifiers can also be added to the polymer compositions used in the production of the thin films or sheets or extruded profiles according to the invention in order to change the Tg and extend the available application temperature of the films. Examples of different classes of tackifiers include aliphatic resins, polyterpene resins, hydrogenated resins, mixed aliphatic-aromatic resins, styrene / α-methylenestyrene resins, pure monomeric hydrocarbon resins, hydrogenated pure monomeric carbonizers. Includes but is not limited to hydrogen resins, modified styrene copolymers, pure aromatic monomer copolymers, and hydrogenated aliphatic hydrocarbon resins. Examples of aliphatic resins are Escorez ™, Piccotac ™,
Mercures (TM), Wingtack (TM), Hi-Rez (TM)
, Quintone (TM), Tackirol (TM) and the like. Examples of polyterpene resins are Nirez ™, Pi
ccolyte (TM), Wingtack (TM), Zonarez (TM)
And the like. Examples of hydrogenated resins are Escor
Includes resins available under registered trademarks such as ez ™, Arkon ™, Clearon ™, and the like. Examples of mixed aliphatic-aromatic resins are Escorez
(Trademark), Regalite (trademark), Hercures (trademark), AR (trademark), Imprez (trademark), Norsolene (trademark) M, Marukare
z ™, Arkon ™ M, Quintone ™, Wingta
Includes resins available under registered trademarks such as ck ™. One particularly preferred class of tackifiers includes styrene / α-methylenestyrene tackifiers available from Heucules. A particularly preferred class of tackifiers is
Wingtack (TM) 86 and Hercotac (TM) 1149, Ea
stman H-130, and styrene / α-methylstyrene tackifier. These additives are used in functionally equivalent amounts known to those skilled in the art. For example, the amount of antioxidant used is that amount that prevents the polymer or polymer mixture from undergoing oxidation at the temperatures and environments used during storage and ultimate use of the polymer. The amount of such antioxidants usually ranges from 0.01 to 10, preferably 0.05 to 5, more preferably 0.1 to 2 weight percent, based on the weight of the polymer or polymer mixture. Similarly, the amounts of other additives listed may be functionally equivalent, such as making the polymer or polymer mixture anti-blocking, producing the desired result, and providing the desired color from the colorant or pigment. It is the amount that makes it. Such additives may comprise from 0.05 to 50, preferably from 0.1 to 35, based on the weight of the polymer or polymer mixture.
, More preferably in the range of 0.2 to 20 weight percent. Preparation of Mixtures Containing Substantially Random Interpolymers The mixed polymer compositions used to prepare the thin films or sheets or extruded profiles according to the present invention are prepared by dry blending of the individual components and subsequent mixing in a Haake torque rheometer. Melt mixing or melt mixing (m
by any conventional method including melt compounding, or by direct dry blending without melt blending in an extruder or attritor used to produce the final product, followed by partial assembly (eg, Auto parts)
Or a separate extruder or attritor (eg, Banbury mixer)
By pre-melt mixing, or by solution incorporation, or by compression molding, or by calendering. Production of Thin Films or Sheets or Extrusion Profiles According to the Invention Dead-fold thin films according to the invention can be produced by conventional production techniques, such as simple bubble extrusion (usually with high blow rates (BUR)), biaxial orientation processes ( It can be manufactured using simple casting / thin film extrusion, co-extrusion, lamination, etc. Conventional simple bubble extrusion processes (also known as hot blown thin film processes) are described, for example, by Th
e Encyclopedia of Chemical Technology
y, Kirk-Othmer, 3rd Edition, John Wiley & Sons,
New York, 1981, 16: 416-417 and 18: 191-192.
Page. "Double bubbles" of US Pat. No. 3,456,044 (Pahlke)
Biaxially oriented thin film manufacturing process as described in the process and USP 43
No. 52849 (Mueller), US Pat. Nos. 4,820,557 and 483708.
No. 4 (both Warren), USP 4,865,902 (Golike, etc.),
US Pat. No. 4,927,708 (Herran et al.), US Pat. No. 4,952,451 (Mue)
The processes described in US Pat. Nos. 4,963,419 and 5,059,481 (both Lustig et al.) can also be used to produce novel thin film structures according to the present invention. Biaxially oriented thin film structures can also be produced by stretch frame technology as used for oriented polypropylene. Injection molding, thermoforming, extrusion coating, profile extrusion, and sheet extrusion processes have been described, for example, in Plastics Materials and Processes.
s, Seymour S.M. Schwartz and Sidney H.S. Good
man, Van Nostrand Reinhold Company, New York, 1982, pp. 527-563, 632-647, and 596-6.
Page 02. The strips, tapes and ribbons according to the invention can be manufactured by the primary extrusion process itself or by known post-extrusion slitting, cutting or cutting techniques. Profile extrusion is an example of a primary extrusion process that is particularly suited for the manufacture of tapes, bands, and ribbons. The dead-fold film according to the present invention can further be permeable or "breathable" by any method known in the art, including aperturing, slitting, pore formation, mixing with fibers or air bubbles, and the like, and combinations thereof. can do. Examples of such methods are described in Crowe, Jr. USP 315624 by
No. 2, USP 3,881,489 by Hartwell, U by Sissson
Includes SP3989867 and US Pat. No. 5,085,654 by Buell, the contents of which are incorporated herein by reference.

The thin film structure and substantially random interpolymer selected for use in the practice of the present invention will depend in large part on the details of its application; This is different from the preferred properties of the thin film used for stretched wrinkle packaging. The dead-fold thin film structure according to the present invention is a single-phase thin film, or
One or more of the thin film layers may be a multilayer comprising at least one substantially random interpolymer.

In the case of a bear having a multilayered thin film structure, it can be of any conventional structure, for example, two, three, four, five, six, seven, etc. The structure generally has an odd number of layers, and the thin film layer comprising the substantially random interpolymer may be one or both outer layers, or one or more core layers. The layer composed of a polymer other than the substantially random interpolymer can be any suitable material that is generally compatible with thin films composed of the substantially random interpolymer, such as one or more conventional LDPE. , LLDPE, ULDPE, EVA,
EAA may be included. Additives such as those described above for single-layer films can also be used in these multilayer films, and these additives can be used, for example, to incorporate tackifiers and lubricants into one or both outer layers. If desired, the extender can be incorporated in any thin film layer, such as in one or more core layers.

Other multi-layer thin film fabrication techniques for food packaging applications are described in Wilmer A. et al. Je
nkins and James P.N. Packagi by Harrington
ng Foods With Plastics (1991), pp. 19-27,
And Thomas I. "Coextrusion Ba" by Butler
sics ", Film Extrusion Manual: Process,
Materials, Properties, pages 31-80 (TAPPI Pr
Ess (1992)).

[0119] Other desirable properties of the plastic film used in the present invention, depending on the nature of the other thin layers in the structure, are ease of manufacture and good oxygen permeability (especially such as EVA and EAA). Oxygen impervious (especially for films with oxygen barriers such as SARAN or ethylene vinyl alcohol), injection impact, puncture resistance, tension, low modulus, tear resistance, shrinkability, Includes high clarity and low impact on the taste and smell of the packaged food.

The plastic film according to the present invention can be used for a variety of fresh foods, for example, red meat, fish, poultry, vegetables, fruits, cheese, cut at retail, and to be exposed to environmental oxygen. It is very suitable for stretch wrinkle packaging for packaging other foods that benefit from. These films preferably have good oxygen permeability, stretch,
Manufactured as a non-shrink film with elastic restorability and heat tack (eg, without biaxial orientation induced by the double cell process), wholesalers and retailers in any conventional form, eg, stock rolls Is available and can be used for all conventional equipment.

Other plastic films according to the present invention can be used as shrink wrap, skin wrap, and vacuum wrap for food. The film comprising the shrink wrap is typically biaxially oriented, exhibits low shrink tension, has a density of 0.89 g / cm ³ or more,
And typically 0.6 to 2 mils thick. The elastic film structure used for vacuum skin packaging may be multilayer, typically 5 to 12 mils thick.

[0122] Dead-fold films according to the present invention can also be made by an extrusion process, most preferably by a co-extrusion method known in the art.
After co-extrusion, the thin film is poured, for example, with water, or with cooling air.
Cool to solid state. For some structures, the precursor thin film layer (s) can be manufactured by extrusion followed by extrusion coating of additional layers thereon to produce a multilayer thin film. One tube can be made and then coated or laminated to the other to make two multilayer tubes.

Properties of Interpolymers and Mixed Compositions Used in the Production of Thin Films or Sheets or Extruded Profiles According to the Invention

[0124] The polymer composition used to make the thin film or sheet or extruded profile according to the present invention comprises one or more α-olefins and one or more monovinyl aromatic monomers or one or more fats. One or more interpolymers consisting of a group or cycloaliphatic vinyl or vinylidene monomer, or a combination thereof, are combined with 25 to 100, preferably 40 to 95, more preferably 50 to 95 weight percent (substantially (Based on the total weight with the polymer components other than the random interpolymer).

These substantially random interpolymers typically comprise at least one vinyl aromatic monomer or aliphatic or cycloaliphatic vinyl or vinylidene monomer, or a combination thereof, from 29 to 65, preferably from 33 to 65,
More preferably, it contains 35 to 65 mole percent, and at least one aliphatic α-olefin having 2 to 20 carbon atoms, 35 to 71, preferably 35 to 67, more preferably 35 to 65 mole percent.

The average molecular weight (Mn) of the substantially random interpolymer used to produce the thin film or sheet or extruded profile according to the present invention is 10,000
As mentioned above, it is preferably 20,000 to 500,000, more preferably 30,000 to 300,000.

[0127] The melt index (I ₂ ) of the substantially random interpolymer used to produce the thin film or sheet or extruded profile according to the present invention is 0.1.
01 to 100, preferably 0.1 to 20, more preferably 0.1 to 5 g / 10 min.

The molecular weight distribution (M _w / M _n ) of the substantially random interpolymer used to produce the thin film or sheet or the extruded profile according to the present invention is 1.5
-20, preferably 1.8-10, more preferably 2-5.

The density of the substantially random interpolymer used in the production of the thin film or sheet or the extruded profile according to the invention has a density of 0.930 or more, preferably 0.930 to 1.045, more preferably 0. It is 930 to 1.040, most preferably 0.930 to 1.030 g / cm ³ .

The polymer composition used for producing the thin film or sheet or the extruded profile according to the invention may further comprise a homogeneous α-olefin homopolymer or polypropylene, propylene / C ₄ -C ₂₀ α-olefin copolymer, polyethylene , and it may include interpolymers comprising ethylene / C ₃ -C ₂₀ α- olefin copolymers, 0 to at least one polymer other than the substantially random interpolymer 75, preferably 5 to 60, to more preferably not 5 5
0% by weight (based on the combined weight of this component and the substantially random interpolymer), the interpolymer being a heterogeneous ethylene / α-olefin interpolymer, preferably a heterogeneous ethylene / C ₃ -C ₈ α-olefin interpolymers, most preferably heterogeneous ethylene / octene-1 interpolymers, or homogeneous ethylene / α-olefin interpolymers, including substantially linear ethylene / α-olefin interpolymers, preferably Is a substantially linear ethylene / α-olefin interpolymer, most preferably a substantially linear ethylene / C ₃ -C ₈ α-olefin interpolymer; or a heterogeneous ethylene / α-olefin interpolymer; or Thermoplastic olefin, preferably ethyl / Propylene rubber (EPM) or ethylene / propylene diene monomer terpolymer (EPDM) or isotactic polypropylene, most preferably isotactic polypropylene; or styrene block copolymer, preferably styrene-butadiene (SB), styrene-isoprene- (
SI), styrene-butadiene-styrene (SBS), styrene-isoprene-
Styrene (SIS) or styrene-ethylene / butene-styrene (SEBS)
Block copolymers, most preferably styrene-butadiene-styrene (SBS
Or a styrene homopolymer or copolymer, preferably a copolymer of polystyrene, high impact polystyrene, polyvinyl chloride, styrene and at least one of acrylonitrile, methacrylonitrile, maleic anhydride, or α-methylstyrene, most preferably Polystyrene or elastomer, preferably polyisoprene, polybutadiene, natural rubber, ethylene / propylene rubber, ethylene / propylene diene (EPDM) rubber, styrene / butadiene rubber, thermoplastic polyurethane, most preferably thermoplastic polyurethane; or vinyl halide homopolymer Polymers and copolymers, preferably homopolymers or copolymers of vinyl chloride or vinylidene chloride or chlorinated derivatives thereof, most preferred Poly (vinyl chloride) and poly (vinylidene chloride); or engineered thermoplastics, preferably poly (methyl methacrylate) (PMMA
), Cellulosic materials, nylon, poly (ester), poly (acetal); poly (amide), poly (arylate), aromatic polyester, poly (carbonate), poly (butylene) and polybutylene and polyethylene terephthalate, most preferably It may be poly (methyl methacrylate) (PMMA), and poly (ester).

The thin film or sheet or extruded profile according to the invention can be used successfully for packaging in general and especially for the packaging of small articles. Other possible applications are meat packing, paper substitution, standing or flat bottom bags, tablecloths and shower curtains, collapsible bottles or containers, tubes such as toothpaste paste tubes, collapsible structures Objects, boxes, cartons, window boxes, surgical sterile cloth, moldable membranes, toys, tubing and clothing,
Includes, but is not limited to, tapes, laminate films, pressure sensitive labels.

The following examples illustrate the invention and should not be construed as limiting its scope in any manner.

[0133]

Examples

Test Methods a) Melt Flow and Density Measurement

The molecular weight of the polymer composition used in the present invention is determined according to ASTM D-1238, Con
dition 190 ℃ / 2.16kg (formerly as Condition (E), also known was as _{I 2)} is conveniently demonstrated using a melt index measurement by. Melt index is inversely proportional to the molecular weight of the polymer. Thus, although not linearly related, the higher the molecular weight, the lower the melt index.

[0137] useful to indicate the molecular weight of the substantially random interpolymers used in the present invention, Gottfert melt index (G, ^cm 3/10 min), but the melt density of polyethylene at 190 ° C. The melt index (I) was determined using the ASTM D1238 method for an automated plastometer set at 0.7632.
_It is obtained as in ₂ ).

The relationship of melt density to styrene content for ethylene-styrene interpolymers as a function of total styrene content from 29.8% by weight styrene to 81.8
Measured at 190 ° C. in the range of weight percent styrene. The concentration of atactic polystyrene in these samples is typically less than 10%. It was assumed that there was little effect of atactic polystyrene due to low levels. Also, the melt density of atactic polystyrene and the melt viscosity of samples with high total styrene content are very similar. How to measure the melt density, using a Gottfert melt index machine set a melt density parameter 0.7632, was collected melt strands as a function of time during measurement of I ₂ wt. The weight and time of each melt strand was recorded and normalized to give the amount in grams per 10 minutes. I ₂ melt index values the device has calculated was also recorded. The formula for calculating the actual melt index is

Δ = δ _0.7632 × I ₂ / I ₂ Gottfert,

In the above equation, δ _0.7632 = 0.7632, and I ₂ Gottfert = the indicated melt index.

A linear least squares fitting of the calculated melt density to total styrene content yielded the following equation with a correlation coefficient of 0.91:

Δ = 0.00299 × S + 0.723

In the above formula, S = weight percentage of styrene in the polymer. If the styrene content is known, the relationship of total styrene to melt density can be used to determine the actual melt index value from these equations.

Thus, for a polymer whose melt flow (“Gottfert number”) is measured and the total styrene content is 73%, the calculation is as follows:

X = 0.00299 × 0.73 + 0.723 = 0.9412

In the above equation, 0.9412 / 0.7632 = I ₂ / G # (measured value) ≒ 1.23
It is.

The density of the substantially random interpolymer used in the present invention is
It measured according to D-792.

B) Styrene analysis

Interpolymer styrene content and atactic polystyrene concentration were measured using proton nuclear magnetic resonance ( ¹ H NMR). Proton NMR All samples were prepared in 1,1,2,2-tetrachloroethane _{-d 2 (TCE-d 2)} . The resulting solution had a polymer concentration of 1.6-3.2 weight percent. Melt index (I ₂ ) was used as an index in determining sample concentration. Thus, using the interpolymer when 40mg _{of I 2} is greater than 2 g / 10 min; with interpolymers of 30mg is between _{I 2} is 1.5~2g / 10 min; _I less than ₂ 1.5 g / 10 min In this case, 20 mg of the interpolymer was used. The interpolymer was weighed directly into a 5 mm sample tube. T
The _{CE-d 2} was added by syringe by 0.75 mL, were capped with seal plug capable polyethylene cap. The sample was heated in a water bath at 85 ° C. to soften the interpolymer. To mix, the capped sample was heated and refluxed occasionally using a heat gun.

The proton NMR spectrum was measured with a Varian VXR 300 with the sample probe set at 80 ° C. and the residual hydrogen of TCE-d ₂ set at 5.99 ppm. The lag time was varied between 1 second and the data was measured three times for each sample. The interpolymer sample was analyzed using the following apparatus conditions.

Varian VXR-300, standard ¹ H; sweep width, 5000 Hz data acquisition time, 3.002 seconds pulse width, 8 μs frequency, 300 MHz delay, 1 second integration frequency, 16

The total analysis time per sample was 10 minutes.

[0153]

Embedded image

Initially, a polystyrene sample, Styron ^™ 680 (Dow Chem)
The ¹ H NMR spectrum of commercially available from ical Company, Midland, Mich. was measured with a 1 second delay time. Protons are "classified" as b; branched, a; alpha, o; ortho, m; meta, p; para, as shown in FIG.

The integration was measured around the protons classified in FIG. “A” represents aPS. The integral A _7.1 (aromatic ring, around 7.1 ppm) appears to be three ortho / para protons. The integral A _6.6 (aromatic ring, around _6.6 ppm) is two metaprotons. Two aliphatic protons, labeled α, resonate at 1.5 ppm and one proton, denoted b, is at 1.9 ppm. The aliphatic region is increased from 0.8 to 2.5
and integral to _ppm, expressed as _{A al.} The theoretical ratio of A _7.1 : A _6.6 : A _al is 3
: 2: 3 or 1.5: 1: 1.5, and S with some delay time of 1 second
Very consistent with the ratio observed for the tyron ^™ 680 sample. The calculation of the ratio used to check the integration and confirm the peak assignment was performed by dividing the appropriate integration value by the integration value A _6.6 . The ratio _Ar is A _7.1 / A _6.6 .

The area A _6.6 has been assigned a value of 1. The ratio Al is an integral value A _al / A _6.6 . The total spectrum measured is the expected 1 for (o + p): m: (a + b)
. The integrated value was 5: 1: 1.5. The ratio of aromatic ring to aliphatic proton is 5: 3. An aliphatic ratio of 2: 1 is predicted based on the protons classified as a and b, respectively, in FIG. This ratio was observed even when the two aliphatic peaks were integrated separately.

In the ethylene / styrene interpolymer, a 1 second delay time¹H NMR spec
The vector is copolyester with the o and p protons of aPS integrated at 7.1 ppm.
In order to include the total aromatic protons of the_7.1, C_6.6And C_al
Is defined. Similarly, in the spectrum of the interpolymer, the aliphatic region C_alProduct
The fraction separates aliphatic protons from both the aPS and the interpolymer into each polymer.
The signal from is included without being clearly separated at baseline. 6.
Integral C of the peak at 6 ppm_6.6Is separated from other aromatic signals and a
It is thought to be due solely to the PS homopolymer (possibly a metaproton). Atakute
Of peak at 6.6 ppm for the polystyrene (integral value A_6.6), Sure
Sample Styron^TM680 (Dow Chemical Company)
y, available from Midland, MI;
I went. When atactic polystyrene is at very low levels,
This is a reasonable assumption since only weak signals are always visible. Therefore,
The phenyl proton of the copolymer should not contribute to this signal. This assumption
Below, integral value A_6.6Is a standard for quantitatively measuring the aPS content.

The degree of styrene uptake of the ethylene / styrene interpolymer sample can then be determined using the following equation: (C phenyl) = C _7.1 + A _7.1 − (1.5 × A _6.6 ) (C _{aliphatic) = C al - (1.5 ×} A 6.6) S c = (C -phenyl) / _{5 e} c = (C aliphatic _{- (3 × S c))} / 4 E = e c / _{(e c + s c) S} c = s c / (e c + s c) is a mole percent ethylene and styrene in the interpolymer using the following equation can be calculated,

[0159]

(Equation 1) and

[0160]

(Equation 2) In the above equation, s _c and e _c are styrene and ethylene proton fractions in the interpolymer, respectively, Sc and E are mole fractions of styrene monomer and ethylene monomer in the interpolymer, respectively.

The weight percentage of aPS in the interpolymer was determined from the following equation.

[0162]

(Equation 3)

The total styrene content is also measured by quantitative Fourier transform infrared spectroscopy (FTIR). Preparation of ESI interpolymer used in Examples and Comparative Examples of the present invention 1) Preparation of ESI Nos. 1 to 7

ESI Nos. 1-7 are substantially random ethylene / styrene interpolymers prepared using the following catalyst and polymerization procedure. Catalyst A (dimethyl [N- (1,1-dimethylethyl) -1,1-dimethyl-1-
Preparation of [(1,2,3,4,5-η) -1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl] silane aminato (2-)-N] -titanium

1) Preparation of 3,5,6,7-tetrahydro-s-hydrindacene-1 (2H) -one

Indane (94.00 g, 0.7954 mol) and 3-chloropropionyl chloride (100.99 g, 0.7954) were slowly added under a nitrogen stream while AlCl ₃ (130.00 g, 0.9750 mol) was added. Mole) with CH ₂ Cl ₂ (
(300 mL) at 0 ° C. The mixture was stirred at room temperature for 2 hours. The volatiles were then removed. The mixture was cooled to 0 ° C. and concentrated H ₂ SO ₄ (500 mL) was added slowly. In this step, it was necessary to frequently break up the resulting solids with a spatula, since solids formed and agitation stopped immediately. The mixture was left overnight at room temperature under a nitrogen atmosphere. The mixture was then heated until the thermometer reading reached 90 °. This condition was maintained for 2 hours, during which the mixture was occasionally stirred with a spatula. After the reaction time, crushed ice was put into the mixture and moved. The mixture was then transferred to a beaker, washed intermittently with H ₂ O and diethyl ether, and the fractions were collected by filtration. The mixture was washed with _{H 2 O (2 × 200mL)} . The organic layer was separated and volatiles were removed. The desired product was isolated as pale yellow crystals by recrystallization from hexane at 0 ° C. (22.36 g, 16.3% yield).

¹ H NMR (CDCl ₃ ): d 2.04-2.19 (m, 2H), 2.65
(T, ³ J _HH = 5.7 Hz, 2H), 2.84-3.0 (m, 4H), 3.0
3 (t, ³ J _HH = 5.5 Hz, 2H), 7.26 (s, 1H), 7, 53 (s
, 1H)

¹³ C NMR (CDCl ₃ ): d 25.71, 26.01, 32.19, ₃
3.24, 36.93, 118.90, 122.16, 135.88, 144.
06,152.89,154.36,206.50

GC-MS: calcd. For C ₁₂ H ₁₂ O 172.09, found 172.05

2) Preparation of 1,2,3,5-tetrahydro-7-phenyl-s-indacene

PhMgBr (0.105 mol, 35.00 of 3.0 M diethyl ether solution)
of 3,5,6,7-tetrahydro-s-hydrindacene-1 (2H) -one (12.00 g, 0.06967 mol) in diethyl ether (200 mL) at 0 ° C. while slowly adding did. The mixture was stirred overnight at room temperature. At the end of the reaction time, the mixture was poured on ice and quenched. The mixture was acidified (pH = 1) with HCl and stirred vigorously for 2 hours. Then the organic layer was separated and H ₂ O (
2 × 100 mL) and dried over MgSO ₄ . The desired product was isolated as a black oil by filtration and removal of volatiles (14.68 g, 90.3% yield).
).

¹ H NMR (CDCl ₃ ): d2.0-2.2 (m, 2H), 2.8-3.
1 (m, 4H), 6.54 (s, 1H), 7.2-7.6 (m, 7H)

GC-MS: calcd for C ₁₈ H ₁₆ 232.13, found 232.05.

3) Preparation of 1,2,3,5-tetrahydro-7-phenyl-s-indacene dilithium salt

While slowly adding n-BuLi (0.080 mol, 40 mL of a 2.0 M cyclohexane solution), 1,2,3,5-tetrahydro-7-phenyl-s-indacene (14.68 g, 0. (06291 mol) was stirred in hexane (150 mL). The mixture was stirred overnight. At the end of the reaction time, the solid was collected by suction filtration as a yellow solid, washed with hexane, dried under vacuum and used without purification and analysis (12.2075 g, 81.1% yield).

4) Preparation of chlorodimethyl (1,5,6,7-tetrahydro-3-phenyl-s-indacene-1-yl) silane

1,2,3,5-tetrahydro-7-phenyl-s- in THF (50 mL)
Indacene dilithium salt (12.2075 g, 0.05102 mol) was added to THF
(100 mL) dissolved in Me ₂ SiCl ₂ (19.5010 g, 0.151 g).
1 mol) at 0 ° C. The mixture was stirred overnight at room temperature. After the reaction time, the volatiles were removed and the residue was extracted with hexane and filtered. Upon removal of the hexane, the desired product was isolated as a yellow oil (15.1492 g, 91.1 yield).
%).

¹ H NMR (CDCl ₃ ): d0.33 (s, 3H), 0.38 (s, 3H)
) 2.20 (p, ³ J _HH = 7.5 Hz, 2H), 2.9-3.1 (m, 4H)
_{^{, 3.84 (s, 1H),}} 6.69 (d, 3 J HH = 2.8Hz, 1H), 7.
_{^{3-7.6 (m, 7H), 7.68}} (d, 3 J HH = 7.4Hz, 2H)

¹³ C NMR (CDCl ₃ ): d 0.24, 0.38, 26.28, 33.
05, 33.18, 46.13, 116.42, 119.71, 127.51,
128.33,128.64,129.56,136.51,141.31,1
41.86, 142.17, 142.41, 144.62

GC-MS: Calcd. For C ₂₀ H ₂₁ ClSi 324.11, found 324.0.
5

5) N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6
Preparation of (7,7-tetrahydro-3-phenyl-s-indacen-1-yl) silaneamine

NEt ₃ (3.5123 g, 0.03471 mol) and t-butylamine (
While adding 2.6074 g (0.03565 mol), chlorodimethyl (1,5
, 6,7-Tetrahydro-3-phenyl-s-indacen-1-yl) silane (
(10.8277 g, 0.03322 mol) was stirred in hexane (150 mL). The mixture was stirred for 24 hours. After the reaction time, the mixture was filtered and volatiles removed to isolate the desired product as a deep reddish yellow oil (10.6551 g, 88.7% yield).

¹ H NMR (CDCl ₃ ): d 0.02 (s, 3H), 0.04 (s, 3H)
), 1.27 (s, 9H), 2.16 (p, ³ J _HH = 7.2 Hz, 2H), 2
. 9-3.0 (m, 4H), 3.68 (s, 1H), 6.69 (s, 1H), 7
. _{^{3-7.5 (m, 4H), 7.63}} (d, 3 J HH = 7.4Hz, 2H)

¹³ C NMR (CDCl ₃ ): d-0.32, -0.09, 26.28, 3
3.39, 34.11, 46.46, 47.54, 49.81, 115.80,
119.30, 126.92, 127.89, 128.46, 132.99, 1
37.30, 140.20, 140.81, 141.64, 142.08, 14
4.83

6) N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6
Preparation of (7,7-tetrahydro-3-phenyl-s-indacen-1-yl) silaneamine dilithium salt

N-BuLi (35.00 m of a 0.070 mol, 2.0 M cyclohexane solution)
L) while slowly adding N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s-indacene-
1-yl) silaneamine (10.6551 g, 0.02947 mol) was stirred in hexane (100 mL). The mixture was stirred overnight, during which no salt was formed from the dark red solution. After the reaction time, the volatiles were removed and the residue was quickly washed with hexane (2 × 50 mL). The dark red residue was pump dried and used without purification and analysis (9.6517 g, 87.7% yield).

7) Dichloro [N- (1,1-dimethylethyl) -1,1-dimethyl-1- [
Preparation of (1,2,3,4,5-η)-(1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl] silane aminato (2-)-N] titanium

N- (1,1-dimethylethyl) -1,1-dimethyl-1- (1,5,6,7-tetrahydro-3-phenyl-s-indacene-1- in THF (50 mL).
Il) silane amine dilithium salt (4.5355 g, 0.01214 mol)
TiCl ₃ (THF) _{3 in} THF (100 mL) (4.5005 g, 0.01
(214 mol) of slurry. The mixture was stirred for 2 hours. Then Pb
Cl ₂ (1.7136g, 0.006162 mol) was added and the mixture stirred for a further 1 hour. After the reaction time, the volatiles were removed, the residue was extracted with toluene and filtered. The toluene was removed and the black residue was isolated. The residue was slurried in hexane and cooled to 0 ° C. The desired product was isolated by filtration as a red-brown crystalline solid (2.5280 g, 43.5% yield).

¹ H NMR (CDCl ₃ ): s0.71 (s, 3H), 0.97 (s, 3H)
), 1.37 (s, 9H), 2.0-2.2 (m, 2H), 2.9-3.2 (m
, 4H), 6.62 (s, 1H), 7.35-7.45 (m, 1H), 7.50.
(T, ³ J _HH = 7.8 Hz, 2H), 7.57 (s, 1H), 7.70 (d,
³ J _HH = 7.1 Hz, 2H), 7.78 (s, 1H)

¹ H NMR (C ₆ D ₆ ): d 0.44 (s, 3H), 0.68 (s, 3H)
, 1.35 (s, 9H), 1.6-1.9 (m, 2H), 2.5-3.9 (m,
4H), 6.65 (s, 1H), 7.1-7.2 (m, 1H), 7.24 (t,
³ J _HH = 7.1 Hz, 2H), 7.61 (s, 1H), 7.69 (s, 1H)
, 7.77-7.8 (m, 2H)

¹³ C NMR (CDCl ₃ ): d1.29, 3.89, 26.47, 32.
62, 32.84, 32.92, 63.16, 98.25, 118.70, 12
1.75, 125.62, 128.46, 128.55, 128.79, 129
. 01, 134.11, 134.53, 136.04, 146.15, 148.
93

¹³ C NMR (C ₆ D ₆ ): d 0.90, 3.57, 26.46, 32.5
6, 32.78, 62.88, 98.14, 119.19, 121.97, 12
5.84, 127.15, 128.83, 129.03, 129.55, 134
. 57, 135.04, 136.41, 136.51, 147.24, 148.
96

8) Dimethyl [N- (1,1-dimethylethyl)]-1,1-dimethyl-1-
Preparation of [(1,2,3,4,5-η) -1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl] silane aminato (2-)-N] -titanium

A MeMgBr (0.0021 mol, 3.0 M diethyl ether solution was added to 0.70
mL) while slowly adding dichloro [N- (1,1-dimethylethyl)-
1,1-Dimethyl-1-[(1,2,3,4,5-η)-(1,5,6,7-tetrahydro-3-phenyl-s-indacen-1-yl] silane aminato (2-
) -N] titanium (0.4970 g, 0.001039 mol) was stirred in diethyl ether (50 mL). The mixture was stirred for 1 hour. After the reaction time, the volatiles were removed and the residue was extracted and filtered with hexane. Upon removal of the hexane, the desired product was isolated as a golden solid (0.4546 g, 66.7% yield).

¹ H NMR (C ₆ D ₆ ): d 0.071 (s, 3H), 0.49 (s, 3H)
), 0.70 (s, 3H), 0.73 (s, 3H), 1.49 (s, 9H), 1
. 7-1.8 (m, 2H), 2.5-2.8 (m, 4H), 6.41 (s, 1H)
), 7.29 (t, ³ J _HH = 7.4 Hz, 2H), 7.48 (s, 1H), 7
. 72 (d, ³ J _HH = 7.4 Hz, 2H), 7.92 (s, 1H)

¹³ C NMR (C ₆ D ₆ ): d 2.19, 4.61, 27.12, 32.8.
6, 33.00, 34.73, 58.68, 58.82, 118.62, 121
. 98, 124.26, 127.32, 128.63, 128.98, 131.
23, 134.39, 136.38, 143.19, 144.85

Catalyst B (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t
Preparation of -butylamido) -silanetitanium 1,4-diphenylbutadiene

1) Preparation of 1H-cyclopenta [l] phenanthren-2-yl

In a 250 mL round bottom flask containing 1.42 g (0.00657 mol) of 1H-cyclopenta [l] phenanthrene and 120 mL of benzene, 4.2 mL of a 1.6 M solution of n-BuLi dissolved in mixed hexane. Was added dropwise. The solution was stirred overnight. The lithium salt was isolated by filtration and 2 mL with 25 mL of benzene.
Washed twice and dried under vacuum. The isolated yield is 1.426 g (97.7%)
Met. ¹ H NMR analysis showed that the isomer substituted at the 2-position was predominant.

2) Preparation of (1H-cyclopenta [l] phenanthren-2-yl) dimethylchlorosilane

4.16 g (0.0322 mol) of dimethyldichlorosilane (Me ₂ SiCl
₂ ) and 250 mL of tetrahydrofuran (THF) in a 500 mL round bottom flask were charged with 1.45 g (0.0064 mol) of lithium 1H-cyclopenta [
l] A solution of phenanthren-2-yl in THF was added and added. The solution was stirred for about 16 hours, after which the solvent was removed under reduced pressure leaving an oily solid which was extracted with toluene, filtered through diatomaceous earth filter aid (Celite ^™ ) and washed twice with toluene. And dried under reduced pressure. The isolated yield is 1.98 g (
99.5%).

[0202] 3. (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t-
Preparation of butylamino) silane

50 charged with 1.98 g (0.0064 mol) of (1H-cyclopenta [l] phenanthren-2-yl) dimethylchlorosilane and 250 mL of hexane.
To a 0 mL round bottom flask was added 2.00 mL (0.0160 mol) of t-butylamine. The reaction mixture was stirred for several days, filtered through diatomaceous earth filter aid (Celite ^™ ) and washed twice with hexane. The product was isolated by removing the remaining solvent under reduced pressure. The isolated yield was 1.98 g (88.9%).

[0204] 4. Preparation of dilithio (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t-butylamido) silane

In a 250 mL round bottom flask containing 1.03 g (0.0030 mol) of (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t-butylamino) silane and 120 mL of benzene, 1.6 M was added. 3.90 ml of a mixed hexane solution of n-BuLi was added dropwise. The reaction mixture was stirred for about 16 hours. The product was isolated by filtration, washed twice with benzene and dried under reduced pressure. The isolated yield was 1.08 g (100%).

[0206] 5. (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t-
Preparation of butylamido) silane titanium dichloride

[0207] 1.17g in 250mL round-bottom flask containing THF of TiCl ₃ · 3THF and 120mL of (0.0030 mol), dilithio (1H-Shikupenta [l]
A solution of 1.08 g of phenanthren-2-yl) dimethyl (t-butylamido) silane in THF was added at a rapid dropping rate of 50 ml. The mixture was stirred at 20 ° C. for 1.5 hours, during which 0.55 g (0.002 mol) of solid PbCl ₂ was added. After stirring for an additional 1.5 hours, the THF was removed under vacuum and the residue was extracted with toluene, filtered and dried under reduced pressure to give an orange solid. The yield was 1.31 g (93.5%).

[0208] 6. (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t-
Preparation of butyramido) silane titanium 1,4-diphenylbutadiene

(1H-Cyclopenta [l] phenanthren-2-yl) dimethyl (t-butylamido) silanetitanium dichloride (3.48 g, 0.0075 mol) and 1.551 g (0.0075 mol) in 80 mL toluene To a 70 ° C. slurry of 1,4-diphenylbutadiene was added 9.9 ml of a 1.6 M solution of n-BuLi.
(0.0150 mol) was added. The solution darkened immediately. The temperature was raised and the mixture was refluxed and kept at that temperature for 2 hours. The mixture was cooled to -20 <0> C and volatiles were removed under reduced pressure. The residue was slurried in 60 ml of mixed hexane at 20 ° C. for about 16 hours. The mixture was cooled to -25 C for 1 hour. The solid was collected on a glass frit by vacuum filtration and dried under reduced pressure. The dried solid was placed in a cylindrical glass fiber and continuously extracted with hexane using a Soxhlet extractor. After 6 hours, a crystalline solid was found in the boiling pot. The mixture was cooled to −20 ° C., isolated by filtration from the cold mixture and dried under reduced pressure to give 1.62 g of a black crystalline solid. The filtrate was discarded. Stirring of the solids in the extractor and continued extraction with an additional amount of mixed hexane provided an additional 0.46 g of the desired product as a black crystalline solid.

Preparation of cocatalyst E (bis (hydrogenated tallowalkyl) methylamine

Methylcyclohexane (1200 mL) was placed in a 2 L cylindrical flask. While stirring, bis (hydrogenated tallowalkyl) methylamine (ARMENE, M2
HT, 104 g, pulverized to fine particles) was added to the flask and stirred until completely dissolved. Aqueous HCl (1M, 200 mL) was added to the flask and the mixture was stirred for 30 minutes. A white precipitate formed immediately. At the end of this period, LiB (
_{C 6 F 5) 4 · Et} 2 O · 3LiCl (Mw = 887.3; the 177.4G) was added to the flask. The solution began to turn milky. The flask was fitted with a 6 inch Vigreux column with a distillation apparatus on top and the mixture was heated (outer wall temperature 1
40 ° C). A mixture of ether and methylcyclohexane was distilled from the flask. The biphasic solution was now only slightly cloudy. The mixture was allowed to cool to room temperature and the contents were placed in a 4 L separatory funnel. The aqueous layer was removed and discarded, the organic layer was washed twice with water and the aqueous layer was discarded again. When a water-saturated methylcyclohexane solution is measured,
. It contained 48% by weight of diethyl ether (Et ₂ O).

The solution (600 mL) was transferred to a 1 L flask, sparged thoroughly with nitrogen, and transferred into a dry box. The solution was passed through a column (1 inch in diameter, 6 inches in height) containing 13X molecular sieves. Thereby, the concentration of Et ₂ O was 0.48% by weight.
To 0.28% by weight. Use this material as a fresh 13X molecular sieve (
20 g) for 4 hours. The Et ₂ O concentration was measured to be 0.19% by weight. When the mixture was stirred overnight, the Et ₂ O concentration dropped further to about 40 ppm.
The mixture was filtered through a funnel with a glass frit of 10-15 μm pore size to give a clear solution (molecular sieves rinsed with additional dry methylcyclohexane). The concentration was determined by gravimetric analysis, giving a value of 16.7% by weight.

Polymerization

ESI numbers 1-7 were prepared in a 6 gallon (22.7 L) oil jacketed autoclave continuous stirred tank reactor (CSTR). LightningA
The mixing was carried out with a magnetically coupled stirrer with -320 stirring blades. The reactor is filled with liquid at 475 psig (3,275 kPa). The process flow entered at the bottom and exited at the top. Heat transfer oil was circulated through the reactor jacket to remove some of the heat of reaction. There was a fine flow meter at the outlet of the reactor to measure the flow rate and solution density. All lines at the outlet of the reactor were 50 psi (344.
(7 kPa) steam and insulated.

[0215] Toluene solvent was fed to the reactor at 30 psig (207 kPa). Feed to the reactor was measured with a Micro-Motion mass flow meter. The feed rate was controlled by a variable speed diaphragm pump. Upon discharge of the solvent pump, a side stream was drawn to draw the catalyst injection line (1 lb / hr (0.45 kg / hr)) and reactor agitator (
The wash flow was provided at 0.75 pounds / hour (0.34 kg / hour). These flows were measured by a differential pressure flow meter and controlled by manual adjustment with a micro-flow needle valve. 30 psig (207 kPa) of styrene monomer without polymerization inhibitor
To the reactor. Feed to the reactor was measured with a Micro-Motion mass flow meter. The feed rate was controlled by a variable speed diaphragm pump. The styrene stream and the remaining solvent stream were mixed. 600 psig of ethylene (4.137 k
Pa). Ethylene flow is preceded by Mi before the Research valve control flow.
It was measured with a cro-Motion mass flow meter. Hydrogen was supplied to the ethylene stream at the outlet of the ethylene control valve using a Brooks flow meter / controller.
The ethylene / hydrogen mixture was combined with the solvent / styrene stream at room temperature. As the solvent / monomer temperature entered the reactor, it was lowered to -5 ° C by a circulating exchanger of -5 ° C glycol in the jacket. This stream entered the bottom of the reactor. The ternary catalyst system and its solvent stream also entered the bottom of the reactor, but from a separate inlet to the monomer stream. Preparation of the catalyst component was performed in a glove box in an inert atmosphere. The diluted components were placed in a nitrogen-filled cylinder and charged to the catalyst operation tank in the process area. From these operation tanks, the catalyst pressure is increased by a piston pump, and the flow rate is set to Mic.
It was measured by a ro-Motion mass flow meter. These streams merged and the catalyst flushed the solvent before the entrance through a single injection line to the reactor.

After the fine flow meter measured the solution density, the polymerization was stopped by adding a catalyst kill (water mixed with solvent) to the reaction product line. Other polymer additives may be added with the catalyst kill. A static mixer in the line dispersed the catalyst kill and additives in the reactor effluent. This stream then enters the reactor post heater, where the solvent removal stream gains additional energy. This flow occurred when the effluent exited the post-reactor heater and the pressure went from 475 psig (3.275 kPa) to about 250 mm absolute of the reactor pressure control valve. The polymer flowed into a hot oil jacketed devolatilizer. About 85% volatiles were removed from the polymer in the devolatilizer. Volatiles exited the top of the devolatilizer. This stream was condensed by a glycol-jacketed exchanger and entered the vacuum pump suction and discharged to a glycol-jacketed solvent and / or styrene / ethylene separation vessel. Solvent and styrene were removed from the bottom of the vessel and ethylene was removed from the top.
Ethylene flow was measured with a Micro-Motion mass flow meter and its composition was analyzed. Ethylene conversion was calculated using measurements of the ethylene discharged and the calculated gas dissolved in the solvent / styrene stream. The polymer separated in the devolatilizer was discharged by a gear pump and put into a ZSK-30 devolatilizing vacuum extruder. The dried polymer exited the extruder as a single strand. The strand was cooled while being pulled in a water bath. Excess moisture was blown off from the strand by air, and the strand was cut into pellets by a strand chopper.

The various catalysts, cocatalysts and process conditions used to prepare the various ethylene styrene interpolymers (ESI Nos. 1-7) are summarized in Table 1 and their properties are summarized in Table 2.

[0218]

[Table 1]

A The catalyst A is (dimethyl [N- (1,1-dimethylethyl)]-1,1-dimethyl-1-[(1,2,3,4,5-η) -1,5,6 , 7-Tetrahydro-3
-Phenyl-s-indacen-1-yl] silane aminato (2-)-N] -titanium.

B Catalyst B is (1H-cyclopenta [l] phenanthren-2-yl) dimethyl (t-butylamido) -silanetitanium 1,4-diphenylbutadiene.

C Catalyst C was prepared as described in US Pat. No. 5,556,928 Example 17 (t-butylamido) dimethyl (tetramethylcyclopentadienyl)
Silane-titanium (II) 1,3-pentadiene.

D Promoter D is tris (pentafluorophenyl) borane (CAS number 001109-15-5),

E Promoter E is (bis (hydrogenated tallowalkyl) methylammonium tetrakis (pentafluorophenyl) borane.

F Modified methylaluminoxane commercially available as MMAO-3A from Akzo Nobel (CAS number 146905-79-5)

[0225]

[Table 2]

Example 1

Sample ESI2 containing 38.4 mol% styrene (69.8% by weight) and having a Gottfeld melt index (G #) of 0.9 cm3 / 10 minutes was prepared using 12
Operating at 415 ° F. with / 6/6 24: 1 L / D screw1.
The film was processed using a 25-inch extruder. The die had a 60 mil die gap and a 3 ″ diameter. (The extrusion conditions are summarized in Table 3.) The resulting film having a thickness of about 1.5 mil-2.0 mil is noted here. A force relaxation test was performed to determine the permanent fold properties as described, and the results are summarized in Table 4 and show a desired% force relaxation of 40% or more for MD or CD or both.

Embodiment 2

A sample ESI3 containing 43.5 mol% of styrene (74.6% by weight) and having a Gottfeld melt index (G #) of 1.3 cm3 / 10 minutes was processed into a film in the same manner as in Example 1. Tested. The results are summarized in Table 4 and MD
Or a desired% force relaxation greater than 40% for CD or both.

Embodiment 3

A sample ESI1 containing 43.1 mol% of styrene (73.73% by weight) and having a Gottfeld melt index (G #) of 2.4 cm 3/10 minutes was processed into a film in the same manner as in Example 1. Tested. The results are summarized in Table 4, MD or C
The desired% force relaxation greater than 40% for D, or both, was not shown.

Comparative Experiment 1

A sample ESI1 containing 15.4 mol% of styrene (40.8% by weight) and having a Gottfeld melt index (G #) of 1.4 cm 3/10 minutes was processed into a film in the same manner as in Example 1. Tested. The results are summarized in Table 4.
The desired% power relaxation greater than 40% for D, or both, was not shown.

Comparative Experiment 2

A sample ESI4 containing 10.5 mol% styrene (30.3% by weight) and having a Gottfeld melt index (G #) of 1.6 cm 3/10 minutes was processed into a film in the same manner as in Example 1. Tested. The results are summarized in Table 4 and are either MD or CD
, Or both, did not exhibit the desired% force relaxation greater than 40%.

Comparative Experiment 3

A sample ESI5 containing 26.2 mol% of styrene (56.9% by weight) and having a Gottfeld melt index (G #) of 1.2 cm 3/10 minutes was processed into a film in the same manner as in Example 1. Tested. The results are summarized in Table 4 and are either MD or CD
, Or both, did not exhibit the desired% force relaxation greater than 40%.

Comparative Experiment 4

A sample ESI6 containing 17.2 mol% of styrene (43.6% by weight) and having a Gottfeld melt index (G #) of 1.0 cm3 / 10 minutes was processed into a film in the same manner as in Example 1. Tested. The results are summarized in Table 4 and are either MD or CD
, Or both, did not exhibit the desired% force relaxation greater than 40%.

[0240]

[Table 3]

Test method

The sample size of the force relaxation MD (vertical direction) is CD (horizontal direction) width 25 mm and MD length 1
It was 27 mm. The sample was pulled using a tensile tester with a 50 mm gauge length set to 100% at 250 mm / min. The sample was then fixed in its extended state for 30 seconds. The initial force and the force after 30 seconds are recorded. Next, the load was removed at the same speed until the sample became the original 50 mm gauge length. The sample was then unloaded at the same speed until it returned to its original 50 mm gauge length.
Percent power relaxation is defined as: (Average of five measurements is reported below)

(Initial force at maximum elongation−force after 30 seconds of maximum elongation) × 100) / First time at maximum elongation
Period

To obtain a permanent fold behavior, the material must have a% force relaxation of at least 40% in the machine direction.

[0245]

[Table 4]

Both Examples 2 and 3 showed good permanent fold properties with high force relaxation for both CD and MD based on their high styrene content. In Example 1, C
It showed good permanent fold properties with acceptable% force relaxation for both D and MD. Comparative experiments 1, 2, 3 and 4 were all based on their low styrene content,
It exhibited poor permanent crease properties with low% force relaxation for both CD and MD.

[Procedural Amendment] Submission of translation of Article 34 Amendment of the Patent Cooperation Treaty

[Submission date] August 31, 2000 (2000.8.31)

[Procedure amendment 1]

[Document name to be amended] Statement

[Correction target item name] 0008

[Correction method] Change

[Correction contents]

[0008] In many cases, attempts to solve these problems have involved making multilayer films containing polymer blends. Also, many such films often required an additional stretching process in the film manufacturing process to obtain the desired combination of permanent crease properties and other properties. U.S. Patent No. 5,739,200 (YW Cheung et al., Assigned to The Dow Chemical Company) describes property improvements that can be achieved by the addition of a plasticizer to an alpha-olefin / vinylidene aromatic monomer interpolymer. ing. The plasticized composition is useful for a wide range of applications, including films, sheets, adhesives, sealants, and molded parts. WO 95/05418 (Dow Chemical Company) describes an elastic material comprising a film made from at least one substantially linear ethylene polymer having 100 percent strain and at least about 80 percent recovery. WO 98/16582 (Dow Chemical Company) discloses alpha-olefin / vinylidene aromatic monomers present in amounts of 0.5 to 15 and 17 to 65 mol%.
A thermoplastic blend of an interpolymer of vinylidene aromatic monomers and a styrenic block copolymer is described.

[Procedure amendment 2]

[Document name to be amended] Statement

[Correction target item name] 0009

[Correction method] Change

[Correction contents]

No. 5,128,183 (P. Buzio, Borden, Ind.)
c. The entire content of the present invention relates to a modified polyolefin film having stable torsion-retaining and permanent fold properties, which is generally used for packaging and especially for packaging small items. The film of the present invention is obtained by extrusion and stretching of a ternary mixture composed of (1) isotactic polypropylene, (2) high density polyethylene, and (3) glassy amorphous low molecular weight resin.

[Procedure amendment 3]

[Document name to be amended] Statement

[Correction target item name] 0010

[Correction method] Change

[Correction contents]

Japanese Patent No. 59-68212 (Mitsui Toatsu Chemicals) relates to a polyolefin film having improved stiffness and twist retention obtained by uniaxial longitudinal stretching. However, such films have poor lateral properties and are prone to tearing and parallel cracking, which limits their use to longitudinal twist packaging.

[Procedure amendment 4]

[Document name to be amended] Statement

[Correction target item name] 0011

[Correction method] Change

[Correction contents]

German Patent DE 35 14 398 A1 (Hoechst) describes a biaxially stretched film, which consists of polypropylene, a filler and a polymer such as polyamide or polymethyl methacrylate. However, such films have poor twist retention.

[Procedure amendment 5]

[Document name to be amended] Statement

[Correction target item name] 0012

[Correction method] Change

[Correction contents]

[0012] European Application No. 0288227 (Exxo published on October 26, 1988)
n Chemicals) describes a biaxially oriented film, which comprises a polypropylene compound (or a copolymer of propylene and up to 20 weight percent of another olefin, such as ethylene) with 20 to 30 weight percent of a low molecular weight rosin. Alternatively, it can be obtained by extrusion molding of a two-component blend comprising a resin. The process described therein for obtaining extruded stretched films causes significant problems in the extrusion and stretching steps.

[Procedure amendment 6]

[Document name to be amended] Statement

[Correction target item name] 0013

[Correction method] Change

[Correction contents]

[0013] US Patent No. 4, issued June 27, 1989 to Janocha et al.
No. 842,187 describes an opaque two-time stretched thermoplastic film for candy twist packaging. This film is formed from a polymer mixture comprising 40 to 60% by weight of polypropylene, 35 to 50% by weight of polystyrene and 5 to 15% by weight of inorganic or organic filler.

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, CY, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE ), OA (BF, BJ, CF, CG, CI, CM, GA, GN, GW, ML, MR, NE, SN, TD, TG), AP (GH, GM, KE, LS, MW, SD, SL, SZ, UG, ZW), EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AE, AL, AM, AT, AU, AZ, BA, BB, BG, BR , BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GD, GE, GH, GM, HR, HU, ID, IL, IN, IS , JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZA, ZW (72) Inventor Guest, Martin Jay. United States, Texas 77566, Lake Jackson, Greenbrier 106 (72) Inventor Van Volkenberg, William Earl. United States, Texas 77566, Ray click Jackson, Sequoia 126 F-term (reference) 4F071 AA15 AA15X AA20 AA22 AA22X AA24 AA25 BC01 4F100 AK04A AK04J AK07A AK07J AK08A AK08J AK11A AK11J AK12A AK14A AK16A AK16J AK25A AK29A AK45A AK48A AK63A AK64A AK73A AK74A AK75A AL02A AL03A AL05A AL09A AN01A AN02A BA02 BA03 BA04 BA05 CA23A EH20 GB16 GB23 JA06A JA07A JB16A JB20A JK20 YY00 YY00A 4J002 BB04W BB05X BB12X BB14W BB15X BB16W BC03X BC04W BC04X BC06X BD03X BBXX BK03X BB10X

Claims (24)

[Claims] 1. A film or sheet having at least one layer comprising:
Or (A) at least one essentially random copolymer comprising: (1) a polymer unit derived from: (i) at least one vinyl aromatic monomer Or (ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (iii) a combination of at least one aromatic vinyl monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer. And (2) a polymer unit derived from at least one C2-20 α-olefin, and optionally (3) one or more ethylenically unsaturated polymerizable other than (1) and (2). A polymer unit derived from a monomer; or (B) a mixture of component A and at least one polymer other than component A Article: wherein the film or sheet or extruded profile has a force relaxation of at least 40% in the transverse or longitudinal direction or in both directions. 2. The film or sheet or extruded profile of claim 1 wherein: (I) 25 to 100% by weight of said essentially random copolymer component A;
In amounts (based on the total weight of the polymer excluding component A and component A) and I
2 is 0.01 to 100 g / 10 min, Mv / Mn is 1.5 to 20, and (1) 29 to 65 mol% of a polymer unit derived from: (i) at least one kind of vinyl An aromatic monomer, or (ii) at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, or (iii) at least one aromatic vinyl monomer and at least one aliphatic or cycloaliphatic vinyl or (2) 35-71 mol% of polymer units derived from at least one C2-20α-olefin; and (3) at least one other than those derived from (1) or (2). From 0 to 20 mol% of one or more of said ethylenically unsaturated polymerizable monomers; and II) to the polymer other than the component A is not 0 75 wt% (as present in an amount of, based on the total weight of the polymer other than component A and component A). 3. The film or sheet or extruded profile of claim 1, wherein (I) said essentially random copolymer component (A) is present in an amount of from 40 to 95% by weight (component (Based on the total weight of the polymer other than A and component A) and I2 is between 0.1 and 20 g / 10 min, Mw / Mn is between 1.8 and 10, and (1) from 33 To 65 mol% of polymer units; (i) the vinyl aromatic monomer represented by the following formula: Wherein R1 is selected from the group of radicals including hydrogen, alkyl radicals containing 3 or less carbons, and Ar is a phenyl group or halo, C1-
A phenyl group substituted by 1 to 5 substituents selected from the group consisting of 4-alkyl and C1-4-haloalkyl, wherein n has a value of 0 to 4; or (ii) said aliphatic or The alicyclic vinyl or vinylidene monomer is represented by the following general formula: Wherein A1 is generally a sterically large aliphatic or cycloaliphatic substituent having up to 20 carbons, and R1 is a group of radicals consisting of hydrogen and alkyl radicals containing 1 to 4 carbon atoms. Each R2 is independently selected from the group consisting of hydrogen and an alkyl radical containing 1 to 4 carbon atoms; l; or R1 and A1 together form a ring system; and (2) ethylene, or 35 to 67 mol% of polymer units derived from the α-olefin comprising ethylene and at least one propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1; and (3) ( The ethylenically unsaturated polymerizable monomer other than 1) and (2) is norbornene, or C1-10 alkyl, or C6-10 And (II) the polymer other than Component A is present in an amount of from 5 to 60% by weight (based on the total weight of Component A and the polymer other than Component A); Or more. a) Homogeneous copolymer b) Heterogeneous copolymer c) Thermoplastic olefin d) Styrene floc copolymer e) Styrene homo or copolymer f) Elastomer g) Vinyl halide polymer or h) Engineering thermoplastic . 4. The film or sheet or extruded profile of claim 1, wherein (I) said essentially random copolymer component (A) is present in an amount of 50 to 95% by weight (component (Based on the total weight of the polymer other than A and component A) and I2 is between 0.1 and 5 g / 10 min, Mv / Mn is between 2 and 5, and (1) 35-65 mol% of A polymer unit derived from: (i) the vinyl aromatic monomer including styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, and cyclic halogenated styrene, or (ii) 5-ethylidene- 2-norbornene monomers or aliphatic or cycloaliphatic vinyls, including 1-vinylcyclo-hexene, 3-vinylcyclo-hexene and 4-vinylcyclohexene, or vinylidene A monomer containing (2) ethylene or ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 and octene-1;
35-67 mol% of polymer units derived from olefins; and (3) the ethylenically unsaturated polymerizable monomer other than that derived from (1) and (2) is norbornene. (II) those in which the polymer other than component A is present in an amount of 5 to 50% by weight (based on the total weight of the polymer other than component A and component A) and comprising one or more of the following: a) essentially linear ethylene / α-olefin copolymer, b) heterogeneous ethylene / C3-C8α-olefin copolymer, c) ethylene / propylene rubber (EPM), ethylene / propylene diene monomer Polymer (EPDM), isotactic polypropylene, d) styrene / ethylene-butene copolymer, styrene / ethylene-propylene copolymer, styrene / ethylene-butene / styrene (SEBS) copolymer, styrene / ethylene-propylene / styrene (SEPS) copolymer, e) acrylonitrile-butadiene-styrene (ABS) polymer, styrene-acrylonitrile (SAN), polystyrene, high-impact polystyrene, f) polyisoprene, polybutadiene, natural rubber, ethylene / propylene rubber, ethylene / Propylene diene (EPDM) rubber, styrene / butadiene rubber, thermoplastic polyurethane g) homopolymer or copolymer of vinyl chloride or vinylidine chloride, h) poly (methyl methacrylate), polysester, nylon-6, nylon-6,6 Poly (acetal); poly (amide), poly (arylate)
, Poly (carbonate), poly (butylene) and polybutylene, polyethylene terephthalate. 5. The film or sheet or extruded profile of claim 4, wherein component A1 (i) is styrene, component A2 is ethylene, and the polymer other than component A is polystyrene. 6. Component A1 (i) is styrene; component A2 is ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1, or octene-1; 5. The film or sheet or extruded profile of claim 4, wherein said polymer other than component A is polystyrene. 7. A processed product comprising the film or sheet of claim 1 or an extruded profile. 8. A processed product comprising the film or sheet of claim 5 or an extruded profile. 9. A processed product comprising the film or sheet of claim 6, or an extruded profile. 10. Wrapping meat, substitute paper, free standing or flat bottom bags, tablecloths, shower curtains, folding bottles or containers, tubes for toothpaste, folding structures, boxes, cartons, window boxes, surgical drapes, 10. The processed product of claim 7-9, in the form of a shape membrane, toy, tube, cloth, tape, laminating film, or pressure sensitive label. 11. A multilayer film or sheet or extruded profile comprising at least two layers, wherein at least one of the layers comprises: a force of more than 40% in the transverse or longitudinal direction, or in both directions. A film or sheet having relaxation or an extruded profile; (A) at least one essentially random copolymer comprising: (1) a polymer unit derived from: (I) at least one vinyl aromatic monomer, or (ii) at least one aliphatic or cycloaliphatic vinyl, or vinylidene monomer, or (iii) at least one aromatic vinyl monomer and at least one fat A combination of an aromatic or cycloaliphatic vinyl or vinylidene monomer, and (2) at least one C2-20α (B) a polymer unit derived from an olefin, and (3) a polymer unit derived from one or more ethylenically unsaturated polymerizable monomers other than (1) and (2); A mixture with at least one polymer other than component A: wherein the film or sheet or extruded profile has a force relaxation of at least 40% in the transverse or longitudinal direction or in both directions. 12. The multilayer film or sheet or extruded profile of claim 11, wherein: (I) 25-100% by weight of said essentially random copolymer component A;
(Based on the total weight of component A and component B) and I2 is from 0.01 to 100 g / 10 min, Mv / Mn is from 1.5 to 20, and (1) 29 to 65 mol % Polymer units derived from: (i) at least one vinyl aromatic monomer, or (ii) at least one aliphatic or cycloaliphatic vinyl, or vinylidene monomer, or (iii) at least one aromatic (3) a combination of an aromatic vinyl monomer and at least one aliphatic or cycloaliphatic vinyl or vinylidene monomer, and (2) 35 to 71 mol% of a polymer unit derived from at least one C2-20α-olefin; 0) 20 mol% of one or more of said ethylenes other than those derived from (1) or (2) And (II) 0 to 75% by weight of at least one polymer other than component A (the polymer other than component A and the polymer other than component A). (Based on the total weight of the). 13. The multilayer film or sheet or extruded profile of claim 11, wherein (I) the essentially random copolymer component (A) is present in an amount of 40 to 95% by weight ( (Based on the total weight of components A and B) and I2 is from 0.1 to 20 g / 10 min, Mw / Mn is from 1.8 to 10, and (1) polymer units 33 to (I) the vinyl aromatic monomer represented by the following formula: Wherein R 1 is selected from the group of radicals consisting of hydrogen, alkyl radicals containing 3 or less carbons, and Ar is a phenyl group or halo, C 1
1 selected from the group consisting of -4-alkyl and C1-4-haloalkyl
A phenyl group substituted by 5 substituents, and n has a value of 0 to 4; or (ii) the aliphatic or cycloaliphatic vinyl or vinylidene monomer is represented by the following general formula: Embedded image Wherein A1 is generally a sterically large aliphatic or cycloaliphatic substituent having up to 20 carbons and R1 is selected from the group consisting of hydrogen and alkyl radicals containing 1 to 4 carbon atoms. Each R 2 is independently selected from the group of radicals consisting of hydrogen and alkyl radicals containing 1 to 4 carbon atoms;
Or R1 and A1 together form a ring system; and (2) ethylene or the α-containing ethylene and at least one propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1. 35 to 67 mol% of polymer units derived from olefins; and (3) the ethylenically unsaturated polymerizable monomer other than those derived from (1) and (2) is norbornene, or C1-10. Alkyl or C6-10
And (II) the polymer other than component A is present in an amount of from 5 to 60% by weight (based on the total weight of component A and the polymer other than component A); Or more. a) Homogeneous copolymer b) Heterogeneous copolymer c) Thermoplastic olefin d) Styrene floc copolymer e) Styrene homo or copolymer f) Elastomer g) Vinyl halide polymer or h) Engineering thermoplastic . 14. The multilayer film or sheet or extruded profile of claim 11, wherein (I) the essentially random copolymer component (A) is present in an amount of 50 to 95% by weight ( (Based on the total weight of component A and the polymer other than component A) and I2 is from 0.1 to 5 g / 10 min, and Mv / Mn is from 2 to 5, and (1) 35 to 65 mol% A polymer unit derived from: (i) a vinyl aromatic monomer containing styrene, α-methylstyrene, ortho-, meta- and para-methylstyrene, and cyclic halogenated styrene; or (ii) 5- Said aliphatic or cycloaliphatic vinyls, including ethylidene-2-norbornene or 1-vinylcyclo-hexene, 3-vinylcyclo-hexene and 4-vinylcyclohexene; (2) 35 to 67 moles derived from the α-olefin, containing ethylene or ethylene and at least one of propylene, 4-methyl-1-pentene, butene-1, hexene-1 or octene-1 % Of polymer units; or (3) the ethylenically unsaturated polymerizable monomer other than those derived from (1) and (2) is norbornene. Wherein the polymer is present in an amount of from 5 to 50% by weight (based on the total weight of the polymer excluding component A and component A) and comprises one or more of: a) essentially linear ethylene / α-olefin copolymer, b) heterogeneous ethylene / C3-C8α-olefin copolymer, c) ethylene / propylene rubber (EPM), ethylene / propylene diene monomer Polymer (EPDM), isotactic polypropylene, d) styrene / ethylene-butene copolymer, styrene / ethylene-propylene copolymer, styrene / ethylene-butene / styrene (SEBS) copolymer, styrene / ethylene-propylene / styrene (SEPS) copolymer, e) acrylonitrile-butadiene-styrene (ABS) polymer, styrene-acrylonitrile (SAN), polystyrene, high-impact polystyrene, f) polyisoprene, polybutadiene, natural rubber, ethylene / propylene rubber, ethylene / Propylene diene (EPDM) rubber, styrene / butadiene rubber, thermoplastic polyurethane g) homopolymer or copolymer of vinyl chloride or vinylidine chloride, h) poly (methyl methacrylate), polysester, nylon-6, nylon-6,6 Poly (acetal); poly (amide), poly (arylate)
, Poly (carbonate), poly (butylene) and polybutylene, polyethylene terephthalate. 15. The multilayer film or sheet or extruded profile of claim 14, wherein component A1 (i) is styrene, component (A2) is ethylene, and said polymer other than component A is polystyrene. 16. Component A1 (i) is styrene; component A2 is ethylene and at least one of polypropylene, 4-methyl-1-pentene, butene-1, hexene-1, or octene; 15. The multilayer film or sheet according to claim 14, wherein the polymer other than A is polystyrene. 17. A processed article comprising the multilayer film or sheet of claim 11, or an extruded profile. 18. A processed article comprising the multilayer film or sheet of claim 15, or an extruded profile. 19. A processed article comprising the multilayer film or sheet of claim 16, or an extruded profile. 20. Meat packaging wrap, substitute paper, free-standing or flat-bottomed bags, tablecloths, shower curtains, folding bottles or containers, toothpaste tubes, folding structures, boxes, cartons, window boxes, surgical drapes, 20. The processed product of claims 17-19, in the form of a shaped membrane, toy, tube, cloth, tape, laminating film, or pressure sensitive label. 21. The film or sheet or extruded profile of claim 1, further comprising a filler. 22. The film or sheet according to claim 11, further comprising a filler. 23. The film or sheet according to claim 1, wherein component A is crosslinked.
Or extruded profiles. 24. The film or sheet or extruded profile of claim 11, wherein component A is crosslinked.