Synthetic resins or natural rubbers -- part of the class 520 ser – Synthetic resins – Mixing of two or more solid polymers; mixing of solid...
Reexamination Certificate
1999-02-22
2001-06-12
Wu, David W. (Department: 1713)
Synthetic resins or natural rubbers -- part of the class 520 ser
Synthetic resins
Mixing of two or more solid polymers; mixing of solid...
C526S351000, C428S516000
Reexamination Certificate
active
06245857
ABSTRACT:
FIELD OF THE INVENTION
This invention relates to the use of highly crystalline polypropylene (HCPP) for film applications. Soft, strong films may be made by the practice of this invention.
BACKGROUND OF THE INVENTION
It is known that HCPP or highly isotactic polypropylene, being polymer with a particularly low error rate, finds use in injection molding applications with usable handling characteristics and beneficial product results. Generally HCPP is recognized as a comparatively brittle material which is limited in its usefulness by its inherently brittle nature.
Use in film applications, particularly, has not been considered for HCPP in light of the material's tendency to be brittle, tear easily, and have an unpleasant or “hard” feeling to the touch.
Generally those in the field of development of useful polymer compositions have tended to bypass highly isotactic poly-&agr;-olefin in light of its processing difficulty and properties liabilities. Such material is avoided in spite of the potential benefits to be gained from its high level of crystallinity including enhanced strength.
To take advantage of the properties of highly crystalline polyolefin yet mitigate its brittleness some have pursued composite or multi-layer films. An example of such strategy is found in JP 844 167 filed Dec. 1, 1984 and assigned to Sumitomo Chemical Industries, K.K.
Others, as demonstrated by Shel et al. in U.S. Pat. No. 5,603,696 as issued Feb. 18, 1997, have sought to gain advantage of moderate crystallinity of isotactic polypropylene by including up to about 15% of it in a blend of polypropylene with moderate syndiotactic character.
Goins et al. describe, in EP 747 430 published Nov. 12, 1996, blend of isotactic polypropylene and syndiotactic polypropylene having comparatively broad MWD, in an amount of up to 4 wt. %. Polymer used is, however, standard isotactic polypropylene, not the HCPP of the current invention.
Others, including DeLucia et al. describe, in WO 9623095, use the lower melt point or flow temperature of sPP simply to provide an agent for thermal point bonding in non-woven fabric applications. Use of HCPP in combinations with sPP, however, is not demonstrated.
JP 7 149 968 A, as published Jun. 13, 1995, JP 7 126 458 A as published May 16, 1995, and EP 650 818 A3 as published Jun. 14, 1995, all of which are assigned to Mitsui-Toatsu Chemical Company, describe resin of syndiotactic polypropylene and isotactic polypropylene, as well as their films.
A further example of attempts to gain some benefit from the crystalline nature of isotactic polypropylene but maintaining ease of processing is found in U.S. Pat. No. 5,603,696 in which minor amounts of isotactic polypropylene is included with a majority of sPP to form molded articles. This concept is applied again in U.S. Pat No. 5,269,807 in which suture material is produced from blended sPP and iPP or static PP.
SUMMARY OF THE INVENTION
Our invention provides, at least, polymer composition comprising highly isotactic polypropylene and syndiotactic polypropylene (sPP). Our composition provides material useful in numerous applications, particularly in production of films and articles made from films including pouches, bags, barriers, and other items. Such articles, including these films and articles from them, provide notable clarity, toughness, and yet are soft and pleasant to the touch. Films also display elastomeric character low solvent solubility, particularly in xylene.
DETAILED DESCRIPTION
This invention provides embodiments of composition of poly-&agr;-olefin which is highly isotactic yet provides articles, particularly films and their manufactured articles, which display beneficial properties derived from isotactic materials yet are softer than the generally more brittle pure isotactic compositions. Highly isotactic, therefore highly crystalline, polypropylene is particularly beneficially useful in the practice of our invention. For the purposes of describing our invention, “highly isotactic” intends polymer having isotactic character of greater than about 93%, preferably greater than about 96%; in other words, the polymer chain usefully will display an error rate of non-isotactic monomer insertion of less than about 7%, preferably less than about 4%.
One embodiment of our invention provides at least polymer composition comprising at least about 70% highly crystalline isotactic polypropylene and syndiotactic poly-&agr;-olefin in an amount in the range of about 0.01% through about 30%. Other processing and performance additives may be usefully included in such composition.
Polyolefin composition, the majority of which is highly isotactic polyolefin, comprising the property of heat of melting (&Dgr;H
m
) greater than or equal to about 89 J/g. Usefully, such composition will, when cast into film of thickness of about 0.08 mm (0.003 in.) comprise properties such that film displays
a) 1% Secant Modulus in machine, transverse, or both direction of less than or equal to about 850 MPa;
b) dart drop impact of equal to or greater than about 250 g; or
d) combinations thereof.
Notably usefully, such material will provide film properties such that:
a) 1% Secant Modulus in machine, transverse, or both direction of less than or equal to about 800 MPa;
b) dart drop impact of equal to or greater than about 200 g; or
c) combinations thereof.
Useful additives to compositions of these embodiments include stabilizers able to inhibit oxidation and thermal degradation including hindered phenolics and amines and their combinations, melt stabilizers or secondary stabilizers to assist prevention of degradation during melt processing including various phosphite inhibitors, and mold release agents or die lubricants including metal stearates, fluoropolymers, and their combinations. Other useful additives may include those particularly designed for ultraviolet (UV) stabilization and radiation stabilizers for materials and articles to be subjected to irradiation or sterilization by electron bombardment (&bgr; radiation) or gamma radiation as well as nucleators or clarifiers, antiblock agents such as silica, and anti-static materials including glycerol monostearate, fatty amides, and fluoropolymers.
Each of the polymer compositions described here may benefit from variations in the makeup of composition. Progressively preferred lower limits of HCPP will be at least about 70%, about 80% , and at least about 90%. Progressively preferred lower levels of syndiotactic material will be at least about 1% and at least about 7%.
Films of all of these compositions will have beneficial properties as the level of the HCPP is increased. Articles of films of these compositions will find beneficial use relating to the combination of useful properties deriving from high crystallinity and better flexibility, respectively, from high isotacticity and introduction of sPP.
REFERENCES:
patent: 5260395 (1993-11-01), Asanuma et al.
patent: 5969021 (1999-10-01), Reddy et al.
patent: 6063482 (2000-05-01), Peiffer et al.
patent: 6080818 (2000-06-01), Thakker et al.
Hanyu Aiko
Harris, III Theodore G.
Kim Se-hyun
Shamshoum Edwar Shoukri
Butts Evan K.
Fina Technology, Inc.
Harlan R.
Wheelington Jim D.
Wu David W.
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