Stock material or miscellaneous articles – Hollow or container type article – Polymer or resin containing
Reexamination Certificate
2000-03-03
2003-04-01
Dawson, Robert (Department: 1712)
Stock material or miscellaneous articles
Hollow or container type article
Polymer or resin containing
C428S035700, C428S447000, C428S448000, C428S451000, C428S452000, C427S302000, C427S382000, C427S407100, C427S487000, C427S493000, C427S496000, C427S532000, C427S551000, C427S595000, C522S172000, C522S173000, C522S182000, C556S413000, C556S424000
Reexamination Certificate
active
06541088
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to coatings containing a polyamine, a bis-silane and an ethylenically unsaturated acid which have barrier properties useful in packaging applications.
BACKGROUND OF THE INVENTION
It is well known that coatings containing polyamine silane compounds and itaconic acid improve the gas, oil, and flavor barrier performance of organic polymer film substrates (See PCT/BE98/00009, the U.S. equivalent of which is U.S. Ser. No. 09/341,252, filed Jul. 15, 1999, now U.S. Pat. No. 6,389,171). Moreover, the adhesion of the coating to the film surface, as well as the improved barrier characteristics provided by the silane coating, are greatly enhanced by exposing the coated film to electron beam radiation.
These coatings represent a significant advance in the art. However, it has been observed that while the barrier properties of the prior art coatings are excellent in environments at relative humidities of 80% or less, their performance suffers significantly at relative humidities of 90% or more.
The present inventors have surprisingly discovered that the combination of a polyamine, an ethylenically unsaturated acid, and a bis-silane gives excellent gas barrier properties at low to moderate relative humidity values, as well as excellent gas barrier properties at very high relative humidity values of 90% or more. The key improvement is the addition of a bis-silane, which results in excellent barrier at humidities of greater than 90%. The composition may be crosslinked to further improve barrier. As used herein, the term “barrier” means improving to at least 750 cc/m
2
/day a 30 &mgr;m uncoated biaxilly oriented, corona treated polypropylene film, having a permeability measured at 0% relative humidity to oxygen of 1191 cc/M
2
/day and a permeability measured at 90% relative humidity to oxygen of 1238 cc/M
2
/day as measured at ASTM D3985-81.
None of the prior art teaches the present invention. For example, U.S. Pat. No. 4,761,435 claims UV curable polyethylenically unsaturated compositions in combination with a polyamine resin, which use an aryl ketone photosensitizer. The '435 patent teaches that acid functionality in the compositions is undesirable (col. 5, line 24). The patentees indicate that the formation of amine salts is to be avoided, because the photosensitizer reacts only with an amine, and not an amine salt. This is in contrast to the present invention, which teaches that the formation of acid salts is desirable and results in superior barrier properties.
Another example, U.S. Pat. No. 4,943,600, teaches the combination of a tertiary amine containing resin, allyl terminated resin, and a maleate functional resin. Likewise the patentee teaches that the compositions are formulated to minimize or eliminate carboxyl functionality, which contrasts directly with the present invention.
U.S. Pat. No. 5,017,406 claims UV curable compositions which contain reactive unsaturated compounds, but does not teach the use of a polyamine or an unsaturated acid as does the present invention.
JP (Kokai) publication 7-18221 published on Jan. 20, 1995 teaches a surface treatment composition for gas barrier comprising an aminosilane and a compound having an aromatic ring or hydrogenated ring. The present invention is distinguishable, however, because it does not require the addition of cyclic compounds having an aromatic ring, nor does the reference teach the addition of an ethylenically unsaturated acid.
The present invention is distinguishable from the prior art because none teach the use of a polyamine, a bis-silane and an ethylenically unsaturated acid to achieve gas barrier properties.
SUMMARY OF THE INVENTION
The present invention teaches a composition which provides gas, flavor, and aroma barrier to substrates, where the composition is formed by mixing an ethylenically unsaturated acid, a bis-silane and a polyamine, wherein said polyamine optionally has a crosslinker reacted therein, and wherein said polyamine has four or more A, B, or C units, where:
A is an —R
2
—N(R
1
)
2
unit, B is an R
1
—N(R
2
—)
2
unit, and C is an (—R
2
)
3
N— unit, where: R
1
is independently a monovalent group selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, and alkylaryl, and R
2
is independently selected from the group consisting of: linear or branched alkylene groups or substituted alkylene groups having from 1 to 18 carbon atoms, and arylene groups or substituted arylene groups having from 6 to 18 carbon atoms.
The composition is coated on a substrate then optionally treated to initiate a free radical reaction. The invention can be applied as a coating to a variety of substrates used in packaging applications.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
While the invention is susceptible of embodiment in many different forms there is described herein in detail preferred and alternate embodiments of the invention. It should be understood, however, that the present disclosure is to be considered an exemplification of the principles of the invention and is not intended to limit the spirit and scope of the invention and/or claims of the embodiments illustrated.
Polyamines
The polyamines of the present invention are polymeric, either homopolymeric or copolymeric polyamines having four or more A, B, or C units, where:
A is an —R
2
—N(R
1
)
2
unit, B is an R
1
—N(R
2
—)
2
unit, and C is an (—R
2
)
3
N— unit, where: R
1
is independently a monovalent group selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, and alkylaryl, and R
2
is independently selected from the group consisting of: linear or branched alkylene groups or substituted alkylene groups having from 1 to 18 carbon atoms, and arylene groups or substituted arylene groups having from 6 to 18 carbon atoms.
R
1
is independently selected from hydrogen, alkyl, substituted alkyl, aryl, substituted aryl, arylalkyl, alkylaryl, and R
2
is independently selected from the group consisting of linear or branched alkylene groups or substituted alkylene groups having from 1 to 18 carbon atoms and arlylene groups or substituted arylene groups having 6 to 18 carbon atoms. For example, R
1
or R
2
can be substituted with hydroxyl groups.
The amines of the present invention are polymeric in nature, preferably having molecular weights of from about 150 to about 2,000,000, with about 400 to about 400,000 preferred, and most preferred being from about 600 to about 80,000. The high degree of polymerization of the amine provides a lower degree of tackiness in the final composition. The lower molecular weight polyamines can be further polymerized to form higher molecular weight polyamines by methods well known in the art, such as by reaction with dialkyl halides (i.e. ethylene dichloride), diisocynates (e.g. tolydiisocyanate, hexamethylene diisocyanate), di(meth)acrylate esters (e.g. hexene diol diacrylate pentaerythritol diacrylate), diepoxides (ethylene glycol diglycidyl ether).
Examples of polyamines useful for the invention include polyvinyl amines, aminofinctional polyacryl amides, poly-DADMAC's polyvinyl pyrrolidone copolymers, polyethylenimine and the reaction product of ethylene diamine and epichlorohydrin copolymers.
A preferred polyamine that can be used to achieve varying degrees of tackiness is the class of polyamines referred to as polyalkylenimines, such as polyethylenimine, which is readily available in a wide range of molecular weights and different degrees of branching. Polyethylenimines consist of a large family of water-soluble, i.e. hydrophilic, polyamines of varying molecular weight and degree of chemical modification. It is generally known that the polymerization of ethylenimine does not result in a polymer that is completely composed of units having a linear structure, but that also the degree of branching in polyethylenimine depends on the acid concentration and the temperature during polymerization. This degree of branching may, for example, vary between 12 and 38 percent. The formula of polyethylenimine can be represented in the form of
Gallez Laurence
Merlin Patrick Jacques Jean
Nanavati Shrenik Mahesh
Rangwalla Imtiaz J.
Seibel Lisa Marie
Dawson Robert
De Cesare Jim L.
EG Technology Partners, L.P.
Gearhart Richard
Robertson Jeffrey B.
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