Stock material or miscellaneous articles – Hollow or container type article – Polymer or resin containing
Reexamination Certificate
2000-03-03
2002-08-20
Chen, Vivian (Department: 1773)
Stock material or miscellaneous articles
Hollow or container type article
Polymer or resin containing
C428S034100, C428S035200, C428S036900, C428S446000, C428S447000, C428S448000, C428S449000, C428S451000, C428S457000, C428S458000, C428S461000, C428S474400, C428S480000, C428S483000, C428S492000, C428S515000, C428S516000, C428S523000, C156S272200, C156S275500, C156S297000, C156S299000, C156S307100, C156S329000, C156S330900, C156S331100, C156S331800
Reexamination Certificate
active
06436498
ABSTRACT:
FIELD OF THE INVENTION
The invention relates to polyamine containing coatings having both barrier and adhesive properties which are useful in packaging applications.
BACKGROUND OF THE INVENTION
It is well known that coatings containing polyamine compounds and itaconic acid improve the gas, oil, and flavor barrier performance of organic polymer film substrates, i.e., see for example PCT/BE98/00007, the US equivalent of which is U.S. Ser. No. 09/341,254 which was filed on Jul. 15, 1999. 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 and improved resistance to water. 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 90 cc/m
2
/day a 12 &mgr;m uncoated biaxially oriented, corona treated polyethylene terephthalate (PET) film, having a permeability measured at 0% relative humidity to oxygen of 144 cc/M
2
/day and a permeability measured at 90% relative humidity to oxygen of 123 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 and adhesive characteristics.
SUMMARY OF THE INVENTION
The present invention relates to a method of laminating two substrates by coating at least one side of a substrate with a laminating adhesive, bringing a coated side of said substrate into contact with a second substrate to form a three layer film, and treating said three layer film with a free radical initiator, wherein said laminating adhesive 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 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 invention can be used to laminate a variety of substrates for use 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 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 arylene 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. hexanediol diacrylate pentaerythritol diacrylate), diepoxides (ethylene glycol diglycidyl ether).
Examples of polyamines useful for the invention include polyvinyl amines, aminofunctional polyacrylamides, poly-DADMAC's, i.e., polydiallyl dimethyl ammonium chloride, polyvinyl pyrrolidene copolymers, polyethylene imine and the reaction product of ethylenediamine and epichlorohydic copolymers.
A preferred polyamine that can be used to achieve varying degrees of tackiness is the class of polyamines referred to as polyalkylene imines, such as polyethylene imine, which is readily available in a wide range of molecular weights and different degrees of branching. Polyethylene imines 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 ethyleneimine does not result in a polymer that is completely composed of units having a linear structure, but that also the degree of branching in polyethylene imine depends on the acid concentration and the temperatur
Gallez Laurence
Merlin Patrick Jacques Jean
Nanavati Shrenik Mahesh
Rangwalla Imtiaz J.
Seibel Lisa Marie
Chen Vivian
De Cesare Jim L.
Dow Corning Corporation
Zombeck Alan
LandOfFree
Reactive silicone/alkyleneimine barrier laminating adhesives... does not yet have a rating. At this time, there are no reviews or comments for this patent.
If you have personal experience with Reactive silicone/alkyleneimine barrier laminating adhesives..., we encourage you to share that experience with our LandOfFree.com community. Your opinion is very important and Reactive silicone/alkyleneimine barrier laminating adhesives... will most certainly appreciate the feedback.
Profile ID: LFUS-PAI-O-2910335