Thermoset polymer coating with organopolysiloxane for closure assembly

A thermoset polymer coating with an effective ink-releasing amount of a liquid, organic soluble dimethyl- or methyl/alkyl organopolysiloxane for use in a closure assembly, the assembly including a metal closure with a top and depending skirt, the thermoset polymer coating being applied to the inside closure top and printed with ink indicia, a polyvinyl acetate coating applied over the ink, and the ink indicia being removed on the polyvinyl acetate-coated liner by the customer for promotional purposes such as for prizes, etc.

BACKGROUND OF THE INVENTION 
The present invention relates to a thermoset polymer coating with an 
effective ink-releasing amount of a liquid, organic solvent soluble 
dimethyl- or methyl/alkyl organopolysiloxane for use in a closure 
assembly, the assembly including a metal closure with a top and depending 
skirt, the thermoset polymer coating being applied to the inside closure 
top and printed with ink indicia, the ink indicia being removed on a 
coated liner by the customer for promotional purposes such as for prizes, 
etc. 
It is desirable to provide a coating for the inside closure top of a 
closure assembly, whereby the coating can be printed upon by ink indicia 
for later removal on a removable liner. 
OBJECTS OF THE INVENTION 
It is an object of the present invention to provide a thermoset coating for 
a closure assembly as well as to provide a novel closure assembly, the 
thermoset coating being adapted for printing thereon with ink indicia, 
that is subsequently easily removed on an adjacent liner by pulling the 
liner away for promotional purposes. 
It is an object of the present invention to provide a method of making a 
closure assembly comprising a closure with a top and depending skirt and a 
thermoset polymer coating on the inside top of the closure, ink indicia 
printed on the thermoset polymer coating, a polyvinyl acetate coating next 
to the ink indicia and adhered to a polyolefin liner adapted for removal 
from the closure assembly, the method comprising the steps of: (A) mixing 
(1) a water-insoluble, organic solvent soluble, low molecular weight, 
liquid organopolysiloxane partial condensation hydrolysis product of 
##STR1## 
where R.sub.3 is an alkyl group of 1 to 4 carbon atoms and X is chlorine 
or an alkoxy group of 1 to 3 carbon atoms with (2) the thermoset polymer 
to form the thermoset polymer coating on the inside of the closure top, 
(B) printing on the thermoset polymer coating with ink to form ink indicia 
on the surface of the thermoset polymer coating opposite the closure top, 
(C) coating with a polyvinyl acetate coating, adjacent the thermosetting 
coating with ink indicia, (D) providing a circular polyolefin liner, (E) 
removing the liner with the ink indicia that is released with the 
polyvinyl acetate coated liner from the surface of the thermoset polymer 
coating.

SUMMARY OF THE INVENTION 
The present invention provides a thermoset polymer coating for use in a 
closure assembly comprising a plastic closure with a top and a depending 
skirt for engagement with a container finish, the thermoset polymer 
coating being on the inside top surface of the closure top, the thermoset 
polymer coating comprising a thermoset polymer and an effective 
ink-releasing amount of an organic solvent soluble, water-insoluble, 
liquid low molecular weight organopolysiloxane hydrolysis product of: 
##STR2## 
where X is a halogen or an alkoxy group of 1 to 6 carbon atoms, R.sub.1 
and R.sub.2 being alkyl group, at least one of R.sub.1 and R.sub.2 being a 
methyl group, the organopolysiloxane having the following recurring unit: 
##STR3## 
there being ink indicia on the surface of the thermoset coating, the 
thermoset polymer coating having limited adhesion with the ink, there 
being a polyvinyl acetate coating over the ink and adhered to a polyolefin 
liner, the ink adhering to the polyvinyl acetate coating on the liner and 
releasing from the thermoset polymer coating when the liner is removed 
from the surface of the thermoset polymer. The low molecular weight 
organopolysiloxane has a number average molecular weight of about 250 to 
4000. 
The present invention also provides a closure assembly comprising a top and 
a depending skirt for a closure finish, a thermoset polymer coating for 
the inner surface of the closure top, the coating comprising a thermoset 
polymer and an effective ink-releasing amount of a water-insoluble, 
organic solvent soluble, low molecular weight dialkyl organopolysiloxane 
that is a hydrolysis reaction product of a difunctional organo-silane, the 
thermoset polymer coating having a limited adhesion with the ink. 
The present invention provides a method of making a closure assembly for 
promotional purposes such as prizes for customers, the novel method being 
a method of making a closure assembly comprising a closure with a top and 
depending skirt and a thermoset polymer coating on the inside top of the 
closure, ink indicia printed on the thermoset polymer coating a polyvinyl 
acetate coating next to the ink indicia and adhered to a polyolefin liner 
adapted for removal from the closure assembly, the method comprising the 
steps of: (A) mixing (1) a water-insoluble, organic solvent soluble, low 
molecular weight, liquid organopolysiloxane partial condensation 
hydrolysis product of 
##STR4## 
where R.sub.3 is an alkyl group of 1 to 4 carbon atoms and X is chlorine 
or an alkoxy group of 1 to 3 carbon atoms with (2) the thermoset polymer 
to form the thermoset polymer coating on the inside of the closure top, 
(B) printing on the thermoset polymer coating with ink to form ink indicia 
on the surface of the thermoset polymer coating opposite the closure top, 
(C) coating a polyvinyl acetate coating adjacent to the thermoset polymer 
coating with the ink indicia, (D) providing a circular olefin copolymer 
liner, (E) removing the liner with the ink indicia that is released with 
the polyvinyl acetate coated liner from the surface of the thermoset 
polymer coating. 
DETAILED DESCRIPTION OF THE INVENTION 
In the above thermoset coating, the closure assembly and the novel method, 
it is preferred that the organic solvent soluble liquid organopolysiloxane 
be a partial condensation hydrolysis product of 
##STR5## 
2 
The number average molecular weight of the condensation product is 
generally about 500 to 4000, preferably about 750 to 2000 and optimally, 
about 800 to 1500. 
The hydrolyzable group of the starting silane is preferably chlorine, 
although good results are obtained with alkoxy groups, preferably ethoxy, 
such as methoxy, propoxyl and butoxy. Other halogens can be used such as 
bromine as the hydrolyzable group. 
Excellent results have been obtained by using Dow Corning silicone 
fluids--preferably the liquid dimethyl polysiloxanes. Outstanding results 
are obtained with Masil 265HV-liquid alkyl methyl siloxane fluid. 
EXAMPLE 
A test was designed to evaluate Mazer Chemical Company's printable 
lubricants, commonly utilized in metal litho printing inks, as additives 
to the alkyd size coat used in transfer print coating system. 
Watson-Standard furnished a non-lubricated version of 22-492A coating for 
the test. The W-S non-lubricated coating is numbered 29-020. 
The Mazer lubricants tested in this study were: 
Masil 1066C-Organo Silicone Surfactant 
Masil 265HV-Alkyl Methyl Fluid 
Masil 266-50% Alkyl Methyl Emulsion 
Masil 260A-Leveling Aid 
The metal coating sequence used was as follows: 
2. Simulated outside bake-390.degree. F., 10 min. 
2. 29-020+lubricant-325.degree. F., 10 min. 
3. Acme M-99524 transfer ink. 
4. Mobil 9806 EVA adhesive (wet inked)-325.degree. F., 10 min. 
5. Simulated outside bake-325.degree. F., 10 min. 
Coatings were applied with an 18# Meyer Bar. After the coating sequence, 
EVA III blue liner (polyethylene vinyl acetate copolymer) was adhered by 
bonding for 11/2 seconds at 350.degree. F. 
The lubricants were tested at concentrations of 5% and 10% dry film 
concentrations (3 oz. and 6 oz./gallon, respectively). 
Considering lubricant miscibility, surface uniformity, wetting, and ink 
transfer, the Masil 265HV lubricant was outstanding as an additive to the 
size coat to improve ink transfer. 
Masil 265HV fluid is a proprietary silicon fluid that is a clear, inert, 
non-toxic, and odorless product. The liquid product demonstrates excellent 
thermal resistance even when subjected to 400.degree. F. (200.degree. C.) 
for over eight hours with no detrimental effects. Surfaces of the metal 
article, if desired, can be finished with little or no need of cleaning. 
The product also provides increased organo-compatibility and lubricity as 
shown in the following Table of Physical Properties. 
______________________________________ 
TYPICAL PROPERTIES OF 
MASIL 265 HV FLUID 
______________________________________ 
APPEARANCE CLEAR 
YELLOW 
LIQUID 
ODOR NIL 
TO TRACE 
SPECIFIC GRAVITY AT 25.degree. C. 
1.015 
VISCOSITY AT 25.degree. C. 
1650 CPS. 
REFRACTIVE INDEX AT 25.degree. C. 
1.4725 
POUR POINT, .degree.C. BELOW -20 
FLASH POINT (PMCC), .degree.F. 
GREATER 
THAN 350 
FALEX 
LUBRICITY, TORQUE POUND INCHES 
18 TYPICAL 
AT 1000 PSI LOAD 
THERMAL STABILITY, 8 HRS. AT 200.degree. C. 
PASS 
COMPATIBILITY MOST 
ORGANIC 
SOLVENTS 
______________________________________ 
Generally the liquid polyorganosiloxane is used in amounts of about 1 to 20 
wt.%, and preferably about 5 to 10 wt.% of the thermoset coating. 
As to the thermosetting polymer for the thermoset polymer coating, suitable 
polymers are alkyds or other polyesters that are crosslinked, for 
instance, with a compatible monomer such as styrene; polyurethanes; 
phenol-formaldehyde polymers; and crosslinkable vinyl polymers and acrylic 
polymers. 
The liner, that is removable, is preferably polyethylene or polypropylene 
copolymer. Generally the liner is about 20 to 40 mils thick, the polyvinyl 
acetate coating on the liner (that is a copolymer of an olefin such as 
ethylene or propylene or butylene and a copolymerizible monomer such as 
vinyl acetate, ethylene acrylate) is about 1/2 to 3 mils thick, and the 
thermoset coating is about 1/2 to 3 mils in thickness. 
In the drawings, a metal closure 5 is shown. A thermoset coating 10 is 
provided on the inside of the closure top. Ink indicia 15, in FIG. 1, is 
shown printed on the thermoset polymer surface. In FIG. 1 a polypropylene 
liner 20 is shown before assembly of the closure structure. 
The closure asssembly is shown in FIG. 2, a polyvinyl acetate coating 25 
being provided on one side of the liner adjacent the ink indicia. 
FIG. 1 shows the closure after removal of the liner 20, the ink indicia 15 
being removed from the thermoset polymer coating 10 and the ink being 
adhered to the polyvinyl acetate coating 25 of the liner 20.