CA2236759A1 - Protective and decorative plastic coating system - Google Patents
Protective and decorative plastic coating system Download PDFInfo
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- CA2236759A1 CA2236759A1 CA 2236759 CA2236759A CA2236759A1 CA 2236759 A1 CA2236759 A1 CA 2236759A1 CA 2236759 CA2236759 CA 2236759 CA 2236759 A CA2236759 A CA 2236759A CA 2236759 A1 CA2236759 A1 CA 2236759A1
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Abstract
Frangible articles, such as dishes and vessels and including drinking glasses are coated with a protective coating of plastic preferably high temperature plastic. The plastic may serve as a safety coating, to diminish handling breakage and to act as a safeguard and contain glass particles in the event of breakage.
The coating may comprise a laminate of two or more coatings, a first inner coating to enhance adhesion of subsequent coatings to the glacis or other material of the vessel, and a protective, high temperature outer coating, resistant to washing in a washing machine. An intermediate, softer coating of polyethylene copolymer may serve to better retain the particles of glass parent material, in the event of breakage of the vessel. The outer protective coating may be of high temperature thermoplastic or of thermoset plastic, to withstand handling and wear, including the effects of hot water, encountered in a dishwasher, and the heat of its drying cycle. The plastic coatings are well suited to enhancement, as by the application of decoration, including colour by inclusion with the plastic, the use of irridescent or pearlescent additives, heat-reponsive colour-change materials and I/R responsive materials. Also printing and tactile enhancements are possible. The plastic coating system may be used with ceramics.
The coating may comprise a laminate of two or more coatings, a first inner coating to enhance adhesion of subsequent coatings to the glacis or other material of the vessel, and a protective, high temperature outer coating, resistant to washing in a washing machine. An intermediate, softer coating of polyethylene copolymer may serve to better retain the particles of glass parent material, in the event of breakage of the vessel. The outer protective coating may be of high temperature thermoplastic or of thermoset plastic, to withstand handling and wear, including the effects of hot water, encountered in a dishwasher, and the heat of its drying cycle. The plastic coatings are well suited to enhancement, as by the application of decoration, including colour by inclusion with the plastic, the use of irridescent or pearlescent additives, heat-reponsive colour-change materials and I/R responsive materials. Also printing and tactile enhancements are possible. The plastic coating system may be used with ceramics.
Description
F~OTECT]:VE ~ND DECO~TIvE-- PL~STI~ l_O~TING SYSTE~
~C~:B~OlJND OF THE INvENT r ON
1. FIELr~ OF THE INvENTION
The present invention is directed to the protection of frangible objects such a- glassware and ceramics by way of plastic coating, including the application of deco~ative finishes 7 and to plastic~ application systems therefor.
~C~:B~OlJND OF THE INvENT r ON
1. FIELr~ OF THE INvENTION
The present invention is directed to the protection of frangible objects such a- glassware and ceramics by way of plastic coating, including the application of deco~ative finishes 7 and to plastic~ application systems therefor.
2. ~E~CF~IFTION OF THE P~IOR ~T
The app].ication of sur-face coatings to glass products is well known.
One type of coating comprises a so-called lubricious coating which can be applied to the e:cterior surface of bottles and the like, which are subj~ect to mechanical handling. The lubricious coating diminishes the frictional contact of bottles against each other, and agaiGst handling machinery, so as to diminish stres~ and break:age occu~ences during processing. This is taught in United States Fatent No. ~ b,~55 June 4 19~8.
In United States Patent INo. 4"~5,5~ Dec ~ 7, there is taught the appplication of a protective plastic coating for glass soft drir-k: bottles for carbonated beverages~ Such bottles~ more particularly the larger variety of 16-ounce capacit~ and greater~ were known to fracture upon inpact and e:cplode in dangerous fashion, scattering glass frag~ent~.
This problem has dissapeared with the advent of plastic soft drink bottlQ , which have superceded glass for this area of use The abovse-mentioned protective plastic coating for glass soft drink bottles was susceptible to damage from hot water, such ~.
CA 022367~9 1998-0~-0~
as is encounter-ed in com~er-cial washing machine~.
There is one field of glass usage where plastic has not supplan1:ed glass, namely in beverage glasses.
~ue to 1:he visual appeal of glass, hoth in its clarity and its mass or "heft", and also its relatively low cost and suitability for machine washing, as compared with the e~-:treme lightness and higher cost of thin-walled plastic products, drinking "glasses"
of glass have retained a major share of the market. However~
even in a small populatiDn such as that of Canada, there i5 an annual replacement requirement of some ~l~~million glasses. Much of this figure represents breakage los~ that occurs in handling, transportation and use.
The ha2ards associated with the breakage of glass drink-war-e are such that its use around swimming pools constitutes a very real sa-Fety ha2ard. In the case of a pool with a vinyl liner, the inc:ident of broken gLass in the pool generally requires the complete drainage of the pool, for safe remaval of the glass, and to c~afeguard the vin~l line~ This action, in turn, may require professional re-setting of the liner.
In addi-tion to breakages of beverage glasses which occur in use there is also the hazard of rim chipping, which can lead to liability claims against the prop~ietor of a har or restaurant.
SU~ Y OF THE INvENTION
While the present disclosure and its associated research is particu:Larly directed to the pr-otection of glassware, in the form of drinking glasses, it will be appr-eciated that, in light CA 022367~9 1998-0~-0~
of wide<,pr-ead other usag~es of glass and ceramics in common with drin~;in(~ glasses, the present finding6 and teachings appear also to appl~ ther-eto, par-ticularly in regard to aspects of safety.
The p~esent in~ention provides a method of treating a frangib:Le object, normally subject to breakage upon impact, comprising the steps of applying a first protective plastic coating to a majo surface of the object in protective~ adhering relation therewi1:h, together with an adhesion modifier to promote the integri1iy of the object.
The adhesion modifier enhances the bonding of plastic to the object, and in the case Df drinking glasses and the like, is necessa~y in order for the object to withstand commercial dishwashing, and to enable it to retain p~rticles and shards in case of subsequent break:age.
The adhesion modifier is applied to the object, preferably prior to the application of the first plastic coating.
The method may include the step of applying an enhancement mater-ia:L to at least a p,3rtion of a plastic coated surface of the obiect; most, if not all of these enhancement materials may be comb:Lned with one or more of the applied layers.
The step of applying enhancement material may comprise imprint:ing a perceptible patte~n on a plastic coating.
l~he perceptible patte~n may c:omprise printed text.
The method may include the step of applying a protective coat of substantially clear plastic over the enhanced layer.
The perceptible pattern ~ay be perceptible by touch, such as raised dots.
CA 022367~9 1998-0~-0~
The perceptible pat~ern may be vis~ally per-ceptible.
The metho~i may include the step of applying a protective coat of substanl:ially clear plastic over the perceptible pattern. The method may include the step of applying a second protective plastic coating over at least a portion of the major surface, the second protective coatin~ bein~ applied prior to the first coating, and subsequent to the application of the adhesion modifiel-, to thereby promote the adhesive bond between the second coating and the object.
The firc~t protective coating may be a high temperature plastic, resistant to wear within a hot environment, such as a commercial dishwasher.
The enh1ancement step may comprise the addition of at least one coloured layer to the object, preferably hy the addition of enhancement material such as colour to one of the applied layers.
Thus, there is provided a frangible article, normally subject t~
break:age upon impact, having a first protective plastic coatinq applied to a major surface of the object together with an adhesion modifier, in pr~tective, adherinq relation with the article, to promote the inteyrity of the article. The article may incLude enhancement ~aterial applied to the article, which may comprise a perceptible pattern imprin~ed on a plastic coating.
The enhancement material may be selected from the group consist:ing of print, col3ur addition, irri.descent mater-ial~
pearles,_ent material, thermally responsive colour chan~ing CA 022367~9 1998-0~-0~
materiaL and infra-red rlesponsive luminescent material.
The art~,cle may include a layer of substantially clear plastic over-lying the enhancement material in protective relation th l-h erewl .
In car-r-~Jing uut the preslent invention, in order to facilitate the appiication of coatings to smooth glass and ceramic surfaces and al~o to control adhesion (i.e. peel~ strength, use is made of an adhesion modifier, to increase peel strength. Enhanced adhe~ive characteristics for the coating are obtained with the use of a prime coat of ol~ganofunctional silane.
In partic~lar it is found that silicones, Silane ~-llC~ and Silane f~ b (trademark~), supplied by OSI, a Division of Witchco Corp.,a chemical company of Connecticut, used as a coupling agent greatly enhance the adhesion of a plastic coating to the gliass parent material, and facilitate application of the plastic layer.
~est result~ in adhesion enhancement of a parent glass material were obl:ained by first applying a Silane coating to the parent glas~ m~aterial, and permitting the coating to dry. Upon then applying a coating of ethylene acrylic acid copolymer as the copolymer coating it was found that the wetting and adhesion of the copolymer coating to the parent material was significantly enhanced. This is to distinguish from fi~-st blending one of the Silanes with the coating material.
~ protective coating, in particular a temperatu~e-resistant coating in the case of dl~inking glasses, was then applied over the eth~;lene copolymer coating.
~i CA 022367~9 1998-0~-0~
It was found that applying a catalysed cross-lin~;eci polyuret:hane protective outer coating yielded excellent dishwasher protection to the ethylene copolymer, in resisting the heat: and chemical environment of a comme~cial dishwasher.
The croc;s-link:ed polyurethane protective outer coating possesses a degree of fle:cibility to complement the impact ~esistance of the underlying ethylene copolymer~ while possessing a long-lastin~ clear and spark:ling appearance, suitable with d~ink:ing g:Lasses.
The ethylene copolymer intermediate coating serves as a cushion, in the manner oF a shock:-~bsorber.
It has been found that e~ccellent coating results and good materia]. utili2ation are obtained using the flow coating process., as desc~ibed in : Industrial Painting: Frinciples ~~.
P~actice by No~man ~. ~oobal 1991 page 91.
The pla~;tic i5 flow coated at about ~C~ C ciegrees, applying low-solvent fluid plastic by no2~1e under non-impact flow conditions, to flow a smooth laye~ over the object being coated. In the instance of inverted glasses, these may be rotated to facilitate application of the plastic, with eccess plastic falling into drip pans, fo~ recycling in the process.
In addit:ion to the application of plastic coatings for purposes of durability and safety, the p~esent p~ocess also enables the economic int~oduction to the article, at or afte~
one or other of its coating stages, of decorative enhancement such as colour, the prov:ision of irridescence or pearlescence, and the application of a~iditives to provide the characteri~tic CA 022367~9 1998-0~-0~
of therrnally-reponsive colour char-ge.
~lso contemplated is the blending of additives that glow when illuminated under "black:" i.e. infra-red light.
The inc:Lusion of perceptible mark:ings, su~h as visible printing, or raised Braille dots for tactile "reading" is greatly facilitated by the provisiQn of a plastic coating tu receive versati].e and economical application of such enhancements upon an otherwise difficult-tD-print glass or other, ceramic surface.
5uch perceptible marking, may be protected by overlying plastic layers.
It will be understood th~t many of the above recited techniques and their associated advantages apply to other frangib:le obiects such as ceramics-ware.
The virl:ual increase in article strength, and reduced vulnerability to impact damage may permit the adoption of less bu;Lk:y sections i.e. thinner walls and lighter structure.
Significant cost savings may be achievable due to reduction in break:age during handling, shipping and ultimate use, and reduced shipping charges due to weight reduction, as well as savings in the costs of material per se for the pr-oducts.
The coating of a hollow product in an inverted position, in a flow coating application process, removes any need to mask:-off the interior of the hollow vessel being coated, due to the inverted position, while facilitating recovery of excess coating materia:L.
Spray applications, as in spray painting, have been used success-Fully~
_, CA 022367~9 1998-0~-0~
The pre-ent invention thus provides a me~hod of coating an object~ such as an open-topped glassware vessel~ including the steps of coating a major surface of the vessel with an ethylene acrylic acid copolymer over an organofunctional silicone (Silane) coating, and applying a protective coating of heat-resistant plastic tlhereover.
~pplication of the ethylene copolymer in a serie~ of set~uentia:L
coatings, with intermediate drying phases to remove the solvent from tht~ plastic, enables the build-up of a smooth coating to a desired thic~ness.
~ tough pr-otective plastic over-coating such as the heat resistar-t plastic can then be applied over the ethylene copolymer.
The use, where feas3ible, of water as the solvent has many advantages. In one embodiment four coatings of ethylene acryl:ic acid copolymer in water 501 ution were applied, with intermediate drying, to build up an agregate thickness of about 4 1~2 mil (o.(:)t~45 inches~.
Gr-eater or lesser thic~:nesses may be readily achieved.
The pre1Ferred protective outer coating is selected from the group consisting of ther~o-setting plastics.
~lso, tilermoplastics having a minimum useful tempe~ature of at least about 82 C. degrees and 5Ui ted to withstand commerc.ial and household dishwashing may prove suitable, particu:larly for ylasses.
The vessel, such as a drin~ing glassl with its applied coating thereby provides a reinf~rced vessel having glass chip B
CA 022367~9 1998-0~-0~
retention capability, and the capa~ility to withstand commercial or- household dishwashinia.
In the case of a thermosetting plastic outer coating, the final, t:hermosetting coal:ing is cured under predetermined conditions of time and temper-ature.
The prot:ective outer coal:ing may be selected from a catalysed acrylic or polyester. ~ 501 vent such as ethyl acetate may be used, in the cae of flow-coated or sprayed-on application.
Certain ther-~oplastics having a softening point at least close to the boiling point of water may also prove suitable for the outer coating, in the case of drin~ing glasses.
The use of polycarbonate as a protective coating is contemp].ated, particular-ly as an outer coating.
The coat:ings are preferably liquid, in order to utili~e a flow-coating or spray-on process. For the copolymer cushion layer water is the preferred solvent.
The vessel is ln a heated condition, for the application of each of the coatings, at about ~l:) C. degrees.
Provisit~n is usually made for flash-drying off of the solvent using infra-red panels o~ by ovens, before setting-up and curing of the coatings occur.
It will be understood that for drin~ing glasses or commestible dishes all the coating materials need to be "Food and Drug"
approved, and environmentally compatible.
Coating of moulded glass vessels may ta~e place on the vessel manufac1-uring line, at comparatively low t.:emperatures.
In the case of catalysed outer coatings, these may cure at CA 022367~9 1998-0~-0 room temperature in some instances~
In acidition to use of the subject laminated coating for cirin~ing glasses, its use may e tend to include glassware such as mi~ing bowl 5, punch bowls, and the like where improved safety is a factor~
One advantage of the pFesent invention is in the potential use of color~ or other appearance enhancements.
In the case of normal, uncoated glassware, the economics governing the color appl:ication process necessitate large scale actiori, in that, wlhen adding color to glass in the molten stage large produl-tion runs are necessary, and colour change-overs are highly uneconomical.
~s a consequence the ran,~e of colors is generally very limited.
The sub.iect plastic coating process may include the addition of color to the glassware, by way of or upon the coating, in one or- other of its stages, thereby enabling small batches or even individual color-ation of articles.
The color- may be a component of one or both of the coatings, so that the scale of a batch is no longer significant.
Consequently, the range of colors can ~e e~tended without undue ec:onomic penalty.
~ further advantage of the subject process is that a plastic--coated surface may be readily printed upon, using catalysed ink:s with conventional printing processes, which may inc].ude the use of u:Ltra-viole~ or heat curing, to enhance dish washer and l~ear resistance~ ~n outer plastic coat mav be applied in protective relation over the printing, 11~
CA 022367~9 1998-0~-0~
colour or other selecte~ enhancement decoration .
~ further advantage of tlhis process is that the coatings, whether single or laminated tan be readily applied to a wide range of object configurations, enabling the products to compete with equivalent plastic products.
It is contemplated that a composite vessel in accordance with thi.s invention may be of lighter construction, having a thinner wall constFuCtiOn~ capable of 6ustaining usage and handling stresses. This~ for drin~ing glasses, can afford very real savings in terms of hot water and drying requiremer7ts.
In some circumstance6 adhesion mod:ification may be desired 7 to r-educe to a selected ~egree the peel strength of a plastic film applied to a glass object, us:ing an adhesion modifier selected from polyethylene glycol and magnesium oside, along the lines taught in the above-mentioned U~S.patent No 4~:36'S,5qC3. However, adhesion enhar-cement as taught above i3 the pre~Ferred mode for- pl~otecting drinking glasses, the above identif:ied prior art method having been found to be inadequate in regard to its use with articles that are subject to dishwasher use.
Testing evaluation of thle subject glasses coated in accordance with the present inventic3n was carried out using a pendulum impact test. With a test specimen glass i.mmoveably mounted upon a test stand, a steel ball, positioned to impact the glass at its more vulnerable upper portion, is released to swing through a standard, predetermined arc, to impact the glass.
The conditions of ball weight, diameter, and7 imp~ct velocity CA 022367~9 1998-0~-0~
were se].ected to provide a standardized test such that in the case of unprl3tected glasses taken at random from a standard batch of glasses, two out of ten non-coated glasses survived the test unbro~en~
In the i.nstance of glasses of the same batch, but protectively coated i.n accordance with the present invention, the brea~age surviva,L rate was eight out of ten so tested, giving a factor- of two and a half to th~ee of impr-oved break:age resistance.
The tes1- stand incorporates a heavy base carrying a rigid mast. f~ cross bar- adjustably secured to the mast has a pendulum cord secured th,ereto to which a steel ball of a given weight is secured. The cross bar is adjusted in accordance with the length of the cord selected for that type of glass, and in accordance with the height of the glasses being tested, such that impact of the ball will ta~:e place against the vulnerab].e upper portion of the glass, when supported upon the base.
For each test the ball i 13 released from d predetermined measured height, with the cord just taut, for the ball to swing arcuate3.y down and directly impact the ~lass being tested.
In orde~ to calibrate the test apparatus f or a given batch of glasses, the length of the cord and the drop height are selecteli, with corresponiing adju~tment to the height of the cross-bar on the mast, in order to achieve a measurable high rate of brea~;age such as ~C3~o of the virgin (untreated~ glasses.
The treated glasses are then also ~ested under precisely the same conditions, enabling a statistical measurement of the 1 :~
CA 022367~9 l998-0~-0~
improvemen~ in durability to be c~b~ained.
It i5 noteworthy that, in the destruction of the untreated "virgin" glasses, when impacted by the ball they literally e~plocieci into shards and fragments, being widely dispersed. In contrast:, the coated glas6es fractured in an entirely different mode. E~ven when glass pieces brok;e free from the protective coating they were not si~3nificantly dispersed, but fell in close pro~imi1:y to the point oF destruction.
It appears that the protective coa~ing functions first to cushion the impact, to initially impede breakage of the c3lass.
Then, when failure occurs, the detachment of the glass pieces i5 impeded by the plastic bond, such that the energy of dispersion of any 1:ree glass particLes and shards is much reduced.
In addil:ion to impact te~ting, the subject coated articles, specifically, cirink:ing g:Lasses, were subject tu repeated washin~ cycles in a commercial dishwasher, to establish the commerci.al suitabili y o-F the coated glass articles.
The fle~ibility of the present process, with its sever-al options in number and different types of coatings and appearance enhancements provides a wide range of potential products, beyonci the range of specific embodiments herein illustrated.
~ost such products are safety-enhanced by the process.
Use of t:he process for permanant labelling of products, such as iars, with lettering or Braille characters~ is contemplated.
B~IEF DESOPIPTION OF THE Dfi~WING~
~ertain embodiments of the invention are described by way 1~
CA 022367~9 l998-0~-0~
of illustration, without limitation o~ the invention thereto, other than as set forth in the claims hereof, reference being made to the accompanying drawings, wherein:
Figure 1 is a view Df a drinking glass coated in accordance with the present invention;
Figure ~ is a view of a bowl coated with the subject coating;
Figure -~ is a schematic side view of a flow coating instal-ation for the articles presently illustrated;
Figure 4 is a t.abular summary of the pr-ocess; and, Figure 5 is a side elevational view af a test stand for impact te~ting of the illustrated drinking glass articles.
DET~ILED DES~IPTION OF THE INvENTION
Figure 1 shows a drin~:ing glass article l(:~, the outer s~rface 11 of which is coated with a pr-otective coat 14, in accordance with the present invention.
Figure ~ shows a decorative bowl 1~, the surface of which has a protective coat 14 thereon. The coat 14 lends itself to the application therewith both of color and of printed patterns, etc.
~eferriny to the proces~ embodiment illustrated in Figure ~, a moving belt 16 carries a batch of glasses lf~ past eight work:stations. The work:~tations comprise flowcoating or spray stations ~ 4, ~6 and ~B, having drier stations ~
and ~4 in interposed relation~ and curing station ~.
l~he dr~ying stations ~f~ 9 ~4 may comprise infra-red panels.
Figure 4 shows the sequence of steps for the illustrated process of Figure ~.
CA 022367~9 l998-0~-0~
It will be understood that alternative sequences an~ different embodiments may be produced, for the purposes of the invention.
In the testing apparatus 41~ of Figure 5 a baseplate 4~ carries a mast 44, having a cantilever aF-m 46 adiustably secured at 48.
loop 5~ has a cord 5~ secured thereto 9 the cord 5~ car~ying a metal ball 54.
~djacent the foot of the mast 44 a bracket 58 positions a glass 1l:~ in secured, supported rPlation upon the baseplate 4~.
The length of the cord 5~ is selected in accordance with an elected protocul of desired breakage of urltreated glasses, in order to establish a basis for comparative testing of glasses treated in accordance with the present invention.
Having determined the desired cord length in order to achieve the des1red breakage protocol for untreated articles, the height of the arm 46 upon the mast 44 is set so as to impact the ball 54 against the upper, most vulnerable portion of the glass 11:~ being tested.
TEST AFPAPATUS FOfi ~UfiA~ILITY GALIB~TION
With the testing apparatus equipped with a 94-gram steel ball, it was found that a ~ 5~8 inch effective length of cord, positioned such that the ball impacted the upper portion of the test glass, as a durability test, produced a survival probability of two out of ten for unt~-eated glasses~ i.e. an 8l~%
breakage rate.
TEST 1.
~rinking glasses treated with a Silane ~T.M.~ or~ano-functional silicone~ were dried and then coated with a ~~mil ~ inch~
CA 022367~9 1998-0~-0~
under-coating of ethylene copolymer and a protective high temperature outer coating of ~:~.5 mil polyurethar-e.
Three out of ten survived the durability ~impact) test, i.e. a ~,~% brea~age r-ate.
These coated drin~:ing glasses were undamaged after 3(~ machine dishwashings.
TEST .~
Glasses treated with the Silane ~T.~.) coating and having a 3-mil polyvinyl~utyral coating showed reduced durability on the dishwasher test, with loss of adhesion of the protective coating and were considered to have failed the dishwasher test. ~reah: resistance was also inadequate~
~lasses with a silane coating were given four coatings of ethylene copolymer, for a total 5 to ~ mil thic~ness, and a high temperature coat of ~:~.5--mil polyurethane.
Eight out of ten glasses i.e. 8(:~% survived the durability test.
These glasses also survived ~ machine dic;hwashings, undamaged.
In the instances of brea~age under the impact test, high fragment retention held virtually all the glass fragments.
While greater thic~.:nesses of ethylene copolymer can be applied, the desired high degree of clarity and spark:le may be adversely affected CO~ME~GI~L USE
The method and its products have widespFead application f OF
domestic and commercial products, world-wide.
1~
The app].ication of sur-face coatings to glass products is well known.
One type of coating comprises a so-called lubricious coating which can be applied to the e:cterior surface of bottles and the like, which are subj~ect to mechanical handling. The lubricious coating diminishes the frictional contact of bottles against each other, and agaiGst handling machinery, so as to diminish stres~ and break:age occu~ences during processing. This is taught in United States Fatent No. ~ b,~55 June 4 19~8.
In United States Patent INo. 4"~5,5~ Dec ~ 7, there is taught the appplication of a protective plastic coating for glass soft drir-k: bottles for carbonated beverages~ Such bottles~ more particularly the larger variety of 16-ounce capacit~ and greater~ were known to fracture upon inpact and e:cplode in dangerous fashion, scattering glass frag~ent~.
This problem has dissapeared with the advent of plastic soft drink bottlQ , which have superceded glass for this area of use The abovse-mentioned protective plastic coating for glass soft drink bottles was susceptible to damage from hot water, such ~.
CA 022367~9 1998-0~-0~
as is encounter-ed in com~er-cial washing machine~.
There is one field of glass usage where plastic has not supplan1:ed glass, namely in beverage glasses.
~ue to 1:he visual appeal of glass, hoth in its clarity and its mass or "heft", and also its relatively low cost and suitability for machine washing, as compared with the e~-:treme lightness and higher cost of thin-walled plastic products, drinking "glasses"
of glass have retained a major share of the market. However~
even in a small populatiDn such as that of Canada, there i5 an annual replacement requirement of some ~l~~million glasses. Much of this figure represents breakage los~ that occurs in handling, transportation and use.
The ha2ards associated with the breakage of glass drink-war-e are such that its use around swimming pools constitutes a very real sa-Fety ha2ard. In the case of a pool with a vinyl liner, the inc:ident of broken gLass in the pool generally requires the complete drainage of the pool, for safe remaval of the glass, and to c~afeguard the vin~l line~ This action, in turn, may require professional re-setting of the liner.
In addi-tion to breakages of beverage glasses which occur in use there is also the hazard of rim chipping, which can lead to liability claims against the prop~ietor of a har or restaurant.
SU~ Y OF THE INvENTION
While the present disclosure and its associated research is particu:Larly directed to the pr-otection of glassware, in the form of drinking glasses, it will be appr-eciated that, in light CA 022367~9 1998-0~-0~
of wide<,pr-ead other usag~es of glass and ceramics in common with drin~;in(~ glasses, the present finding6 and teachings appear also to appl~ ther-eto, par-ticularly in regard to aspects of safety.
The p~esent in~ention provides a method of treating a frangib:Le object, normally subject to breakage upon impact, comprising the steps of applying a first protective plastic coating to a majo surface of the object in protective~ adhering relation therewi1:h, together with an adhesion modifier to promote the integri1iy of the object.
The adhesion modifier enhances the bonding of plastic to the object, and in the case Df drinking glasses and the like, is necessa~y in order for the object to withstand commercial dishwashing, and to enable it to retain p~rticles and shards in case of subsequent break:age.
The adhesion modifier is applied to the object, preferably prior to the application of the first plastic coating.
The method may include the step of applying an enhancement mater-ia:L to at least a p,3rtion of a plastic coated surface of the obiect; most, if not all of these enhancement materials may be comb:Lned with one or more of the applied layers.
The step of applying enhancement material may comprise imprint:ing a perceptible patte~n on a plastic coating.
l~he perceptible patte~n may c:omprise printed text.
The method may include the step of applying a protective coat of substantially clear plastic over the enhanced layer.
The perceptible pattern ~ay be perceptible by touch, such as raised dots.
CA 022367~9 1998-0~-0~
The perceptible pat~ern may be vis~ally per-ceptible.
The metho~i may include the step of applying a protective coat of substanl:ially clear plastic over the perceptible pattern. The method may include the step of applying a second protective plastic coating over at least a portion of the major surface, the second protective coatin~ bein~ applied prior to the first coating, and subsequent to the application of the adhesion modifiel-, to thereby promote the adhesive bond between the second coating and the object.
The firc~t protective coating may be a high temperature plastic, resistant to wear within a hot environment, such as a commercial dishwasher.
The enh1ancement step may comprise the addition of at least one coloured layer to the object, preferably hy the addition of enhancement material such as colour to one of the applied layers.
Thus, there is provided a frangible article, normally subject t~
break:age upon impact, having a first protective plastic coatinq applied to a major surface of the object together with an adhesion modifier, in pr~tective, adherinq relation with the article, to promote the inteyrity of the article. The article may incLude enhancement ~aterial applied to the article, which may comprise a perceptible pattern imprin~ed on a plastic coating.
The enhancement material may be selected from the group consist:ing of print, col3ur addition, irri.descent mater-ial~
pearles,_ent material, thermally responsive colour chan~ing CA 022367~9 1998-0~-0~
materiaL and infra-red rlesponsive luminescent material.
The art~,cle may include a layer of substantially clear plastic over-lying the enhancement material in protective relation th l-h erewl .
In car-r-~Jing uut the preslent invention, in order to facilitate the appiication of coatings to smooth glass and ceramic surfaces and al~o to control adhesion (i.e. peel~ strength, use is made of an adhesion modifier, to increase peel strength. Enhanced adhe~ive characteristics for the coating are obtained with the use of a prime coat of ol~ganofunctional silane.
In partic~lar it is found that silicones, Silane ~-llC~ and Silane f~ b (trademark~), supplied by OSI, a Division of Witchco Corp.,a chemical company of Connecticut, used as a coupling agent greatly enhance the adhesion of a plastic coating to the gliass parent material, and facilitate application of the plastic layer.
~est result~ in adhesion enhancement of a parent glass material were obl:ained by first applying a Silane coating to the parent glas~ m~aterial, and permitting the coating to dry. Upon then applying a coating of ethylene acrylic acid copolymer as the copolymer coating it was found that the wetting and adhesion of the copolymer coating to the parent material was significantly enhanced. This is to distinguish from fi~-st blending one of the Silanes with the coating material.
~ protective coating, in particular a temperatu~e-resistant coating in the case of dl~inking glasses, was then applied over the eth~;lene copolymer coating.
~i CA 022367~9 1998-0~-0~
It was found that applying a catalysed cross-lin~;eci polyuret:hane protective outer coating yielded excellent dishwasher protection to the ethylene copolymer, in resisting the heat: and chemical environment of a comme~cial dishwasher.
The croc;s-link:ed polyurethane protective outer coating possesses a degree of fle:cibility to complement the impact ~esistance of the underlying ethylene copolymer~ while possessing a long-lastin~ clear and spark:ling appearance, suitable with d~ink:ing g:Lasses.
The ethylene copolymer intermediate coating serves as a cushion, in the manner oF a shock:-~bsorber.
It has been found that e~ccellent coating results and good materia]. utili2ation are obtained using the flow coating process., as desc~ibed in : Industrial Painting: Frinciples ~~.
P~actice by No~man ~. ~oobal 1991 page 91.
The pla~;tic i5 flow coated at about ~C~ C ciegrees, applying low-solvent fluid plastic by no2~1e under non-impact flow conditions, to flow a smooth laye~ over the object being coated. In the instance of inverted glasses, these may be rotated to facilitate application of the plastic, with eccess plastic falling into drip pans, fo~ recycling in the process.
In addit:ion to the application of plastic coatings for purposes of durability and safety, the p~esent p~ocess also enables the economic int~oduction to the article, at or afte~
one or other of its coating stages, of decorative enhancement such as colour, the prov:ision of irridescence or pearlescence, and the application of a~iditives to provide the characteri~tic CA 022367~9 1998-0~-0~
of therrnally-reponsive colour char-ge.
~lso contemplated is the blending of additives that glow when illuminated under "black:" i.e. infra-red light.
The inc:Lusion of perceptible mark:ings, su~h as visible printing, or raised Braille dots for tactile "reading" is greatly facilitated by the provisiQn of a plastic coating tu receive versati].e and economical application of such enhancements upon an otherwise difficult-tD-print glass or other, ceramic surface.
5uch perceptible marking, may be protected by overlying plastic layers.
It will be understood th~t many of the above recited techniques and their associated advantages apply to other frangib:le obiects such as ceramics-ware.
The virl:ual increase in article strength, and reduced vulnerability to impact damage may permit the adoption of less bu;Lk:y sections i.e. thinner walls and lighter structure.
Significant cost savings may be achievable due to reduction in break:age during handling, shipping and ultimate use, and reduced shipping charges due to weight reduction, as well as savings in the costs of material per se for the pr-oducts.
The coating of a hollow product in an inverted position, in a flow coating application process, removes any need to mask:-off the interior of the hollow vessel being coated, due to the inverted position, while facilitating recovery of excess coating materia:L.
Spray applications, as in spray painting, have been used success-Fully~
_, CA 022367~9 1998-0~-0~
The pre-ent invention thus provides a me~hod of coating an object~ such as an open-topped glassware vessel~ including the steps of coating a major surface of the vessel with an ethylene acrylic acid copolymer over an organofunctional silicone (Silane) coating, and applying a protective coating of heat-resistant plastic tlhereover.
~pplication of the ethylene copolymer in a serie~ of set~uentia:L
coatings, with intermediate drying phases to remove the solvent from tht~ plastic, enables the build-up of a smooth coating to a desired thic~ness.
~ tough pr-otective plastic over-coating such as the heat resistar-t plastic can then be applied over the ethylene copolymer.
The use, where feas3ible, of water as the solvent has many advantages. In one embodiment four coatings of ethylene acryl:ic acid copolymer in water 501 ution were applied, with intermediate drying, to build up an agregate thickness of about 4 1~2 mil (o.(:)t~45 inches~.
Gr-eater or lesser thic~:nesses may be readily achieved.
The pre1Ferred protective outer coating is selected from the group consisting of ther~o-setting plastics.
~lso, tilermoplastics having a minimum useful tempe~ature of at least about 82 C. degrees and 5Ui ted to withstand commerc.ial and household dishwashing may prove suitable, particu:larly for ylasses.
The vessel, such as a drin~ing glassl with its applied coating thereby provides a reinf~rced vessel having glass chip B
CA 022367~9 1998-0~-0~
retention capability, and the capa~ility to withstand commercial or- household dishwashinia.
In the case of a thermosetting plastic outer coating, the final, t:hermosetting coal:ing is cured under predetermined conditions of time and temper-ature.
The prot:ective outer coal:ing may be selected from a catalysed acrylic or polyester. ~ 501 vent such as ethyl acetate may be used, in the cae of flow-coated or sprayed-on application.
Certain ther-~oplastics having a softening point at least close to the boiling point of water may also prove suitable for the outer coating, in the case of drin~ing glasses.
The use of polycarbonate as a protective coating is contemp].ated, particular-ly as an outer coating.
The coat:ings are preferably liquid, in order to utili~e a flow-coating or spray-on process. For the copolymer cushion layer water is the preferred solvent.
The vessel is ln a heated condition, for the application of each of the coatings, at about ~l:) C. degrees.
Provisit~n is usually made for flash-drying off of the solvent using infra-red panels o~ by ovens, before setting-up and curing of the coatings occur.
It will be understood that for drin~ing glasses or commestible dishes all the coating materials need to be "Food and Drug"
approved, and environmentally compatible.
Coating of moulded glass vessels may ta~e place on the vessel manufac1-uring line, at comparatively low t.:emperatures.
In the case of catalysed outer coatings, these may cure at CA 022367~9 1998-0~-0 room temperature in some instances~
In acidition to use of the subject laminated coating for cirin~ing glasses, its use may e tend to include glassware such as mi~ing bowl 5, punch bowls, and the like where improved safety is a factor~
One advantage of the pFesent invention is in the potential use of color~ or other appearance enhancements.
In the case of normal, uncoated glassware, the economics governing the color appl:ication process necessitate large scale actiori, in that, wlhen adding color to glass in the molten stage large produl-tion runs are necessary, and colour change-overs are highly uneconomical.
~s a consequence the ran,~e of colors is generally very limited.
The sub.iect plastic coating process may include the addition of color to the glassware, by way of or upon the coating, in one or- other of its stages, thereby enabling small batches or even individual color-ation of articles.
The color- may be a component of one or both of the coatings, so that the scale of a batch is no longer significant.
Consequently, the range of colors can ~e e~tended without undue ec:onomic penalty.
~ further advantage of the subject process is that a plastic--coated surface may be readily printed upon, using catalysed ink:s with conventional printing processes, which may inc].ude the use of u:Ltra-viole~ or heat curing, to enhance dish washer and l~ear resistance~ ~n outer plastic coat mav be applied in protective relation over the printing, 11~
CA 022367~9 1998-0~-0~
colour or other selecte~ enhancement decoration .
~ further advantage of tlhis process is that the coatings, whether single or laminated tan be readily applied to a wide range of object configurations, enabling the products to compete with equivalent plastic products.
It is contemplated that a composite vessel in accordance with thi.s invention may be of lighter construction, having a thinner wall constFuCtiOn~ capable of 6ustaining usage and handling stresses. This~ for drin~ing glasses, can afford very real savings in terms of hot water and drying requiremer7ts.
In some circumstance6 adhesion mod:ification may be desired 7 to r-educe to a selected ~egree the peel strength of a plastic film applied to a glass object, us:ing an adhesion modifier selected from polyethylene glycol and magnesium oside, along the lines taught in the above-mentioned U~S.patent No 4~:36'S,5qC3. However, adhesion enhar-cement as taught above i3 the pre~Ferred mode for- pl~otecting drinking glasses, the above identif:ied prior art method having been found to be inadequate in regard to its use with articles that are subject to dishwasher use.
Testing evaluation of thle subject glasses coated in accordance with the present inventic3n was carried out using a pendulum impact test. With a test specimen glass i.mmoveably mounted upon a test stand, a steel ball, positioned to impact the glass at its more vulnerable upper portion, is released to swing through a standard, predetermined arc, to impact the glass.
The conditions of ball weight, diameter, and7 imp~ct velocity CA 022367~9 1998-0~-0~
were se].ected to provide a standardized test such that in the case of unprl3tected glasses taken at random from a standard batch of glasses, two out of ten non-coated glasses survived the test unbro~en~
In the i.nstance of glasses of the same batch, but protectively coated i.n accordance with the present invention, the brea~age surviva,L rate was eight out of ten so tested, giving a factor- of two and a half to th~ee of impr-oved break:age resistance.
The tes1- stand incorporates a heavy base carrying a rigid mast. f~ cross bar- adjustably secured to the mast has a pendulum cord secured th,ereto to which a steel ball of a given weight is secured. The cross bar is adjusted in accordance with the length of the cord selected for that type of glass, and in accordance with the height of the glasses being tested, such that impact of the ball will ta~:e place against the vulnerab].e upper portion of the glass, when supported upon the base.
For each test the ball i 13 released from d predetermined measured height, with the cord just taut, for the ball to swing arcuate3.y down and directly impact the ~lass being tested.
In orde~ to calibrate the test apparatus f or a given batch of glasses, the length of the cord and the drop height are selecteli, with corresponiing adju~tment to the height of the cross-bar on the mast, in order to achieve a measurable high rate of brea~;age such as ~C3~o of the virgin (untreated~ glasses.
The treated glasses are then also ~ested under precisely the same conditions, enabling a statistical measurement of the 1 :~
CA 022367~9 l998-0~-0~
improvemen~ in durability to be c~b~ained.
It i5 noteworthy that, in the destruction of the untreated "virgin" glasses, when impacted by the ball they literally e~plocieci into shards and fragments, being widely dispersed. In contrast:, the coated glas6es fractured in an entirely different mode. E~ven when glass pieces brok;e free from the protective coating they were not si~3nificantly dispersed, but fell in close pro~imi1:y to the point oF destruction.
It appears that the protective coa~ing functions first to cushion the impact, to initially impede breakage of the c3lass.
Then, when failure occurs, the detachment of the glass pieces i5 impeded by the plastic bond, such that the energy of dispersion of any 1:ree glass particLes and shards is much reduced.
In addil:ion to impact te~ting, the subject coated articles, specifically, cirink:ing g:Lasses, were subject tu repeated washin~ cycles in a commercial dishwasher, to establish the commerci.al suitabili y o-F the coated glass articles.
The fle~ibility of the present process, with its sever-al options in number and different types of coatings and appearance enhancements provides a wide range of potential products, beyonci the range of specific embodiments herein illustrated.
~ost such products are safety-enhanced by the process.
Use of t:he process for permanant labelling of products, such as iars, with lettering or Braille characters~ is contemplated.
B~IEF DESOPIPTION OF THE Dfi~WING~
~ertain embodiments of the invention are described by way 1~
CA 022367~9 l998-0~-0~
of illustration, without limitation o~ the invention thereto, other than as set forth in the claims hereof, reference being made to the accompanying drawings, wherein:
Figure 1 is a view Df a drinking glass coated in accordance with the present invention;
Figure ~ is a view of a bowl coated with the subject coating;
Figure -~ is a schematic side view of a flow coating instal-ation for the articles presently illustrated;
Figure 4 is a t.abular summary of the pr-ocess; and, Figure 5 is a side elevational view af a test stand for impact te~ting of the illustrated drinking glass articles.
DET~ILED DES~IPTION OF THE INvENTION
Figure 1 shows a drin~:ing glass article l(:~, the outer s~rface 11 of which is coated with a pr-otective coat 14, in accordance with the present invention.
Figure ~ shows a decorative bowl 1~, the surface of which has a protective coat 14 thereon. The coat 14 lends itself to the application therewith both of color and of printed patterns, etc.
~eferriny to the proces~ embodiment illustrated in Figure ~, a moving belt 16 carries a batch of glasses lf~ past eight work:stations. The work:~tations comprise flowcoating or spray stations ~ 4, ~6 and ~B, having drier stations ~
and ~4 in interposed relation~ and curing station ~.
l~he dr~ying stations ~f~ 9 ~4 may comprise infra-red panels.
Figure 4 shows the sequence of steps for the illustrated process of Figure ~.
CA 022367~9 l998-0~-0~
It will be understood that alternative sequences an~ different embodiments may be produced, for the purposes of the invention.
In the testing apparatus 41~ of Figure 5 a baseplate 4~ carries a mast 44, having a cantilever aF-m 46 adiustably secured at 48.
loop 5~ has a cord 5~ secured thereto 9 the cord 5~ car~ying a metal ball 54.
~djacent the foot of the mast 44 a bracket 58 positions a glass 1l:~ in secured, supported rPlation upon the baseplate 4~.
The length of the cord 5~ is selected in accordance with an elected protocul of desired breakage of urltreated glasses, in order to establish a basis for comparative testing of glasses treated in accordance with the present invention.
Having determined the desired cord length in order to achieve the des1red breakage protocol for untreated articles, the height of the arm 46 upon the mast 44 is set so as to impact the ball 54 against the upper, most vulnerable portion of the glass 11:~ being tested.
TEST AFPAPATUS FOfi ~UfiA~ILITY GALIB~TION
With the testing apparatus equipped with a 94-gram steel ball, it was found that a ~ 5~8 inch effective length of cord, positioned such that the ball impacted the upper portion of the test glass, as a durability test, produced a survival probability of two out of ten for unt~-eated glasses~ i.e. an 8l~%
breakage rate.
TEST 1.
~rinking glasses treated with a Silane ~T.M.~ or~ano-functional silicone~ were dried and then coated with a ~~mil ~ inch~
CA 022367~9 1998-0~-0~
under-coating of ethylene copolymer and a protective high temperature outer coating of ~:~.5 mil polyurethar-e.
Three out of ten survived the durability ~impact) test, i.e. a ~,~% brea~age r-ate.
These coated drin~:ing glasses were undamaged after 3(~ machine dishwashings.
TEST .~
Glasses treated with the Silane ~T.~.) coating and having a 3-mil polyvinyl~utyral coating showed reduced durability on the dishwasher test, with loss of adhesion of the protective coating and were considered to have failed the dishwasher test. ~reah: resistance was also inadequate~
~lasses with a silane coating were given four coatings of ethylene copolymer, for a total 5 to ~ mil thic~ness, and a high temperature coat of ~:~.5--mil polyurethane.
Eight out of ten glasses i.e. 8(:~% survived the durability test.
These glasses also survived ~ machine dic;hwashings, undamaged.
In the instances of brea~age under the impact test, high fragment retention held virtually all the glass fragments.
While greater thic~.:nesses of ethylene copolymer can be applied, the desired high degree of clarity and spark:le may be adversely affected CO~ME~GI~L USE
The method and its products have widespFead application f OF
domestic and commercial products, world-wide.
1~
Claims (36)
1. The method of treating a frangible object, normally subject to breakage upon impact, comprising the steps of applying a first protective plastic coating to a major surface of the object in protective, adhering relation therewith, together with an adhesion modifier to promote the integrity of the object.
2. The method as set forth in Claim 1, wherein said adhesion modifier enhances the bonding of plastic to said object.
3. The method as set forth in Claim 1, wherein said adhesion modifier is applied to said object prior to the application of said first coating.
4. The method as set forth in Claim 1, including the step of applying an enhancement material to at least a portion of a plastic coated surface of said object.
5. The method as set forth in Claim 4, said step of applying said enhancement material comprising imprinting a perceptible pattern on said plastic coating.
6. The method as set forth in Claim 5, said perceptible pattern comprising printed text.
7. The method as set forth in Claim 4, 5 or 6, including the step of applying a protective coat of substantially clear plastic over said enhanced layer.
8. The method as set forth in Claim 5, said perceptible pattern being perceptible by touch.
9. The method as set forth in Claim 5, said perceptible pattern being visually perceptible.
10. The method as set forth in Claim 7 or claim 8, including the step of applying a protective coat of substantially clear plastic over said perceptible pattern.
11. The method as set forth in Claim 4, wherein said enhancement material comprises colour, combined with said plastic coated upon said object.
12. The method as set forth in Claim 1, including the step of applying a second protective plastic coating over at least a portion of said major surface.
13. The method as set forth in Claim 12, wherein said second protective coating is applied prior to said first coating, subsequent to the application of said adhesion modifier, to thereby promote the adhesive bond between said second coating and said object.
14. The method as set forth in Claim 3, wherein said first protective coating is a high temperature plastic, resistant to wear within a hot environment.
15. The method as set forth in Claim 4, said decorative layer step comprising the addition of at least one coloured layer to said object.
16. A frangible article, normally subject to breakage upon impact, having a first protective plastic coating applied to a major surface of the object together with an adhesion modifier, in protective, adhering relation with the article, to promote the integrity of the article.
17. The article as set forth in Claim 16, including decorative material applied to the article.
18. The article as set forth in Claim 17, said decorative material comprising a perceptible pattern imprinted on a plastic coating.
19. The article as set forth in Claim 17, said decorative material being selected from the group consisting of print, colour addition, irridescent material, pearlescent material, thermally responsive colour changing material and infra-red responsive luminescent material.
20. The article as set forth in Claim 17, 18 or 19, including a layer of substantially clear plastic overlying said decorative material in protective relation therewith.
21. The article as set forth in Claim 18, said perceptible pattern comprising words.
22. The article as set forth in Claim 19, said perceptible pattern being raised, and perceptible by touch.
23. The article as set forth in Claim 16, said perceptible pattern being visually perceptible.
24. The article as set forth in Claim 16, including a second protective plastic coating underlying said first coating and overlying said adhesion modifier, and extending over at least a portion of said major surface.
25. The article as set forth in Claim 24, said adhesion modifier promoting adhesion of said second coat to said article.
26. The article as set forth in Claim 16, said first plastic coating being selected from the group consisting of thermosetting plastics, and thermoplastics having a minimum useful temperature of at least about 95 C., to withstand the heat and chemicals of commercial dishwashing, and to provide a reinforced article having chip retention capability.
27. The article as set forth in Claim 16, comprising a glass vessel.
28. The article as set forth in Claim 20, said adhesion modifier comprising a silane material to enhance plastic adhesion to a surface of said vessel, said second layer comprising an ethylene copolymer, and said firt layer being selected from a thermoset plastic and a high temperature plastic, to protect the vessel against breakage, and to limit fragment dispersion in case of breakage.
29. The article as set forth in Claim 16, comprising a drinking glass having said protective coating applied to the exterior thereof.
30. The article as set forth in Claim 16, comprising a ceramic object.
31. The article as set forth in Claim 28, wherein said high temperature plastic is polyurethane.
32. The article as set forth in Claim 16, 17 or 18, said first coating being resistant to damage within the heat and chemical environent of a dishwasher.
33. The article as set forth in Claim 19, 21 or 22, said first coating being resistant to damage within the heat and chemical environent of a dishwasher.
34. The article as set forth in Claim 23, 24 or 25, said first coating being resistant to damage within the heat and chemical environent of a dishwasher.
35. The article as set forth in Claim 27, 28 or 29, said first coating being resistant to damage within the heat and chemical environent of a dishwasher.
36. The article as set forth in Claim 30 or 31, said first coating being resistant to damage within the heat and chemical environent of a dishwasher.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US85213697A | 1997-06-06 | 1997-06-06 | |
| US08/852,136 | 1997-06-06 | ||
| US95404197A | 1997-10-20 | 1997-10-20 | |
| US08/954,041 | 1997-10-20 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2236759A1 true CA2236759A1 (en) | 1998-12-06 |
Family
ID=27127048
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA 2236759 Withdrawn CA2236759A1 (en) | 1997-06-06 | 1998-05-05 | Protective and decorative plastic coating system |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA2236759A1 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000043324A1 (en) * | 1999-01-25 | 2000-07-27 | Henry Sawatsky | Safety coating of frangible ware |
| WO2003055817A1 (en) | 2001-12-21 | 2003-07-10 | Bormioli Rocco & Figlio S.P.A. | Method for laying a protective and/or containment coating on glass objects |
| WO2003061848A2 (en) * | 2002-01-17 | 2003-07-31 | Hank Sawatsky | Decorative and protective system for wares |
| US8910998B1 (en) | 2014-03-27 | 2014-12-16 | Srinivas S. Devathi | Systems and methods for altering the color, appearance, or feel of a vehicle surface |
-
1998
- 1998-05-05 CA CA 2236759 patent/CA2236759A1/en not_active Withdrawn
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2000043324A1 (en) * | 1999-01-25 | 2000-07-27 | Henry Sawatsky | Safety coating of frangible ware |
| WO2003055817A1 (en) | 2001-12-21 | 2003-07-10 | Bormioli Rocco & Figlio S.P.A. | Method for laying a protective and/or containment coating on glass objects |
| WO2003061848A2 (en) * | 2002-01-17 | 2003-07-31 | Hank Sawatsky | Decorative and protective system for wares |
| WO2003061848A3 (en) * | 2002-01-17 | 2004-02-12 | Hank Sawatsky | Decorative and protective system for wares |
| US8910998B1 (en) | 2014-03-27 | 2014-12-16 | Srinivas S. Devathi | Systems and methods for altering the color, appearance, or feel of a vehicle surface |
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| EEER | Examination request | ||
| AZWI | Withdrawn application |