CA2122998C - Method of preventing grease buildup in ductwork - Google Patents
Method of preventing grease buildup in ductworkInfo
- Publication number
- CA2122998C CA2122998C CA002122998A CA2122998A CA2122998C CA 2122998 C CA2122998 C CA 2122998C CA 002122998 A CA002122998 A CA 002122998A CA 2122998 A CA2122998 A CA 2122998A CA 2122998 C CA2122998 C CA 2122998C
- Authority
- CA
- Canada
- Prior art keywords
- weight
- grease
- film
- coating
- ductwork
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F13/00—Details common to, or for air-conditioning, air-humidification, ventilation or use of air currents for screening
- F24F13/02—Ducting arrangements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B17/00—Methods preventing fouling
- B08B17/02—Preventing deposition of fouling or of dust
- B08B17/04—Preventing deposition of fouling or of dust by using removable coverings
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/008—Temporary coatings
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F2221/00—Details or features not otherwise provided for
- F24F2221/22—Cleaning ducts or apparatus
Abstract
A method of protecting vent hoods and exhaust ductwork from buildup of grease an d grime comprising coating the vent hoods and exhaust ductwork with a thin coating of a grease repelling removable non-hygroscopic composition.
Description
W093/l~ 2 1 2 2 9 9 8 PCT/US92/09577 METHOD OF PREVENTING GREASE BUILDUP IN DUCTWORK
Technical Field This invention relates to a method for preventing the S adherence and ultimate buildup of grease and other grime in vent hoods and exhaust vent ductwork.
In particular, this invention is useful in~p~eventing the buildup of grease and grime and facilitating in the removal of grease and grime from exhaust vent hoods as are 10 commonly used in commercial and institutional kitchens.
In commercial and institutional kitchens, it is n~reCc~ry to vent fumes, smoke, etc., which are generated during the rooking process. Associated with these fumes and smoke are elements of grease and grime which are airborne 15 solids or are volatilized until they contact the relatively colder surfaces of the hoods and vents. Also, certain amounts of grease and grime are also carried along as finely susrQn~ed particulate matter in smoke, etc.
Vent hoo~s and the ~crociated ducts and fans must be 20 kept clean or otherwise grease and grime which accumulates therein can buildup, increasing the danger of grease fires which can start in the hoods and vent ducts.
The cl~ning out of these hoo~s and vent ducts is a difficult and laborious process, often requiring the physical 2S scraping of the h~oAC and ductwork to remove the baked-on grease and ~c~o~iated grime or the use of very caustic materials along with high pressure power wAchin~ systems.
- SummarY of the Tnvention This invention r-lates to a method of preventing the 30 buildup and-associated grime in vent hoods and the ~oriated ductwork by coating the ductwork and vent hoo~c with a thin film of a removable non-hygroscopic coating which al~o is repellent to the adherence of grease and which enables the ~ vent hood and duct work to be cl~A~e~ using much less effort, -~ 35 in some C~QS as simply as using an alkaline cleaner in a spray bottle with a wiping cloth.
Summar~ Disclosure of Invention The present invention relates to a method of preventing the buildup of grease and grime from vent hoods and ductwork ::
A WO 93/1~W~ 2 1 2 2 9 9 ~ 2 PCT/US92/09 77 comprising coating the vent hoods and ductwork with a thin continuous removeable coating of a grease repelling composition comprising from about 2 to 17% by weight of a low molecular weight alkali resin; from about 0.07 to 0.6~ by 5 weight of a temporary metal crosslinking agent selected from the ~lOU~ consisting of zinc oxide and zirconium oxide;
sufficient ammonium hyd~oxide to substanti~ally neutralize the resins; about 2 to 10% by weight of a coalescing solvent;
about 3.5 to 13.5% by weight of a high molecular weight lO acrylic emulsion polymer; about 0.0015 to 0.15% by weight a fluoLo-~,factant selected from the y-ou~f consisting of (RfCH2CH20)2 P(O)(ONH4) and mixtures of (RfCH2CH20) P(O)(ONH2)2 with a nonfluorinated surfactant where Rf is F(CF2CF2)n with n being a mixture of numbers from 3 to 8; and lS water.
Best Mode For Carryinq Out the Invention As indicated previously, the process of maintaining vent ho~AC and ~sFociated ductwork in sufficiently clean condition to prevent or lessen the danger of fire in these hoods and 20 exhaust ducts is a difficult and laborious process, often involving manual scraping of the built-up grease and grime from these hooAc and vent work. This is obviously a highly Iabor intensive and arduous task which often is not done in co ercial establishments l~AAing to incr~A~ed danger or risk 25 of fire.
~ The ~-ent i..~e..~ion provides for a removable, temporary ..~n hy~L~-osric coating which is impermeable or sYbsta-ntially impermeable to tSe~grease and grime preventing the adhe~ence-of these materials to the metal substrate of 30 the hood~and/or~ductwork.~ In addition, the composition of the ~-ent invention is oil or grease repellent thereby further ~e..~ing the-buildup of the grease and grime -- materials on~the vent :hooAC and lengthening the time between which~the vents hoof~c need be~fully clean~d.
~ ;If the compositions of the ~f~-cnt invention were merely sacrificial removeabIe coatings without being grease and/or oil repellent, the vent hoods and ductwork would soon be coated to~the same degree as in the past, the only difference being that the vent hood might be more easily cleaned ~ ~ SUBSTI~UrE SHEET
_ WOg3/~ 2 1 2 2 9 ~ 8 PCT/US92~09577 assuming that the person-cleaning the vent hoods and ductwork is able to disrupt the film layer and thereby remove the grime and grease which has collected thereon.
In the p,~-ent invent;ion however, the thin continuous 5 film is also grease and oil repellent thereby preventing substantial buildup of grease and grime in the hood and exhaust vent ductwork over the period of ~se and thus both extenAin~ the useful period between which the hoods and vents need be cleaned and facilitating the removal of the 10 accumulated grease and grime from the hoods and ductwork when cl~Aning becomes nec~ss~ry.
Typically in commercial establishments, cleaning is done on a routine or periodic basis. The process of the present invention lends itself to this periodic maintenance approach 15 since if the vent hood and ductwork is cleaned at intervals of every three months, the repellent properties of the film used in the method of the present invention are sufficient to ~le~ent substantial buildup thereby allowing the underlining removable film to be easily disturbed carrying away with it 20 any additional materials which haYe been deposited thereon.
As noted above, it is very important that the films le in the ~L~-~nt invention be c~p~hle of provîding a thin contin~o~C film, which is also easily removeable and which is non-hy~L~~c~.pic. If the film were not continuous, 25 there~would be ar-as of tbe vent hood and/or exhaust ducts ; wh~ch would be left e~ , creating difficulties for r-~h-~.quent cl~nin~. Furthe~rmore, since the eY~ose~ areas would~not be~rep~ ent,~the grease and grime would buildup in these areas.~Therefore, the~composition rhs-~ld level 30 reasonably well and~should b~ easiIy applied by either wiping the co~position onto the vent hood and eYh-nct ductwork or by ~spraying the composition~ onto these surfaces. The films must be~n~.- hy~r~-copic~because the environment in a cooking hood - and exhaust d w t often will~ include steam~or other water 35 ~o ~. If the films are effected by ambient moisture, they will degrade over time and the protective effect will be lost.
The compositions which are yseable in the methods of the present invention comprise seven components. The first SUB~ JTE SHEET
WO93/l~W~ 2 1 2 2 9 9 8 4 _ PCT/US92/04C?7 material in the composition of the present invention is a low molecul~r weight alkali soluble acrylic resin. These acrylic resins typically have a number average molecular weight of less than 3,000 and should be present in an amount of from 2 5 to 17% by weight in the composition.
Suitable resin materials include the following:
31~ styrene, 37% alpha methyl styrene, 32%~crylic-acid (31S/37ANS/32/AA), 67% styrene, 33% acrylic acid (67S/33AA);
45% alpha methyl styrene, 30% ethyl acrylate; 25% acrylic 10 acid (45AMS/30EA/25AA); 82% methyl methacrylate, 18%
methacrylic acid (82MMA/18MAA) and the like.
With regard to the amount of resins present in the composition useful in the method of the present invention, it has been found that from 2 to 17% of resin is ~ecesfiAry.
15 Below about 2%, the film becomes discontinuous and does not -' wet-out properly on the metal surfaces of the vent hoods and ductwork. At amounts over the 17%, the film becomes too brittle and the overall film tends to loose water resistance.
Water resistance is an importa~t property of the ultimate 20 films ~LG~uced by the composition~ of the present invention since during the cooking ~L ~ S in industrial, institutional and commercial establishments a substantial amount of moi ~,e~in the form~of steam also is exhausted through the vent hooAc. -If'~these films were not water resistant, steam 25 from cooXIn~ wo~uld attack the films making them more ' '~
discontinuous and therefore less effective.
Typical reslns suitable for use in the method of the ~re~nt i-l~:ell~ion are 'low mol~c~llAr weight materials, i.e., ;; those resins~'with-~a'weight average molec~ r weight (Mw) of 30 lesg than 15,000 and-pref~era~bly less than-10,000. At high mo~e~l~r weights the Le~ ting films become too brittle to be-used.;~
Preférréd~amounts of the alkali~soluble acrylic resins are from~'4~to 9S;. The preferred~alkali s~luble acrylic resin ~'~ 35 ~is 32S/32.9 M /35.1AMS.
'The compos~itions useful in the method of the present invention also include from about 0.07 to 0.6% by weight of a metal temporary cros~sIinking agent: selected from the group consisting of zinc oxide and zirconium oxide.
SUBSmUTE SHEET : -212~998 W093/l~W~ ' PCT/US92/09577 ~ The activity of zirconium oxide and zinc oxides in basic compositions to perform crosslinks upon drying is well known and has been used for many years in the floor coating art.
The preferred metal temporary crosslinking agent is zinc 5 oxide which in combination with ammonium forms a zinc ammonium carbonate complex.
The compositions useful in the method~QS the present invention also include ammonium hydroxide as the base.
Sufficient ammonium hydroxide must be present in the lO composition both to form to substantially neutralize the ~lk~li soluble resin present and to assist the metal temporary crossli~kin~ agent. The amounts of the ammonium hyJ~oxide .~cessAry to accomplish these tasks are well known in the art. Typically, from about 0.7 to about 6.25% by ~5 weight of ammonium hydroxide is preferred.
The compositions useful in the method of the present i~v~ ion also include from about 2 to about 10% of a coalescing solvent. Suitable coalescing solvents include diethyl qlycol mG~ hyl ether, dipropylene glycol methyl 20 ether, ethylene glycol ethyl ether, ethylene glycol butyl ether and the like.
~ As noted above, the coalescing should be present in an amount of from 2 to 10%~by weight. It is preferred to in~o~oLate from 3 to~5% by weight of coAl~cing solvent. If 25 the~solvent composition is too high, the films will take too - long to dry to be~u ed~effectively. -Also the film will tend to be gummy~and~sticky~. If the~composition includes too t~ coale8cing~.solvent, th~e-films~will powder or stress cr~ok~-and will~;not~properly repel~the~grease and other 30 ~atérial~
The compositions ~uit~able for use in the method of the t il-ff--Lion~al~o~include;~from~;about 3.5 to 13.5% by w~ t~of a;~high-~molec~ weight acrylic emulsion polymer.
These-emulsion~polymers~can~be~made;by an~ conventional 35; e~ulsion polymerization~o~ Suitable emulsion polymers ~ ~includ- ~y,~ne, AlFh~ethyl~ yLene,~ methyl methacrylate, - butyl acrylate, methacrylic acid, and 2-ethylhexylacrylate as monomers. Typical monomer~compositions include 43% methyl methacr~late, 48% butyl acrylate, 9%~methacrylic acid SU~ 1TE SHEET
wo g3~l~w~ 2 1 2 2 ~ 9 8 - 6 - PCT/US92/Og~77 (43MMA/488A/9MAA); 35% styrene, 12% of alpha methylstyrene, 7% methyl methacrylate, 33% butyl acrylate, 13% methacrylic acid (35S/12AMS/7MMA/33BA/13MAA); 10% styrene, 55% methyl methacrylate, 30% butyl acrylate, 5% methacrylic acid (lOS/55MMA/33BA/5MAA); 25% ~y,ene, 35% methyl methacrylate, 30% butyl acrylate, 10% methacrylic acid (25S/35MMA/30BA/10MAA); 30% styrene, 10% ~a~hamethastyrene, 33% butyl acrylate, 10% methyl methacrylic, 17% methacrylic acid (30S/lOAMS/33BA/lOMMA/17MAA); 35% styrene, 15% methyl 10 methacrylate, 26% butyl acrylate, 10% 2-ethylhexylacrylate, and 14% methyl methacrylate (35S/15MMA/26BA/10 2-EHA/14MAA) and the like. Typica~
emulsion polymers suitable for use in the present invention are in~o~o~ated as from 30 to 50% by weight of solids.
On a solids basis, the composition suitable for use in the method of the p~~ent invention should contain from 3.5 to 13.5% of the emulsion polymer material. Typical weight average molecular weights of these emulsion polymers are in ~Y~-S of 100,000 weight average molec~tlAr weight. These 20 emul8ion polymers typically have a glass transition tempera~a greater than about 30~C. The polymer is in the composition to provide film integrity. Films without polymers tend to be too brittle to be used in the method of the ~ -~nt invention. Use of an ~Y~ss of polymer causes 25 the~film~to take too long to dry.
The~compositions suitable for use in the method of the ~~ont i~ ion also include a fluorosurfactant. Only a 8mall p~.~ age of f~ trfactant is neceC~~ry to be included in~the composition of the~present invention.
30 Typically on a solids~basis, 0.0015 to 0.15%~by weight of the fluorosurfactant ~o~ld be included. It is preferred to use from-0.01~to~0.09% of a~ fluorosurfactant. m ese - fluorosurfactants s~9~lA be selected from the group consisting of ~RfCH2CH20)2 P(O)(ONH4) and-mixtures of 35 RfCH2CH20 P~(O)(ONH2)2 with a nonfluorinated surfactant where Rf is~F~CF2CF2)n with n being a mixture of numbers from 3 to 8. It has been found that only certain fluorinated surfactants work in the compositions of the method of the present invention. Other fluorinated sur~factants do not SUBSTITUTE SHEET
W093/10004 2 1 2 2 9 9 ~ PCr/US92/OgS77 sufficiently repel grease and grime to be sufficiently useful in the method of the present invention. If the composition contains too little fluo~G_aL~actant, the composition is not sufficiently repellent to grease. If the level of s fluo~o_~Cactant is too high, then film loses its integrity and tends to become too brittle and powder.
The compositions suitable for use in the method of the ~.~~ent invention need to be non-hy~L.-~oric, i.e., be relatively unaffected by moisture so that the exposure to lO steam from cooking does not soften or de~L~oy the film. The compositions sho~ld also be readily removable with a relatively mild cleAning solution such as an alkaline cleaner as is often used to remove floor finishes. Lastly, the compositions should have a contact angle of greater than 43~
lS to peAn11t oil on stainless steel. Films with a contact angle of greater than 43~ are sufficiently repellent to grease to be usable in the present invention. Although the amount of material used to coat the hood and duct ~ork is mostly dictated by economic considerations, the coating must be 20 cont~n11o1~ otherwise grease will build up in the ~ inuous areas. Typical applications range from lO0 gms/m2 to 300 gms/m2 of coating.
The films suitable for use in the method of the present iJ-~ ion must be sufficiently non-hy~lo_coric to withstand 25 at least one month in a commercial kitchen vent hood without no~ic~Ahle effect, i.e., softenin~ loss of integrity, etc.
due~to mois-uLe. ~h~-efore the *erm ~non-hygroscopic~ when used in this h.v~l~-ion means~ a film which will not show any substantial ~-n~ ~in physical properties after e~po~re to 30 conditions which exist in a commercial kitchen vent hood for r, aiperiod bf at least one mohth. ~
- As a last component the compositions of the method of the ~-ont invention is water as a carrier. The water is A~ to the composition in order to make the composition 35~ suitable to be applied to the vent hoo~ and ductwork.
~ep~nAin~ upon whether the compositions applied by a roll coater or other physical application means or by spraying, the composition and solids level of the components of the SUBSmUTE SHE~
wo g3/~ 2 1 2 2 9 9 8 - 8 - PC~rJUS92/09$77 present invention may vary. Typically, however, the solids should be in an amount of from 15 to 25% by weight. -The method of the present invention will now be illustrated by way of the following Examples which are for S the pUl~O. e- of illustration only.
Example 1 A coating composition having the following formulation was prepared by mi~Cing the following components together.
Parts by Weiqht Acrylic Resin 7.44 32S/33AMS/35AA Mw=5800 Ammonium Hydroxide (28%~ 2.75 Zinc Oxide 0.27 Emulsion Polymer (35%) 15.43 35S/12AMS/7MMA/33BA/12MAA Mw=125,000 AC-392 Polyethylene Wax Emulsion (18.8%) 4.32 E-43 Pol~LG~ylene Wax Emulsion (30%) 5.40 Fragrance 0.lS
Octyl Phènol Ethoxylate 30 Moles EO 0.77 FC-120 Fluorochemical (3M) 0.01 Zonyl~ FSJ Fluorochemical (DuPont) (4096) 0.05 Oleic Acid 0.54 Tributoxyethyl Phosphate o.72 25 Diethylene Glycol Monoethyl Ether 3.00 Water 59.15 AC-392 is a polyethylene wax available from Allied Signal.
It has been emulsified with 14.69~ Diethylaminoethanol oleate.
'E-43 i8 Epolene~ E-43 polypropylene wax available from Eastman Chemical. It has been emulsified with 8.7%
NeodolO 25-9, linear C12-C15 alcohol ethoxylate, 9 moles EO from Shell along with 2.7% of a 53.2%
3S so}ution of zinc ammonium carbonate and 4.7% of a 4S%
solution of KOH.
FC-120 is a 501ution of an anionic fluorochemical surfactant available from 3M.
SUBSmUTE SHEET
WO93/l~W~ 2 1 2 2 ~ 9 8 PCT/US92/09577 ZonylO FSJ i~ a mixture of a nonfluorinated surfactant and (RtCH2CH20)P(O) (ONH~)2 with Rf = F(CF2CF2)3-s available from DuPont.
Place about 24 parts of Water into a stirred kettle, S heat to 130~ F ~54~C) and begin agitation. Add the Ammonium Hydroxide and Zinc Oxide. Then add the Acrylic Resin, Oleic Acid and Tributoxyethyl Phosr~te and agitated until the Zinc Oxide is in solution. Add the rest of the components in the following order: Octyl Phenol Ethoxylate, the rest of the 10 water, Diethylene Glycol Monoethyl Ether, both Fluorochemicals, the Acrylic Emulsion Polymer, both Wax Emulsions and fragrance. Agitate the mixture to uniformity.
The formula may need to passed through a 10 micron filter.
The above formulation was applied to a vent hood and 15 vent duct in a commercial kitchen at a rate of 170 gms/m2.
After the Hood was used to exhaust smoke from the kitchen for 3 months, it was inspected and it was found that the grease did not adhere to the surface of the hood and the ductwork.
Al~o it was found that the film was intact and substantially 20 unaifected by the moi~ e ~~ent in the exhaust materials.
The hood and ductwork could be cleAr-~ using an alkaline cleaner.
Example 2 The following coating composition was prepared using the 25 ~o~ e of Example 1.
Parts by Weiqht Acrylic Resin 7.44 , - ~ 32S/33AMSt35AA ~Mw=5800 ~ 30 A~monium Hy~o~i~e (28%) 2.75 ! i Zinc Oxid$ ' 0.27 Emulsion Polymer (35~) 15.43 35S/12AMS/7MMA/338A/~ Mw=125,000 Octyl Phenol Ethoxy}ate 30 Moles~EO 0.77 ..
~ 35~ FC-120 Fluorochemical (3M) 0.01 , Zonyl~ FSJ Fluorochemical (DuPont) 0.05 Oleic Acid 0.54 Tributoxyethyl Pho~rh~te 0.72 Diethylene Glycol Monoethyl Ether 3.00 40 Water 69.02 SU~ JTE SHEET
W093/l0004 212 2 9 9 8 - lo - Pcrlusg2/09$~?7 The above composition was spread onto steel ~Q" panels, test p~-le of steel available from the Q Panel Corporation, and allowed to cure for 48 hours. This composition formed a good film. 1 ml of peanut oil was placed on the film and 5 spread with a chee-~.cloth. The oil immediately beaded up.
Examples 3-4 and Comparative Examples A-L
The following base formula was prepared using the e of Example 1:
Parts by Weiqht Acrylic Resin 7.55 32S/33AMS/35AA Mw=5800 Ammonium Hydroxide (28%) 2.79 -Zinc Oxide 0.~7 15 Water 60.03 Diethylene Glycol Monoethyl Ether 3.05 Octyl Phenol Ethoxylate 30 Moles EO 0.78 Emul~ion Polymer (35%) 15.66 355/12AMS/7MMA/33BA/12MAA Mw=125,000 20 AC-392 Polyethylene Wax Emulsion (18.8%) 4.39 E-43 Polypropylene Wax~Emulsion (30%) 5.48 -The fluorochémicals as shown in Table 1 were added as 1.5 parts by~weight of a 1% aqueous solution to 98.5% by w ight~of the baso~for~ula~. The films formed from these 25 formulas~were~allowed to cure as in Example 2 and the film properti-s~were~observed.~ The~films were~tested with the peanut oil test as~de8cribed in Example 2.
' , .
t~
~: .: : :
' SU~ JlE SHEET
WO93/l~ ~ 2 1 2 2 9 9 8 PCT/US92/09S77 - Table 1 Example Fluorochemical Oil Test Film Appearance 3 Zonyl0 FSJ Pass Good Film 4 Zonyl~ FSE Pass Good Film S A FC-120 Fail Good Film B FC-99 (3M) Fail Good Film C FC-100 (3M) Fail ~Good Film D FC-129 (3M) Fail Good Film E FC-170C (3M) Fail Good Film 10 F FC-135 (3M) Fail Good Film G FC-430 (3M) Fail Good ~ilm H Zonyl~ FSK Fail Good Film I Zonyl~ FSP Pass Pocked J Zonyl~ FSN Fail Good Film lS K Zonyl D TBS Fail Good Film L Zonyl0 FSO ~ail Good Film M Zonyl~ FSA ~ail Good Film Good = The Oil beads up.
20 Fail = The Oil remains spread out.
Good Film = The film is continuous and does not crack or powder.
Por~e~ = The film is pock marked and irregular.
FC-99 is a solution of amine perfluoroalkyl sulfonate available from 3M.
FC-100 i~ a solution of sodium fluoroalkyl sulfonate available from 3M.
FC-129 is a solution of potassium fluoroalkyl carboxylate available from 3M.
30 FC-170C is a nonionic fluorochemical surfactant available from 3M.
FC-135 is a cationic fluorochemical surfactant available from 3M.
FC-430 is a nonionic fluorochemical surfactant available from 353M.
Zonyl0 FSE is (RfCH2CH2O)2P(O)(ONH~ with Rf = F(CF2CF2)38 a~ailable from DuPont Zonyl0 FSK is RfCHzCH(OCOCH3)CHzN'(CH3)2CH2CO2- available from DuPont.
SUBSTITUTE SHEET
WO 93~10004 2 1 2 2 9 9 8 - 12 - PCr/US92/09~77 Zonyl~ FSP is (RfCH2CH20)P(O)(ONH4)2 available from DuPon~.
Zonyl0 FSN ~s R~CH2CH2O(CH2CH2)xH available from DuPont.
Zonyl~ TBS is R~CH2CH2S03X (X= H and N~) available from DuPont.
5 Zonyl~ FSO is R~CH2CH2O(CH2CH2)yH available from DuPont.
Zonyl0 FSA is R~CH2CH2SCH2CH2COzLi available from DuPont.
The above Examples show that only cer~in ~
fluo~ochemicals will ~Lo~erly work in the method of the present invention.
10 Example 5 and Comparative Example N
The following two formulas were prepared as in Example 1:
Ex. 5 Comp. Ex. N
Acrylic Resin7 55 ? . 55 32S/33AMS/35AA Mw=5800 15 A~oniu~ Hydroxide (28%) 2.79 2.79 Zinc Oxide 0.27 0.27 Emulsion Polymer (35%) 15.43 15.43 35S/12AMS/7MM,~/33BA/12MAA Mw=125,000 FC-120 (3N) (1% Soln.) 0.25 0.25 20 ~onyl~ FSJ (DuPont) (1% Soln) 1.25 1.25 Diethylene Glycol Monoethyl Ether 3.00 0.0 Water 69.46 72.46 Both compositions were coated on steel~ ~Q~ nrl~. The film of Example 5 looks good both initially and after one 25 week. Tho film of Comparative Example N looks good initially, but after 3 days begins to powder and shows severe powdering and lack ~of~film integrity after one week. The film of EYample ~5~when~tes~ed~for oil repellency, as in Example 2, i~mediately he~~ oil.
~ ,~ , , , ~ Example 6 Parts by Weiqht .~a~aLion of Resin ~:ut A:
Water~ . 70 35 35 Zinc- Oxide~ 0.77 Acrylic Resin ~ 21.09 32S/33AMS/35A~ Mw=5800 Am~onium Hydroxide (28%) 7.79 The above components were mixed together in a three-40 necke~l flask. The order of addition is as listed. Agitate - : , :
SU~5 I l~ ~E SHEET
W093/1~H~ - 13 - PCT/US92/Og577 the flask after each addition and heat to 125~F (S2~C) with agitation for two hours. The solution is initially hazy, but clears overnight.
Parts by Weight Resin Cut A 35.28 Water ~ ~ 44 79 Emulsion Polymer (35%) 15.43 35S/12AMS/7MMA/33BA/12MAA Mw=125,000 10 Zonyl~ FSJ (DuPont) (1% Soln) 1.50 Diethylene Glycol Monoethyl Ether 3.00 The formulation is cast as a film on a steel ~Qn panel.
Al~ho~h the film does not level well and shows evidence of brush marks, the film is continuous and shows not evidence of 15 powdering or other ~i~continuities.
Example 7 and Comparative Examples 0-P
The formula of Example 6 was modified to determine the levels of Fluorochemical that can be used. As the fluo~o~llemical is r~n~l the water content is changed to 20 make 100 parts. The amount of Water and 1% solution of Zonyl0 FSJ are shown in Table 2.
Table 2 Example Parts WaterParts Zonyl0 FSJ
7A 46.14 0.15 25 7B 33.29 13.00 C. Ex. O 31.29 15.00 C.- Ex. P 16.29 30.00 For Examples 7A and 7B, the films formed have good fiIm integrlty,~although Example 7B shows some striation in the 30 ~film and but no evidence of powdering along the striations.
, Comparati~e Examples 0 and P have film discontinuities, with Ccrparative Example P~being much worst showing strong film ~fra~u~e~and~powdering.
~In~the oil repellency test, Example 7A shows some 35 ~ of the oil and the oil collects into streaks of oil.
Ex~mple 7B shows strong beading of oil. Comparative Examples O and P show he~A;n~ of oil only in the continuous portions of the film.
SUt~S 111 ~JTE SHE ~ET
WOg3/l~W~ 2 1 2 2 9 9 8 - 14 - PCT/US92/~77 Example 8 and Comparative Ex,amples Q
The formulation of ~xample 6 is repeated except that the level of the Resin Cut A is varied as shown in Table 3. The ' Water content is also varied to make 100 parts.
Table 3 Example Parts Water Parts Resin Cut A
8A 70.07 10;~
8B 20.07 60.00 8C 10.07 70.00 10 8D 0.07 '80.00 C. Ex. Q 75.07 5.00 Examples 8A-D all formed continuous films with excellent oil beading. comparative Example Q did not form a continuous film and did not coat areas of the steel plate that were not 15 perfectly clean, such as fingerprints. Oil beads in the continuous areas.
Example 9 and Comparative Examples R-S
The formulation of Example 6 is repeated except that the level of the Diethylene Glycol Nonoethyl Ether (Solvent) is 20 varied as shown in Table 4. The Water content is also varied to make 100 parts.
Table 4 Example Parts Water Parts Solvent 9A ~ 45.79 2.00 25 9B 44.79 3.00 ,9C 37.79 10.00 '' C. Ex. R 32.79 15.00 C. Ex. S~ 46.2~9 1.50 - ~ Examples 9A-C,~all formed~continuous films with excellent 30 oil h~A~n~. Example 9A showed very slight stress cracking ' ~ ovér time. Example'9C took about 1~ hours to dry. ~-Comparative~Example~R;~was~still tacky and gummy after hours, while Comparative,~Example S showed heavy stress crac~;nq re~sulting ~in~a~ir~ontinuous fi;~m.
Example l0 and~Comparative Examples T-U
The formulation of Example 6 is repeated except that the leveI of the Emulsion Polymer is varied as shown in Table 5.
The Water ~content i$ also varied to~make 100 parts.
~: SUBSTITUTE SHEET
~ W093/l~W~ 2 1 2 2 9 ~ 8 PCT/US92/09s7~
Table 5 Example Parts WaterParts Emuls. Polymer lOA 50.22 10.00 lOB 30.22 30.00 5 lOC 20.22 40.00 lOD 10.22 50.00 C. EX. T 5.22 ~oo C. Ex. U 55.22 5.00 Examples 10 A-C produced good films with good oil 10 repellency. Example lOD showed slight cracking in thicker areas of the film with good oil repellency. Comparative Example T ~ ced a film with heavy cracking and ~continuities. Comparative Example U formed a good film initially but the film formed stress cracks after 4 days.
Example 11 The formulations as shown in Table 6 were prepared as in Example 6.
Table 6 llA B C D E
20 Resin Cut A (Ex. 6) 35.28 35.28 35.28 35.28 35.28 Water 46.72 43.85 4 85 44.79 46~72 Emulsion Polymer A 13.50 Emulcion Polymer B -- 16.37 -- -- --Emulsion Polymer C -- -- 16.37 -- --25 Emulsion Polymer D ~ - 15.43 --Emu1sion Polymer E -- -- -- -- 13.50 Zonyl- FSJ (1%~Soln) 1.5 1.5 1.5 l.S 1.5 -Diethylene glycol~
~ monoethyl ether 3.0 3.0 3.0 3.0 3.0 Emulsion-Polymer A is 43MMA/48BA/9MAA with a Mw of 265,000 (40%~solids~.
Emul~ion Polymer B is lOS/55MMAl30BA/5MAA with a Mw of 383,000 (33% solids).
35 Emulsion Polymer C is 25S/35MMA/30BA/lOMAA with a Mw of 325,000 (33% soli~s).
Emulsion Polymer D is 30SllOAMS/33BAllOMMA/17MAA with a Mw of ~50,000 (35% solids).
Emulsion Polymer E is 35S/15NMA/26BA/40 2-EHA/14MMA with a Mw o~ 9Z,000 (40% solids).
WO93/10004 21 2 2 9 9 8 Pcr/usg2/0~?
Each of the above formulations produced a good film which shows oil repellent properties, however Example llE was not as effective as the other Examples in beading oil.
Industrial ApplicabilitY
The method of the present invention is useful in preventing the buildup of grease and grime in vent hoods and other exhaust devices for kitche~c and ot ~ areas where cooking occurs. The method makes the cleaning of these vent areas easier and aids in the prevention of fires.
SUBSTITUTE SHEET
Technical Field This invention relates to a method for preventing the S adherence and ultimate buildup of grease and other grime in vent hoods and exhaust vent ductwork.
In particular, this invention is useful in~p~eventing the buildup of grease and grime and facilitating in the removal of grease and grime from exhaust vent hoods as are 10 commonly used in commercial and institutional kitchens.
In commercial and institutional kitchens, it is n~reCc~ry to vent fumes, smoke, etc., which are generated during the rooking process. Associated with these fumes and smoke are elements of grease and grime which are airborne 15 solids or are volatilized until they contact the relatively colder surfaces of the hoods and vents. Also, certain amounts of grease and grime are also carried along as finely susrQn~ed particulate matter in smoke, etc.
Vent hoo~s and the ~crociated ducts and fans must be 20 kept clean or otherwise grease and grime which accumulates therein can buildup, increasing the danger of grease fires which can start in the hoods and vent ducts.
The cl~ning out of these hoo~s and vent ducts is a difficult and laborious process, often requiring the physical 2S scraping of the h~oAC and ductwork to remove the baked-on grease and ~c~o~iated grime or the use of very caustic materials along with high pressure power wAchin~ systems.
- SummarY of the Tnvention This invention r-lates to a method of preventing the 30 buildup and-associated grime in vent hoods and the ~oriated ductwork by coating the ductwork and vent hoo~c with a thin film of a removable non-hygroscopic coating which al~o is repellent to the adherence of grease and which enables the ~ vent hood and duct work to be cl~A~e~ using much less effort, -~ 35 in some C~QS as simply as using an alkaline cleaner in a spray bottle with a wiping cloth.
Summar~ Disclosure of Invention The present invention relates to a method of preventing the buildup of grease and grime from vent hoods and ductwork ::
A WO 93/1~W~ 2 1 2 2 9 9 ~ 2 PCT/US92/09 77 comprising coating the vent hoods and ductwork with a thin continuous removeable coating of a grease repelling composition comprising from about 2 to 17% by weight of a low molecular weight alkali resin; from about 0.07 to 0.6~ by 5 weight of a temporary metal crosslinking agent selected from the ~lOU~ consisting of zinc oxide and zirconium oxide;
sufficient ammonium hyd~oxide to substanti~ally neutralize the resins; about 2 to 10% by weight of a coalescing solvent;
about 3.5 to 13.5% by weight of a high molecular weight lO acrylic emulsion polymer; about 0.0015 to 0.15% by weight a fluoLo-~,factant selected from the y-ou~f consisting of (RfCH2CH20)2 P(O)(ONH4) and mixtures of (RfCH2CH20) P(O)(ONH2)2 with a nonfluorinated surfactant where Rf is F(CF2CF2)n with n being a mixture of numbers from 3 to 8; and lS water.
Best Mode For Carryinq Out the Invention As indicated previously, the process of maintaining vent ho~AC and ~sFociated ductwork in sufficiently clean condition to prevent or lessen the danger of fire in these hoods and 20 exhaust ducts is a difficult and laborious process, often involving manual scraping of the built-up grease and grime from these hooAc and vent work. This is obviously a highly Iabor intensive and arduous task which often is not done in co ercial establishments l~AAing to incr~A~ed danger or risk 25 of fire.
~ The ~-ent i..~e..~ion provides for a removable, temporary ..~n hy~L~-osric coating which is impermeable or sYbsta-ntially impermeable to tSe~grease and grime preventing the adhe~ence-of these materials to the metal substrate of 30 the hood~and/or~ductwork.~ In addition, the composition of the ~-ent invention is oil or grease repellent thereby further ~e..~ing the-buildup of the grease and grime -- materials on~the vent :hooAC and lengthening the time between which~the vents hoof~c need be~fully clean~d.
~ ;If the compositions of the ~f~-cnt invention were merely sacrificial removeabIe coatings without being grease and/or oil repellent, the vent hoods and ductwork would soon be coated to~the same degree as in the past, the only difference being that the vent hood might be more easily cleaned ~ ~ SUBSTI~UrE SHEET
_ WOg3/~ 2 1 2 2 9 ~ 8 PCT/US92~09577 assuming that the person-cleaning the vent hoods and ductwork is able to disrupt the film layer and thereby remove the grime and grease which has collected thereon.
In the p,~-ent invent;ion however, the thin continuous 5 film is also grease and oil repellent thereby preventing substantial buildup of grease and grime in the hood and exhaust vent ductwork over the period of ~se and thus both extenAin~ the useful period between which the hoods and vents need be cleaned and facilitating the removal of the 10 accumulated grease and grime from the hoods and ductwork when cl~Aning becomes nec~ss~ry.
Typically in commercial establishments, cleaning is done on a routine or periodic basis. The process of the present invention lends itself to this periodic maintenance approach 15 since if the vent hood and ductwork is cleaned at intervals of every three months, the repellent properties of the film used in the method of the present invention are sufficient to ~le~ent substantial buildup thereby allowing the underlining removable film to be easily disturbed carrying away with it 20 any additional materials which haYe been deposited thereon.
As noted above, it is very important that the films le in the ~L~-~nt invention be c~p~hle of provîding a thin contin~o~C film, which is also easily removeable and which is non-hy~L~~c~.pic. If the film were not continuous, 25 there~would be ar-as of tbe vent hood and/or exhaust ducts ; wh~ch would be left e~ , creating difficulties for r-~h-~.quent cl~nin~. Furthe~rmore, since the eY~ose~ areas would~not be~rep~ ent,~the grease and grime would buildup in these areas.~Therefore, the~composition rhs-~ld level 30 reasonably well and~should b~ easiIy applied by either wiping the co~position onto the vent hood and eYh-nct ductwork or by ~spraying the composition~ onto these surfaces. The films must be~n~.- hy~r~-copic~because the environment in a cooking hood - and exhaust d w t often will~ include steam~or other water 35 ~o ~. If the films are effected by ambient moisture, they will degrade over time and the protective effect will be lost.
The compositions which are yseable in the methods of the present invention comprise seven components. The first SUB~ JTE SHEET
WO93/l~W~ 2 1 2 2 9 9 8 4 _ PCT/US92/04C?7 material in the composition of the present invention is a low molecul~r weight alkali soluble acrylic resin. These acrylic resins typically have a number average molecular weight of less than 3,000 and should be present in an amount of from 2 5 to 17% by weight in the composition.
Suitable resin materials include the following:
31~ styrene, 37% alpha methyl styrene, 32%~crylic-acid (31S/37ANS/32/AA), 67% styrene, 33% acrylic acid (67S/33AA);
45% alpha methyl styrene, 30% ethyl acrylate; 25% acrylic 10 acid (45AMS/30EA/25AA); 82% methyl methacrylate, 18%
methacrylic acid (82MMA/18MAA) and the like.
With regard to the amount of resins present in the composition useful in the method of the present invention, it has been found that from 2 to 17% of resin is ~ecesfiAry.
15 Below about 2%, the film becomes discontinuous and does not -' wet-out properly on the metal surfaces of the vent hoods and ductwork. At amounts over the 17%, the film becomes too brittle and the overall film tends to loose water resistance.
Water resistance is an importa~t property of the ultimate 20 films ~LG~uced by the composition~ of the present invention since during the cooking ~L ~ S in industrial, institutional and commercial establishments a substantial amount of moi ~,e~in the form~of steam also is exhausted through the vent hooAc. -If'~these films were not water resistant, steam 25 from cooXIn~ wo~uld attack the films making them more ' '~
discontinuous and therefore less effective.
Typical reslns suitable for use in the method of the ~re~nt i-l~:ell~ion are 'low mol~c~llAr weight materials, i.e., ;; those resins~'with-~a'weight average molec~ r weight (Mw) of 30 lesg than 15,000 and-pref~era~bly less than-10,000. At high mo~e~l~r weights the Le~ ting films become too brittle to be-used.;~
Preférréd~amounts of the alkali~soluble acrylic resins are from~'4~to 9S;. The preferred~alkali s~luble acrylic resin ~'~ 35 ~is 32S/32.9 M /35.1AMS.
'The compos~itions useful in the method of the present invention also include from about 0.07 to 0.6% by weight of a metal temporary cros~sIinking agent: selected from the group consisting of zinc oxide and zirconium oxide.
SUBSmUTE SHEET : -212~998 W093/l~W~ ' PCT/US92/09577 ~ The activity of zirconium oxide and zinc oxides in basic compositions to perform crosslinks upon drying is well known and has been used for many years in the floor coating art.
The preferred metal temporary crosslinking agent is zinc 5 oxide which in combination with ammonium forms a zinc ammonium carbonate complex.
The compositions useful in the method~QS the present invention also include ammonium hydroxide as the base.
Sufficient ammonium hydroxide must be present in the lO composition both to form to substantially neutralize the ~lk~li soluble resin present and to assist the metal temporary crossli~kin~ agent. The amounts of the ammonium hyJ~oxide .~cessAry to accomplish these tasks are well known in the art. Typically, from about 0.7 to about 6.25% by ~5 weight of ammonium hydroxide is preferred.
The compositions useful in the method of the present i~v~ ion also include from about 2 to about 10% of a coalescing solvent. Suitable coalescing solvents include diethyl qlycol mG~ hyl ether, dipropylene glycol methyl 20 ether, ethylene glycol ethyl ether, ethylene glycol butyl ether and the like.
~ As noted above, the coalescing should be present in an amount of from 2 to 10%~by weight. It is preferred to in~o~oLate from 3 to~5% by weight of coAl~cing solvent. If 25 the~solvent composition is too high, the films will take too - long to dry to be~u ed~effectively. -Also the film will tend to be gummy~and~sticky~. If the~composition includes too t~ coale8cing~.solvent, th~e-films~will powder or stress cr~ok~-and will~;not~properly repel~the~grease and other 30 ~atérial~
The compositions ~uit~able for use in the method of the t il-ff--Lion~al~o~include;~from~;about 3.5 to 13.5% by w~ t~of a;~high-~molec~ weight acrylic emulsion polymer.
These-emulsion~polymers~can~be~made;by an~ conventional 35; e~ulsion polymerization~o~ Suitable emulsion polymers ~ ~includ- ~y,~ne, AlFh~ethyl~ yLene,~ methyl methacrylate, - butyl acrylate, methacrylic acid, and 2-ethylhexylacrylate as monomers. Typical monomer~compositions include 43% methyl methacr~late, 48% butyl acrylate, 9%~methacrylic acid SU~ 1TE SHEET
wo g3~l~w~ 2 1 2 2 ~ 9 8 - 6 - PCT/US92/Og~77 (43MMA/488A/9MAA); 35% styrene, 12% of alpha methylstyrene, 7% methyl methacrylate, 33% butyl acrylate, 13% methacrylic acid (35S/12AMS/7MMA/33BA/13MAA); 10% styrene, 55% methyl methacrylate, 30% butyl acrylate, 5% methacrylic acid (lOS/55MMA/33BA/5MAA); 25% ~y,ene, 35% methyl methacrylate, 30% butyl acrylate, 10% methacrylic acid (25S/35MMA/30BA/10MAA); 30% styrene, 10% ~a~hamethastyrene, 33% butyl acrylate, 10% methyl methacrylic, 17% methacrylic acid (30S/lOAMS/33BA/lOMMA/17MAA); 35% styrene, 15% methyl 10 methacrylate, 26% butyl acrylate, 10% 2-ethylhexylacrylate, and 14% methyl methacrylate (35S/15MMA/26BA/10 2-EHA/14MAA) and the like. Typica~
emulsion polymers suitable for use in the present invention are in~o~o~ated as from 30 to 50% by weight of solids.
On a solids basis, the composition suitable for use in the method of the p~~ent invention should contain from 3.5 to 13.5% of the emulsion polymer material. Typical weight average molecular weights of these emulsion polymers are in ~Y~-S of 100,000 weight average molec~tlAr weight. These 20 emul8ion polymers typically have a glass transition tempera~a greater than about 30~C. The polymer is in the composition to provide film integrity. Films without polymers tend to be too brittle to be used in the method of the ~ -~nt invention. Use of an ~Y~ss of polymer causes 25 the~film~to take too long to dry.
The~compositions suitable for use in the method of the ~~ont i~ ion also include a fluorosurfactant. Only a 8mall p~.~ age of f~ trfactant is neceC~~ry to be included in~the composition of the~present invention.
30 Typically on a solids~basis, 0.0015 to 0.15%~by weight of the fluorosurfactant ~o~ld be included. It is preferred to use from-0.01~to~0.09% of a~ fluorosurfactant. m ese - fluorosurfactants s~9~lA be selected from the group consisting of ~RfCH2CH20)2 P(O)(ONH4) and-mixtures of 35 RfCH2CH20 P~(O)(ONH2)2 with a nonfluorinated surfactant where Rf is~F~CF2CF2)n with n being a mixture of numbers from 3 to 8. It has been found that only certain fluorinated surfactants work in the compositions of the method of the present invention. Other fluorinated sur~factants do not SUBSTITUTE SHEET
W093/10004 2 1 2 2 9 9 ~ PCr/US92/OgS77 sufficiently repel grease and grime to be sufficiently useful in the method of the present invention. If the composition contains too little fluo~G_aL~actant, the composition is not sufficiently repellent to grease. If the level of s fluo~o_~Cactant is too high, then film loses its integrity and tends to become too brittle and powder.
The compositions suitable for use in the method of the ~.~~ent invention need to be non-hy~L.-~oric, i.e., be relatively unaffected by moisture so that the exposure to lO steam from cooking does not soften or de~L~oy the film. The compositions sho~ld also be readily removable with a relatively mild cleAning solution such as an alkaline cleaner as is often used to remove floor finishes. Lastly, the compositions should have a contact angle of greater than 43~
lS to peAn11t oil on stainless steel. Films with a contact angle of greater than 43~ are sufficiently repellent to grease to be usable in the present invention. Although the amount of material used to coat the hood and duct ~ork is mostly dictated by economic considerations, the coating must be 20 cont~n11o1~ otherwise grease will build up in the ~ inuous areas. Typical applications range from lO0 gms/m2 to 300 gms/m2 of coating.
The films suitable for use in the method of the present iJ-~ ion must be sufficiently non-hy~lo_coric to withstand 25 at least one month in a commercial kitchen vent hood without no~ic~Ahle effect, i.e., softenin~ loss of integrity, etc.
due~to mois-uLe. ~h~-efore the *erm ~non-hygroscopic~ when used in this h.v~l~-ion means~ a film which will not show any substantial ~-n~ ~in physical properties after e~po~re to 30 conditions which exist in a commercial kitchen vent hood for r, aiperiod bf at least one mohth. ~
- As a last component the compositions of the method of the ~-ont invention is water as a carrier. The water is A~ to the composition in order to make the composition 35~ suitable to be applied to the vent hoo~ and ductwork.
~ep~nAin~ upon whether the compositions applied by a roll coater or other physical application means or by spraying, the composition and solids level of the components of the SUBSmUTE SHE~
wo g3/~ 2 1 2 2 9 9 8 - 8 - PC~rJUS92/09$77 present invention may vary. Typically, however, the solids should be in an amount of from 15 to 25% by weight. -The method of the present invention will now be illustrated by way of the following Examples which are for S the pUl~O. e- of illustration only.
Example 1 A coating composition having the following formulation was prepared by mi~Cing the following components together.
Parts by Weiqht Acrylic Resin 7.44 32S/33AMS/35AA Mw=5800 Ammonium Hydroxide (28%~ 2.75 Zinc Oxide 0.27 Emulsion Polymer (35%) 15.43 35S/12AMS/7MMA/33BA/12MAA Mw=125,000 AC-392 Polyethylene Wax Emulsion (18.8%) 4.32 E-43 Pol~LG~ylene Wax Emulsion (30%) 5.40 Fragrance 0.lS
Octyl Phènol Ethoxylate 30 Moles EO 0.77 FC-120 Fluorochemical (3M) 0.01 Zonyl~ FSJ Fluorochemical (DuPont) (4096) 0.05 Oleic Acid 0.54 Tributoxyethyl Phosphate o.72 25 Diethylene Glycol Monoethyl Ether 3.00 Water 59.15 AC-392 is a polyethylene wax available from Allied Signal.
It has been emulsified with 14.69~ Diethylaminoethanol oleate.
'E-43 i8 Epolene~ E-43 polypropylene wax available from Eastman Chemical. It has been emulsified with 8.7%
NeodolO 25-9, linear C12-C15 alcohol ethoxylate, 9 moles EO from Shell along with 2.7% of a 53.2%
3S so}ution of zinc ammonium carbonate and 4.7% of a 4S%
solution of KOH.
FC-120 is a 501ution of an anionic fluorochemical surfactant available from 3M.
SUBSmUTE SHEET
WO93/l~W~ 2 1 2 2 ~ 9 8 PCT/US92/09577 ZonylO FSJ i~ a mixture of a nonfluorinated surfactant and (RtCH2CH20)P(O) (ONH~)2 with Rf = F(CF2CF2)3-s available from DuPont.
Place about 24 parts of Water into a stirred kettle, S heat to 130~ F ~54~C) and begin agitation. Add the Ammonium Hydroxide and Zinc Oxide. Then add the Acrylic Resin, Oleic Acid and Tributoxyethyl Phosr~te and agitated until the Zinc Oxide is in solution. Add the rest of the components in the following order: Octyl Phenol Ethoxylate, the rest of the 10 water, Diethylene Glycol Monoethyl Ether, both Fluorochemicals, the Acrylic Emulsion Polymer, both Wax Emulsions and fragrance. Agitate the mixture to uniformity.
The formula may need to passed through a 10 micron filter.
The above formulation was applied to a vent hood and 15 vent duct in a commercial kitchen at a rate of 170 gms/m2.
After the Hood was used to exhaust smoke from the kitchen for 3 months, it was inspected and it was found that the grease did not adhere to the surface of the hood and the ductwork.
Al~o it was found that the film was intact and substantially 20 unaifected by the moi~ e ~~ent in the exhaust materials.
The hood and ductwork could be cleAr-~ using an alkaline cleaner.
Example 2 The following coating composition was prepared using the 25 ~o~ e of Example 1.
Parts by Weiqht Acrylic Resin 7.44 , - ~ 32S/33AMSt35AA ~Mw=5800 ~ 30 A~monium Hy~o~i~e (28%) 2.75 ! i Zinc Oxid$ ' 0.27 Emulsion Polymer (35~) 15.43 35S/12AMS/7MMA/338A/~ Mw=125,000 Octyl Phenol Ethoxy}ate 30 Moles~EO 0.77 ..
~ 35~ FC-120 Fluorochemical (3M) 0.01 , Zonyl~ FSJ Fluorochemical (DuPont) 0.05 Oleic Acid 0.54 Tributoxyethyl Pho~rh~te 0.72 Diethylene Glycol Monoethyl Ether 3.00 40 Water 69.02 SU~ JTE SHEET
W093/l0004 212 2 9 9 8 - lo - Pcrlusg2/09$~?7 The above composition was spread onto steel ~Q" panels, test p~-le of steel available from the Q Panel Corporation, and allowed to cure for 48 hours. This composition formed a good film. 1 ml of peanut oil was placed on the film and 5 spread with a chee-~.cloth. The oil immediately beaded up.
Examples 3-4 and Comparative Examples A-L
The following base formula was prepared using the e of Example 1:
Parts by Weiqht Acrylic Resin 7.55 32S/33AMS/35AA Mw=5800 Ammonium Hydroxide (28%) 2.79 -Zinc Oxide 0.~7 15 Water 60.03 Diethylene Glycol Monoethyl Ether 3.05 Octyl Phenol Ethoxylate 30 Moles EO 0.78 Emul~ion Polymer (35%) 15.66 355/12AMS/7MMA/33BA/12MAA Mw=125,000 20 AC-392 Polyethylene Wax Emulsion (18.8%) 4.39 E-43 Polypropylene Wax~Emulsion (30%) 5.48 -The fluorochémicals as shown in Table 1 were added as 1.5 parts by~weight of a 1% aqueous solution to 98.5% by w ight~of the baso~for~ula~. The films formed from these 25 formulas~were~allowed to cure as in Example 2 and the film properti-s~were~observed.~ The~films were~tested with the peanut oil test as~de8cribed in Example 2.
' , .
t~
~: .: : :
' SU~ JlE SHEET
WO93/l~ ~ 2 1 2 2 9 9 8 PCT/US92/09S77 - Table 1 Example Fluorochemical Oil Test Film Appearance 3 Zonyl0 FSJ Pass Good Film 4 Zonyl~ FSE Pass Good Film S A FC-120 Fail Good Film B FC-99 (3M) Fail Good Film C FC-100 (3M) Fail ~Good Film D FC-129 (3M) Fail Good Film E FC-170C (3M) Fail Good Film 10 F FC-135 (3M) Fail Good Film G FC-430 (3M) Fail Good ~ilm H Zonyl~ FSK Fail Good Film I Zonyl~ FSP Pass Pocked J Zonyl~ FSN Fail Good Film lS K Zonyl D TBS Fail Good Film L Zonyl0 FSO ~ail Good Film M Zonyl~ FSA ~ail Good Film Good = The Oil beads up.
20 Fail = The Oil remains spread out.
Good Film = The film is continuous and does not crack or powder.
Por~e~ = The film is pock marked and irregular.
FC-99 is a solution of amine perfluoroalkyl sulfonate available from 3M.
FC-100 i~ a solution of sodium fluoroalkyl sulfonate available from 3M.
FC-129 is a solution of potassium fluoroalkyl carboxylate available from 3M.
30 FC-170C is a nonionic fluorochemical surfactant available from 3M.
FC-135 is a cationic fluorochemical surfactant available from 3M.
FC-430 is a nonionic fluorochemical surfactant available from 353M.
Zonyl0 FSE is (RfCH2CH2O)2P(O)(ONH~ with Rf = F(CF2CF2)38 a~ailable from DuPont Zonyl0 FSK is RfCHzCH(OCOCH3)CHzN'(CH3)2CH2CO2- available from DuPont.
SUBSTITUTE SHEET
WO 93~10004 2 1 2 2 9 9 8 - 12 - PCr/US92/09~77 Zonyl~ FSP is (RfCH2CH20)P(O)(ONH4)2 available from DuPon~.
Zonyl0 FSN ~s R~CH2CH2O(CH2CH2)xH available from DuPont.
Zonyl~ TBS is R~CH2CH2S03X (X= H and N~) available from DuPont.
5 Zonyl~ FSO is R~CH2CH2O(CH2CH2)yH available from DuPont.
Zonyl0 FSA is R~CH2CH2SCH2CH2COzLi available from DuPont.
The above Examples show that only cer~in ~
fluo~ochemicals will ~Lo~erly work in the method of the present invention.
10 Example 5 and Comparative Example N
The following two formulas were prepared as in Example 1:
Ex. 5 Comp. Ex. N
Acrylic Resin7 55 ? . 55 32S/33AMS/35AA Mw=5800 15 A~oniu~ Hydroxide (28%) 2.79 2.79 Zinc Oxide 0.27 0.27 Emulsion Polymer (35%) 15.43 15.43 35S/12AMS/7MM,~/33BA/12MAA Mw=125,000 FC-120 (3N) (1% Soln.) 0.25 0.25 20 ~onyl~ FSJ (DuPont) (1% Soln) 1.25 1.25 Diethylene Glycol Monoethyl Ether 3.00 0.0 Water 69.46 72.46 Both compositions were coated on steel~ ~Q~ nrl~. The film of Example 5 looks good both initially and after one 25 week. Tho film of Comparative Example N looks good initially, but after 3 days begins to powder and shows severe powdering and lack ~of~film integrity after one week. The film of EYample ~5~when~tes~ed~for oil repellency, as in Example 2, i~mediately he~~ oil.
~ ,~ , , , ~ Example 6 Parts by Weiqht .~a~aLion of Resin ~:ut A:
Water~ . 70 35 35 Zinc- Oxide~ 0.77 Acrylic Resin ~ 21.09 32S/33AMS/35A~ Mw=5800 Am~onium Hydroxide (28%) 7.79 The above components were mixed together in a three-40 necke~l flask. The order of addition is as listed. Agitate - : , :
SU~5 I l~ ~E SHEET
W093/1~H~ - 13 - PCT/US92/Og577 the flask after each addition and heat to 125~F (S2~C) with agitation for two hours. The solution is initially hazy, but clears overnight.
Parts by Weight Resin Cut A 35.28 Water ~ ~ 44 79 Emulsion Polymer (35%) 15.43 35S/12AMS/7MMA/33BA/12MAA Mw=125,000 10 Zonyl~ FSJ (DuPont) (1% Soln) 1.50 Diethylene Glycol Monoethyl Ether 3.00 The formulation is cast as a film on a steel ~Qn panel.
Al~ho~h the film does not level well and shows evidence of brush marks, the film is continuous and shows not evidence of 15 powdering or other ~i~continuities.
Example 7 and Comparative Examples 0-P
The formula of Example 6 was modified to determine the levels of Fluorochemical that can be used. As the fluo~o~llemical is r~n~l the water content is changed to 20 make 100 parts. The amount of Water and 1% solution of Zonyl0 FSJ are shown in Table 2.
Table 2 Example Parts WaterParts Zonyl0 FSJ
7A 46.14 0.15 25 7B 33.29 13.00 C. Ex. O 31.29 15.00 C.- Ex. P 16.29 30.00 For Examples 7A and 7B, the films formed have good fiIm integrlty,~although Example 7B shows some striation in the 30 ~film and but no evidence of powdering along the striations.
, Comparati~e Examples 0 and P have film discontinuities, with Ccrparative Example P~being much worst showing strong film ~fra~u~e~and~powdering.
~In~the oil repellency test, Example 7A shows some 35 ~ of the oil and the oil collects into streaks of oil.
Ex~mple 7B shows strong beading of oil. Comparative Examples O and P show he~A;n~ of oil only in the continuous portions of the film.
SUt~S 111 ~JTE SHE ~ET
WOg3/l~W~ 2 1 2 2 9 9 8 - 14 - PCT/US92/~77 Example 8 and Comparative Ex,amples Q
The formulation of ~xample 6 is repeated except that the level of the Resin Cut A is varied as shown in Table 3. The ' Water content is also varied to make 100 parts.
Table 3 Example Parts Water Parts Resin Cut A
8A 70.07 10;~
8B 20.07 60.00 8C 10.07 70.00 10 8D 0.07 '80.00 C. Ex. Q 75.07 5.00 Examples 8A-D all formed continuous films with excellent oil beading. comparative Example Q did not form a continuous film and did not coat areas of the steel plate that were not 15 perfectly clean, such as fingerprints. Oil beads in the continuous areas.
Example 9 and Comparative Examples R-S
The formulation of Example 6 is repeated except that the level of the Diethylene Glycol Nonoethyl Ether (Solvent) is 20 varied as shown in Table 4. The Water content is also varied to make 100 parts.
Table 4 Example Parts Water Parts Solvent 9A ~ 45.79 2.00 25 9B 44.79 3.00 ,9C 37.79 10.00 '' C. Ex. R 32.79 15.00 C. Ex. S~ 46.2~9 1.50 - ~ Examples 9A-C,~all formed~continuous films with excellent 30 oil h~A~n~. Example 9A showed very slight stress cracking ' ~ ovér time. Example'9C took about 1~ hours to dry. ~-Comparative~Example~R;~was~still tacky and gummy after hours, while Comparative,~Example S showed heavy stress crac~;nq re~sulting ~in~a~ir~ontinuous fi;~m.
Example l0 and~Comparative Examples T-U
The formulation of Example 6 is repeated except that the leveI of the Emulsion Polymer is varied as shown in Table 5.
The Water ~content i$ also varied to~make 100 parts.
~: SUBSTITUTE SHEET
~ W093/l~W~ 2 1 2 2 9 ~ 8 PCT/US92/09s7~
Table 5 Example Parts WaterParts Emuls. Polymer lOA 50.22 10.00 lOB 30.22 30.00 5 lOC 20.22 40.00 lOD 10.22 50.00 C. EX. T 5.22 ~oo C. Ex. U 55.22 5.00 Examples 10 A-C produced good films with good oil 10 repellency. Example lOD showed slight cracking in thicker areas of the film with good oil repellency. Comparative Example T ~ ced a film with heavy cracking and ~continuities. Comparative Example U formed a good film initially but the film formed stress cracks after 4 days.
Example 11 The formulations as shown in Table 6 were prepared as in Example 6.
Table 6 llA B C D E
20 Resin Cut A (Ex. 6) 35.28 35.28 35.28 35.28 35.28 Water 46.72 43.85 4 85 44.79 46~72 Emulsion Polymer A 13.50 Emulcion Polymer B -- 16.37 -- -- --Emulsion Polymer C -- -- 16.37 -- --25 Emulsion Polymer D ~ - 15.43 --Emu1sion Polymer E -- -- -- -- 13.50 Zonyl- FSJ (1%~Soln) 1.5 1.5 1.5 l.S 1.5 -Diethylene glycol~
~ monoethyl ether 3.0 3.0 3.0 3.0 3.0 Emulsion-Polymer A is 43MMA/48BA/9MAA with a Mw of 265,000 (40%~solids~.
Emul~ion Polymer B is lOS/55MMAl30BA/5MAA with a Mw of 383,000 (33% solids).
35 Emulsion Polymer C is 25S/35MMA/30BA/lOMAA with a Mw of 325,000 (33% soli~s).
Emulsion Polymer D is 30SllOAMS/33BAllOMMA/17MAA with a Mw of ~50,000 (35% solids).
Emulsion Polymer E is 35S/15NMA/26BA/40 2-EHA/14MMA with a Mw o~ 9Z,000 (40% solids).
WO93/10004 21 2 2 9 9 8 Pcr/usg2/0~?
Each of the above formulations produced a good film which shows oil repellent properties, however Example llE was not as effective as the other Examples in beading oil.
Industrial ApplicabilitY
The method of the present invention is useful in preventing the buildup of grease and grime in vent hoods and other exhaust devices for kitche~c and ot ~ areas where cooking occurs. The method makes the cleaning of these vent areas easier and aids in the prevention of fires.
SUBSTITUTE SHEET
Claims (8)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A method of protecting vent hoods and exhaust ductwork from buildup of grease and grime comprising coating the vent hoods and the ductwork with a thin coating of grease repelling composition which is removable using a cleaner having a pH of between 9-12, which coating contains an effective amount of a fluorosurfactant to repel grease and which has a contact angle on stainless steel of greater than 43° to peanut oil and which coating is non hygroscopic, wherein the grease repelling composition comprises:
a) about 2 to 17% by weight of a low molecular weight alkali soluble acrylic resin;
b) about 0.07 to 0.6% by weight of temporary metal crosslinking agent selected from the group consisting of zinc oxide and zirconium oxide;
c) sufficient ammonium hydroxide to substantially neutralize the resin;
d) about 2 to 10% by weight of a coalescing solvent;
e) about 3.5 to 13.5% by weight of a high molecular weight acrylic emulsion polymer;
f) about 0.0015 to 0.15% by weight of a fluorosurfactant selected from the group consisting of (Rf CH2CH2O)2 P(O) (ONH4) and mixtures of (Rf CH2CH2O) P(O) (ONH2)2 with a nonflurinated surfactant where Rf is F(CF2CF2)n, with n being a mixture of numbers from 3 to 8, and g) water.
a) about 2 to 17% by weight of a low molecular weight alkali soluble acrylic resin;
b) about 0.07 to 0.6% by weight of temporary metal crosslinking agent selected from the group consisting of zinc oxide and zirconium oxide;
c) sufficient ammonium hydroxide to substantially neutralize the resin;
d) about 2 to 10% by weight of a coalescing solvent;
e) about 3.5 to 13.5% by weight of a high molecular weight acrylic emulsion polymer;
f) about 0.0015 to 0.15% by weight of a fluorosurfactant selected from the group consisting of (Rf CH2CH2O)2 P(O) (ONH4) and mixtures of (Rf CH2CH2O) P(O) (ONH2)2 with a nonflurinated surfactant where Rf is F(CF2CF2)n, with n being a mixture of numbers from 3 to 8, and g) water.
2. The method of claim 1 wherein the coating is applied at a rate of 100 to 300 gm/m2.
3. The method of claim 1 wherein the emulsion polymer has a weight average molecular weight of greater than 100,000.
4. The method of claim 1 wherein the resin has a weight average molecular weight of less than 15,000.
5. The method of claim 1 wherein the solvent is selected from the group consisting of diethyl glycol monoethyl ether, dipropylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol butyl ether.
6. The method of claim 1 wherein the crosslinking agent is zinc oxide.
7. The method of claim 1 wherein the fluorosurfactant is a mixture of (Rf CH2CH2) P(O) (ONH2)2 with a nonfluorinated surfactant.
8. The method of claim 1 wherein the composition comprises:
a) 4 to 9% of alkaline soluble acrylic resin with a Mw of less than 10,000;
b) 0.07 to 0.6% of zinc oxide;
c) 0.7 to 6.25% of ammonium hydroxide;
d) 3 to 5% of a coalescing solvent;
e) 3.5 to 13.5% of an acrylic emulsion polymer with weight average molecular weight of greater than 100,000;
f) 0.01 to 0.09% of a fluorosurfactant selected from the group consisting of (Rf CH2CH2O)2 P(O) (ONH4) and mixtures of (Rf CH2CH2O) P(O) (ONH2)2 with a nonfluorinated surfactant where Rf is F(CF2CF2)n, with n being a mixture of numbers from 3 to 8, and g) water.
a) 4 to 9% of alkaline soluble acrylic resin with a Mw of less than 10,000;
b) 0.07 to 0.6% of zinc oxide;
c) 0.7 to 6.25% of ammonium hydroxide;
d) 3 to 5% of a coalescing solvent;
e) 3.5 to 13.5% of an acrylic emulsion polymer with weight average molecular weight of greater than 100,000;
f) 0.01 to 0.09% of a fluorosurfactant selected from the group consisting of (Rf CH2CH2O)2 P(O) (ONH4) and mixtures of (Rf CH2CH2O) P(O) (ONH2)2 with a nonfluorinated surfactant where Rf is F(CF2CF2)n, with n being a mixture of numbers from 3 to 8, and g) water.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/790,959 | 1991-11-12 | ||
| US07/790,959 US5271959A (en) | 1991-11-12 | 1991-11-12 | Method of preventing grease buildup in ductwork |
| PCT/US1992/009577 WO1993010004A1 (en) | 1991-11-12 | 1992-11-05 | Method of preventing grease buildup in ductwork |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2122998A1 CA2122998A1 (en) | 1993-05-27 |
| CA2122998C true CA2122998C (en) | 1999-05-25 |
Family
ID=25152251
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002122998A Expired - Fee Related CA2122998C (en) | 1991-11-12 | 1992-11-05 | Method of preventing grease buildup in ductwork |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5271959A (en) |
| EP (1) | EP0612297A4 (en) |
| JP (1) | JPH07501262A (en) |
| CA (1) | CA2122998C (en) |
| WO (1) | WO1993010004A1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6086198A (en) * | 1996-02-01 | 2000-07-11 | Hewlett-Packard Company | Bleed alleviation between two inks |
| FR2746039B1 (en) * | 1996-03-12 | 1998-05-22 | METHOD AND DEVICE FOR CLEANING CONDUITS BY REMOTE CONTROLLED ROBOT | |
| US5984007A (en) * | 1998-01-09 | 1999-11-16 | Halliburton Energy Services, Inc. | Chip resistant buttons for downhole tools having slip elements |
| US6191389B1 (en) * | 2000-03-31 | 2001-02-20 | General Electric Company | Grease resistant oven grille |
| US9175533B2 (en) | 2013-03-15 | 2015-11-03 | Halliburton Energy Services, Inc. | Drillable slip |
| DE102013109359A1 (en) * | 2013-08-29 | 2015-03-05 | Witzenmann Gmbh | Method for cleaning objects |
| NL2013175B1 (en) * | 2014-07-11 | 2016-06-14 | Rz Int B V | Method for treating an inner surface of a suction channel contaminated with grease deposits and channel treated in this way. |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2890970A (en) * | 1954-07-23 | 1959-06-16 | Gen Electric | Method of treating rails to prevent oil films |
| FR2163808A5 (en) * | 1971-12-02 | 1973-07-27 | Ugine Kuhlmann | Surface coatings - esp on metals comprising highly fluorinated surface active cpds |
| ZA743846B (en) * | 1973-06-18 | 1975-06-25 | Ardrox Ltd | A method of cleaning surfaces and compositions for use in this method |
| US4039717A (en) * | 1973-11-16 | 1977-08-02 | Shell Oil Company | Method for reducing the adherence of crude oil to sucker rods |
| JPS5711692B2 (en) * | 1974-05-08 | 1982-03-05 | ||
| US4097297A (en) * | 1975-08-07 | 1978-06-27 | E. I. Du Pont De Nemours And Company | Barrier coatings |
| JPS5535904A (en) * | 1978-09-05 | 1980-03-13 | Toshiba Corp | Formation of polyvinyl alcohol film on surface of instrument |
| JPS62167373A (en) * | 1986-01-18 | 1987-07-23 | Lion Corp | Agent for forming coating film removable with water |
| US4869934A (en) * | 1988-09-16 | 1989-09-26 | Sterling Drug Inc. | Floor polishing and coating composition |
| FR2639353A1 (en) * | 1988-11-23 | 1990-05-25 | Atochem | Aqueous compositions for the antisoiling treatment of construction materials |
-
1991
- 1991-11-12 US US07/790,959 patent/US5271959A/en not_active Expired - Fee Related
-
1992
- 1992-11-05 WO PCT/US1992/009577 patent/WO1993010004A1/en not_active Application Discontinuation
- 1992-11-05 CA CA002122998A patent/CA2122998C/en not_active Expired - Fee Related
- 1992-11-05 JP JP5509331A patent/JPH07501262A/en active Pending
- 1992-11-05 EP EP92924334A patent/EP0612297A4/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| US5271959A (en) | 1993-12-21 |
| CA2122998A1 (en) | 1993-05-27 |
| EP0612297A1 (en) | 1994-08-31 |
| EP0612297A4 (en) | 1995-07-19 |
| WO1993010004A1 (en) | 1993-05-27 |
| JPH07501262A (en) | 1995-02-09 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |