CA1092742A - Coating composition comprising a silicone resin, a fluorocarbon polymer, an epoxy resin, a silicone fluid, and an inorganic hardening agent - Google Patents
Coating composition comprising a silicone resin, a fluorocarbon polymer, an epoxy resin, a silicone fluid, and an inorganic hardening agentInfo
- Publication number
- CA1092742A CA1092742A CA272,978A CA272978A CA1092742A CA 1092742 A CA1092742 A CA 1092742A CA 272978 A CA272978 A CA 272978A CA 1092742 A CA1092742 A CA 1092742A
- Authority
- CA
- Canada
- Prior art keywords
- weight
- binder
- resin
- coating composition
- hardening agent
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/70—Siloxanes defined by use of the MDTQ nomenclature
Abstract
ABSTRACT OF THE DISCLOSURE
A coating composition comprising an inert liquid carrier and solids including a binder containing a methyl-phenyl polysiloxane resin, a thermocarbon polymer and an epoxy resin, and also a dimethyl polysiloxane fluid and an inorganic hardening agent. The composition forms finishes that have thermal stability, release properties, high glass, hardness, abrasion resistance, and excellent adhesion to unprimed, untreated metal substrates.
A coating composition comprising an inert liquid carrier and solids including a binder containing a methyl-phenyl polysiloxane resin, a thermocarbon polymer and an epoxy resin, and also a dimethyl polysiloxane fluid and an inorganic hardening agent. The composition forms finishes that have thermal stability, release properties, high glass, hardness, abrasion resistance, and excellent adhesion to unprimed, untreated metal substrates.
Description
10~274Z
BACKGROUND OF THE INVE~ITION
~1) Field of the Invention Thi9 invention i9 directed to a coating composition that i8 useful as a finish for cooking vessels because of its thermal stability, release properties, gloss, hardness, abrasion resistance, and adhesion to untreated, unprimed metal substrates.
BACKGROUND OF THE INVE~ITION
~1) Field of the Invention Thi9 invention i9 directed to a coating composition that i8 useful as a finish for cooking vessels because of its thermal stability, release properties, gloss, hardness, abrasion resistance, and adhesion to untreated, unprimed metal substrates.
(2) Prior Art Cookware and bakeware items have been coated with fluorocarbon polymers such as polytetrafluoroethylene and copolymers thereof. Finishes of fluorocarbons have excellent thermal stability and good release properties and have been widely used and well accepted.
However, a primer is generally required for these coatings, along with special treatment of the metal substrate, to obtain excellent adhesion of the coating.
Moreover, the few coating compositions which do not require a primer or substrate treatment are only available in dark colors.
Therefore, it would be desirable to have a coating composition that could be applied to an unprimed untreated substrate and which could provide a light colored finish upon baking.
The coating composition of this invention meets the above desires while forming a finish that has release properties, thermal stability, high gloss, good hardness, and abrasion resistance, and is an ideal coating composition for cooking vessels, particularly bakeware, and commercial food processing equipment.
10!92742 gU~MARY OF T9~ IJVE~TIO~
A coating eo~pooltlon o~ this lnvention ha~ a ~olld~
content Or 25-80% b~ ~elght ln an ln-rt llquld carrler and is coaprloed Or (a) a binder eo~prl~ed o~
(1) 40-93% b~ ~elght, ba~ed on the ~-ltht o~
the binder, o~ a sllleono re~in ~hleh i8 a h-at curabl- struetur-d ~othylphenyl poly8110xane r~o~n ha~ing the repeatlng struetural ~or~ula r ~ 1 r 3 1 r ~ 1 r t Sl - O ~ Si - O ~ Sl - O ~ Sl - O
c~3 a X X X
~h-r~ln - x 1~ a ruDctlonal group ~hleh allo~8 erw s-linkin~ at $t8 81te, and a, ~, c, and d ar- posltl~o int-8ers ~hleh are surrlelently l~rge to pro~lde tho resin, ~hen ~easured ~ .
at 60% resin sollds in xylen- at 25-C, ~lth a vl~co~lty o~ 30-50 contlpolse~, speclrlc gr~ity Or 1 03-1 2, and rerracti~e ind-x Or i~
1.45-1.57; and having a ~llanol cont~nt abo~e 4~ bas-d on the ~elght Or the resln;
t2) 5-50% by l~elght, baaed on tho lelcht Or the blnder, Or a rluorocarbon pol~er; nd
However, a primer is generally required for these coatings, along with special treatment of the metal substrate, to obtain excellent adhesion of the coating.
Moreover, the few coating compositions which do not require a primer or substrate treatment are only available in dark colors.
Therefore, it would be desirable to have a coating composition that could be applied to an unprimed untreated substrate and which could provide a light colored finish upon baking.
The coating composition of this invention meets the above desires while forming a finish that has release properties, thermal stability, high gloss, good hardness, and abrasion resistance, and is an ideal coating composition for cooking vessels, particularly bakeware, and commercial food processing equipment.
10!92742 gU~MARY OF T9~ IJVE~TIO~
A coating eo~pooltlon o~ this lnvention ha~ a ~olld~
content Or 25-80% b~ ~elght ln an ln-rt llquld carrler and is coaprloed Or (a) a binder eo~prl~ed o~
(1) 40-93% b~ ~elght, ba~ed on the ~-ltht o~
the binder, o~ a sllleono re~in ~hleh i8 a h-at curabl- struetur-d ~othylphenyl poly8110xane r~o~n ha~ing the repeatlng struetural ~or~ula r ~ 1 r 3 1 r ~ 1 r t Sl - O ~ Si - O ~ Sl - O ~ Sl - O
c~3 a X X X
~h-r~ln - x 1~ a ruDctlonal group ~hleh allo~8 erw s-linkin~ at $t8 81te, and a, ~, c, and d ar- posltl~o int-8ers ~hleh are surrlelently l~rge to pro~lde tho resin, ~hen ~easured ~ .
at 60% resin sollds in xylen- at 25-C, ~lth a vl~co~lty o~ 30-50 contlpolse~, speclrlc gr~ity Or 1 03-1 2, and rerracti~e ind-x Or i~
1.45-1.57; and having a ~llanol cont~nt abo~e 4~ bas-d on the ~elght Or the resln;
t2) 5-50% by l~elght, baaed on tho lelcht Or the blnder, Or a rluorocarbon pol~er; nd
(3) 2-40% by ~elght, based on the ~elght o~ the binder, Or an poxy re-ln ha~ing thc ror~ula , . . .
10927~2 C}~2-\ C~2~-0-R-~-OCH2C C}I2~;0-~-R-~-OCH2-C~I-C~2 ~horeln n 18 ~n int-ger ~ro~ 0-42, and R 1~ an alkylene group Or 1-4 carbon ato~s;
(b) 0 2-10% by ~elght, based on the ~olght Or the bind~r, Or a ~ilicon~ ~luld ~hich i8 a di~ethyl --polyslloxane rluld havlng a vlsco~lty Or 50-5000 c~ntlstokes ~easured at 25C;
10(c) a rln~ly dl~ldod inorganlc hardoning agent in a hardening agont to binder ratlo o~ about 5/100 to 400/100; and (d) an inert llquld carrler ~ ~etal coo~ing ve~sel coat-d ~ith a cured produeed ~ro~ the abo~e composltion i8 also part o~ the inv~ntion ~SCRIPTIOII OF ~IIC~ IllVl!~TiOJ
The coating co~positlon o~ the inventlon prererably has a relatlvely high solid~ content Or about 40-70% by ~-~ght in ~uitsble llquld carrler.
The ~ rorming binder con-tituent~ ~ro dis~ol~-d ln organlc ol~ents ~uch ~ tolu~ne, xrl~ne, tetralvaroruran, butyl CARBITOL*, cth~l~ne glycol ~onoethyl ethcr, cthylene glycol ~onobu~yl ether, ana the like. -:
Th0 blnder o~ the novel Co~til~g compo~ltlon Or the inveation i8 a blend Or a slllcone re~in which 1~
highl~ reactlve nethylph~nyl poly~ilo~ane resin, an epoxy resin, and 8 rluorocarbo~ poly~ r den~tes trade ~ark ~09274Z
The binder contains about 40-93% by weight of silicone resin, 5-50% by weight of fluorocarbon polymer, and 2-40% by weight of epoxy resin in amounts necessary to equal 100%. Preferably, the binder contains 65-85%
by weight of silicone resin, 10-20% by weight of fluoro-carbon polymer, and 5-15% by weight of epoxy resin.
Also present in the composition is a silicone fluid which is a dimethyl polysiloxane. The amount of dimethyl polysiloxane fluid utilized is based on the total lO weight of binder. The amount of fluid will range from 0.2-10% by weight, based on the weight of the binder;
preferably, the xange will be l-3% by weight.
` A finely divided inorganic hardening agent is used in the composition of the invention to provide a finish having increased scratch resistance, abrasion - resistance, hardness, blister resistance, and decreased porosity. The hardening agent is added to the composition in a ratio of hardening agent to binder of about 5/100 to about 400/100, preferably, about 10/100 to about 20 70/100, more preferably, 20/100-40/100.
The combination of these cornponents provides a coating composition that adheres well to unprimed un-treated substrates, and produces a flnish which may be llght colored and has desireable thermal stability and release properties.
The highly reactive methyl phenyl polysiloxane resin is heat curable, has a silanol content above 4%, preferably 5%, based on the weight of the resin and has the repeating structural formula {~
CH3 X X c X d ~heraln X 18 a functlonal group ~hleh allo~
eross-lin~ing at lts ~lte, and a, b, c, and d aro po~itlve lntogers ~hlch are su~rlcl-ntly lar~e to pro~ide the re~ln, ~hon nea~ured at 60% rosin sollds ln xylone at 25-C, ~lth a V18CQ~lty Or 30-50 centlpoiscs, speclric gravlty Or 1.03-1.2~ and rerraetiv- ~ndex 1.45-1.57. ~; -A partleularly prererred ~ethyl ph-nol polyslloxane rc~ln ~h~n ~easurcd at 60% sollds ln xyleno at 25C, has a v18c08ity Or about 35-45 centlpol~o, a speclrle ~ravlty Or about 1.05-1.12, a r tractl~e index Or about 1.50-1.53, and lt al~o has a so~tenln~ po~nt Or about 75-85~C-The rluorocarbon poly~ers used in tho ¢omposltlon ~ ,, Or th- in~e~tlon are ho~opoly~ers and copoly~ers (~ean~ng -the poly~or contalns t~o or re alrrerent ~ono~er unlts) Or ~onoethrlenlcally uAsaturatea hydrocarbon ~ono~er .;~
co~pletely substltuted ~lth rluorine ato~s or co~pletely substitutod ~lth a co~binatlon Or rluorlne atoms and ehlorino atoms. Included in thls group are perrluoroolerln poly~ors such as polytotrarluoroethylene ~PTFS) snd . ~:
copolraers Or tetrarluorocthylene and hoxarluoropropylene 1A all ~ono~er unlt Yelght ratlos, rluorochlorocaibon Bi .. . . , ~ . . ...... ......... ... ... ... .. .
` 10~Z742 poly~ers ~uch as polymonochlorotrlrluoroethyl~n~, and nor~lly solid copolymers Or tetrarluoro~thylene and perrlu~roalkyl vlnyl ethers (~herein the alkyl troup i8 Or 1-5 carbon atoms) Mixtures Or these can also be used A prererrcd rluoropolymer is a copoly~r Or tetrarluoroeth~leno (TFE) copoly~erized ~ith either a rluoroolerin or a perrluoro (alkyl vinyl ether) When the TFE 1~ copolym~rized ~ith a rluoro-olerln, the copoly~er ~111 contaln about 50-95~ by ~c~ht Or TFE unlt, and about 50-5% by ~ei~ht Or hexa~luoro-propylene or other sultable rluoroolerin havlng the rormula CF2-CFY, ~herein Y i8 a Cl to C8 per~luoroslkyl radlc~l Copolym~rs Or the type are descrlbed ln Unlted States Patents 2,833,686 Or B W Sandt, ~hich lssued 1958 ~ay 6;
2,946,763 Or ~ I Bro and B W Sandt, whlch l~sued 1960 July 26; ant 3,085,083 Or B C Schrcyer ~hlch lssued 1963 April 9 Especl-lly u~erul 18 a tetrarluoroethylene/
hexarluoropropylone copolyoer ( Æ P). Preferably, hexa-~luoropropylene (HFP) contont 18 bet~een about 6.75 and about 27 ~ol~ht percent Or the copoly~er and more prererably bet~een about 8 and about 18 ~elght pcrcent. These ~-copoly~ers aro prepared by reacting TF~ and HFP 1~ an aqueous system contalning a dlsper~lng agent and a rree radlcal polymerl~atlon lnltlator according to procedures disclosed ln Couture, Uhlted Stat-s Patent 3,132,12~.
Additlonally, the F~P copolyuer prererred 18 partlculate an~ has a specirle ~elt vlscosity rrom 5- 60X104 pol#es, ore prerer~bly 5- 25Xl04, and even more prererably 6-lOX10 pols~s.
By the ter~ "sp~clrlc melt vlscoslty" as used hereln, 18 meant the appareat melt vlsco~lty as measured at 372C under a shear stre~s of 6.5 pound~ per #quare ~ ' ~
~092742 inch. The values herein re~erred to are determlned uslng a melt lndlcator Or the type described in the Americ~n Soclety Or Tosting Materlals Test DL1238-57 T, modlfied for corroslon re6istance to embody a cyllnder and orlfice Or AMPCO* alumlnum bronze and a piston welghlng 60 grams, havlng a STELLITE* cobalt-chromlum-tungston alloy tip.
The resln 18 charged to the 0.375-lnch I.D. cylinder which 18 held at 372C + .5C, allowed to come to an equillbrlum temperature during 5 minutes, and extruded through the 0.0825-lnch dlameter, 0.315-lnch long orl~lce under a plston loadlng Or 5,000 grams. The speclflc melt vlscoslty ln polses 18 calculated as 53,150 divided by the observed extrusion rate ln grams per mlnute.
The epoxy resin~ utillzed in the present lnven-tlon are co~monly known in the art. One clas~ Or such resins has the generalized rormula CN2-CNC~ EO~ )-OCN2C CN~;;o-~>-R-~-ocN2-cN
~here n is an integer rrom 0-42 and R lB an alkylene group o~ l-4 carbon atoms. The epo~y reslns utilized ln the present lnventlon contain at least two epoxy groups per molecule and, therefore, upon curing of the composltion, introduce no uncross-linkable extractable portions into the coating.
Prefer~bly, to obtain a coatlng wlth high gloss, liquld epo~y resln i8 used. ~n undiluted liquid epoxy resin where the average value Or n 18 about 0-3, R is lsopropylidene, the viscoslty 18 1 . 2-225 poises at 25C
as measured by ASTM-DL445, and the epo~y equivalent is * denotes trademark ~A, ''~` la~742 l( about 150-470 ls preferred. The epoxy equivalent l defined as the grams of resin containlng l gram-equlvalent of epoxide functionality as mea~ured by ASTM-D-1652. A
coating composition contalnlng EPON 828* 18 partlcularly preferred because finishes produced by such compo~ltlons have high gloss while maintalning high adheslon. EPON 828 is a liquid epoxy resin where the average value of n i~
about 0, R is isopropylidene, the viscosity of the un-diluted resin is 100-160 poises at 25C as meaRured by ASTM-D-~5, and the epoxy equivalent is 185-192.
Modificatlons of epoxy reslns can also be utllized in the coating composition of the present inven-tion. ~or example, it i8 known to those skilled in the art that when an epoxy compound containing a hydroxy group is brought in contact with an acid, there results an ester or mixture of esters. Thus, when phosphoric acid is added to an epoxy resin, a reactlon occuræ at one or more of the epoxy groups of the molecule and the resulting mixtuxe contains both the mono- and diesters of phosphoric acid. A product of ~is reaction is exemplifled by t~e formula CR2-CH CR2-Eo-~-R-<~-o-cN2cR-cR2~o~o n+l OH
These modified epoxy resins can still function as epoxy resins in the coating compositions of the invention.
The dimethyl polyslloxane fluid utilized in the coating composition of this invention can have a viscosity of 0~65 to over a million centistokes measured at 25C, .
but pre~erably~ haæ a viscosity of 100-5000 centistokes.
~`
* denotes trade mark _ g _ ~ , . .
109;;~742 To rnrm partlcularly high guality co~posltlon~, a Ylscoslty Or 500-1500 centlstokes 18 pre~err-d Th- dl~ th~rl poly-silo~ane rluld 18 a release agent ~hlch alds tho release characterlstlcs Or tho rllma producod The hardenlng agents that can be used ln the co~posltion o~ this lnv~ntlon include zirconlu~ slllcate, zirconiu~l oxlde, slllcon dloxlde, and reactlvo and unr-actlve alumlnas l~xa~plos Or aluo~lnas which can be used are calclned alu~nas, lol-soda alu~ina~, reactlve 10 alu~llnas, hlgh-purity alumina~, tabular alumlnas, calciu~
alu~illate co~ent, alld hydrated aluminas ~e prererred hardenl~g ag~ts are reactlvo aluoli~a A prererr-d reacti~o alu~lna whlch le usorul ln a coatlng co~posltlon ha~ g exce~l-nt proportles 18 R~AC~lv~ A A-15S~
~hich is sold by Al¢oa mls alumina conslsts Or A12C3 99- 5+f ~a2o . o8 F~203 . 01;
20 lt, lrith co~pacti0n and sintering, can provldo an all-a1U~1~ co~posltion with a green body denslty Or 2 86 a~/cc st 5000 p~l, and rired density of 3 93 gl~/CC. with onl~r 10 1 porcent linear shrinkage arter one hour at ~ hen a reactive aludna i8 used as the hardenlng agent, lts ratlo to binder 18 about 10/100 to about 70/100, prc~erabl~r, 20/100 to 40/100 - Sultable llquid carriers include ~uch org~nlc sQlv~nts as those used ~or dlssolvi~ the rll~-ro~ing 30 ~inder constltuents, ~or exa~ple, tolu~e, x~rl~e, * denotes trade ~ark 1~
1 0 ~2~7~ 2 tetrahydroruran~ butyl CARBITOL, ethylene glycol monoethyl ethor, ethJlene glycol ~onobutyl other, and the llko.
Optlonally, plgments (heat stable, riller or reinrorcing plg~ent) can be u~ed in the coatlng co~posltlon Or the lnvcntlon. A ratlo Or plg~ent to bind~r Or about 1/100-400/100 can bc utllized, prererably, about 1/100-200/100, more pre~erabl~, ~n co~posltlon~ having excellent proportie~, 1/100-50/100. Typlcal pigments that can be used are, ror e~ample, carbon black, tltanium dloxide, bro~n, black, and yello~ lron oxides, ~ica, talc, china clay, ~etal po~ders, carbonates, potassiu~ titanate ~lbrlls, tltaniu~ dloxide rlbrlls, and the llko.
To ensure ~etting o~ the plg~ents and a stable dlsperslon, ~etting agent ~y be added to the co~posltion in a concentratlon Or 0.2-10% by ~olght bascd on the ~elght Or the binder. ~etting agents uscrul are ~ctal salts, partlcularly ~etal salts Or ratty acld~ such as zlnc octoat~ and cobalt naphthenate. A prororred zinc octoate 18 ~uod~x~ (a zinc octoate ~olutlon ha~ing ô% z~nc ~ctal cont~nt sold by Tenneco). A coupliAg solvent, such as V.~. an~ P. ~aphtha, 18 someti~e~ used to ensure solubility o~ the ~etting agent ~lthln the coating compositlon.
The coating compositlon Or this invention can be prepared by Yarlous methods ~noun to the artisan. One ~ethod 18 to dls~olve the ~lllcone resln and wetting agent ln suitable solvent, then blending the solutlon ~lth tho othor con~tltuents. Then the blend 18 ground by conventlonal tochniques such as pebble mlll grinding, ball ~11 grinding, sand mill grindlag, and tho llke.
The composltion Or this ln~entlon can be applled to a smooth substrate, which has been cleaned by solvent wiping techniques, such as spraying, electrostatic spraying, roller coating, and the like. If desired, the sub6trate may be surface treated by such methods as frit coating and grit blasting and a primer may be applied.
The composition is applied to the substrate to a thickness of 0.2-5 mil (dry), preferably 0.5-1.5 mil (dry), and is then baked for about 5-45 minutes at about 200-400C.
The coating composition of this invention forms excellent finishes not only on cookware but also on ice cube trays, dough cutters, paper cutters, and can be used as a lubricant coating on bearing and curtain rods and can be used as a coating on coin machine slots, fan vents, shovels, and discardable aluminum utensils.
The following example illustrates the invention.
All quantities are on a weight basis unless otherwise indicated.
A coating composition was prepared as follows:
~a) Preparing a resin solution by mixing until dissolved:
Parts by Weight Silicone resin flake which is a heat curable structured methyl phenyl polysiloxane resin having the repeating structural formula 109~742 -~Sl-~Sl-~Sl-~
CH3 a X b X X
whereln X i8 a runctlonal group ~hich allows cro~s-linking at its slto, and a, b, c and d are posi-tlve integers which aro surrlciently large to pro~ldo the re~in, ~hen ~easured at 60~ resin ~ollds in xylene at 25C, with a vlscoslty o~ 40 centlpolse, specl~ic grarity Or 1.08, and rerractive inde~ Or 1.518;
and a ~llanol contont above Part~ by 5~ based on tho woight ofWeight the ro~ln. 80.00 - x~lene 80.00 -V.~. and P. Naphtha 10.00 NuodexD (a ~inc octo~te 801u tion containing 8% zinc ~etal, sold by Tenneco) 9-25 (b) adding the rollo~ing in order to the product Or (a) and pebble grinding for 21 hours:
sillcone rluid (DC-200*, A polydi~ethyl donotes trade mark B
,- ~ . ~ .. . .
10~274Z
~iloxane having a vlscoslty of 1000 centistokes, sold by Dow Cornlng) 2.0 tltanium dioxlde pigment 15.0 reactlve alumina (A-15 SGD sold by Alcoa) 10.0 Teflon2 TE-9061- (a dry FEP flake sold by E.I. du Pont de Nemours and Company) 15.0 (c) adding, ln order, wlth stlrrlng to Parts by Welght the product of (b) and then mixing; EPON 828 (a liquld epoxy resin sold by Shell Chemlcal Company) 5.0 xylene 11.2 An aluminum muffin pan was wiped clean wlth acetone to remoYe any resldue grea6e. m e above coatlng was then sprayed onto the pan to a thickness of O.7 mil (dry), alr dried for about 10 minutes and then baked for 7 minutes at 325C. The resulting finish on the pan had a good glossy appearance, excellent adhesion to smooth clean aluminum, pencil hardness of HB-F, a light color, and was fully cured as measured by a 50 double wipe test with toluene. m e coated pan was sub~ected to a 25 bake test at 220C with blueberry muffin mix and meat loaf mix.
After the test, the finishes release properties, ease of cleaning, and appearance remained excellent.
- 14 - ~ ;
, :... . .
10927~2 C}~2-\ C~2~-0-R-~-OCH2C C}I2~;0-~-R-~-OCH2-C~I-C~2 ~horeln n 18 ~n int-ger ~ro~ 0-42, and R 1~ an alkylene group Or 1-4 carbon ato~s;
(b) 0 2-10% by ~elght, based on the ~olght Or the bind~r, Or a ~ilicon~ ~luld ~hich i8 a di~ethyl --polyslloxane rluld havlng a vlsco~lty Or 50-5000 c~ntlstokes ~easured at 25C;
10(c) a rln~ly dl~ldod inorganlc hardoning agent in a hardening agont to binder ratlo o~ about 5/100 to 400/100; and (d) an inert llquld carrler ~ ~etal coo~ing ve~sel coat-d ~ith a cured produeed ~ro~ the abo~e composltion i8 also part o~ the inv~ntion ~SCRIPTIOII OF ~IIC~ IllVl!~TiOJ
The coating co~positlon o~ the inventlon prererably has a relatlvely high solid~ content Or about 40-70% by ~-~ght in ~uitsble llquld carrler.
The ~ rorming binder con-tituent~ ~ro dis~ol~-d ln organlc ol~ents ~uch ~ tolu~ne, xrl~ne, tetralvaroruran, butyl CARBITOL*, cth~l~ne glycol ~onoethyl ethcr, cthylene glycol ~onobu~yl ether, ana the like. -:
Th0 blnder o~ the novel Co~til~g compo~ltlon Or the inveation i8 a blend Or a slllcone re~in which 1~
highl~ reactlve nethylph~nyl poly~ilo~ane resin, an epoxy resin, and 8 rluorocarbo~ poly~ r den~tes trade ~ark ~09274Z
The binder contains about 40-93% by weight of silicone resin, 5-50% by weight of fluorocarbon polymer, and 2-40% by weight of epoxy resin in amounts necessary to equal 100%. Preferably, the binder contains 65-85%
by weight of silicone resin, 10-20% by weight of fluoro-carbon polymer, and 5-15% by weight of epoxy resin.
Also present in the composition is a silicone fluid which is a dimethyl polysiloxane. The amount of dimethyl polysiloxane fluid utilized is based on the total lO weight of binder. The amount of fluid will range from 0.2-10% by weight, based on the weight of the binder;
preferably, the xange will be l-3% by weight.
` A finely divided inorganic hardening agent is used in the composition of the invention to provide a finish having increased scratch resistance, abrasion - resistance, hardness, blister resistance, and decreased porosity. The hardening agent is added to the composition in a ratio of hardening agent to binder of about 5/100 to about 400/100, preferably, about 10/100 to about 20 70/100, more preferably, 20/100-40/100.
The combination of these cornponents provides a coating composition that adheres well to unprimed un-treated substrates, and produces a flnish which may be llght colored and has desireable thermal stability and release properties.
The highly reactive methyl phenyl polysiloxane resin is heat curable, has a silanol content above 4%, preferably 5%, based on the weight of the resin and has the repeating structural formula {~
CH3 X X c X d ~heraln X 18 a functlonal group ~hleh allo~
eross-lin~ing at lts ~lte, and a, b, c, and d aro po~itlve lntogers ~hlch are su~rlcl-ntly lar~e to pro~ide the re~ln, ~hon nea~ured at 60% rosin sollds ln xylone at 25-C, ~lth a V18CQ~lty Or 30-50 centlpoiscs, speclric gravlty Or 1.03-1.2~ and rerraetiv- ~ndex 1.45-1.57. ~; -A partleularly prererred ~ethyl ph-nol polyslloxane rc~ln ~h~n ~easurcd at 60% sollds ln xyleno at 25C, has a v18c08ity Or about 35-45 centlpol~o, a speclrle ~ravlty Or about 1.05-1.12, a r tractl~e index Or about 1.50-1.53, and lt al~o has a so~tenln~ po~nt Or about 75-85~C-The rluorocarbon poly~ers used in tho ¢omposltlon ~ ,, Or th- in~e~tlon are ho~opoly~ers and copoly~ers (~ean~ng -the poly~or contalns t~o or re alrrerent ~ono~er unlts) Or ~onoethrlenlcally uAsaturatea hydrocarbon ~ono~er .;~
co~pletely substltuted ~lth rluorine ato~s or co~pletely substitutod ~lth a co~binatlon Or rluorlne atoms and ehlorino atoms. Included in thls group are perrluoroolerln poly~ors such as polytotrarluoroethylene ~PTFS) snd . ~:
copolraers Or tetrarluorocthylene and hoxarluoropropylene 1A all ~ono~er unlt Yelght ratlos, rluorochlorocaibon Bi .. . . , ~ . . ...... ......... ... ... ... .. .
` 10~Z742 poly~ers ~uch as polymonochlorotrlrluoroethyl~n~, and nor~lly solid copolymers Or tetrarluoro~thylene and perrlu~roalkyl vlnyl ethers (~herein the alkyl troup i8 Or 1-5 carbon atoms) Mixtures Or these can also be used A prererrcd rluoropolymer is a copoly~r Or tetrarluoroeth~leno (TFE) copoly~erized ~ith either a rluoroolerin or a perrluoro (alkyl vinyl ether) When the TFE 1~ copolym~rized ~ith a rluoro-olerln, the copoly~er ~111 contaln about 50-95~ by ~c~ht Or TFE unlt, and about 50-5% by ~ei~ht Or hexa~luoro-propylene or other sultable rluoroolerin havlng the rormula CF2-CFY, ~herein Y i8 a Cl to C8 per~luoroslkyl radlc~l Copolym~rs Or the type are descrlbed ln Unlted States Patents 2,833,686 Or B W Sandt, ~hich lssued 1958 ~ay 6;
2,946,763 Or ~ I Bro and B W Sandt, whlch l~sued 1960 July 26; ant 3,085,083 Or B C Schrcyer ~hlch lssued 1963 April 9 Especl-lly u~erul 18 a tetrarluoroethylene/
hexarluoropropylone copolyoer ( Æ P). Preferably, hexa-~luoropropylene (HFP) contont 18 bet~een about 6.75 and about 27 ~ol~ht percent Or the copoly~er and more prererably bet~een about 8 and about 18 ~elght pcrcent. These ~-copoly~ers aro prepared by reacting TF~ and HFP 1~ an aqueous system contalning a dlsper~lng agent and a rree radlcal polymerl~atlon lnltlator according to procedures disclosed ln Couture, Uhlted Stat-s Patent 3,132,12~.
Additlonally, the F~P copolyuer prererred 18 partlculate an~ has a specirle ~elt vlscosity rrom 5- 60X104 pol#es, ore prerer~bly 5- 25Xl04, and even more prererably 6-lOX10 pols~s.
By the ter~ "sp~clrlc melt vlscoslty" as used hereln, 18 meant the appareat melt vlsco~lty as measured at 372C under a shear stre~s of 6.5 pound~ per #quare ~ ' ~
~092742 inch. The values herein re~erred to are determlned uslng a melt lndlcator Or the type described in the Americ~n Soclety Or Tosting Materlals Test DL1238-57 T, modlfied for corroslon re6istance to embody a cyllnder and orlfice Or AMPCO* alumlnum bronze and a piston welghlng 60 grams, havlng a STELLITE* cobalt-chromlum-tungston alloy tip.
The resln 18 charged to the 0.375-lnch I.D. cylinder which 18 held at 372C + .5C, allowed to come to an equillbrlum temperature during 5 minutes, and extruded through the 0.0825-lnch dlameter, 0.315-lnch long orl~lce under a plston loadlng Or 5,000 grams. The speclflc melt vlscoslty ln polses 18 calculated as 53,150 divided by the observed extrusion rate ln grams per mlnute.
The epoxy resin~ utillzed in the present lnven-tlon are co~monly known in the art. One clas~ Or such resins has the generalized rormula CN2-CNC~ EO~ )-OCN2C CN~;;o-~>-R-~-ocN2-cN
~here n is an integer rrom 0-42 and R lB an alkylene group o~ l-4 carbon atoms. The epo~y reslns utilized ln the present lnventlon contain at least two epoxy groups per molecule and, therefore, upon curing of the composltion, introduce no uncross-linkable extractable portions into the coating.
Prefer~bly, to obtain a coatlng wlth high gloss, liquld epo~y resln i8 used. ~n undiluted liquid epoxy resin where the average value Or n 18 about 0-3, R is lsopropylidene, the viscoslty 18 1 . 2-225 poises at 25C
as measured by ASTM-DL445, and the epo~y equivalent is * denotes trademark ~A, ''~` la~742 l( about 150-470 ls preferred. The epoxy equivalent l defined as the grams of resin containlng l gram-equlvalent of epoxide functionality as mea~ured by ASTM-D-1652. A
coating composition contalnlng EPON 828* 18 partlcularly preferred because finishes produced by such compo~ltlons have high gloss while maintalning high adheslon. EPON 828 is a liquid epoxy resin where the average value of n i~
about 0, R is isopropylidene, the viscosity of the un-diluted resin is 100-160 poises at 25C as meaRured by ASTM-D-~5, and the epoxy equivalent is 185-192.
Modificatlons of epoxy reslns can also be utllized in the coating composition of the present inven-tion. ~or example, it i8 known to those skilled in the art that when an epoxy compound containing a hydroxy group is brought in contact with an acid, there results an ester or mixture of esters. Thus, when phosphoric acid is added to an epoxy resin, a reactlon occuræ at one or more of the epoxy groups of the molecule and the resulting mixtuxe contains both the mono- and diesters of phosphoric acid. A product of ~is reaction is exemplifled by t~e formula CR2-CH CR2-Eo-~-R-<~-o-cN2cR-cR2~o~o n+l OH
These modified epoxy resins can still function as epoxy resins in the coating compositions of the invention.
The dimethyl polyslloxane fluid utilized in the coating composition of this invention can have a viscosity of 0~65 to over a million centistokes measured at 25C, .
but pre~erably~ haæ a viscosity of 100-5000 centistokes.
~`
* denotes trade mark _ g _ ~ , . .
109;;~742 To rnrm partlcularly high guality co~posltlon~, a Ylscoslty Or 500-1500 centlstokes 18 pre~err-d Th- dl~ th~rl poly-silo~ane rluld 18 a release agent ~hlch alds tho release characterlstlcs Or tho rllma producod The hardenlng agents that can be used ln the co~posltion o~ this lnv~ntlon include zirconlu~ slllcate, zirconiu~l oxlde, slllcon dloxlde, and reactlvo and unr-actlve alumlnas l~xa~plos Or aluo~lnas which can be used are calclned alu~nas, lol-soda alu~ina~, reactlve 10 alu~llnas, hlgh-purity alumina~, tabular alumlnas, calciu~
alu~illate co~ent, alld hydrated aluminas ~e prererred hardenl~g ag~ts are reactlvo aluoli~a A prererr-d reacti~o alu~lna whlch le usorul ln a coatlng co~posltlon ha~ g exce~l-nt proportles 18 R~AC~lv~ A A-15S~
~hich is sold by Al¢oa mls alumina conslsts Or A12C3 99- 5+f ~a2o . o8 F~203 . 01;
20 lt, lrith co~pacti0n and sintering, can provldo an all-a1U~1~ co~posltion with a green body denslty Or 2 86 a~/cc st 5000 p~l, and rired density of 3 93 gl~/CC. with onl~r 10 1 porcent linear shrinkage arter one hour at ~ hen a reactive aludna i8 used as the hardenlng agent, lts ratlo to binder 18 about 10/100 to about 70/100, prc~erabl~r, 20/100 to 40/100 - Sultable llquid carriers include ~uch org~nlc sQlv~nts as those used ~or dlssolvi~ the rll~-ro~ing 30 ~inder constltuents, ~or exa~ple, tolu~e, x~rl~e, * denotes trade ~ark 1~
1 0 ~2~7~ 2 tetrahydroruran~ butyl CARBITOL, ethylene glycol monoethyl ethor, ethJlene glycol ~onobutyl other, and the llko.
Optlonally, plgments (heat stable, riller or reinrorcing plg~ent) can be u~ed in the coatlng co~posltlon Or the lnvcntlon. A ratlo Or plg~ent to bind~r Or about 1/100-400/100 can bc utllized, prererably, about 1/100-200/100, more pre~erabl~, ~n co~posltlon~ having excellent proportie~, 1/100-50/100. Typlcal pigments that can be used are, ror e~ample, carbon black, tltanium dloxide, bro~n, black, and yello~ lron oxides, ~ica, talc, china clay, ~etal po~ders, carbonates, potassiu~ titanate ~lbrlls, tltaniu~ dloxide rlbrlls, and the llko.
To ensure ~etting o~ the plg~ents and a stable dlsperslon, ~etting agent ~y be added to the co~posltion in a concentratlon Or 0.2-10% by ~olght bascd on the ~elght Or the binder. ~etting agents uscrul are ~ctal salts, partlcularly ~etal salts Or ratty acld~ such as zlnc octoat~ and cobalt naphthenate. A prororred zinc octoate 18 ~uod~x~ (a zinc octoate ~olutlon ha~ing ô% z~nc ~ctal cont~nt sold by Tenneco). A coupliAg solvent, such as V.~. an~ P. ~aphtha, 18 someti~e~ used to ensure solubility o~ the ~etting agent ~lthln the coating compositlon.
The coating compositlon Or this invention can be prepared by Yarlous methods ~noun to the artisan. One ~ethod 18 to dls~olve the ~lllcone resln and wetting agent ln suitable solvent, then blending the solutlon ~lth tho othor con~tltuents. Then the blend 18 ground by conventlonal tochniques such as pebble mlll grinding, ball ~11 grinding, sand mill grindlag, and tho llke.
The composltion Or this ln~entlon can be applled to a smooth substrate, which has been cleaned by solvent wiping techniques, such as spraying, electrostatic spraying, roller coating, and the like. If desired, the sub6trate may be surface treated by such methods as frit coating and grit blasting and a primer may be applied.
The composition is applied to the substrate to a thickness of 0.2-5 mil (dry), preferably 0.5-1.5 mil (dry), and is then baked for about 5-45 minutes at about 200-400C.
The coating composition of this invention forms excellent finishes not only on cookware but also on ice cube trays, dough cutters, paper cutters, and can be used as a lubricant coating on bearing and curtain rods and can be used as a coating on coin machine slots, fan vents, shovels, and discardable aluminum utensils.
The following example illustrates the invention.
All quantities are on a weight basis unless otherwise indicated.
A coating composition was prepared as follows:
~a) Preparing a resin solution by mixing until dissolved:
Parts by Weight Silicone resin flake which is a heat curable structured methyl phenyl polysiloxane resin having the repeating structural formula 109~742 -~Sl-~Sl-~Sl-~
CH3 a X b X X
whereln X i8 a runctlonal group ~hich allows cro~s-linking at its slto, and a, b, c and d are posi-tlve integers which aro surrlciently large to pro~ldo the re~in, ~hen ~easured at 60~ resin ~ollds in xylene at 25C, with a vlscoslty o~ 40 centlpolse, specl~ic grarity Or 1.08, and rerractive inde~ Or 1.518;
and a ~llanol contont above Part~ by 5~ based on tho woight ofWeight the ro~ln. 80.00 - x~lene 80.00 -V.~. and P. Naphtha 10.00 NuodexD (a ~inc octo~te 801u tion containing 8% zinc ~etal, sold by Tenneco) 9-25 (b) adding the rollo~ing in order to the product Or (a) and pebble grinding for 21 hours:
sillcone rluid (DC-200*, A polydi~ethyl donotes trade mark B
,- ~ . ~ .. . .
10~274Z
~iloxane having a vlscoslty of 1000 centistokes, sold by Dow Cornlng) 2.0 tltanium dioxlde pigment 15.0 reactlve alumina (A-15 SGD sold by Alcoa) 10.0 Teflon2 TE-9061- (a dry FEP flake sold by E.I. du Pont de Nemours and Company) 15.0 (c) adding, ln order, wlth stlrrlng to Parts by Welght the product of (b) and then mixing; EPON 828 (a liquld epoxy resin sold by Shell Chemlcal Company) 5.0 xylene 11.2 An aluminum muffin pan was wiped clean wlth acetone to remoYe any resldue grea6e. m e above coatlng was then sprayed onto the pan to a thickness of O.7 mil (dry), alr dried for about 10 minutes and then baked for 7 minutes at 325C. The resulting finish on the pan had a good glossy appearance, excellent adhesion to smooth clean aluminum, pencil hardness of HB-F, a light color, and was fully cured as measured by a 50 double wipe test with toluene. m e coated pan was sub~ected to a 25 bake test at 220C with blueberry muffin mix and meat loaf mix.
After the test, the finishes release properties, ease of cleaning, and appearance remained excellent.
- 14 - ~ ;
, :... . .
Claims (11)
1. A coating composition having a solids content of 25-80% by weight in an inert liquid carrier and com-prised of:
(a) a binder comprised of (1) 40-93% by weight, based on the weight of the binder, of a silicone resin which is a heat curable structured methylphenyl poly-siloxane resin having the repeating structural formula wherein X is a functional group which allows cross-linking at its site, and a, b, c, and d are positive integers which are sufficiently large to provide the resin, when measured at 60% resin solids in xylene at 25°C, with a viscosity of 30-50 centipoises, specific gravity of 1.03-1.2, and refractive index of 1.45-1.57; and having a silanol content above 4% based on the weight of the resin;
(2) 5-50% by weight, based on the weight of the binder, of a fluorocarbon polymer; and (3) 2-40% by weight, based on the weight of the binder, of an epoxy resin having the formula wherein n is an integer from 0-42, and R is an alkylene group of 1-4 carbon atoms;
(b) 0.2-10% by weight, based on the weight of the binder, of a silicone fluid which is a dimethyl polysiloxane fluid having a viscosity of 50-5000 centistokes measured at 25°C;
(c) a finely divided inorganic hardening agent in a hardening agent to binder ratio of about 5/100 to 400/100; and (d) an inert liquid carrier.
(a) a binder comprised of (1) 40-93% by weight, based on the weight of the binder, of a silicone resin which is a heat curable structured methylphenyl poly-siloxane resin having the repeating structural formula wherein X is a functional group which allows cross-linking at its site, and a, b, c, and d are positive integers which are sufficiently large to provide the resin, when measured at 60% resin solids in xylene at 25°C, with a viscosity of 30-50 centipoises, specific gravity of 1.03-1.2, and refractive index of 1.45-1.57; and having a silanol content above 4% based on the weight of the resin;
(2) 5-50% by weight, based on the weight of the binder, of a fluorocarbon polymer; and (3) 2-40% by weight, based on the weight of the binder, of an epoxy resin having the formula wherein n is an integer from 0-42, and R is an alkylene group of 1-4 carbon atoms;
(b) 0.2-10% by weight, based on the weight of the binder, of a silicone fluid which is a dimethyl polysiloxane fluid having a viscosity of 50-5000 centistokes measured at 25°C;
(c) a finely divided inorganic hardening agent in a hardening agent to binder ratio of about 5/100 to 400/100; and (d) an inert liquid carrier.
2. The coating composition of claim 1 wherein the binder is comprised of (a) 65-85% by weight, based on the weight of the binder, silicone resin, (b) 10-20% by weight, based on the weight of binder, fluorocarbon polymer; and (c) 5-15% by weight, epoxy resin.
3. The coating composition of claim 2 comprised of 1-3% by weight, based on the weight of the binder, silicone fluid; and hardening agent in a hardening agent to binder ratio of about 10/100 to about 70/100.
4. The coating composition of claim 1 wherein the silicone resin has a silanol content above 5%, based on the weight of the resin, softening point of about 75-88°C; and, when measured at 60% resin solids in xylene at 25°C, a viscosity of about 35-45 centipoise, specific gravity of about 1.05-1.12, and refractive index of about 1.50-1.53.
5. The coating composition of Claim 1 wherein the fluorocarbon polymer is a copolymer of tetrafluoro-ethylene and hexafluoropropylene.
6. The coating composition of claim 1 wherein the epoxy resin is a liquid having a viscosity of 1.2-225 poises at 25°C, and an epoxy equivalent of 150-470; and wherein n is an integer from 0-3 and R is isopropylidene
7. The coating composition of claim 1 wherein the silicone fluid has a viscosity at 25°C of about 500-1500 centistokes.
8. The coating composition of claim 1 wherein the hardening agent is an alumina.
9. The coating composition of claim 1 containing pigment in a pigment to binder ratio of about 1/100 to about 400/100; and a wetting agent in a concentration of 0.2-10% by weight, based on the weight of the binder.
10. The coating composition of claim 1 wherein (a) the binder is comprised of (1) 65-85% by weight, based on the weight of the binder, of a silicone resin having (a) silanol content above 5% based on the weight of the resin, (b) softening point of about 75-85°C, and (c) when measured at 60% resin solids in xylene viscosity of about 35-45 centi-poises, specific gravity of about 1.05-1.112, and refractive index of about 1.50-1.53;
(2) 10-20% by weight, based on the weight of the binder of fluorocarbon polymer which is a copolymer of tetrafluoroethylene and hexafluoropropylene; and (3) 5-15%, by weight, based on the weight of the binder, of liquid epoxy resin having a viscosity of 1.2-225 poise at 25°C, and an epoxy equivalent of 150-470; and wherein n is an integer from 0-3 and R is isopropylidene;
(b) 1-3% by weight based on the weight of the binder of a silicone fluid having a viscosity of 500-1500 at 25°C;
(c) hardening agent which is alumina in a hardening agent to binder ratio of about 10/100-70/100;
(d) pigment in a pigment to binder ratio of about 1/100 to about 400/100;
(e) wetting agent in a concentration of 0.2-10%
by weight, based on the weight of the binder; and (f) inert liquid carrier.
(2) 10-20% by weight, based on the weight of the binder of fluorocarbon polymer which is a copolymer of tetrafluoroethylene and hexafluoropropylene; and (3) 5-15%, by weight, based on the weight of the binder, of liquid epoxy resin having a viscosity of 1.2-225 poise at 25°C, and an epoxy equivalent of 150-470; and wherein n is an integer from 0-3 and R is isopropylidene;
(b) 1-3% by weight based on the weight of the binder of a silicone fluid having a viscosity of 500-1500 at 25°C;
(c) hardening agent which is alumina in a hardening agent to binder ratio of about 10/100-70/100;
(d) pigment in a pigment to binder ratio of about 1/100 to about 400/100;
(e) wetting agent in a concentration of 0.2-10%
by weight, based on the weight of the binder; and (f) inert liquid carrier.
11. A cooking vessel having its food-contacting surface coated with a film produced by curing the coating composition of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US05/871,698 US4121000A (en) | 1976-03-05 | 1978-01-23 | Coating composition comprising a polysiloxane resin-forming precondensate, a fluorocarbon polymer, an epoxy resin, a silicone fluid, and an inorganic hardening agent |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66423376A | 1976-03-05 | 1976-03-05 | |
| US664,233 | 1976-03-05 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1092742A true CA1092742A (en) | 1980-12-30 |
Family
ID=24665158
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA272,978A Expired CA1092742A (en) | 1976-03-05 | 1977-03-02 | Coating composition comprising a silicone resin, a fluorocarbon polymer, an epoxy resin, a silicone fluid, and an inorganic hardening agent |
Country Status (3)
| Country | Link |
|---|---|
| CA (1) | CA1092742A (en) |
| FR (1) | FR2343036A1 (en) |
| GB (1) | GB1577649A (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0003760B1 (en) * | 1978-02-02 | 1982-09-15 | E.I. Du Pont De Nemours And Company | Article suitable for use as bakeware with multi-layer nonstick coating |
| FR2581649B1 (en) * | 1985-05-10 | 1987-08-28 | Seb Sa | NON-STICK COATING FOR A PLASTIC MATERIAL, CULINARY CONTAINER HAVING SUCH A COATING AND METHOD FOR APPLYING THIS COATING ON A MEDIUM |
| FR2643806B1 (en) * | 1989-03-01 | 1994-07-08 | Seb Sa | BOTTLE COOKING CONTAINER COATED WITH SILICONE RESIN |
| EP1835002B1 (en) * | 2006-03-14 | 2014-07-23 | Cerasol Hong Kong Limited | Non-stick ceramic coating composition and process |
| CN107964329B (en) * | 2017-10-20 | 2019-12-24 | 浙江亘元涂料科技有限公司 | Production method of high-temperature-resistant non-stick coating |
| CN115052941A (en) * | 2020-02-07 | 2022-09-13 | Ppg工业俄亥俄公司 | Coating composition |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL222072A (en) * | 1956-11-16 | Union Chimique Belge Sa | ||
| US3801522A (en) * | 1971-12-17 | 1974-04-02 | Du Pont | Coating composition of a silicone fluid,a silicone resin and a zirconium silicate hardening agent |
| US4066817A (en) * | 1976-03-10 | 1978-01-03 | The Dexter Corporation | Release coating for aluminum and tinplate steel cookware |
-
1977
- 1977-03-02 CA CA272,978A patent/CA1092742A/en not_active Expired
- 1977-03-04 FR FR7706490A patent/FR2343036A1/en active Granted
- 1977-03-04 GB GB920177A patent/GB1577649A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| GB1577649A (en) | 1980-10-29 |
| FR2343036A1 (en) | 1977-09-30 |
| FR2343036B1 (en) | 1982-05-21 |
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