CA1105165A - Fluoropolymer finishes having improved scratch resistance - Google Patents
Fluoropolymer finishes having improved scratch resistanceInfo
- Publication number
- CA1105165A CA1105165A CA257,230A CA257230A CA1105165A CA 1105165 A CA1105165 A CA 1105165A CA 257230 A CA257230 A CA 257230A CA 1105165 A CA1105165 A CA 1105165A
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- Canada
- Prior art keywords
- composition
- total
- polymer
- methyl methacrylate
- acid
- Prior art date
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- Expired
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-
- 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
- C09D127/00—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 a halogen; Coating compositions based on derivatives of such polymers
- C09D127/02—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment
- C09D127/12—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 a halogen; Coating compositions based on derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/14—Carbides
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/34—Silicon-containing compounds
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
- C08L27/02—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L27/12—Compositions of 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 a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
-
- 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
-
- 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
- C08L33/062—Copolymers with monomers not covered by C08L33/06
- C08L33/066—Copolymers with monomers not covered by C08L33/06 containing -OH groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Cookers (AREA)
- Frying-Pans Or Fryers (AREA)
Abstract
ABSTRACT OF THE DISCLOSURE
Compositions containing (a) fluoropolymer, (b) mica particles, mica particles coated with pigment, or metal flake, (c) a polymer of ethylencially unsaturated monomers and (d) a liquid carrier are useful for coating metal, especially cookware, to give lubricious surfaces.
Compositions containing (a) fluoropolymer, (b) mica particles, mica particles coated with pigment, or metal flake, (c) a polymer of ethylencially unsaturated monomers and (d) a liquid carrier are useful for coating metal, especially cookware, to give lubricious surfaces.
Description
Cookware coated wit~ :~luoropolg~ae~3~ esp~cially pol~tra~luoxoethylene (PTFE) ~ has csme in~o w~despxead us~
~ re~ent year~ cook~ prefer to u8e~ ~3uch cOOk:~a~8 be-ca.~e o~ lts non~t~ck propertie~ and becau~e i~ o ~a~y to cle~.
Nhi:Le cookware o~ thi~ type 13 quit~ d~lrable,, the fluoropol~mor coal;in~3: t~nas to become ~cratch~d ag~ter ~e~de~
u~e becau~e i~ ~ 80m8Wh~Lt ~o~t~r than the utell~ils u~ed to 10 stir and tur~ the ~o~d in the ware.
~U~ Opl ~E I~ TION
I~ has now been ~ound that th~ scratch res~sta~ce o~
. ~ ~luo~opoly~er coa~ can be ~r~v~. i~ th~ CoD~?~si~ion ~ro~
which t~e ~s:~at~g ~5 der~ed compr~ses luoxopol~mer~
(~) m~cai p~cle i m:Lca p~icleg coated with plgme~tg. or metal ~Iak~, ~c) a po~me~ o~ ~onoeth~le~ca~ atuxate~
~on~er~ ~i;ch depo~er~ze~ and ~aporizes ~0 a~ ~out th~ ~luoropolymer~ fusion temperatlare5, a~d (d~ a liquid ca~ri.e~, Such ~ coating ~:Lso hs~ ~xcelle~ crack re~ista~ce ~d bl~3~r resi3ta~c~,~ and ha~ a~the~icaIly plea~ing a~pear~n~e..
:~ :
- . . . ..
.
.
P$~
~*3~
~ e ~luoropoly~er~ used; in the compo3itions o~ t~e in~re~tion are homspolymers a~d copolymea~ (meaning the polymer conta~ two or more d:~fere~ monomer ~t~) o~ monoet~
le~ical:L~ unsatuxate~ h~drocar~o~ mon~mers compl~ y 3ubst~-tut~ ~th ~luorin~ atom~ or co~pletely ~ubstitu~ed ~ith a combirlation of ~luorine a~om~ and chlor~n~ atom~. In~_luded in thi~ group are per:eluorolerin pol~7mers ~uch ~ polytetra:eluoro-ethyl~n~ a~ copoly~era o~ t~tra~luoroethyle~e ~n~ hexa~laoro-propylene in all monomer unit we~ght ratio~ ~luorochloxocarbonpolymers uch as polymonochlorotri~luoroethyle~e,. and the norfflally solid copol~mers of tetr ~luoroethylene and perfluoro-~lkyl vinyl e~hers (wherein the alkyl ~roup is o~ 1-5 carbon atom~). M~ture~ of the~e can also be u~e~.. P~FE is pre~erred ~or its thermal stab~l~ty.
~ The ~luoropolymar~u~ed 1~ partlc~late. The p~rtlcle~
ar~ pr~ferabl~ ~ ~ enough to pas~ through the no2æle o~
spr~y g~ wlthou~- clog~ng i~ 2n~ ~re ~l~o ~m~ll e~ough to g~a the re~ultin~ ~ilm ~te~rit~.
2Q The-Pluoropolym~r p~e~s~a~ly ~a~ ~ ~umher ar~r~ge molecul~r ~eigh~ o~ ~t l~a~t sbou~ 20~0~ eYe~ more pre~rab~y ~~~lea~ about 2~0~00 ~ b~cau~e su~h ~luoropo1y~ers~~~hax~er ~ini~h~s.. Nu~e~ aYer~e ~olecular ~elg~t o~ P~F~ easurod : b~ ~h~ethod aesc:~lbe~ by Su~, Tskehl~a &~d Machi ~n Journal olu~e 179 pp~. 325~-3257 ~lg73)~
The ~u~b~r a~erage~mol uIar weigh~ o~ ~ te~ra~luoroeth~len~
; hexa~luoroprop~lene copoly~er iæ~me~sured by ~rst determinlng .
i~* mèlt ~lo~r rate (~) accord~ng tQ AST~ D21l6, u~i~ the MFR ~:~
to dete~ni2l~ ;melt ~i~Go3ity (MV) accordl~g to the equation , ~ 1?~ ;~ pr~3~ur~ u~ed. (mm) ac or~i.c~ radi~
an~ then d~te~l~g moleculaE ~eight (MW) accord~g ~v the e~uation \ 3~4/ 3~V
6 ~ lQ ~
~lmiber average mol~cul~ ~reight o~ a ~luo:roch:loroc~r~on poly m~r 1~ measured by ASTM D1~30..
Although a po~de~ o~ ~luoropslymer can be u~ed ~d a c~r~er provided Se!!paratel9`3 a polymer in th~ ~O~D o~ an aqueous dlsp~rsiorl i~ pr~erred ~or i~s s~abllity and b~cau~e 10 it is most eas~r ob~ained ~ that ~rm.
~ he ~luoropolymer is ordillar~ly pr~nt ~ the compo~$-ti.o~ a~- a concentrat~on G:~ abou~ 80 9~ , pre~rabl5~ about 85-982~ by Me~ o~ ~he total ol~ ~luoropol~mer ~ iC~L parti-Cl~r mic~ ~ert~cl ~-co~l~c~ ~el- p~gmen~g or ~o~al ~ke.
e 3~ic~ p~lcles.~ 60~edL mica par~icle~- ~d metal ~ke us~ i~ the com~os~tlons o~ the t~entio~ ean b~ an~ Or . tho~e ~ilable~ comm~rci~ly. The~ partic~s~ e~ ~a an averag~ 10~Jt di~en~lors o~ lO to l~0 ~rons; pro~erab3~r 15-~0 m~crons~. ~lth no p~ticles or ~ e~ h~ ~ longe~t 20 dinension o~e ~or~ t~ about 200 ~crons~ Partlcle and ~lake ~iz~ ~ m~a~ured o~p~cally ga~ ~ 3tandard..
T`he :m~c~ part~c~e~ coatedt ~rith pi~e~t pre~erred ~or use are ~hose d~scr~b~d ~ U,S. Pat~t ~,087,827~ to KIenke and Sbratton~ and U~ Paterlt~ 33087,828 asld~ 3,087,829~ to Iinton~
T~e d~closure~ o~ the~ pat~t~ are lncorporated i~to this ~ ` , ' .
~ ~ ~ : 4 _ , , .
.,: . ~- . ' - . . .
3p~C :Eication to d~scr~b~ th~ ~rar~ou~ coalte~ ~ic~ ho~
~hey are prepared~ ~
The mlca~ described in thes~ patents are coated ~h o~ des .or hydrou~ oxides of tita~itIm, zir~o~i~, aluminum~
:~inc, ant~ony~ tirl, iron~ copper, ~cl~el, cobalt~ chrom7~m or Y~rladium. Tltanium dioxide coated mica ls pre~erred beca~e o~ ~t~ &vai:Lab1lity.. MiX~ !8 oi~ coa~ed mica~ c~
also be u~ed~
Repres~ntati~r~ OI the metal fla~e whi.ch can b2 u3ed 10 are alumlnum ~lake, ~tainl~s ste~ ke,~ nickel fïake and bronze flake~ cture~ of flake can ~lso be u~ed.
The mica9 coated mi a or metal ~laks i~ ordinar~ly pre~ent i~ a compo~ition o~ the invention at a concentration o~ about 0,,2-2~, by weight o~ the t~tal OI ~luoropolymer and mica~ coated m~c~ or metal ~la~se, pre~erabl~ about 2 15~6, e~en more pre~era,bly about 8~
T~ polymer o~ morloeth~lenicall~ un~lLrated mono-mers usea in the compo~ltlon~ o~ th~ e~ltio~ c~ be any ~olymer or copolymer (in th~ ~en~e of bei2lg compo~ed o~ two or 20 more type~s of monomer~) o~ ~thyl~n~cally- uIlsat~r~ed motlomer~
whic~ à~oly~eriæ~ ~d who$~ depol~n~r~zation products Y~por-~:Z:~3 in the temperatux ~ r~ge o~ ~rom abou~ 150 0C . belo~ the ~ion temper~eure o~ the ~luoropolgmer used to about the ~luoropolymer ' s decompo~ tion t~erature . The closer th~
depo~rmeriæat~on a~d vapQr~za.t~on t~mperature~ are to th~
fluoropolymert~ f~on te~per~ure, the bette~.
'rDepoly~.erization'r m~s d~gradation of th~ polymer to the polnt at ~hich the degradatio~ products are volat~l~
at ~he t;emp~ratures ~ncountered ~n curing the Ilnal ~llm;
3 T~e~e d~;radatio~ product~ can be mollom~r~9 dim~rs or ollgomer~.
~ 5 --~5~5 '1Vaporize" means volatilization o~ the degrada~ion product~ and their evaporation ~rom the film. Ideally, all o~ the degradation products pass ~rom the film, but as a practical matter, a small but ins:Lgn~ficant amount generally remains.
Illustrative o~ the.pol~mers which can be used are polymers o~ monoethylenically unsatura~ed monomers which con-tain one or more mono~th~lenically unsaturat~d acid ~lit~.
Representati~ o~ these monoethylenically unsaturated monomers are alkyl acrylates and methacrylates hav~ng 1-8 carbon atoms ~n the alkyl group, styrene, a-methyl styr~ne, vinyl toluene and glycldyl esters o~ 4-14 carbon atoms. Re-presentative of the monoethylenically unsakurated ~cid~ are acrylic acid, methacrylic acid~ fumaric acid, itaconic acid and maleic acid (or anhydride), Mixtures of these polymers can also be used~
Pre~erred ~or the denslt~ a~d g10SB 0~ the ~inishes obtain~d when ~hey are used are the polymers of alXyl acrylates~
alkyl methacr~lates~ acrylic acid, methacrylic acid and a glycidyl ester sold by Shell Chemical Company as "Cardura E' ester, which i~ a mixed ester o~ the general ~ormula : :
: ~ ~ \ / R~
H2C - CH - C~2 - 0 - C - C - R2 where Rl i~ CH3 and :, :
~ . . . . - . - .
' ~, , JJ~
and ~3 are lo~er alkyl groups 3 Rl, ~ and R3 containing a total o~
7-9 carbon atoms.
The polymers ~pec~ally pre~erred for the ~ame rea~on~ ar~
1. methyl methacrylate/2-ethylhexyl acryl~te/
methacryllc acid ~erpolymer~, pre~0rably ~h~
40 50/48-52/1-4 (wei~hk ratio) terpolym~r~;
~ re~ent year~ cook~ prefer to u8e~ ~3uch cOOk:~a~8 be-ca.~e o~ lts non~t~ck propertie~ and becau~e i~ o ~a~y to cle~.
Nhi:Le cookware o~ thi~ type 13 quit~ d~lrable,, the fluoropol~mor coal;in~3: t~nas to become ~cratch~d ag~ter ~e~de~
u~e becau~e i~ ~ 80m8Wh~Lt ~o~t~r than the utell~ils u~ed to 10 stir and tur~ the ~o~d in the ware.
~U~ Opl ~E I~ TION
I~ has now been ~ound that th~ scratch res~sta~ce o~
. ~ ~luo~opoly~er coa~ can be ~r~v~. i~ th~ CoD~?~si~ion ~ro~
which t~e ~s:~at~g ~5 der~ed compr~ses luoxopol~mer~
(~) m~cai p~cle i m:Lca p~icleg coated with plgme~tg. or metal ~Iak~, ~c) a po~me~ o~ ~onoeth~le~ca~ atuxate~
~on~er~ ~i;ch depo~er~ze~ and ~aporizes ~0 a~ ~out th~ ~luoropolymer~ fusion temperatlare5, a~d (d~ a liquid ca~ri.e~, Such ~ coating ~:Lso hs~ ~xcelle~ crack re~ista~ce ~d bl~3~r resi3ta~c~,~ and ha~ a~the~icaIly plea~ing a~pear~n~e..
:~ :
- . . . ..
.
.
P$~
~*3~
~ e ~luoropoly~er~ used; in the compo3itions o~ t~e in~re~tion are homspolymers a~d copolymea~ (meaning the polymer conta~ two or more d:~fere~ monomer ~t~) o~ monoet~
le~ical:L~ unsatuxate~ h~drocar~o~ mon~mers compl~ y 3ubst~-tut~ ~th ~luorin~ atom~ or co~pletely ~ubstitu~ed ~ith a combirlation of ~luorine a~om~ and chlor~n~ atom~. In~_luded in thi~ group are per:eluorolerin pol~7mers ~uch ~ polytetra:eluoro-ethyl~n~ a~ copoly~era o~ t~tra~luoroethyle~e ~n~ hexa~laoro-propylene in all monomer unit we~ght ratio~ ~luorochloxocarbonpolymers uch as polymonochlorotri~luoroethyle~e,. and the norfflally solid copol~mers of tetr ~luoroethylene and perfluoro-~lkyl vinyl e~hers (wherein the alkyl ~roup is o~ 1-5 carbon atom~). M~ture~ of the~e can also be u~e~.. P~FE is pre~erred ~or its thermal stab~l~ty.
~ The ~luoropolymar~u~ed 1~ partlc~late. The p~rtlcle~
ar~ pr~ferabl~ ~ ~ enough to pas~ through the no2æle o~
spr~y g~ wlthou~- clog~ng i~ 2n~ ~re ~l~o ~m~ll e~ough to g~a the re~ultin~ ~ilm ~te~rit~.
2Q The-Pluoropolym~r p~e~s~a~ly ~a~ ~ ~umher ar~r~ge molecul~r ~eigh~ o~ ~t l~a~t sbou~ 20~0~ eYe~ more pre~rab~y ~~~lea~ about 2~0~00 ~ b~cau~e su~h ~luoropo1y~ers~~~hax~er ~ini~h~s.. Nu~e~ aYer~e ~olecular ~elg~t o~ P~F~ easurod : b~ ~h~ethod aesc:~lbe~ by Su~, Tskehl~a &~d Machi ~n Journal olu~e 179 pp~. 325~-3257 ~lg73)~
The ~u~b~r a~erage~mol uIar weigh~ o~ ~ te~ra~luoroeth~len~
; hexa~luoroprop~lene copoly~er iæ~me~sured by ~rst determinlng .
i~* mèlt ~lo~r rate (~) accord~ng tQ AST~ D21l6, u~i~ the MFR ~:~
to dete~ni2l~ ;melt ~i~Go3ity (MV) accordl~g to the equation , ~ 1?~ ;~ pr~3~ur~ u~ed. (mm) ac or~i.c~ radi~
an~ then d~te~l~g moleculaE ~eight (MW) accord~g ~v the e~uation \ 3~4/ 3~V
6 ~ lQ ~
~lmiber average mol~cul~ ~reight o~ a ~luo:roch:loroc~r~on poly m~r 1~ measured by ASTM D1~30..
Although a po~de~ o~ ~luoropslymer can be u~ed ~d a c~r~er provided Se!!paratel9`3 a polymer in th~ ~O~D o~ an aqueous dlsp~rsiorl i~ pr~erred ~or i~s s~abllity and b~cau~e 10 it is most eas~r ob~ained ~ that ~rm.
~ he ~luoropolymer is ordillar~ly pr~nt ~ the compo~$-ti.o~ a~- a concentrat~on G:~ abou~ 80 9~ , pre~rabl5~ about 85-982~ by Me~ o~ ~he total ol~ ~luoropol~mer ~ iC~L parti-Cl~r mic~ ~ert~cl ~-co~l~c~ ~el- p~gmen~g or ~o~al ~ke.
e 3~ic~ p~lcles.~ 60~edL mica par~icle~- ~d metal ~ke us~ i~ the com~os~tlons o~ the t~entio~ ean b~ an~ Or . tho~e ~ilable~ comm~rci~ly. The~ partic~s~ e~ ~a an averag~ 10~Jt di~en~lors o~ lO to l~0 ~rons; pro~erab3~r 15-~0 m~crons~. ~lth no p~ticles or ~ e~ h~ ~ longe~t 20 dinension o~e ~or~ t~ about 200 ~crons~ Partlcle and ~lake ~iz~ ~ m~a~ured o~p~cally ga~ ~ 3tandard..
T`he :m~c~ part~c~e~ coatedt ~rith pi~e~t pre~erred ~or use are ~hose d~scr~b~d ~ U,S. Pat~t ~,087,827~ to KIenke and Sbratton~ and U~ Paterlt~ 33087,828 asld~ 3,087,829~ to Iinton~
T~e d~closure~ o~ the~ pat~t~ are lncorporated i~to this ~ ` , ' .
~ ~ ~ : 4 _ , , .
.,: . ~- . ' - . . .
3p~C :Eication to d~scr~b~ th~ ~rar~ou~ coalte~ ~ic~ ho~
~hey are prepared~ ~
The mlca~ described in thes~ patents are coated ~h o~ des .or hydrou~ oxides of tita~itIm, zir~o~i~, aluminum~
:~inc, ant~ony~ tirl, iron~ copper, ~cl~el, cobalt~ chrom7~m or Y~rladium. Tltanium dioxide coated mica ls pre~erred beca~e o~ ~t~ &vai:Lab1lity.. MiX~ !8 oi~ coa~ed mica~ c~
also be u~ed~
Repres~ntati~r~ OI the metal fla~e whi.ch can b2 u3ed 10 are alumlnum ~lake, ~tainl~s ste~ ke,~ nickel fïake and bronze flake~ cture~ of flake can ~lso be u~ed.
The mica9 coated mi a or metal ~laks i~ ordinar~ly pre~ent i~ a compo~ition o~ the invention at a concentration o~ about 0,,2-2~, by weight o~ the t~tal OI ~luoropolymer and mica~ coated m~c~ or metal ~la~se, pre~erabl~ about 2 15~6, e~en more pre~era,bly about 8~
T~ polymer o~ morloeth~lenicall~ un~lLrated mono-mers usea in the compo~ltlon~ o~ th~ e~ltio~ c~ be any ~olymer or copolymer (in th~ ~en~e of bei2lg compo~ed o~ two or 20 more type~s of monomer~) o~ ~thyl~n~cally- uIlsat~r~ed motlomer~
whic~ à~oly~eriæ~ ~d who$~ depol~n~r~zation products Y~por-~:Z:~3 in the temperatux ~ r~ge o~ ~rom abou~ 150 0C . belo~ the ~ion temper~eure o~ the ~luoropolgmer used to about the ~luoropolymer ' s decompo~ tion t~erature . The closer th~
depo~rmeriæat~on a~d vapQr~za.t~on t~mperature~ are to th~
fluoropolymert~ f~on te~per~ure, the bette~.
'rDepoly~.erization'r m~s d~gradation of th~ polymer to the polnt at ~hich the degradatio~ products are volat~l~
at ~he t;emp~ratures ~ncountered ~n curing the Ilnal ~llm;
3 T~e~e d~;radatio~ product~ can be mollom~r~9 dim~rs or ollgomer~.
~ 5 --~5~5 '1Vaporize" means volatilization o~ the degrada~ion product~ and their evaporation ~rom the film. Ideally, all o~ the degradation products pass ~rom the film, but as a practical matter, a small but ins:Lgn~ficant amount generally remains.
Illustrative o~ the.pol~mers which can be used are polymers o~ monoethylenically unsatura~ed monomers which con-tain one or more mono~th~lenically unsaturat~d acid ~lit~.
Representati~ o~ these monoethylenically unsaturated monomers are alkyl acrylates and methacrylates hav~ng 1-8 carbon atoms ~n the alkyl group, styrene, a-methyl styr~ne, vinyl toluene and glycldyl esters o~ 4-14 carbon atoms. Re-presentative of the monoethylenically unsakurated ~cid~ are acrylic acid, methacrylic acid~ fumaric acid, itaconic acid and maleic acid (or anhydride), Mixtures of these polymers can also be used~
Pre~erred ~or the denslt~ a~d g10SB 0~ the ~inishes obtain~d when ~hey are used are the polymers of alXyl acrylates~
alkyl methacr~lates~ acrylic acid, methacrylic acid and a glycidyl ester sold by Shell Chemical Company as "Cardura E' ester, which i~ a mixed ester o~ the general ~ormula : :
: ~ ~ \ / R~
H2C - CH - C~2 - 0 - C - C - R2 where Rl i~ CH3 and :, :
~ . . . . - . - .
' ~, , JJ~
and ~3 are lo~er alkyl groups 3 Rl, ~ and R3 containing a total o~
7-9 carbon atoms.
The polymers ~pec~ally pre~erred for the ~ame rea~on~ ar~
1. methyl methacrylate/2-ethylhexyl acryl~te/
methacryllc acid ~erpolymer~, pre~0rably ~h~
40 50/48-52/1-4 (wei~hk ratio) terpolym~r~;
2~ butyl acrylat~/meth~l m~thacrylat~/CARDURA E*/
acryllc acid qu~dripolymers3 pre~rably the 23-27/33-37/21-25/15-19 quadr~polymers;
ætyrene/methyl ~ethacrylate/CA~DURA E/
acr~lic aci~ ~uadrlp~lymers, p~Per~bly the 28-32/~-32/21-25/15-19 quadrlp~lymer~;
4. methyl methacrylate/ethyl acryl~te/methacrylic ;~ acid terpolymers~ pre~erably the 37-41~55-59/1-6 terpol~mer~.
; Such a polymer ~s ordlnarily prese~t in a comp~s~-- tion ~ the l~vention at a conce~tr~ti~n o~ a~ouk 2-3Q0~ by weight o~ the ~luoropQlymer, preferabl~ about 5-20%, I~
can be made by any ~ the conventional free-radical techni-que3 famlllar to any polym~r chemist~ :
~ The carrier used in the co~position o~ the ln~e~tlo~
; ca~ be any o~ ~ho~e normally used 1~ e~mp~sitio~ of this ty~O
It is a~ lnert, n~t a reac~lve or functlon~ the sense of * denotes trade olark ~ .
~ ' .:~
- ' .~
.
contributing to the w~rking c~ the inve~tt on ) component and it~ nature i~ the~e~ore o~ secondary importance. The carrier ser~e~ only to keep th~ composition homogerleou~ and a~ts as a mecha~ or convey~ the ~olid cos~ponent~ to the sub~tr~te.
er a coat~g ha~ been deposited, the carrier e~aporate~.
It i~ nece~ary., there:eore~ only 1;hat lt be compatlble wikh the other component~ o~ the compo~l;tivn and that it ~ re no ad~rerse e~ect~ on the coat~g it~eli~
Co~only, the ~luorocar~on pol~mer u~ed in the 10 composit;ion i~ provid~d i21 the ~oxm of` a~ aqu~ous di3persion, and the wster introduced into th~ compo~ltion wi.th the polymer also ser~e~ ~s ~11. or as part of the carrler for khe composi-tion ~ Organic l:iquid~ such as alcohols ~ ketone~, aliphatic and a~omatic h;ydrocarbons, or mix~ures o~ theseJ ca2l also be used ., The composl~ion~ o~ the i~vention c~n ~lso con~ain such convent~orlal additiv~s a~3~ flow control agen~3. sur-~cta~t~a~d p:La~tic~zer~ as are nece~sar~r or 3eem de~able~. .
rhese add~t~v~ are added for the usual re~oIl~, in the usu~l 20 ~ ~d in the usu~ aou~s.
The ~mou~t oi~ ~otal solld~ in the coat~g compost-tions will be gover2~ed by the substPate to wh~ch the compos~;
tlon~ to be applied,, the method o~ appllcation" the curlng procedura~, a~d like ~actor~ the usual ca e, the composi-tio~ 1 contain ~bout lO-80%~ by welght, o~ solids, - The compos~tio~s can be made b~ ~lmply mixing together appropriate amounts o~ th~ proper compone2~ts. Pigmerlts ean be added, 1:1~ th;~ ~s desired, by ~irst conventlonally preparing : ' .
a suitable pigment dispersion and then adding this dispersi.on to the compo 8 ition.
The composltions can be applied in any o~ the usual ways. Spraying, roller-coating, dippingg doctor-blading --all are suitable, although spraying is generally the method of choice. The article to be coated is preferably pretreated by grit~blasting, by the flame-spraying of metals or by frit-coating. The article is then primed with a compositlon of`
the type disclosed in U S. Patent 3,655~604 or 3,694,392.
In a preferred embodiment the priming procedure is as ~ollows:
1. The ~ollowing were mixed together:
PTFE dispersion 478.76 parts aqueous, 60~ solids Deionized water 130.23 parts Colloidal silica sol,327.18 par~s 30~ solids in water (LUDQX AM* colloidal silica~ E.I. du Pont de Nemours and Company) 2. The following were separately mixed:
TRITON X-100* 17.52 parts (Non-ionic sufactant sold by Rohm & Haas Co.) Toluene 31~ ~6 parts Butyl carbitol 13.36 parts Silicone 34.56 parts (Dow Corni~g DC-8O1J
60% solids in x~lene) 85.52 part~ o~ (2) were added to (1) in a small stream, with stirring, over a 2-3 minute period. To this were then added, with stirring, * denotes trade mark , .
TiO2 (45% sollds disperslon35.46 parts in water3 Channel black (22~ solicls0.85 parts dispersion in water) Stirring was continued ~or 10-20 minutes. The resultlng composition was then sprayed to a frit coated alumlnum fry pan to a thickness o~ 0.2-0,6 mil (dry) and dried in air.
The coating compositions of the invention are ordin~rily applied to a thickness of about 20-30 microns (dry) and the coated article is then baked at a tempera-ture and for a time sufficient to fuse the fluoropolymer used.
The compositions o~ the invention are most useful for coating met~l cookware, especiall~ frypans, but the compositions can also be used to coat other articles requiring scratch resistant fluoropolymer coatings.
These other articles can be made of glass or any other mater-lal capable of withstanding the baking temperatures used.
For example, the compositions can be used to coat bearings~
valves, wire, metal foil, boilers9 pipesJ ship bottoms, oven liners, irorl soleplates~ waffle irons, ice cube trays, snow shovels a~d plows~ chutes, conveyors, dies, tools such ~-as saws, files and drills 9 hoppers and other industrial containers and mcilds. ~ ~--- .
,
acryllc acid qu~dripolymers3 pre~rably the 23-27/33-37/21-25/15-19 quadr~polymers;
ætyrene/methyl ~ethacrylate/CA~DURA E/
acr~lic aci~ ~uadrlp~lymers, p~Per~bly the 28-32/~-32/21-25/15-19 quadrlp~lymer~;
4. methyl methacrylate/ethyl acryl~te/methacrylic ;~ acid terpolymers~ pre~erably the 37-41~55-59/1-6 terpol~mer~.
; Such a polymer ~s ordlnarily prese~t in a comp~s~-- tion ~ the l~vention at a conce~tr~ti~n o~ a~ouk 2-3Q0~ by weight o~ the ~luoropQlymer, preferabl~ about 5-20%, I~
can be made by any ~ the conventional free-radical techni-que3 famlllar to any polym~r chemist~ :
~ The carrier used in the co~position o~ the ln~e~tlo~
; ca~ be any o~ ~ho~e normally used 1~ e~mp~sitio~ of this ty~O
It is a~ lnert, n~t a reac~lve or functlon~ the sense of * denotes trade olark ~ .
~ ' .:~
- ' .~
.
contributing to the w~rking c~ the inve~tt on ) component and it~ nature i~ the~e~ore o~ secondary importance. The carrier ser~e~ only to keep th~ composition homogerleou~ and a~ts as a mecha~ or convey~ the ~olid cos~ponent~ to the sub~tr~te.
er a coat~g ha~ been deposited, the carrier e~aporate~.
It i~ nece~ary., there:eore~ only 1;hat lt be compatlble wikh the other component~ o~ the compo~l;tivn and that it ~ re no ad~rerse e~ect~ on the coat~g it~eli~
Co~only, the ~luorocar~on pol~mer u~ed in the 10 composit;ion i~ provid~d i21 the ~oxm of` a~ aqu~ous di3persion, and the wster introduced into th~ compo~ltion wi.th the polymer also ser~e~ ~s ~11. or as part of the carrler for khe composi-tion ~ Organic l:iquid~ such as alcohols ~ ketone~, aliphatic and a~omatic h;ydrocarbons, or mix~ures o~ theseJ ca2l also be used ., The composl~ion~ o~ the i~vention c~n ~lso con~ain such convent~orlal additiv~s a~3~ flow control agen~3. sur-~cta~t~a~d p:La~tic~zer~ as are nece~sar~r or 3eem de~able~. .
rhese add~t~v~ are added for the usual re~oIl~, in the usu~l 20 ~ ~d in the usu~ aou~s.
The ~mou~t oi~ ~otal solld~ in the coat~g compost-tions will be gover2~ed by the substPate to wh~ch the compos~;
tlon~ to be applied,, the method o~ appllcation" the curlng procedura~, a~d like ~actor~ the usual ca e, the composi-tio~ 1 contain ~bout lO-80%~ by welght, o~ solids, - The compos~tio~s can be made b~ ~lmply mixing together appropriate amounts o~ th~ proper compone2~ts. Pigmerlts ean be added, 1:1~ th;~ ~s desired, by ~irst conventlonally preparing : ' .
a suitable pigment dispersion and then adding this dispersi.on to the compo 8 ition.
The composltions can be applied in any o~ the usual ways. Spraying, roller-coating, dippingg doctor-blading --all are suitable, although spraying is generally the method of choice. The article to be coated is preferably pretreated by grit~blasting, by the flame-spraying of metals or by frit-coating. The article is then primed with a compositlon of`
the type disclosed in U S. Patent 3,655~604 or 3,694,392.
In a preferred embodiment the priming procedure is as ~ollows:
1. The ~ollowing were mixed together:
PTFE dispersion 478.76 parts aqueous, 60~ solids Deionized water 130.23 parts Colloidal silica sol,327.18 par~s 30~ solids in water (LUDQX AM* colloidal silica~ E.I. du Pont de Nemours and Company) 2. The following were separately mixed:
TRITON X-100* 17.52 parts (Non-ionic sufactant sold by Rohm & Haas Co.) Toluene 31~ ~6 parts Butyl carbitol 13.36 parts Silicone 34.56 parts (Dow Corni~g DC-8O1J
60% solids in x~lene) 85.52 part~ o~ (2) were added to (1) in a small stream, with stirring, over a 2-3 minute period. To this were then added, with stirring, * denotes trade mark , .
TiO2 (45% sollds disperslon35.46 parts in water3 Channel black (22~ solicls0.85 parts dispersion in water) Stirring was continued ~or 10-20 minutes. The resultlng composition was then sprayed to a frit coated alumlnum fry pan to a thickness o~ 0.2-0,6 mil (dry) and dried in air.
The coating compositions of the invention are ordin~rily applied to a thickness of about 20-30 microns (dry) and the coated article is then baked at a tempera-ture and for a time sufficient to fuse the fluoropolymer used.
The compositions o~ the invention are most useful for coating met~l cookware, especiall~ frypans, but the compositions can also be used to coat other articles requiring scratch resistant fluoropolymer coatings.
These other articles can be made of glass or any other mater-lal capable of withstanding the baking temperatures used.
For example, the compositions can be used to coat bearings~
valves, wire, metal foil, boilers9 pipesJ ship bottoms, oven liners, irorl soleplates~ waffle irons, ice cube trays, snow shovels a~d plows~ chutes, conveyors, dies, tools such ~-as saws, files and drills 9 hoppers and other industrial containers and mcilds. ~ ~--- .
,
3~
~ followlng example~ lllu~;tr~te the in7Jellt:Lon.
In these e~amples, all part~ and percent~ge~ ~re by weight unless indicated otherwise.
The followlng were mixed~, in the order listed:
( 1 ) PTFE dispers ivn 64 . 9 pa~ts (60% q~lid~ ln water~
TEFLON* Tp~ uorocQrbo~
~sin, Aqueou~ DlspersionJ
T 30, sold by E. I. du Pont de Nemour~ and Compa~
(2) Deionized wa~er 10.5 parts ( 3 ) T102 coated mica 4 . 00 parts (.AFFI AIR* NF- 140-D, sold by :1:. I. du PoIlt de Ne~ours and Compa~y) t4) Red mill base 0.2 part (made by b~ll milling a rQlxture of Red iron o~ide44.9 parts Deionized w~tel~ 33.7 parts Ole~ c acid30 3 part~
Trietha~olamir~e 6 . 7 part~
But~l c~rbitol2 . 9 p~Lrts Toluene 8.5 parts) (5~ A mixture o~
Triethanolamine . 92 part Ol~ic acid ~ 75 part To:Luene 3.48 paxts Bul;yl carbitol 1.3 parts * denotes trade ~Irk .. ~ ,.
' , - ' ' (6~ Methyl methacrylate/ethyl 14 parts acrylate/methacrylic acid 39/57/4 terpolymer disper-sion (40% in water) The resulting compositioll was applied to an aluminum frypan3 which had been fi:rst fritcoated and primed according to the ~referred embodiment of a priming procedure described hereinbefore.
The composition was applied by spraying ts a thick-ness of 25 microns (dry). The coated pan was khen baked for5 minutes at 425C. to give a scratch-resiskant gold fini~h.
Example 2 The procedure of Example 1 was repeated, except that the following were substituted for (3) and (4):
(3) TiO coated mica 4 parts (~FFL~IR NF-154-D
sold by E,I. du Pont de Nemours and Company)
~ followlng example~ lllu~;tr~te the in7Jellt:Lon.
In these e~amples, all part~ and percent~ge~ ~re by weight unless indicated otherwise.
The followlng were mixed~, in the order listed:
( 1 ) PTFE dispers ivn 64 . 9 pa~ts (60% q~lid~ ln water~
TEFLON* Tp~ uorocQrbo~
~sin, Aqueou~ DlspersionJ
T 30, sold by E. I. du Pont de Nemour~ and Compa~
(2) Deionized wa~er 10.5 parts ( 3 ) T102 coated mica 4 . 00 parts (.AFFI AIR* NF- 140-D, sold by :1:. I. du PoIlt de Ne~ours and Compa~y) t4) Red mill base 0.2 part (made by b~ll milling a rQlxture of Red iron o~ide44.9 parts Deionized w~tel~ 33.7 parts Ole~ c acid30 3 part~
Trietha~olamir~e 6 . 7 part~
But~l c~rbitol2 . 9 p~Lrts Toluene 8.5 parts) (5~ A mixture o~
Triethanolamine . 92 part Ol~ic acid ~ 75 part To:Luene 3.48 paxts Bul;yl carbitol 1.3 parts * denotes trade ~Irk .. ~ ,.
' , - ' ' (6~ Methyl methacrylate/ethyl 14 parts acrylate/methacrylic acid 39/57/4 terpolymer disper-sion (40% in water) The resulting compositioll was applied to an aluminum frypan3 which had been fi:rst fritcoated and primed according to the ~referred embodiment of a priming procedure described hereinbefore.
The composition was applied by spraying ts a thick-ness of 25 microns (dry). The coated pan was khen baked for5 minutes at 425C. to give a scratch-resiskant gold fini~h.
Example 2 The procedure of Example 1 was repeated, except that the following were substituted for (3) and (4):
(3) TiO coated mica 4 parts (~FFL~IR NF-154-D
sold by E,I. du Pont de Nemours and Company)
(4) Mill base (made by ball milling a ~ mixture Or : Deionized water ~5 par~s C~balt oxide blue 45 parts) The resulting composition was applied to a frit coated, primed aluminum frypan, as in Example 1, to give a scratch resistant silver finish.
- ' ~E3 ' . .
~e~
The following were mix~d, in the srdel listed:
(1) PT~E di~per~l~n ~ Example 1 69.7 parts (2) D~ionized water 8.7 par~s ( 3 ) T~02 coated mica 1. 0 pQrts (AFPLAIR NF-140~I), 301dl by E. I. du Po~t de Nemours and Compa~y) ( 4 ) Red mlll bas ~ o:E Example 1 0 . 2 part
- ' ~E3 ' . .
~e~
The following were mix~d, in the srdel listed:
(1) PT~E di~per~l~n ~ Example 1 69.7 parts (2) D~ionized water 8.7 par~s ( 3 ) T~02 coated mica 1. 0 pQrts (AFPLAIR NF-140~I), 301dl by E. I. du Po~t de Nemours and Compa~y) ( 4 ) Red mlll bas ~ o:E Example 1 0 . 2 part
(5) The mi~sture in (5) o~ Example 1 6,45 p~r~s
(6) ~he disperslon of (6) in Example 1 14.0 part~
The r~sultirlg c~p~sition was applied to a ~:rit-coated, primed alumi~um ~ryp~n3 as i~ :E5xample 1, t~ give a ~cratch resistant copper ~ini~h..
~ ~ .
12_ ~
: . : , , :, - ~ ,
The r~sultirlg c~p~sition was applied to a ~:rit-coated, primed alumi~um ~ryp~n3 as i~ :E5xample 1, t~ give a ~cratch resistant copper ~ini~h..
~ ~ .
12_ ~
: . : , , :, - ~ ,
Claims (10)
1. A coating composition consisting essentially of (a) about 80-99.8% by weight of the total of (a) and (b), of a particulate polymer of one or more monoethylenically unsaturated hydrocarbon monomers completely substituted with fluorine atoms or a combination of fluorine atoms and chlorine atoms;
(b) about 0.2-20%, by weight of the total of (a) and (b), of mica particles, mica particles coated with pigment or metal flake;
the total of (a) and (b) equaling 100%;
(c) about 2-300%, by weight of (a), of one or more polymers of monoethylenically unsaturated monomers which depolymerize and whose depolymerization products vaporize in the temperature range of about 150°C below the fusion temperature of (a) to about the decomposition temperature of (a);
and (d) a liquid carrier, said coating composition being suitable for forming finishes having improved scratch resistance.
(b) about 0.2-20%, by weight of the total of (a) and (b), of mica particles, mica particles coated with pigment or metal flake;
the total of (a) and (b) equaling 100%;
(c) about 2-300%, by weight of (a), of one or more polymers of monoethylenically unsaturated monomers which depolymerize and whose depolymerization products vaporize in the temperature range of about 150°C below the fusion temperature of (a) to about the decomposition temperature of (a);
and (d) a liquid carrier, said coating composition being suitable for forming finishes having improved scratch resistance.
2. The composition of claim 1 in which (b) is present at a concentration of about 2-15%, by weight of the total of (a) and (b).
3. The composition of claim 1 in which (b) is present at a concentration of about 8-12%, by weight of the total of (a) and (b).
4. The composition of claim 1 wherein the polymer in (a) is PTFE.
5. The composition of claim 1 wherein the mica particles in (b) are coated with an oxide of titanium, zirconium, aluminum, zinc, antimony, tin, iron, copper, nickel, cobalt, chromium or vanadium.
6. The composition of claim 1 wherein the polymer in (c) contains one or more monoethylenically unsaturated carboxylic acid units.
7. The composition of claim 6 wherein the polymer in (c) is of one or more of an alkyl acrylate or methacrylate having 1-8 carbon atoms in the alkyl group, styrene, alpha-methylstyrene, vinyl toluene and the acid unit is of acrylic acid, methacrylic acid, fumaric acid, itaconic acid, or maleic acid, optionally esterified with a glycidyl ester of 4-14 carbon atoms (total).
8. The composition of claim 1 wherein the polymer in (c) is (1) a methyl methacrylate/2-ethylhexl acrylate/
methacrylic acid terpolymer, (2) a butyl acrylate/methyl methacrylate/acrylic acid terpolymer esterified with a mixed ester having the structure where R1 is CH3 and R2 and R3 are lower alkyl groups, R1, R2 and R3 containing a total of 7-9 carbon atoms.
(3) a styrene/methyl methacrylate/acrylic acid terpolymer esterified with a mixed ester having the structure where R1 is CH3 and R2 and R3 are lower alkyl groups, R1, R2 and R3 containing a total of 7-9 carbon atoms.
or (4) a methyl methacrylate/ethyl acrylate/methacrylic acid terpolymer.
methacrylic acid terpolymer, (2) a butyl acrylate/methyl methacrylate/acrylic acid terpolymer esterified with a mixed ester having the structure where R1 is CH3 and R2 and R3 are lower alkyl groups, R1, R2 and R3 containing a total of 7-9 carbon atoms.
(3) a styrene/methyl methacrylate/acrylic acid terpolymer esterified with a mixed ester having the structure where R1 is CH3 and R2 and R3 are lower alkyl groups, R1, R2 and R3 containing a total of 7-9 carbon atoms.
or (4) a methyl methacrylate/ethyl acrylate/methacrylic acid terpolymer.
9. The composition of claim 1 wherein the carrier in (d) is water.
10. The composition of claim 1 wherein the polymer in (a) is PTFE, the mica particles in (b) are coated with titanium dioxide, the polymer in (c) is a methyl methacrylate/
ethyl acrylate/methacrylic acid terpolymer and the carrier in (d) is water.
ethyl acrylate/methacrylic acid terpolymer and the carrier in (d) is water.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US59749175A | 1975-07-21 | 1975-07-21 | |
| US597,491 | 1975-07-21 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1105165A true CA1105165A (en) | 1981-07-14 |
Family
ID=24391730
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA257,230A Expired CA1105165A (en) | 1975-07-21 | 1976-07-19 | Fluoropolymer finishes having improved scratch resistance |
Country Status (11)
| Country | Link |
|---|---|
| JP (1) | JPS595225B2 (en) |
| BE (1) | BE844357A (en) |
| BR (1) | BR7604696A (en) |
| CA (1) | CA1105165A (en) |
| DE (1) | DE2632838C2 (en) |
| FR (1) | FR2318911A1 (en) |
| GB (1) | GB1557230A (en) |
| IT (1) | IT1062134B (en) |
| LU (1) | LU75412A1 (en) |
| NL (1) | NL7608075A (en) |
| SE (1) | SE434516B (en) |
Families Citing this family (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA1121930A (en) * | 1977-12-29 | 1982-04-13 | Alkis Christofas | Synergistic primer for fluoropolymer coatings |
| US4353950A (en) * | 1979-07-06 | 1982-10-12 | E. I. Du Pont De Nemours And Company | Stain-resistant cookware multi-layer coating system comprising pigments and a transluscent outer layer |
| WO1981002161A1 (en) | 1980-01-21 | 1981-08-06 | Daikin Ind Ltd | Composition for coating fluoroplastics |
| JPS57190036A (en) * | 1981-05-18 | 1982-11-22 | Kureha Chem Ind Co Ltd | Vinylidene fluoride resin composition |
| JPS5943071A (en) * | 1982-09-02 | 1984-03-09 | Toyota Motor Corp | Transparent sealer |
| GB2167317A (en) * | 1984-11-02 | 1986-05-29 | Robert Hamilton Hanker | Melting plastics surfaces |
| JPH02183731A (en) * | 1989-01-10 | 1990-07-18 | Matsushita Electric Ind Co Ltd | Cooker |
| JPH04135504A (en) * | 1990-09-28 | 1992-05-11 | Achilles Corp | Injection molded shoe |
| US8796370B2 (en) | 2007-08-10 | 2014-08-05 | Daikin Industries, Ltd. | Coating composition |
| US8673449B2 (en) | 2009-12-18 | 2014-03-18 | Saint-Gobain Performance Plastics Corporation | Cooking release sheet materials and release surfaces |
| RU2457228C2 (en) * | 2010-08-04 | 2012-07-27 | Открытое акционерное общество Научно-производственное объединение "Наука" (ОАО НПО "Наука") | Method of producing compositions for making antifriction coatings on metal surfaces |
| RU2557530C2 (en) * | 2013-06-14 | 2015-07-20 | Открытое акционерное общество Научно-производственное объединение "Наука" (ОАО НПО "Наука") | Method for producing polyamide acid based additive and compositions for making antiadhesive, non-stick and antifriction coatings for metal surfaces |
| CN109844044B (en) | 2016-10-24 | 2021-12-10 | 美国圣戈班性能塑料公司 | Polymer compositions, materials and methods of preparation |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2681324A (en) * | 1951-08-09 | 1954-06-15 | Du Pont | Polytetrafluoroethylene coating compositions |
| GB1064840A (en) * | 1964-11-23 | 1967-04-12 | Du Pont | Tetrafluoroethylene/hexafluoropropylene copolymer dispersions |
| FR1440738A (en) * | 1965-04-15 | 1966-06-03 | Tefal Sa | Pigmented coating based on polytetrafluoroethylene |
| US3970627A (en) * | 1973-09-24 | 1976-07-20 | E. I. Du Pont De Nemours And Company | Fluorocarbon polymer coating compositions containing mica particles |
| FR2317343A1 (en) * | 1975-07-11 | 1977-02-04 | Du Pont | FLUORINE POLYMER COATING WITH IMPROVED FLAKING RESISTANCE |
-
1976
- 1976-07-19 IT IT25458/76A patent/IT1062134B/en active
- 1976-07-19 LU LU75412A patent/LU75412A1/xx unknown
- 1976-07-19 CA CA257,230A patent/CA1105165A/en not_active Expired
- 1976-07-20 BE BE169102A patent/BE844357A/en not_active IP Right Cessation
- 1976-07-20 GB GB30162/76A patent/GB1557230A/en not_active Expired
- 1976-07-20 SE SE7608257A patent/SE434516B/en not_active IP Right Cessation
- 1976-07-20 BR BR7604696A patent/BR7604696A/en unknown
- 1976-07-20 FR FR7622155A patent/FR2318911A1/en active Granted
- 1976-07-21 DE DE2632838A patent/DE2632838C2/en not_active Expired
- 1976-07-21 NL NL7608075A patent/NL7608075A/en not_active Application Discontinuation
- 1976-07-21 JP JP51087696A patent/JPS595225B2/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| LU75412A1 (en) | 1977-04-04 |
| FR2318911A1 (en) | 1977-02-18 |
| DE2632838A1 (en) | 1977-02-03 |
| JPS595225B2 (en) | 1984-02-03 |
| SE434516B (en) | 1984-07-30 |
| NL7608075A (en) | 1977-01-25 |
| SE7608257L (en) | 1977-01-22 |
| JPS5213531A (en) | 1977-02-01 |
| FR2318911B1 (en) | 1981-04-30 |
| GB1557230A (en) | 1979-12-05 |
| IT1062134B (en) | 1983-06-25 |
| BR7604696A (en) | 1977-08-02 |
| DE2632838C2 (en) | 1986-05-07 |
| BE844357A (en) | 1977-01-20 |
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