CA2133829C - Ozone-friendly correction fluid - Google Patents
Ozone-friendly correction fluidInfo
- Publication number
- CA2133829C CA2133829C CA002133829A CA2133829A CA2133829C CA 2133829 C CA2133829 C CA 2133829C CA 002133829 A CA002133829 A CA 002133829A CA 2133829 A CA2133829 A CA 2133829A CA 2133829 C CA2133829 C CA 2133829C
- Authority
- CA
- Canada
- Prior art keywords
- correction fluid
- solvent
- methacrylate copolymer
- titanium dioxide
- isobutyl methacrylate
- 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
-
- 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
- C09D10/00—Correcting fluids, e.g. fluid media for correction of typographical errors by coating
-
- 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
- C09D133/10—Homopolymers or copolymers of methacrylic acid esters
Abstract
An ozone-friendly correction fluid includes a non-halogenated solvent, a butyl methacrylate copolymer as the polymeric film-forming material, a plasticizer, and an opacifying agent.
Description
W O 93/21261 ~ 2 9 PCT/US93/02493 ,: ~' . ~
~' ~ ` . ! . ~
~'.
~i '~',.
OZONE FRIENDLY CORRECTION FLUID - `
The invention relate6 to correction ~luids.
Correction fluids for correcting handwritten, typewritten or photoeopy marking~
on paper are well known and their performanee `
~.
eharaeteri6tic6 are well defined. Es~ential performanee characteristies include the ability '~
to pro~ide a film or eoaleseed residue on drying ;^
10 whieh ean both effeetively eover erroneou~ ~
marking6 on a paper surfaee and recei~e a ~`
corrected marking. Preferably, the film eovering the marking should be ~trongly bo~s~
to the paper ~urfaee and should also be suffieiently 1exible 80 that the film wi~l not be removed under normal eonditions of hAnAling.
Additionally, the eorreetion fluid ~hould not interaet with the marking to cause sxee~si~Q -"
diseoloration of the re~ulting film (bleeding).
Another important performanee eharaeteristic invol~es the drying rate of the eomposition whieh should be as rapid as po~sible 80 that eorreetions ean be mada relati~ely quiekly.
Nor-^lly, eommercial correetion fluids form ;~-films which are suffieiently dry to reeei~e a ; `.'`
W O 93/21261 ~ 2 ~ PCT/US93/02493 ~orrected marking in about 30-40 ~econd~
Correction fluids typically are a ~-dispersion, i.e., a suspen~ion of solid ..
particle~ in a liquid. When a correction fl~id ~-5 ~its around for some length of time the ~olid . ~
particles begin to settle, causing the flu~d .~.
near the bottom of the container to become more compact. Compact ~ettling i8 undo~irable because it i~ no longer ea~ily redispersed ~`~
10 thereby reducing co~erage or the abil~ty of the .. -fluid to co~er markings.
Correction fluid~ typically include some stan~ard ingredients, including an opacifying agent, a film-forming polymeric ~-material, a ~olatile solvent, and a dispersing agent. The opacifying agent i~ the solid that i8 disporsod in tho fluid and provides the basis white color which can be toned with othor pigment~ to provide a correctio~ fluid closely ..
20 correspQn~n~ to the color of the paper to which . ~.:
tho fluid i8 to be appliod. The film-forming -~
polymeric material i~ ~ubsta~tially solublo in the selected solvo~t and bi~ds pigm~nt to paper and helps to form the floxiblo but ~olid covering that romains onco the ~olvent a~a~olate~. Th~ volat~le solvsnt is a carrior for all i~oliont~ mentioned horein. Th-dl~por~ing ag~nt i~ i~cludod to stabilize th~
d~persion, i.o., to holp en~uro that tho opacifying agont rcmalns unlformly d~pcrscd in . the solvont.
~i~tor~cally, halog natod hydrocarbon~
havo bo~u th- ~olvo~t~ of c~oico for correction ~:
fluld compo~ition~. ~alog~natod Lyd,oc~rho~
aolv~ts proso~t spoc~al advantagos primarily bocau~o thoy havo ~v~G.ation rates which ;.
provido co-~cction fluids that dry rapidly and : ' '.
. .
W093~21261 ~ Y PCT/US93/02493 completely Additionally, they do not interact w~th typewritten mar~ings to cause unacc~ptable ;~
bloeding Also, they can eff~ctively di~solve `~
tho~e film-forming polymeric materials which provide durable but flexible films without cau~ing exces~ivQ cockling or di~tortion of paper surfaces Desp~te their recog~ized advantage~ when used as correction fluid solvents, the use of halogenated hydrocarbon ~;~
solvonts has become a matter of increased concern primarily because of thoir adverse -~`
effoc~ o~ the onvironmont (stratospheric ozon~
depletion) Accordingly, providing an nozone~
friendly~ corroction fluid be aliminating the -`
uso o~ halogo~ated hydrocarbon solv~nts from correction fluids has become a primary objectiv~ ~-.,", for the art and significant effort~ hav- boen dirocted to tho dev-lopment of corroction fluid~
froo of halog-natod hydro~ar~on ~olv~nts sy ozono-friendly correction fluid, we mean a corroction fluid which either doos ~ot contain a -~;
material that migrates to tho stratosphore or, if it cont~ins ~uch a material, th~ matorial I-~
doos not caus- a roduction in tho ozono conc-ntratio~s Th- inv-ntion featur-s, in one aspect, a corr-ction fluid includos a volatilo, non-halogonat-d solv-nt; a butyl m thacrylato copolymor a~ a film-forming mat-rial; a `~
plasticizer; and an opaci.ying agont such as tita~ium dioxlde Preferably, the compo~ltion ~
al~o contains a disp-rsing agent ~y volatilo, "`
it is m ant that tho solvont ha- a ho~ point of 1~8~ t~ 155C
Tho inv-ntion featur-s, in anoth-r a~pect, a corroction fluld that includos a volatlle, non-halogenatod cycloh^Y~o or ~-W093/21261 ~ 2 ~ PCT/US93/02493 ' `~
alkylated cyclohexane cont~;ning 10 or fewer carbon atoms as a solvent; a film-forming polymeric material; an al~yl ~odium sulfosuccinate a~ a di~persing agent; a plasticizer for the film-forming polymeric material and an opacifying agent. ~-~
The invention features, in yet another ~ -aspect, a correction fluid that includes a ~olatile, non-halogenated cycloh~an~ or 10 alkylated cycloh~Y~n~ cont~;n;n~ 10 or fewer ~;
carbon atoms as a sol~ent; a film-forming ;~
polymeric material; a polymeric fatty ester as a disper~ing agent; a plasticizer for tho polymerlc material; and an opacifying agent.
The in~ention features, in still another a~pect, a correction fluid that includ~s a volatile, non-halogonated mixture of paraff~ns and naph~hen~ ae a solvent; a film^~orming polymeric material, proferably an isobutyl methacrylate copolymor or n-butyl methacrylat~
copo}ymer; a copolymeric fatty ester as a ~
disp-r~ing age~t; a plasticizer for tho `-~`
polymeric ~aterial; and an opacifying agont.
Tho proferrod dispers~ng agonts include polym ric fatty esters or ~- rl ~yl sodium sulfo~cq~n~tos. ~xamples of preferrod agonts includ~ dioctyl sodium sulfosuccinat- _nd b~str~docyl sodium sulfo~uccinato.
Prof-rred al~yl cycloh^Yr~ ~olvonts includo mothylcyclohox~ne, ethylcycloh~Ya~, aud dimethylcycloh~Yans; the mo~t preforr~d alkyl cycloh~Y~no sol~nt is m-thylcycloh~xa~o. Whon a paraff~n/naphthene solvont 18 usod according -to the prosont in~entio~, it is desirable to utilizo a mlxturo which is _igh in p_r_ffinic hydrocarbons, pr~forably about 40%, low in aromat~c h~orar~o~, preferably from 0 to 10%
''`','' ,:';'~
'-:' ~ h~
W093/21261 PCT/US93/~2493`~
aromatic, and the bala~ce being ~aphthe~e, pr2ferably about 60%. Most prsferably the paraffinic hydrocarbon is predominantly C7. The most preferred such blend is Tolu-SolTM W~T ~ -manufactured by Shell Oil Co., ~ouston, TX.
These solvents can also be a blend with additional solvent~, preferably, such blend~ -include at least 50~ of the cycloh~Yane, alkylated cyclo~eY~ne and/or naphthe~e/paraffin solvent by weig~t. Preferred additio~al solvents include odorles~ mineral ~pirits, isopropyl alcohol or dibasic Qster (DBE), ~-manufactured by DuPont Ch~m;cals, Wilmington, DE, which i8 a blend of 4S-75% dimethyl -glutarate, 10-25% dimothyl adipate, and 15-30% ~`
-dimethyl succinate.
The preferred correctio~ fluid include~ botweon 35% and 5S% by wotght sol~ent;
between 4% and 13% by w~ig~t copolymer; betwesn ~-~
1~ and 4% by weight plastic~zer; betwoen 0% aQd 3.5% by weight dispersing agent; and botween 35 and 55% by weight opacifying agont.
Tho correct~on fluld pro~tdes excellent co~orage without blseding typed -~
25 originals wrltt~g in~s, and coptes. `~
Importantly, the fluid sxhi~its ~xcollent r;~`'`' pigmont rodlsporsi~iltty after long torm `~
storago. Al~o, bocauso a non-halogonatod ~ol~ont i8 ~ployod ~n the flutd, tt ts ozono- -~
friendly.
Othor foaturo~ and ad~antagos of the inv~tto~ will be appar~t from t~o dosQript~on of tho preferrod ombod~m~nt thereof, a~d ~rom i~`
the claim~
The preferred corroction fluid ~ `
includes mothylcyclohsYrno a~ t~o sol~ont; ``
isobutyl mothacrylate or n-butyl mothacrylato WO93/21261 '~1 3 ~ d 2 9 PCr/US93/02493 - 6 ~
copolymer as the film-forming material;
ditridecyl phthalate plasticizor; titanium dioxide as the opacifying agent; lamp black as a pigment to color match paper; mustard oil as~a donaturant; and a fragrance. Mo~t pr~ferably the correction fluid al~o contains dioctyl sodium sulfosuccinate or a polymeric fatty e~ter --~
as the di~persing agent. -~
A sufficient amount of ~ol~ent should be included to make the fluid thin e~ough to be easily spread. So much ~hould not be used 80 that the hiding power of the fluid ~ ni shes.
Preferably, the correction fluid should include 35%-55% by weight solvent.
The pref~rred i~obutyl methacrylate ~`~
copolymer has a specific gravity of about l.05 gm/ec and i~ available u~der the trado namo ;~
P~EXIG~M~R) P28 and NooCyrl B-705, m~nufaeturod by Roh Gmb~ Chemisehe Fabrik, and ICI Resins ~.S. ro~poetivoly. Tho proforrod n-butyl mothaerylato eopolymors are avallabl~ under tho trade namo Blvaelto 2044, 2045, 2046, ma~ufaeturod by DuPont Compa~y.
A suffieient amount of tho matorial should bo ineludod to prov~de good flexibility to th~ eov~ring, but not 80 mueh that tho -`
~iseosity of the fluid beeomes too high, which ca~ lead to roduc~d cov~ra~e and difficult br~h~ n~, The pro~t eorr-etio~ fluid al80 eontai~s an offoetivo amount of a plastieizor to improvo flexibility of tho eopolymor. Pr~forrod pla~tieizors aro dialkyl phthaIato eompound~ and ``
a most proforrod plastieizor i~ Jayfl~x(R) (DTDP) brand ditridocyl phthalato pla~ticizer ~;
distributod by ~YYon Chemical. Preforably, the corroction fluid includos b-twoe~ 1% and 4~ -plasticizor. Preferably, the correction fluid .~.,.
, ....
W093/~1261 ~ 2 9 PCT/US93/02493 ~
.
includes between 4% and 12% of the copolymer.
The preferred dialkyl sodium sulfosuccinate, dioctyl sodium ~ulfosuccinate, i5 sold under the trade name AERISOL OTS by ~ ;~
5 American Cyanamid Co. The preferred polymeric ~
fatty ester i~ sold under the trade name ~ :
HYP~RM~ LP1 by ICI Specialty Chemicals. A
sufficient amount of the agent ~hould be included to achieve complete dispersion of the ~;
10 titanium dioxide, but not 80 much should be ~
included that the hiding power i8 reduced. The ~-`
preferred fluid includes between 0% and 3.5%
polymeric fatty ester by weight. Bistridecyl ~-sodium sulfosuccinate (sold under the trade name AEROSOL TR70 by American Cyanamid Co.) can al~o be used.
Suitable titanium dioxide pigments include commercially available rutile titanium `~
dioxides and anatase titanium dioxides or blends or mixtures of these which preferably have an average particle size between about 0.2 to about 0.4 microns and an average oil ab~orption of about 14 lbs. oil/100 lbs. pigment to about 36 lbs./100 lbs. The amount of titanium dioxide 25 included in the composition can vary dapsn~; n~ ~.. ``
on the degree of coverage desired. However, amounts between about 30 to about 60 percent by weight titanium dioxide ba~ed on total weight of "
composition are generally suitable. Other opacifying pigments may be used either alone but pre$erably in co~bination with the titanium ;-dioxide. Such pigments include zinc sulfide and zinc oxide. Preferably the fluid inclutes between 35% and 55% of the opacifying agent by "
35 weight. -~ amp black is included as a coloring pigment to match the color of fluid to st~n~rd ..
.
, .
W O 93/21261 ~ g PC~r/US93/02493 ' .
- 8 - .
whita pap~r. Other pigments such as raw umber or yellow oxide can also be included to match ~
the tone of colored paper. ~ ~-A ~mall amount (0.10-2%) of mustard oil i8 included as a denaturant.
A small amo~nt of a fragrance i8 included in the preferred formula to help mask j~`
the odor of the solvent. Preferred i8 Fragrance 759292/6021~5, which is available from Haarmann & Reimer.
Examples of pr-ferred correction ---fluids are the following:
- Exam~le 1 In~redient Wt % `
Methylcycl~h~Y~nO 34.016 `-Odorle~ Mineral Spirits 5.853 Thermaplastic IBMA Copolymer, '~
~T~o ~1 B705 Polymor 7.241 `
. . .
Jayflox DTDP Plasticizer, - 20 D~tridocyl Phthalat- 2.678 Polymeric Fatty ost-r Hypormor LPl, mfg. by ICI Amoricas, Inc. 1.984 Tita~ium Dioxido, Tipuro R-931 48.012 Lamp Rl ir~ 0`. 084 25 Mustard Oll 0.112 ~i Fragra~¢o 759292/0602185 0.020 l ~
100.000 ```''.
. ~:
.. .
.. . . .. ..
. ., ~ .
....
~ ..
: ~.
u ~
WO93/21261 PCT/US93/02493 ~.
Exam~le 2 In~redient Wt Methylcycloh~xane 28.98 Diba~ic ERters (DBE), mfg. by DuPont ChemicalR2.59 Isopropyl Alcohol (~hydrous) 2.S9 Odorless Nineral Spirits 3.81 ~
Ground bulk polymeric ba~ed o~ i-butyl .. ~.,;
methacrylate Pl~xigum P28, mfg. by Rohm Gmb~ 8.49 Jayfl~x DTDP Plasticizer i `
Ditridecyl Phthalate (DTDP) 2.92 Titanium D~ox~de, ,~
Tipure R-931 50.40 .. -15 Lamp Blac~ 0.09 .-Mu~tard O~l 0.11 Fragrance 759292/0602185 0.02 ;-.
100.00 ExamDle 3 ~ `
20 I~L lie~t Wt % :.
Paraffi~/Naphthon~ Sol~ent, Tolu-SolTM :`.
mfg. ~y Shell Oil Co., Houoto~, TX 37.154 Odorleso Mineral Spirit~ 5.572 !~p Thermaplastic IBMA Copolym r, `~
~": yl B705 Polym~r 6.895 ~-~
Jayfl~x DTDP Plasticiz~r, .:
Ditridecyl Phth~lat~ 2.550 Polym~rlc Fatty ~oter ~yperm~r ~Plr mfg. by ICI Am~rica~, Inc. 1.889 Titanium Dioxid~, Tipure R-931 45.712 c~
Lamp Rl~çk 0.076 Mustard Oll 0.130 Fragranc~ 759292/0602185 0.022 100.000 ~.
~'~....
:
: '~
:
WO93/21261 ~ 3 ~ d ~ ~ PCT/US93/02493 ;
- ~ O -ExamPle 4 In~redient W %
Paraffin~Naphthe~e Solvent, Tolu-SolTM
mfg by Shell Oil Co , Housto~, TX 38 473 5 Odorles~ Mineral Spirits 3 858 Thermapla~tic BMA Copolymer, El~acite 2044 Polymer 7 925 Jayflex DTDP Pla~ticizer, Ditridecyl Pht~alate 2 815 ~`
10 Polymeric Fatty e~ter ~-~
Hypermer LPl, mfg by ICI America~, Inc 0 834 `~
Titanium Dioxide, Tipure R-931 45 881 Lamp Black 0 078 -Mu~tard Oil 0 115 Fragrance 759292/0602185 0 021 -100.. 000 ...
: .-Corroction fluids cont~;ning the abovo ingrodients aro preparod by first dissolving tha `-copolymer in tho solYent Noxt, tho polymeric fatty ester disp-rsant, if us-d, a~d titanium dioxide opacifying ag-nt aro A~A and t~e ``
mlxturo d~sF~ for 3 hours in a b~ad mill, --aftor which colorants, mustard oil, fragranco, a~d othor i~gr-dients are ad~9~ to obtain flnal fluid composition Oth-r embodim~nt~ are within the claims For oxample, in additiou to tho mo~t "~
proforrod ingrodie~t~ the compo~itlon may al~o i~clude varlous addltl~-~ known to tho-- s~llled `~`
in the art Tho~e addltlves aro in~oL~oLatod to im~rovo sp~clfic proportl-s Thooe lnclud- , -~
- pla~tlcizors to lmprov- dry film ad~oslon and fl~x~bility, flatt-ning agsnt~ to control fllm gloss, flow addlti~-s and thlc~^ns~s to control br~h~ng, le~oling and s-ttling ~nd pigm~nt xtenders to reduce cost Moreovor, othor ~;
.~, .
~ ~- v ~
dial~yl ~odium sulfosuccinates, in particulAr tho e with alkyl group~ ha~ing les~ than 15 or 20 carbon atoms, can b~ used in place o~ dioctyl sodium sulfosuccinate.
. .
., .. ...
~.
~, ... ~
-~ ~
~`
~ ~, . .
;,,".
~' ~ ` . ! . ~
~'.
~i '~',.
OZONE FRIENDLY CORRECTION FLUID - `
The invention relate6 to correction ~luids.
Correction fluids for correcting handwritten, typewritten or photoeopy marking~
on paper are well known and their performanee `
~.
eharaeteri6tic6 are well defined. Es~ential performanee characteristies include the ability '~
to pro~ide a film or eoaleseed residue on drying ;^
10 whieh ean both effeetively eover erroneou~ ~
marking6 on a paper surfaee and recei~e a ~`
corrected marking. Preferably, the film eovering the marking should be ~trongly bo~s~
to the paper ~urfaee and should also be suffieiently 1exible 80 that the film wi~l not be removed under normal eonditions of hAnAling.
Additionally, the eorreetion fluid ~hould not interaet with the marking to cause sxee~si~Q -"
diseoloration of the re~ulting film (bleeding).
Another important performanee eharaeteristic invol~es the drying rate of the eomposition whieh should be as rapid as po~sible 80 that eorreetions ean be mada relati~ely quiekly.
Nor-^lly, eommercial correetion fluids form ;~-films which are suffieiently dry to reeei~e a ; `.'`
W O 93/21261 ~ 2 ~ PCT/US93/02493 ~orrected marking in about 30-40 ~econd~
Correction fluids typically are a ~-dispersion, i.e., a suspen~ion of solid ..
particle~ in a liquid. When a correction fl~id ~-5 ~its around for some length of time the ~olid . ~
particles begin to settle, causing the flu~d .~.
near the bottom of the container to become more compact. Compact ~ettling i8 undo~irable because it i~ no longer ea~ily redispersed ~`~
10 thereby reducing co~erage or the abil~ty of the .. -fluid to co~er markings.
Correction fluid~ typically include some stan~ard ingredients, including an opacifying agent, a film-forming polymeric ~-material, a ~olatile solvent, and a dispersing agent. The opacifying agent i~ the solid that i8 disporsod in tho fluid and provides the basis white color which can be toned with othor pigment~ to provide a correctio~ fluid closely ..
20 correspQn~n~ to the color of the paper to which . ~.:
tho fluid i8 to be appliod. The film-forming -~
polymeric material i~ ~ubsta~tially solublo in the selected solvo~t and bi~ds pigm~nt to paper and helps to form the floxiblo but ~olid covering that romains onco the ~olvent a~a~olate~. Th~ volat~le solvsnt is a carrior for all i~oliont~ mentioned horein. Th-dl~por~ing ag~nt i~ i~cludod to stabilize th~
d~persion, i.o., to holp en~uro that tho opacifying agont rcmalns unlformly d~pcrscd in . the solvont.
~i~tor~cally, halog natod hydrocarbon~
havo bo~u th- ~olvo~t~ of c~oico for correction ~:
fluld compo~ition~. ~alog~natod Lyd,oc~rho~
aolv~ts proso~t spoc~al advantagos primarily bocau~o thoy havo ~v~G.ation rates which ;.
provido co-~cction fluids that dry rapidly and : ' '.
. .
W093~21261 ~ Y PCT/US93/02493 completely Additionally, they do not interact w~th typewritten mar~ings to cause unacc~ptable ;~
bloeding Also, they can eff~ctively di~solve `~
tho~e film-forming polymeric materials which provide durable but flexible films without cau~ing exces~ivQ cockling or di~tortion of paper surfaces Desp~te their recog~ized advantage~ when used as correction fluid solvents, the use of halogenated hydrocarbon ~;~
solvonts has become a matter of increased concern primarily because of thoir adverse -~`
effoc~ o~ the onvironmont (stratospheric ozon~
depletion) Accordingly, providing an nozone~
friendly~ corroction fluid be aliminating the -`
uso o~ halogo~ated hydrocarbon solv~nts from correction fluids has become a primary objectiv~ ~-.,", for the art and significant effort~ hav- boen dirocted to tho dev-lopment of corroction fluid~
froo of halog-natod hydro~ar~on ~olv~nts sy ozono-friendly correction fluid, we mean a corroction fluid which either doos ~ot contain a -~;
material that migrates to tho stratosphore or, if it cont~ins ~uch a material, th~ matorial I-~
doos not caus- a roduction in tho ozono conc-ntratio~s Th- inv-ntion featur-s, in one aspect, a corr-ction fluid includos a volatilo, non-halogonat-d solv-nt; a butyl m thacrylato copolymor a~ a film-forming mat-rial; a `~
plasticizer; and an opaci.ying agont such as tita~ium dioxlde Preferably, the compo~ltion ~
al~o contains a disp-rsing agent ~y volatilo, "`
it is m ant that tho solvont ha- a ho~ point of 1~8~ t~ 155C
Tho inv-ntion featur-s, in anoth-r a~pect, a corroction fluld that includos a volatlle, non-halogenatod cycloh^Y~o or ~-W093/21261 ~ 2 ~ PCT/US93/02493 ' `~
alkylated cyclohexane cont~;ning 10 or fewer carbon atoms as a solvent; a film-forming polymeric material; an al~yl ~odium sulfosuccinate a~ a di~persing agent; a plasticizer for the film-forming polymeric material and an opacifying agent. ~-~
The invention features, in yet another ~ -aspect, a correction fluid that includes a ~olatile, non-halogenated cycloh~an~ or 10 alkylated cycloh~Y~n~ cont~;n;n~ 10 or fewer ~;
carbon atoms as a sol~ent; a film-forming ;~
polymeric material; a polymeric fatty ester as a disper~ing agent; a plasticizer for tho polymerlc material; and an opacifying agent.
The in~ention features, in still another a~pect, a correction fluid that includ~s a volatile, non-halogonated mixture of paraff~ns and naph~hen~ ae a solvent; a film^~orming polymeric material, proferably an isobutyl methacrylate copolymor or n-butyl methacrylat~
copo}ymer; a copolymeric fatty ester as a ~
disp-r~ing age~t; a plasticizer for tho `-~`
polymeric ~aterial; and an opacifying agont.
Tho proferrod dispers~ng agonts include polym ric fatty esters or ~- rl ~yl sodium sulfo~cq~n~tos. ~xamples of preferrod agonts includ~ dioctyl sodium sulfosuccinat- _nd b~str~docyl sodium sulfo~uccinato.
Prof-rred al~yl cycloh^Yr~ ~olvonts includo mothylcyclohox~ne, ethylcycloh~Ya~, aud dimethylcycloh~Yans; the mo~t preforr~d alkyl cycloh~Y~no sol~nt is m-thylcycloh~xa~o. Whon a paraff~n/naphthene solvont 18 usod according -to the prosont in~entio~, it is desirable to utilizo a mlxturo which is _igh in p_r_ffinic hydrocarbons, pr~forably about 40%, low in aromat~c h~orar~o~, preferably from 0 to 10%
''`','' ,:';'~
'-:' ~ h~
W093/21261 PCT/US93/~2493`~
aromatic, and the bala~ce being ~aphthe~e, pr2ferably about 60%. Most prsferably the paraffinic hydrocarbon is predominantly C7. The most preferred such blend is Tolu-SolTM W~T ~ -manufactured by Shell Oil Co., ~ouston, TX.
These solvents can also be a blend with additional solvent~, preferably, such blend~ -include at least 50~ of the cycloh~Yane, alkylated cyclo~eY~ne and/or naphthe~e/paraffin solvent by weig~t. Preferred additio~al solvents include odorles~ mineral ~pirits, isopropyl alcohol or dibasic Qster (DBE), ~-manufactured by DuPont Ch~m;cals, Wilmington, DE, which i8 a blend of 4S-75% dimethyl -glutarate, 10-25% dimothyl adipate, and 15-30% ~`
-dimethyl succinate.
The preferred correctio~ fluid include~ botweon 35% and 5S% by wotght sol~ent;
between 4% and 13% by w~ig~t copolymer; betwesn ~-~
1~ and 4% by weight plastic~zer; betwoen 0% aQd 3.5% by weight dispersing agent; and botween 35 and 55% by weight opacifying agont.
Tho correct~on fluld pro~tdes excellent co~orage without blseding typed -~
25 originals wrltt~g in~s, and coptes. `~
Importantly, the fluid sxhi~its ~xcollent r;~`'`' pigmont rodlsporsi~iltty after long torm `~
storago. Al~o, bocauso a non-halogonatod ~ol~ont i8 ~ployod ~n the flutd, tt ts ozono- -~
friendly.
Othor foaturo~ and ad~antagos of the inv~tto~ will be appar~t from t~o dosQript~on of tho preferrod ombod~m~nt thereof, a~d ~rom i~`
the claim~
The preferred corroction fluid ~ `
includes mothylcyclohsYrno a~ t~o sol~ont; ``
isobutyl mothacrylate or n-butyl mothacrylato WO93/21261 '~1 3 ~ d 2 9 PCr/US93/02493 - 6 ~
copolymer as the film-forming material;
ditridecyl phthalate plasticizor; titanium dioxide as the opacifying agent; lamp black as a pigment to color match paper; mustard oil as~a donaturant; and a fragrance. Mo~t pr~ferably the correction fluid al~o contains dioctyl sodium sulfosuccinate or a polymeric fatty e~ter --~
as the di~persing agent. -~
A sufficient amount of ~ol~ent should be included to make the fluid thin e~ough to be easily spread. So much ~hould not be used 80 that the hiding power of the fluid ~ ni shes.
Preferably, the correction fluid should include 35%-55% by weight solvent.
The pref~rred i~obutyl methacrylate ~`~
copolymer has a specific gravity of about l.05 gm/ec and i~ available u~der the trado namo ;~
P~EXIG~M~R) P28 and NooCyrl B-705, m~nufaeturod by Roh Gmb~ Chemisehe Fabrik, and ICI Resins ~.S. ro~poetivoly. Tho proforrod n-butyl mothaerylato eopolymors are avallabl~ under tho trade namo Blvaelto 2044, 2045, 2046, ma~ufaeturod by DuPont Compa~y.
A suffieient amount of tho matorial should bo ineludod to prov~de good flexibility to th~ eov~ring, but not 80 mueh that tho -`
~iseosity of the fluid beeomes too high, which ca~ lead to roduc~d cov~ra~e and difficult br~h~ n~, The pro~t eorr-etio~ fluid al80 eontai~s an offoetivo amount of a plastieizor to improvo flexibility of tho eopolymor. Pr~forrod pla~tieizors aro dialkyl phthaIato eompound~ and ``
a most proforrod plastieizor i~ Jayfl~x(R) (DTDP) brand ditridocyl phthalato pla~ticizer ~;
distributod by ~YYon Chemical. Preforably, the corroction fluid includos b-twoe~ 1% and 4~ -plasticizor. Preferably, the correction fluid .~.,.
, ....
W093/~1261 ~ 2 9 PCT/US93/02493 ~
.
includes between 4% and 12% of the copolymer.
The preferred dialkyl sodium sulfosuccinate, dioctyl sodium ~ulfosuccinate, i5 sold under the trade name AERISOL OTS by ~ ;~
5 American Cyanamid Co. The preferred polymeric ~
fatty ester i~ sold under the trade name ~ :
HYP~RM~ LP1 by ICI Specialty Chemicals. A
sufficient amount of the agent ~hould be included to achieve complete dispersion of the ~;
10 titanium dioxide, but not 80 much should be ~
included that the hiding power i8 reduced. The ~-`
preferred fluid includes between 0% and 3.5%
polymeric fatty ester by weight. Bistridecyl ~-sodium sulfosuccinate (sold under the trade name AEROSOL TR70 by American Cyanamid Co.) can al~o be used.
Suitable titanium dioxide pigments include commercially available rutile titanium `~
dioxides and anatase titanium dioxides or blends or mixtures of these which preferably have an average particle size between about 0.2 to about 0.4 microns and an average oil ab~orption of about 14 lbs. oil/100 lbs. pigment to about 36 lbs./100 lbs. The amount of titanium dioxide 25 included in the composition can vary dapsn~; n~ ~.. ``
on the degree of coverage desired. However, amounts between about 30 to about 60 percent by weight titanium dioxide ba~ed on total weight of "
composition are generally suitable. Other opacifying pigments may be used either alone but pre$erably in co~bination with the titanium ;-dioxide. Such pigments include zinc sulfide and zinc oxide. Preferably the fluid inclutes between 35% and 55% of the opacifying agent by "
35 weight. -~ amp black is included as a coloring pigment to match the color of fluid to st~n~rd ..
.
, .
W O 93/21261 ~ g PC~r/US93/02493 ' .
- 8 - .
whita pap~r. Other pigments such as raw umber or yellow oxide can also be included to match ~
the tone of colored paper. ~ ~-A ~mall amount (0.10-2%) of mustard oil i8 included as a denaturant.
A small amo~nt of a fragrance i8 included in the preferred formula to help mask j~`
the odor of the solvent. Preferred i8 Fragrance 759292/6021~5, which is available from Haarmann & Reimer.
Examples of pr-ferred correction ---fluids are the following:
- Exam~le 1 In~redient Wt % `
Methylcycl~h~Y~nO 34.016 `-Odorle~ Mineral Spirits 5.853 Thermaplastic IBMA Copolymer, '~
~T~o ~1 B705 Polymor 7.241 `
. . .
Jayflox DTDP Plasticizer, - 20 D~tridocyl Phthalat- 2.678 Polymeric Fatty ost-r Hypormor LPl, mfg. by ICI Amoricas, Inc. 1.984 Tita~ium Dioxido, Tipuro R-931 48.012 Lamp Rl ir~ 0`. 084 25 Mustard Oll 0.112 ~i Fragra~¢o 759292/0602185 0.020 l ~
100.000 ```''.
. ~:
.. .
.. . . .. ..
. ., ~ .
....
~ ..
: ~.
u ~
WO93/21261 PCT/US93/02493 ~.
Exam~le 2 In~redient Wt Methylcycloh~xane 28.98 Diba~ic ERters (DBE), mfg. by DuPont ChemicalR2.59 Isopropyl Alcohol (~hydrous) 2.S9 Odorless Nineral Spirits 3.81 ~
Ground bulk polymeric ba~ed o~ i-butyl .. ~.,;
methacrylate Pl~xigum P28, mfg. by Rohm Gmb~ 8.49 Jayfl~x DTDP Plasticizer i `
Ditridecyl Phthalate (DTDP) 2.92 Titanium D~ox~de, ,~
Tipure R-931 50.40 .. -15 Lamp Blac~ 0.09 .-Mu~tard O~l 0.11 Fragrance 759292/0602185 0.02 ;-.
100.00 ExamDle 3 ~ `
20 I~L lie~t Wt % :.
Paraffi~/Naphthon~ Sol~ent, Tolu-SolTM :`.
mfg. ~y Shell Oil Co., Houoto~, TX 37.154 Odorleso Mineral Spirit~ 5.572 !~p Thermaplastic IBMA Copolym r, `~
~": yl B705 Polym~r 6.895 ~-~
Jayfl~x DTDP Plasticiz~r, .:
Ditridecyl Phth~lat~ 2.550 Polym~rlc Fatty ~oter ~yperm~r ~Plr mfg. by ICI Am~rica~, Inc. 1.889 Titanium Dioxid~, Tipure R-931 45.712 c~
Lamp Rl~çk 0.076 Mustard Oll 0.130 Fragranc~ 759292/0602185 0.022 100.000 ~.
~'~....
:
: '~
:
WO93/21261 ~ 3 ~ d ~ ~ PCT/US93/02493 ;
- ~ O -ExamPle 4 In~redient W %
Paraffin~Naphthe~e Solvent, Tolu-SolTM
mfg by Shell Oil Co , Housto~, TX 38 473 5 Odorles~ Mineral Spirits 3 858 Thermapla~tic BMA Copolymer, El~acite 2044 Polymer 7 925 Jayflex DTDP Pla~ticizer, Ditridecyl Pht~alate 2 815 ~`
10 Polymeric Fatty e~ter ~-~
Hypermer LPl, mfg by ICI America~, Inc 0 834 `~
Titanium Dioxide, Tipure R-931 45 881 Lamp Black 0 078 -Mu~tard Oil 0 115 Fragrance 759292/0602185 0 021 -100.. 000 ...
: .-Corroction fluids cont~;ning the abovo ingrodients aro preparod by first dissolving tha `-copolymer in tho solYent Noxt, tho polymeric fatty ester disp-rsant, if us-d, a~d titanium dioxide opacifying ag-nt aro A~A and t~e ``
mlxturo d~sF~ for 3 hours in a b~ad mill, --aftor which colorants, mustard oil, fragranco, a~d othor i~gr-dients are ad~9~ to obtain flnal fluid composition Oth-r embodim~nt~ are within the claims For oxample, in additiou to tho mo~t "~
proforrod ingrodie~t~ the compo~itlon may al~o i~clude varlous addltl~-~ known to tho-- s~llled `~`
in the art Tho~e addltlves aro in~oL~oLatod to im~rovo sp~clfic proportl-s Thooe lnclud- , -~
- pla~tlcizors to lmprov- dry film ad~oslon and fl~x~bility, flatt-ning agsnt~ to control fllm gloss, flow addlti~-s and thlc~^ns~s to control br~h~ng, le~oling and s-ttling ~nd pigm~nt xtenders to reduce cost Moreovor, othor ~;
.~, .
~ ~- v ~
dial~yl ~odium sulfosuccinates, in particulAr tho e with alkyl group~ ha~ing les~ than 15 or 20 carbon atoms, can b~ used in place o~ dioctyl sodium sulfosuccinate.
. .
., .. ...
~.
~, ... ~
-~ ~
~`
~ ~, . .
;,,".
Claims (33)
1. An ozone-friendly correction fluid comprising:
a non-halogenated solvent;
a film-forming polymeric material comprising an isobutyl methacrylate copolymer;
a plasticizer comprising ditridecyl phthalate; and an opacifying agent.
a non-halogenated solvent;
a film-forming polymeric material comprising an isobutyl methacrylate copolymer;
a plasticizer comprising ditridecyl phthalate; and an opacifying agent.
2. The correction fluid of claim 1, wherein said solvent comprises a cyclohexane or any alkylated cyclohexane containing 10 or fewer carbon atoms and said film-forming polymeric material is selected from the group consisting of isobutyl methacrylate copolymer, n-butyl methacrylate copolymer or mixtures thereof.
. The correction fluid of claim 2, wherein the opacifying agent is titanium dioxide.
4. The correction fluid of claim 3, wherein said solvent is methylcyclohexane.
5. The correction fluid of claim 3, wherein said solvent is dimethylcyclohexane.
6. The correction fluid of claim 3, wherein said solvent is ethylcyclohexane.
7. The correction fluid of claim 3, comprising between 35% and 55% of said solvent by weight; between 4% and 12% of said copolymer by weight; between 1% and 4% of said plasticizer by weight; and between 35% and 55% of said opacifying agent by weight.
8. The correction fluid of claim 7, wherein said solvent is methylcyclohexane.
9. The correction fluid of claim 8, further comprising an additional solvent component selected from the group consisting of odorless mineral spirits, isopropyl alcohol, dibasic esters or mixtures thereof.
10. The correction fluid of claim 9, further comprising a dispersing agent.
11. The correction fluid of claim 10, wherein said dispersing agent is a dialkyl sodium sulfosuccinate.
12. The correction fluid of claim 11, wherein said dispersing agent is dioctyl sodium sulfosuccinate.
13. The correction fluid of claim 12, wherein said film-forming polymeric material is isobutyl methacrylate copolymer with a specific gravity of about 1.05 gm/cc.
14. The correction fluid of claim 10, wherein said dispersing agent is a polymeric fatty ester.
15. The correction fluid of claim 14, wherein said film-forming polymeric material is isobutyl methacrylate copolymer with a specific gravity of about 1.05 gm/cc.
16. The correction fluid of claim 1, wherein said solvent comprises a mixture of paraffins and naphthenes and said film-forming polymeric material is selected from the group consisting of isobutyl methacrylate, n-butyl methacrylate or mixtures thereof.
17. The correction fluid of claim 16, wherein said solvent is low is aromatic hydrocarbons, high in paraffins hydrocarbons with the remainder being naphthenic hydrocarbons.
18. The correction fluid of claim 17, wherein said paraffinic hydrocarbon is predominantly C7.
19. The correction fluid of claim 17, wherein the opacifying agent is titanium dioxide.
20. The correction fluid of claim 19, comprising between 35% and 55% of said solvent by weight; between 4% and 12% of said copolymer by weight; between 1% and 4% of said plasticizer by weight; and between 35% and 55% of said opacifying agent by weight.
21. The correction fluid of claim 20, further comprising an additional solvent component selected from the group consisting of odorless mineral spirits, isopropyl alcohol, dibasic esters or mixtures thereof
22. The correction fluid of claim 21, further comprising a dispersing agent
23. The correction fluid of claim 22, wherein said dispersing agent is a polymeric fatty ester.
24. The correction fluids of claim 23, wherein said film-forming polymeric material is isobutyl methacrylate copolymer with a specific gravity of about 1.05 gm/cc.
25. The correction fluid of claim 22, wherein said film-forming polymeric material is n-butyl methacrylate copolymer with a specific gravity of about 1.06 gm/cc.
26. A correction fluid comprised of methylcyclohexane, odorless mineral spirits, isobutyl methacrylate copolymer, ditridecyl phthalate, polymeric fatty ester and titanium dioxide.
27. The correction fluid of claim 26, comprising about 34% methylcyclohexane, about 6%
odorless mineral spirits, about 7% isobutyl methacrylate copolymer, about 3% ditridecyl phthalate, about 2% polymeric fatty ester and about 48% titanium dioxide.
odorless mineral spirits, about 7% isobutyl methacrylate copolymer, about 3% ditridecyl phthalate, about 2% polymeric fatty ester and about 48% titanium dioxide.
28. A correction fluid comprised of methylcyclohexane, dibasic esters, isopropyl alcohol, odorless mineral spirits, isobutyl methacrylate copolymers, ditridecyl phthalate and titanium dioxide.
29. The correction fluid of claim 28, comprising about 29% methylcyclohexane, about 3%
dibasic esters, about 3% isobutyl alcohol, about 4% odorless mineral spirits, about 8%
isobutyl methacrylate, about 3% ditridecyl phthalate and 50% titanium dioxide.
dibasic esters, about 3% isobutyl alcohol, about 4% odorless mineral spirits, about 8%
isobutyl methacrylate, about 3% ditridecyl phthalate and 50% titanium dioxide.
30. A correction fluid comprised of a paraffin and naphthene solvent mixture, odorless mineral spirits, isobutyl methacrylate copolymer, ditridecyl phthalate, polymeric fatty ester and titanium dioxide.
31. The correction fluid of claim 32, comprising about 37% paraffin and naphthene mixture, about 6% odorless mineral spirits, about 7% isobutyl methacrylate copolymer, about 2% ditridecyl phthalate, about 2% polymeric fatty ester and about 46% titanium dioxide.
32. A correction fluid comprised of a paraffin and naphthene solvent mixture, odorless mineral spirits, n-butyl methacrylate copolymer, ditridecyl phthalate, polymeric fatty ester and titanium dioxide.
33. The correction fluid of claim 32, comprising about 38.5% paraffin and naphthene mixture, about 4% odorless mineral spirits, about 8% n-butyl methacrylate copolymer, about 3% ditridecyl phthalate, about 1% polymeric fatty ester and about 45.5% titanium dioxide.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US972,676 | 1978-12-26 | ||
| US86615992A | 1992-04-09 | 1992-04-09 | |
| US866,159 | 1992-04-09 | ||
| US07/972,676 US5306755A (en) | 1992-04-09 | 1992-11-06 | Correction fluid containing a butyl methacrylate copolymer ditridecyl phthalate, a non-halogenated solvent and an opacifying agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2133829A1 CA2133829A1 (en) | 1994-10-28 |
| CA2133829C true CA2133829C (en) | 1997-08-12 |
Family
ID=27127934
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002133829A Expired - Fee Related CA2133829C (en) | 1992-04-09 | 1993-03-16 | Ozone-friendly correction fluid |
Country Status (12)
| Country | Link |
|---|---|
| US (1) | US5306755A (en) |
| EP (1) | EP0635039B1 (en) |
| JP (1) | JP3133070B2 (en) |
| AR (1) | AR248154A1 (en) |
| AU (1) | AU3923793A (en) |
| BR (1) | BR9306206A (en) |
| CA (1) | CA2133829C (en) |
| DE (1) | DE69330826T2 (en) |
| ES (1) | ES2160598T3 (en) |
| MY (1) | MY109271A (en) |
| PH (1) | PH31151A (en) |
| WO (1) | WO1993021261A1 (en) |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3414786B2 (en) * | 1993-03-26 | 2003-06-09 | 株式会社ジーシー | Lining for denture base |
| US5464883A (en) * | 1994-06-03 | 1995-11-07 | Eastman Chemical Company | Waterborne correction fluid for correcting laser-jet and photocopied markings |
| US5480920A (en) * | 1994-08-12 | 1996-01-02 | Eastman Chemical Company | Ozone-friendly correction fluid |
| ZA96482B (en) * | 1995-01-31 | 1996-08-13 | Gillette Co | Ozone-friendly correction fluid with improved overwrite characteristic |
| US5700858A (en) * | 1995-06-08 | 1997-12-23 | Thomas Deir | Plastisol paint and method of use |
| US6227737B1 (en) | 1995-12-15 | 2001-05-08 | The Gillette Company | Fluid applicators |
| US5908498A (en) * | 1996-02-16 | 1999-06-01 | Kerr-Mcgee Chemical Llc | Process for preparing an improved low-dusting, free-flowing pigment |
| WO1997030127A1 (en) * | 1996-02-16 | 1997-08-21 | Kerr-Mcgee Chemical Corporation | Process for preparing an improved low-dusting, free-flowing pigment |
| US6083618A (en) * | 1997-06-25 | 2000-07-04 | The Gillette Company | Correction fluids comprising composite polymeric particles |
| US6312180B1 (en) | 1998-04-23 | 2001-11-06 | The Gillette Company | Applicator for correction fluid |
| USD433706S (en) * | 1998-04-23 | 2000-11-14 | The Gillette Company | Tip for correction fluid applicator |
| JP2001158869A (en) * | 1999-09-20 | 2001-06-12 | Sakura Color Prod Corp | Oil-based ink for writing tool |
| US6649213B2 (en) | 2000-11-16 | 2003-11-18 | George Debikey | Methods and compositions for preventing adverse effects of water upon a printed substrate |
| US20090311614A1 (en) * | 2006-05-10 | 2009-12-17 | Hewlett-Packard Development Company, L.P. | Charge Director for Liquid Toner |
| JP6126646B2 (en) * | 2015-06-16 | 2017-05-10 | アース製薬株式会社 | Fragrance liquid and fragrance using the same |
| JP7417441B2 (en) * | 2020-03-09 | 2024-01-18 | 三菱鉛筆株式会社 | Water-based ink composition for marking pen and marking pen |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3674729A (en) * | 1970-07-07 | 1972-07-04 | Battelle Development Corp | Correction fluid composition |
| US3997498A (en) * | 1975-07-24 | 1976-12-14 | Xerox Corporation | Non-smudge correction fluid |
| US4165988A (en) * | 1977-12-27 | 1979-08-28 | Columbia Ribbon And Carbon Manufacturing Co., Inc. | Correction fluid |
| SU891730A1 (en) * | 1980-02-22 | 1981-12-23 | Московский Филиал Всесоюзного Научно-Исследовательского Проектного Института Химической Промышленности | Correcting composition |
| JPS582363A (en) * | 1981-06-30 | 1983-01-07 | Pentel Kk | Liquid paper |
| JPS58180568A (en) * | 1982-04-16 | 1983-10-22 | Pentel Kk | Retouching liquid |
| JPS5959754A (en) * | 1982-09-29 | 1984-04-05 | Pentel Kk | Retouching solution |
| JPS6013982A (en) * | 1983-07-06 | 1985-01-24 | Mitsubishi Electric Corp | Ignition timing control device for internal-combustion engine |
| US4654081A (en) * | 1984-07-02 | 1987-03-31 | Minnesota Mining And Manufacturing Company | Nonsmearing correction fluid |
| JPH02209973A (en) * | 1989-02-10 | 1990-08-21 | Mitsubishi Pencil Co Ltd | Colored correcting ink composition |
-
1992
- 1992-11-06 US US07/972,676 patent/US5306755A/en not_active Expired - Lifetime
-
1993
- 1993-03-12 PH PH45883A patent/PH31151A/en unknown
- 1993-03-16 CA CA002133829A patent/CA2133829C/en not_active Expired - Fee Related
- 1993-03-16 AU AU39237/93A patent/AU3923793A/en not_active Abandoned
- 1993-03-16 JP JP05518329A patent/JP3133070B2/en not_active Expired - Fee Related
- 1993-03-16 EP EP93908404A patent/EP0635039B1/en not_active Expired - Lifetime
- 1993-03-16 BR BR9306206A patent/BR9306206A/en not_active IP Right Cessation
- 1993-03-16 ES ES93908404T patent/ES2160598T3/en not_active Expired - Lifetime
- 1993-03-16 DE DE69330826T patent/DE69330826T2/en not_active Expired - Fee Related
- 1993-03-16 WO PCT/US1993/002493 patent/WO1993021261A1/en active IP Right Grant
- 1993-04-01 AR AR93324645A patent/AR248154A1/en active
- 1993-04-01 MY MYPI93000581A patent/MY109271A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9306206A (en) | 1998-06-23 |
| EP0635039A4 (en) | 1996-09-04 |
| JP3133070B2 (en) | 2001-02-05 |
| MY109271A (en) | 1996-12-31 |
| US5306755A (en) | 1994-04-26 |
| WO1993021261A1 (en) | 1993-10-28 |
| EP0635039A1 (en) | 1995-01-25 |
| AU3923793A (en) | 1993-11-18 |
| CA2133829A1 (en) | 1994-10-28 |
| JPH07505666A (en) | 1995-06-22 |
| PH31151A (en) | 1998-03-20 |
| ES2160598T3 (en) | 2001-11-16 |
| AR248154A1 (en) | 1995-06-30 |
| DE69330826D1 (en) | 2001-10-31 |
| EP0635039B1 (en) | 2001-09-26 |
| DE69330826T2 (en) | 2002-03-28 |
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