CA2085817A1 - Water resistant security ink composition - Google Patents
Water resistant security ink compositionInfo
- Publication number
- CA2085817A1 CA2085817A1 CA002085817A CA2085817A CA2085817A1 CA 2085817 A1 CA2085817 A1 CA 2085817A1 CA 002085817 A CA002085817 A CA 002085817A CA 2085817 A CA2085817 A CA 2085817A CA 2085817 A1 CA2085817 A1 CA 2085817A1
- Authority
- CA
- Canada
- Prior art keywords
- ink composition
- composition according
- weight
- resistant ink
- compound
- 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.)
- Abandoned
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
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M3/00—Printing processes to produce particular kinds of printed work, e.g. patterns
- B41M3/14—Security printing
Abstract
ABSTRACT OF THE DISCLOSURE
A security composition for use with an ink composition including diphenyl guanidine and acrylic resin. The ink composition may further include a glycol ether and a plasticizer and can be printed on paper, for example in the word "VOID". If bleach is used to attempt to alter the document, the initially colorless ink will form a colored image in the shapes or letters printed on the paper. The ink composition is resistant to leaching upon contact with, for example, water.
A security composition for use with an ink composition including diphenyl guanidine and acrylic resin. The ink composition may further include a glycol ether and a plasticizer and can be printed on paper, for example in the word "VOID". If bleach is used to attempt to alter the document, the initially colorless ink will form a colored image in the shapes or letters printed on the paper. The ink composition is resistant to leaching upon contact with, for example, water.
Description
2~8~7 BACRGR()I~ND OF TE~ INV~aTION
ield o Invention This lnvention relates to a leach resistant CHLOROSTAIN ink composition. The invention al80 relate to the use of the leach resi~tant ink a~ a ~ecuri~y ink, i.e., for ~pplication to a document to prevent alteration of information on the document.
The invention further relate~ to a method of forming a document having the security ink thereon.
Description of ~he Prior Art CHLOROSTAIN-based security ink~ are initially colorless inks which are printed on a document, for example in the word ~VOID~.
If bleach or some other oxidizing agent is used in an attempt to alter the document/ the colorle~ ink forms a colored image in the shapes or letter printed on the paper.
CHLOROSTAIN-ba~ed security inks suff~r from the problem that unimaged CHLOROSTAIN can be easily washed out with water. Some government ~uri~diction~ have begun requiring that CHhOROSTAIN
security features be w~ter resistant in the unim~ged state for up 2 0 to one hour.
Th~ use of benzothiazole compounds such ~ CHLOROSTAIN OR
(Mobay Corp. Pittgburgh, PA) in ink compo~itions to prevent document slteration is known. For ~xample, U.S. Patent No.
4,227,719 to McElligott et al. diEclo~es a CHLOROSTAIN OR-based security ink. However, McElligott a~ al., like other known 2~8~7 1 CHLOROSTAIN-ba~d cecurity inks, suffers from the problem that the ink is not water xesistant and can be washed out upon contact with water.
Recently, a security ink using N-N-diphenylguanidine S (Tradename: CHLOROSTAIN BR, by Mobay Corp.) has been disclosed that provides improved water resistance. U.S. Patent No.
5,085,925 ~o Dotson discloses a leach resistant security ink that include~ CHLOROSTAIN BR. However, the ~ecurity ink disclosed by Dotson suffers f.rom several drawbacks. The ink composition requires ~he use of a complexing agent, such as glucose, sucrose, sorbitol and the like, to provide resistanee to leaching. The ink disclosed in Dotson further requires the use of a eparate fixing agent and fixing step to bind the ink composition to ~he document substrate. The separate fixing step requires either two passes through a printing or coating head or two uni~s on the press or coater for thi~ ink alone while the ink of the present invention only re~uire~ one print ~tation. Further, the carrier liquid of Dotson is either alcohol, which is ~lammable, and therefore potentially dangerou~, or water, which may distort the paper and will require d~ying. Further, the two step Dotson operation will either limit the other printing that can be done in one pass or will raise the cost if another printing or coating unit is added or if the paper is run through twice.
An ob~ect of the present invention i~ t~ provide a security composition that can be applied to a document to prevent unauthorized alteration of the document by the use of oxidizing agents .
2 ~ 7 1 Another ob~ect of the present invention is to provide an inkcomposition tha~, while initially col4rless, changes color upon contact with oxidizing agents and additionally, can not be easily leached out with water.
Another ob~ect of the invention is to provide a leach resistant ink composition which does not require the use of a complexing agent.
A fur~her ob~ect of the invention i8 to provide a document protected against alteration by use of a ~ecurity ink composition, which composition can be applied to the document without a fixing agent or a fixing ~tep.
5~ARY OF TH~ I~VENTIO~
These and other ob~ct~ have ~een ac~ieved by the present invention which relateR to a secu~ity composition for use in an ink formulstion. The security composition includes a resin and a diphenyl guanidine compound.
The present invention al o relate~ to a leach resistant ink compo~ition comprising a diphenyl guanidine compound, a resin, a pla~ticizer and a glycol ether. The ink of the present inven~ion is leach re~istant in ~oth the imaged and unimaged states.
The invention further rel~tes to a document resistan~ to alteration by oxidizing agent~. The document compri~es a substrate and the ink composit~on of the present inven~ion. The ink compos~tion can be applied ~o the document Rub~trate without a fixing agent and without a eparate fixing step.
~2~8~7 1 The ink of the present invention is particularly useful as asecurity f~ature on documents where it is important that any attempts ~t alteration be exposed. The colorle~s ink of the presen~ invention can be printed on paper, for example in the word VOID . When bleach is used to attempt to alter the document, the colorless ink of the present invention will form a colored image in the ~hapes or letters prin~ed on the paper.
~dditional ob~ects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The ob~ects and advantages of the invention can be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
DE5CRIP~ION OP TH~ PREF~ED EMBODIM~NTS
The ink composition of the present: invention can be printed on a substrate in a manner 80 that, upon attempt to alter the substrate, the initially colorle~s ink of the present invention will form a colored imsge in the shapes or letters printed on the paper.
According to the present invention, suitable substrates include p~per or paperboard and may be made from natural or synthetic materials, such as films, fabrics, foils, natural and synthetic paperc snd other media. Preferred sub~trates are natural fiber paper~ where enhanced 6ecurity is needed. These may include light and heavy weight papers, coated paper, snd security paper.
2~8~8~7 1 The ink composition of the present invention may be coa~ed over the entire sur~ace of the document substrate or may be coated on selected portions thereof. The ink may be coated in a pattern of tamper indicated indicia, for example, in the word VOID or may be coated on the surface of the 3ubstrate in a continuous film.
The security composition of the invention comprises ~ resin and diphenyl guanidine. This composition provide~ a security feature in that it becomes colored upon contact with oxidizing agents and, additionally, is resistant to being le~ched out from a ~ubstrate by water or other liquids. Thi3 basic security compo~i~ion can be utilized with variouq other known ink composition components in the formula~ion of a leach resistant ink composition.
The leach resistant ink composition of the invention includes a resin, diphanyl guanidine, a glycol ether and a plastici~er.
The resin can be selected from typical ink formulating resins, including acrylic and acrylic copolymer resins snd emulsions, epoxy resins, melamine-formaldehyde resins, polyvinyl acetates, phenolic modified resins, glycerol ester~ of synthetic resins, phenolic-modified pentaerythritol ester3 of synthetic resins, etc.
The prefer~d resin i8 an acryl~c re~in, and even more preferably is JONCRY~ 67 (produced by S.C. John~on & Sons). JONC~YL 67 is a styrene acrylic polymer resin. The resin i8 preferably present in an amoun~ from about 1 to 24~ by weight, and more preferably in an amount of about 8% to 15~ by weight based upon the final composition.
_5_ 2~g5~7 1 Preferred diphenyl guanidine compounds for use according to the pre~ent invention include the compound N-N-diphenyl guanidine, which i~ belie~ed to be the active component in CHLOROSTAIN BR.
The diphenyl guanidine is preferably present in an amount from about 1 to 30~ by weight ba~ed upon the final composition, more preferably an amount of about 5% to 21% by weight. In a preferred embodiment, the diphenyl guanidine is present in an amount of about 12~ by weight based upon the final composition.
Glycol ether compounds useful in the inX composition of the present invention include ethylene and propylene based glycol ethers and glycol ether esters. Preferably, the glycol ether compound is selected from methyl cellosolve and methyl carbitol.
More preferably, the glycol ether compound is methyl carbitol.
The glycol ether compound is preferably pre~ent in an amount from about 29~ to 59~ by weight based upon the final composition. In a preferred embodiment, the glycol ether compound is present in an amount of about 59~ by weight based upon the final composition.
Plasticizers u~eful in the ink compo~ition of the present invention include diethylene glycol, diethylene glycol monoethyl ether, diethyl phthalate, dibutyl phthalate, methyl phthalate, triethanolamine, triethyl citrate, tributoxyethyl phosphate, o,p-toluene ethyl sulfonamide, o,p-toluene ~ul~onamide and methyl phthalyl ethyl glycola~e. Preferably, the plasticizer is selected from dibu~yl phthalate, diethyl phthalate and methyl phthalate.
More preferably, the plasticizer is dibutyl ph halate. The plasticizer is preferably present in an amount from about 0 to 10%
by weight based upon the final composition, more preferably in an 2085~7 1 amount of about 1% to 3% by weight. In a preferred embodiment, the plasticizer is present in an amount of about 2% by weight based upon the final composition.
The ink composition of the present invention may further S include a benzothiazole compound, a solvent or combinations thereof.
The preferred benzothiazole compound uqeful in the ink composition of the present invention i8 Chloros~ain OR. The benzothiazole comp~und is preferably present in an amount from about 0 to 45% by weight based upon the final composition, more preferably in an amount of about 15% to 21~ by weight. In a preferred embodiment, the benzothiazole compound is present in an amount of about 15~ by weight based upon the final composition.
Solvents that are useful in the ink compo~ition of the present invention may include alcohols, such as isopropanol, propanol, ethanol, methanol, and tridecyl alcohol. More preferably, the solvent i5 isopropano:L. The solv~ent is preferably present in an amount from about 0~ to 37~ by weight.
The ink composition according to the present invention can be printed on~o a document substrate using printing methods known in the art. Among the preferred methods of printing are flexographic and gravure printing.
Once the ink composition has been printed onto the substrate, no addi~ional fixing step is necessary to bind the ink to the substrate. The composition of the invention resists leaching by techniques such as soaking in water, etc. Upon an attempt at ~085817 1 alteration of information on the doc~ent, for example by contact with bleach, the colorless ink composition will form a colored composition indicating the tampering.
~ preferred ink composition according to the present invention comprises -- about 29-59% by weigh~ methyl carbitol, -- about 1-3% by weight dibutyl phthalate, -- about 8-15~ by weight Joncryl 67 acrylic resin, -- about 15-21~ by weight CHLOROSTAIN OR, and -- about 5-21~ by weight CXLOROSTAIN BR.
The above compo~ition has a flash point greater than 200F, enabling its use in equipment that is not explo~ion proof. In a preferred embodiment of the invention, both CHLOROSTAIN OR And CHLOROSTAIN BR are used. CHLOROST~IN OR is more easily washed out but develops a color rapidly. CHLOROSTAIN BR is resistant to leachout but is slower to develop color. Thus, by varying the relative proportions of CHLOROSTAIN OR and CHLO~OSTAIN BR present in the composition, the overall ink properties can be selectively controlled to achieve tha desired res~lts.
The following examples are illustrative of the invention embodied herein but are not intended to be limiting in any way.
In a five gallon plastic bucket, 17.7 lbs. of methyl carbitol, and 0.6 lbs. of dibutyl phthalate were mixed. The mixture was stirred with an air driven stirrer. To this mixture, 3.6 lbs. of Joncryl 67 resin was slowly added.` The mixture was 2~8~3~7 1 stirred until the acrylic resin was dissolved, approximately 2 hours . Next, 4 . 5 lbs. of CHLOROSTAIN OR liquid was added and the mixture was stirred until the liquid was completely dissolved, approximately 15 minutes. 3.6 lbs. of CHLOROSTAIN ~R solid was thsn added wi~h stirring until it was dissolved, approximately 30 minutes. The ink was ready for use.
The quantities used in Example 1 represent the following percents:
Pounds ~t.
Methyl carbitol 17.7 59.0 Dibutyl phthalate 0.6 2.0 Joncryl 67 3.6 12.0 C~OROSTAIN OR 4.S 15.0 CHLOROSTAIN BR 3.6 12.0 E~LE ? ( CO~lPARATIVE 1 A control formula of Chlorostain ~R solution was made by mixing 0.38 ~rams 30% hydrochloric acid in 175 grams of tap water.
While mixing, 19.49 grams of solid Chlorostain BR was added. This was mixed un~il dis~olved. The solution was hand printed onto 24 # OCR bond paper and tested as descrilbed in Example 3 below. The results are shown in Tables 1,2,5 and 6.
2~A~LF~
In a five gallon plastic bucket, 1917.5 g of isopropanol, 1917.5 g of me~hyl cello~olve and 130.0 g of dibutyl phthalate were mixed. The mixture was stirred with an air driven stirrer.
To this mixture, 780.0 g of Joncryl 67 resin was added. The mixture was stirred until the acrylic resin ~as dissolved, _g_ 2~8~8~7 1 approximately 1 hour. Next, 975.0 g of CHLOROSTAIN OR liquid was added and the mixture was stirred until the liquid was completely dissolved, approximately 15 minutes. 780.0 g of CHLOROSTAIN BR
solid wa~ then added with stirring until it was dissolved, approximately 30 minutes, The resulting ink was printed on 24 # OCR bond paper. Six 1 inch x 6 inch strips were then cu~ and half of the strip was activated to form the image u ing diluted household bleach and a cot~on swab. The ~trips were allowed to dry for one half hour.
The strips were then placed in 110F water and allowed to soaX. A
s~rip was removed from the beaker at 5, 15, 30, 60, 120 and 240 minutes and allowed to dry. Each strip was reactivated with diluted bleach on the half that was not activated prior to the hot water soak. The results compare the water resistance of the imaged and unimaged ink. See Tables 1 and 2.
The quantities used in Example 3 represent the following percents:
Grams Wt.
IRopropanol 1917.5 ~3.5 Methyl cellosolve 1917.5 29.5 Dibutyl phthalate 130.0 ~2.0 Joncryl 67 780.O 12.0 CHLOROSTAIN O~ 975.0 15.0 C~LOROSTAIN BR ~780.0 12.0 ~AMPL~ 4 Example 4 was c~rried out in the same manner as Example 3, using the following compounds and amounts:
2~58~7 1 Grams Wt. %
Isopropanol 1917.5 29.5 Methyl cellosolve1917.5 29.5 ~ibutyl phthalate130.0 2.0 Joncryl 67 780.0 12.0 CHLOROSTAIN OR 1365.0 21.0 CHLOROSTAIN BR 390.0 6.0 EXAMPL~E S ~COMPAR~TrVE~
Example 5 wa~ carried out in ~he same manner as Example 3, using the following compounds and amoun~s:
Grams ~t. %
Isopropanol 1917.5 29.5 Methyl cellosolve1917.5 29.5 Dibu~yl phthalate130.0 2.0 Joncryl 67 780.0 12.0 CHLOROSTAIN OR 1755.0 27.0 The resulting ink is a control ink using only CHLOROSTAIN OR
without the u~e of any CHLO~OSTAIN 8R.
Example 6 was carried out in the same manner as Example 3, using the following compounds and amounts:
Gram~~to S
Isopropanol 2405.0 37.0 Methyl cello301ve2405.0 37.0 Dibutyl phthalate130.0 2.0 Joncryl 67 780.0 12 . O
CHLOROSTAIN BR 780.0 12 . O
From Table 2, it can be seen that when the inks were imaged before being soaked, complete water washout only occurred in Example 5, which contains only CHLOROSTAIN OR, with CHLOROST~IN BR
being absent. From Table 1, when the same inks were soaked before 20~
1 imaging, Examples 3~ 4 and 6 gave acceptable results. Compaxative Examples 2 and 5 were the only inks showing complete water washout before 240 minutes.
~AKPL~ 7 S Example 7 was carried out in the same manner as Example 1, using the following compounds and amounts:
~c. %
Methyl carbitol 2~.5 Dibutyl phthalate 2.0 Isopropyl Alcohol 29.5 Joncryl 67 lZ.O
CHLOROSTAIN OR 15.0 CHLOROSTAIN BR 12.0 E~AMPLE 8 In a five gallon plastic bucket, 8.85 lbs. of methyl carbitol, 8.85 lbs. of isopropyl alcohol and 0.6 lbs. of dibutyl phthalate were mixed. The mixture wa~ stirred with an air driven stirrer. To this mixture, 3.6 lbs. of Joncryl 67 resin was added.
The mixture was stirred until the acrylic resin was dissolved, approximately 1 hour. Next, 4.5 lbs. of CHLOROSTAIN OR liquid was added and the mixture was stirred unt,il the liquid was completely dissolv~d, approximately 15 minutes. 3.6 lbs. of CHLOROSTAIN BR
solid was then added with stirring until it was dis~olved, approximately 30 m~nutes.
The resulting ink was printed on 24# OCR bond paper and 99#
TAG paper. Strip~ were then cu~ and half of the strip was activated using diluted household bleach and a cotton swab. The ~trips were allowed to dry for one half hour. The strips were ~hen placed in llO~F wa~er and allowed to soak. A strip was 2~3~2~3-419 1 removed from the beaker at 5, 15, 30, 60, 120 and 240 minutes and allowed to dry. Each strip was reactivated with diluted bleach on the half that was not activated prior to the hot water soak. The results compare the water re-~istance of the imaged and unimaged ink. See Tables 3 and 4.
The quan~ities used in Example 8 reprQ~ent the Pollowing percent~:
Pounds ~t. ~
I~opropyl alcohol3.5 29.5 Methyl carbitol 8.5 29.5 Dibutyl phth~late0.6 2.0 Joncryl 67 3.6 12.0 CHLOROSTAIN OR 4.5 15.0 CHLOROSTAIN ~R 3.6 12.0 As can be seen in Table~ 3 and 4, the ink was not suseeptible to water washout in either the imaged or ~nimaged states.
~xampl~ 9 The following ingredien~s were dissolved by mixing:
Foral 65 (~lycerol ester of ~ynthetic24 8.3 resin (Hercule~) Methyl carbitol 118 40.7 I~opropyl alcohol llB 40.7 Chlorostain BR 30 10.3 The solution was hand coated onto 204 Xerographic paper using a smooth rod. The samples ~ere dried and ta~ted 8~ bePore.
~XAMPLE 10 The following ingredients were dissolved by mixing:
. . ., ~ ~., ~
2~8~7 1 GRAMS %
Epon 1002 (epoxy resin) (shell) 24 13.9 Methyl carbitol 118 68.6 Chlorostain BR 30 17.4 The solution was hand coated on o 20# Xerographic paper using a smoo~h rod. The sampleq were dried and tested as before.
~xam~le 11 The following ingredients were dissolved by mixing:
GRA~S %
Parez 613 (melamine formaldehyde resin) (American Cyanamid) 24 13.9 Methyl carbitol 118 68.6 Chlorostain BR 30 17.4 The solution was hand coated onto 20# Xero~raphic paper using a smooth rod. The samples were dried and tested as before.
ExamPle 12 The following ingredients were dissolved by mixing:
GRAMS %
Mowilith S0 (Polyvinyl acetate) (Hoechst Chemical) 24 8.3 Methyl carbitol 118 40.7 Isopropyl alcohol 118 40.7 Chlorostain BR 30 10.3 The solution w~s hand coated onto 20# Xerographic paper using a smooth rod. The sample-c were dried snd tested as before.
E~am~le 13 The following ingredient~ were dissolved by mixing:
G~MS %
Polypale ester 10 (glycerol ester of synthetic resin~ (Hercules) 24 8.3 Methyl carbitol 118 40.7 Isopropyl alcohol 118 40.7 Chlorostain BR 30 10.3 20~
1 Not all of the resin dissolved in 24 hours. The clear liquid was decanted, Chlorostain BR added, dissolved and coated.
The ~olution was hand coated onto 20# Xerographic paper using a smooth rod. The samples were dried and tested a~ before.
x~me~_14 The following ingredients were dissolved by mixing:
GRAMS
Pental~n 802 A (phenolic-modified pentaerythxitol ester of syn~hetic resin) (Hercules) 12 7.5 Methyl carbitol 118 73.8 Chlorostain BR 30 18.8 Not all of the resin dissolved in 24 hours. The clear liquid was decanted, Chlorostain BR added, dissolved and coat~d.
The solution was hand coated onto 20~ Xerographic paper using a smooth rod. The samples were dried and tested as before.
It can be seen from Table 5 that the inks made by Examples 9-14 are not leached from the test paper until at least 15 minutes (Exs. 9, 11 and 12), and in some cases are not leached from the paper even after soaking in water for 30 minutes. On the other hand, the ink made by Example 2, using a mixture of Chlorostain BR, 30~ HCl and tap water, was leached out of the test paper before 5 minu~es.
Other ~mbodiments of the invention will be apparent to those skilled in the ar~ from consideration of the specification and practice of the invention disclosed herein. I~ is intendsd that the specifica~ion and example~ be con~idered aR exemplary only with a true scope and spirit of the invention being indicated by the following claims.
SDI~I U 110' W08~ 2~ 9L9~
_ __ ~_ _~ __ __ __ __ ~ sal~ ~ 13' ~0' ilO~ 120' 2~0 _ __ __ __ ~_ __ __ _~
~u a ~ ~R ~113S ~ ~ ~ ~
_ __ _. ._ ~ __ __ ~a~ ~ ~ ~ ~ a~ ~ ~ n~c _ __ __ __ __ __ __ __ ~il~YU 4 1~ S~ ~rOtlg ~SO~ t~G~la r~s L~
.
~8 ~ ~ ~ ~o~ ~o~ ~ ~ ao~
- - - - - - - -~ - -. - - - -~ ~ a~ Da~ D~ ~ ~C liUB a~
~v- - - - - - l~ - - ~ - - - - ~ - - -S~ ~S 110 ~ --~-----~ ----S~ ~L ~' 1~'~O' ~0' ~0' a40~
_ . . _ ~ __ ~
~r~ a ~ D~ a~n~ D~ s~ D~ ~
_- . . - _ ~ __ __ __ ~u ~ ~ ~ ~ ~ - ~ ~ ~
~ ~ ~ L~ ~S ~a~ L~ LSC~ L~r - - - - - ~- - ~ ~ - - - -I~LI~ 3 ~ 111~ ~t 1~1, 1101111 11 __ _ __ . ._ .
~ ~ D~Jt IU~I: 11~ ~a~ ~U21C i~lllt D~C
_ __ __ __ es~_:, , __ __ __ 20~8~
SOA~ TI~E AT 110 F BEFORE I~AGING ~IT~I BLEACI~
I _ . .__ _ ~ :_ A__ _ _, IPAPER INITI~L ¦ 5 ' 15 ' 30 ~ 60 ' 12 0 ' 2 40 ' I . ._ I .. . __ . _ _ .__ ¦2 4# OCR D~e ¦ DARR DARl~ DAR$ DAR~ D~EUC DABR
~ -- _ . . __ ~= _ ~ ._ ¦99# TAC ¦ DARR DARR DARK DARR DARR DARl~ DAR~
i~ ~ . _ --SOA.K TI~ AT 110 ~ AFrE:R I~G:~NG WITEI BL~C~
_ _ _ _ -----~ ... _ . ~----- ~-- r ---~
PAPER INITIAL 5 ' 15 ' 30 ' 50 ' 120 ' 240 _ _ ~ . _ ,,, __ . I
24# OCR DARK DJU~C D~R~ D~RR DARIC DJ~RR DARX l .. = .. _ .. =_ . . -9 9# T~C ¦ D~ D~ DIU~Y DJ~RK ¦ DARR ¦ DAR~ DARK l . .1 ... ~F_.~ .~ ", _ .. 1 , ~ -8iL7 TABL~
SO~X TI~E AT 110 F BEFO~E I~AGING ~ITH BLEACH
r Ink ¦ Initlal ¦ 5 Minutes ¦ 15 Minutes ¦ 30 Minutes - , -_ ..
E~ample 9 d-rk dark none none ¦
E~ample 10 darkdsrk dark li~ht .. __ _ ...... _.
Esamp 1 e 11 dark llght none r.one . _ Exampla 12 dark llght none none E~ample 13 dark dnrk dark llght ... _ ._ ...... __ . __ E~amlpe 14 darkdark dark dark . _ _ E~ample 2 DarkNone Non~ None SOAR TI~E AT 110'' F AFTER r~AGING ~IT~ BLEACH
Ink ¦ Inltlal ¦ 5 ~inutes ¦ 15 Mlnutes ¦ 30 Mlnutes -- __ ~
Example 9 Dark¦ Dark ¦ Dark Dark == . _ -------~
Example 10 Dark ¦ D4rk Dark ¦ Dsrk .. ,~ _-__ _ E~ample 11 D-rk ¦ Dark Dark Dark ~ - . '- I= _ ~
Example 12 Dsrk Dsrk Dark Dark . ......... . ~ _ - ---- _ ... = .=-------- . , Example 13 D~rk Dark ¦ Dark ¦ Dark . ~ _ 'I
E~amlpe 14 D~rk Dark ¦ Dark Dsrk __ _ - ~ 'I
Esampl~ 2 Dark Dark ¦ Dnrk ¦ Dark .~. ~ ~_, ~, . . .~ . . _ . ._ ~ - _ ~
ield o Invention This lnvention relates to a leach resistant CHLOROSTAIN ink composition. The invention al80 relate to the use of the leach resi~tant ink a~ a ~ecuri~y ink, i.e., for ~pplication to a document to prevent alteration of information on the document.
The invention further relate~ to a method of forming a document having the security ink thereon.
Description of ~he Prior Art CHLOROSTAIN-based security ink~ are initially colorless inks which are printed on a document, for example in the word ~VOID~.
If bleach or some other oxidizing agent is used in an attempt to alter the document/ the colorle~ ink forms a colored image in the shapes or letter printed on the paper.
CHLOROSTAIN-ba~ed security inks suff~r from the problem that unimaged CHLOROSTAIN can be easily washed out with water. Some government ~uri~diction~ have begun requiring that CHhOROSTAIN
security features be w~ter resistant in the unim~ged state for up 2 0 to one hour.
Th~ use of benzothiazole compounds such ~ CHLOROSTAIN OR
(Mobay Corp. Pittgburgh, PA) in ink compo~itions to prevent document slteration is known. For ~xample, U.S. Patent No.
4,227,719 to McElligott et al. diEclo~es a CHLOROSTAIN OR-based security ink. However, McElligott a~ al., like other known 2~8~7 1 CHLOROSTAIN-ba~d cecurity inks, suffers from the problem that the ink is not water xesistant and can be washed out upon contact with water.
Recently, a security ink using N-N-diphenylguanidine S (Tradename: CHLOROSTAIN BR, by Mobay Corp.) has been disclosed that provides improved water resistance. U.S. Patent No.
5,085,925 ~o Dotson discloses a leach resistant security ink that include~ CHLOROSTAIN BR. However, the ~ecurity ink disclosed by Dotson suffers f.rom several drawbacks. The ink composition requires ~he use of a complexing agent, such as glucose, sucrose, sorbitol and the like, to provide resistanee to leaching. The ink disclosed in Dotson further requires the use of a eparate fixing agent and fixing step to bind the ink composition to ~he document substrate. The separate fixing step requires either two passes through a printing or coating head or two uni~s on the press or coater for thi~ ink alone while the ink of the present invention only re~uire~ one print ~tation. Further, the carrier liquid of Dotson is either alcohol, which is ~lammable, and therefore potentially dangerou~, or water, which may distort the paper and will require d~ying. Further, the two step Dotson operation will either limit the other printing that can be done in one pass or will raise the cost if another printing or coating unit is added or if the paper is run through twice.
An ob~ect of the present invention i~ t~ provide a security composition that can be applied to a document to prevent unauthorized alteration of the document by the use of oxidizing agents .
2 ~ 7 1 Another ob~ect of the present invention is to provide an inkcomposition tha~, while initially col4rless, changes color upon contact with oxidizing agents and additionally, can not be easily leached out with water.
Another ob~ect of the invention is to provide a leach resistant ink composition which does not require the use of a complexing agent.
A fur~her ob~ect of the invention i8 to provide a document protected against alteration by use of a ~ecurity ink composition, which composition can be applied to the document without a fixing agent or a fixing ~tep.
5~ARY OF TH~ I~VENTIO~
These and other ob~ct~ have ~een ac~ieved by the present invention which relateR to a secu~ity composition for use in an ink formulstion. The security composition includes a resin and a diphenyl guanidine compound.
The present invention al o relate~ to a leach resistant ink compo~ition comprising a diphenyl guanidine compound, a resin, a pla~ticizer and a glycol ether. The ink of the present inven~ion is leach re~istant in ~oth the imaged and unimaged states.
The invention further rel~tes to a document resistan~ to alteration by oxidizing agent~. The document compri~es a substrate and the ink composit~on of the present inven~ion. The ink compos~tion can be applied ~o the document Rub~trate without a fixing agent and without a eparate fixing step.
~2~8~7 1 The ink of the present invention is particularly useful as asecurity f~ature on documents where it is important that any attempts ~t alteration be exposed. The colorle~s ink of the presen~ invention can be printed on paper, for example in the word VOID . When bleach is used to attempt to alter the document, the colorless ink of the present invention will form a colored image in the ~hapes or letters prin~ed on the paper.
~dditional ob~ects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The ob~ects and advantages of the invention can be realized and attained by means of the elements and combinations particularly pointed out in the appended claims.
DE5CRIP~ION OP TH~ PREF~ED EMBODIM~NTS
The ink composition of the present: invention can be printed on a substrate in a manner 80 that, upon attempt to alter the substrate, the initially colorle~s ink of the present invention will form a colored imsge in the shapes or letters printed on the paper.
According to the present invention, suitable substrates include p~per or paperboard and may be made from natural or synthetic materials, such as films, fabrics, foils, natural and synthetic paperc snd other media. Preferred sub~trates are natural fiber paper~ where enhanced 6ecurity is needed. These may include light and heavy weight papers, coated paper, snd security paper.
2~8~8~7 1 The ink composition of the present invention may be coa~ed over the entire sur~ace of the document substrate or may be coated on selected portions thereof. The ink may be coated in a pattern of tamper indicated indicia, for example, in the word VOID or may be coated on the surface of the 3ubstrate in a continuous film.
The security composition of the invention comprises ~ resin and diphenyl guanidine. This composition provide~ a security feature in that it becomes colored upon contact with oxidizing agents and, additionally, is resistant to being le~ched out from a ~ubstrate by water or other liquids. Thi3 basic security compo~i~ion can be utilized with variouq other known ink composition components in the formula~ion of a leach resistant ink composition.
The leach resistant ink composition of the invention includes a resin, diphanyl guanidine, a glycol ether and a plastici~er.
The resin can be selected from typical ink formulating resins, including acrylic and acrylic copolymer resins snd emulsions, epoxy resins, melamine-formaldehyde resins, polyvinyl acetates, phenolic modified resins, glycerol ester~ of synthetic resins, phenolic-modified pentaerythritol ester3 of synthetic resins, etc.
The prefer~d resin i8 an acryl~c re~in, and even more preferably is JONCRY~ 67 (produced by S.C. John~on & Sons). JONC~YL 67 is a styrene acrylic polymer resin. The resin i8 preferably present in an amoun~ from about 1 to 24~ by weight, and more preferably in an amount of about 8% to 15~ by weight based upon the final composition.
_5_ 2~g5~7 1 Preferred diphenyl guanidine compounds for use according to the pre~ent invention include the compound N-N-diphenyl guanidine, which i~ belie~ed to be the active component in CHLOROSTAIN BR.
The diphenyl guanidine is preferably present in an amount from about 1 to 30~ by weight ba~ed upon the final composition, more preferably an amount of about 5% to 21% by weight. In a preferred embodiment, the diphenyl guanidine is present in an amount of about 12~ by weight based upon the final composition.
Glycol ether compounds useful in the inX composition of the present invention include ethylene and propylene based glycol ethers and glycol ether esters. Preferably, the glycol ether compound is selected from methyl cellosolve and methyl carbitol.
More preferably, the glycol ether compound is methyl carbitol.
The glycol ether compound is preferably pre~ent in an amount from about 29~ to 59~ by weight based upon the final composition. In a preferred embodiment, the glycol ether compound is present in an amount of about 59~ by weight based upon the final composition.
Plasticizers u~eful in the ink compo~ition of the present invention include diethylene glycol, diethylene glycol monoethyl ether, diethyl phthalate, dibutyl phthalate, methyl phthalate, triethanolamine, triethyl citrate, tributoxyethyl phosphate, o,p-toluene ethyl sulfonamide, o,p-toluene ~ul~onamide and methyl phthalyl ethyl glycola~e. Preferably, the plasticizer is selected from dibu~yl phthalate, diethyl phthalate and methyl phthalate.
More preferably, the plasticizer is dibutyl ph halate. The plasticizer is preferably present in an amount from about 0 to 10%
by weight based upon the final composition, more preferably in an 2085~7 1 amount of about 1% to 3% by weight. In a preferred embodiment, the plasticizer is present in an amount of about 2% by weight based upon the final composition.
The ink composition of the present invention may further S include a benzothiazole compound, a solvent or combinations thereof.
The preferred benzothiazole compound uqeful in the ink composition of the present invention i8 Chloros~ain OR. The benzothiazole comp~und is preferably present in an amount from about 0 to 45% by weight based upon the final composition, more preferably in an amount of about 15% to 21~ by weight. In a preferred embodiment, the benzothiazole compound is present in an amount of about 15~ by weight based upon the final composition.
Solvents that are useful in the ink compo~ition of the present invention may include alcohols, such as isopropanol, propanol, ethanol, methanol, and tridecyl alcohol. More preferably, the solvent i5 isopropano:L. The solv~ent is preferably present in an amount from about 0~ to 37~ by weight.
The ink composition according to the present invention can be printed on~o a document substrate using printing methods known in the art. Among the preferred methods of printing are flexographic and gravure printing.
Once the ink composition has been printed onto the substrate, no addi~ional fixing step is necessary to bind the ink to the substrate. The composition of the invention resists leaching by techniques such as soaking in water, etc. Upon an attempt at ~085817 1 alteration of information on the doc~ent, for example by contact with bleach, the colorless ink composition will form a colored composition indicating the tampering.
~ preferred ink composition according to the present invention comprises -- about 29-59% by weigh~ methyl carbitol, -- about 1-3% by weight dibutyl phthalate, -- about 8-15~ by weight Joncryl 67 acrylic resin, -- about 15-21~ by weight CHLOROSTAIN OR, and -- about 5-21~ by weight CXLOROSTAIN BR.
The above compo~ition has a flash point greater than 200F, enabling its use in equipment that is not explo~ion proof. In a preferred embodiment of the invention, both CHLOROSTAIN OR And CHLOROSTAIN BR are used. CHLOROST~IN OR is more easily washed out but develops a color rapidly. CHLOROSTAIN BR is resistant to leachout but is slower to develop color. Thus, by varying the relative proportions of CHLOROSTAIN OR and CHLO~OSTAIN BR present in the composition, the overall ink properties can be selectively controlled to achieve tha desired res~lts.
The following examples are illustrative of the invention embodied herein but are not intended to be limiting in any way.
In a five gallon plastic bucket, 17.7 lbs. of methyl carbitol, and 0.6 lbs. of dibutyl phthalate were mixed. The mixture was stirred with an air driven stirrer. To this mixture, 3.6 lbs. of Joncryl 67 resin was slowly added.` The mixture was 2~8~3~7 1 stirred until the acrylic resin was dissolved, approximately 2 hours . Next, 4 . 5 lbs. of CHLOROSTAIN OR liquid was added and the mixture was stirred until the liquid was completely dissolved, approximately 15 minutes. 3.6 lbs. of CHLOROSTAIN ~R solid was thsn added wi~h stirring until it was dissolved, approximately 30 minutes. The ink was ready for use.
The quantities used in Example 1 represent the following percents:
Pounds ~t.
Methyl carbitol 17.7 59.0 Dibutyl phthalate 0.6 2.0 Joncryl 67 3.6 12.0 C~OROSTAIN OR 4.S 15.0 CHLOROSTAIN BR 3.6 12.0 E~LE ? ( CO~lPARATIVE 1 A control formula of Chlorostain ~R solution was made by mixing 0.38 ~rams 30% hydrochloric acid in 175 grams of tap water.
While mixing, 19.49 grams of solid Chlorostain BR was added. This was mixed un~il dis~olved. The solution was hand printed onto 24 # OCR bond paper and tested as descrilbed in Example 3 below. The results are shown in Tables 1,2,5 and 6.
2~A~LF~
In a five gallon plastic bucket, 1917.5 g of isopropanol, 1917.5 g of me~hyl cello~olve and 130.0 g of dibutyl phthalate were mixed. The mixture was stirred with an air driven stirrer.
To this mixture, 780.0 g of Joncryl 67 resin was added. The mixture was stirred until the acrylic resin ~as dissolved, _g_ 2~8~8~7 1 approximately 1 hour. Next, 975.0 g of CHLOROSTAIN OR liquid was added and the mixture was stirred until the liquid was completely dissolved, approximately 15 minutes. 780.0 g of CHLOROSTAIN BR
solid wa~ then added with stirring until it was dissolved, approximately 30 minutes, The resulting ink was printed on 24 # OCR bond paper. Six 1 inch x 6 inch strips were then cu~ and half of the strip was activated to form the image u ing diluted household bleach and a cot~on swab. The ~trips were allowed to dry for one half hour.
The strips were then placed in 110F water and allowed to soaX. A
s~rip was removed from the beaker at 5, 15, 30, 60, 120 and 240 minutes and allowed to dry. Each strip was reactivated with diluted bleach on the half that was not activated prior to the hot water soak. The results compare the water resistance of the imaged and unimaged ink. See Tables 1 and 2.
The quantities used in Example 3 represent the following percents:
Grams Wt.
IRopropanol 1917.5 ~3.5 Methyl cellosolve 1917.5 29.5 Dibutyl phthalate 130.0 ~2.0 Joncryl 67 780.O 12.0 CHLOROSTAIN O~ 975.0 15.0 C~LOROSTAIN BR ~780.0 12.0 ~AMPL~ 4 Example 4 was c~rried out in the same manner as Example 3, using the following compounds and amounts:
2~58~7 1 Grams Wt. %
Isopropanol 1917.5 29.5 Methyl cellosolve1917.5 29.5 ~ibutyl phthalate130.0 2.0 Joncryl 67 780.0 12.0 CHLOROSTAIN OR 1365.0 21.0 CHLOROSTAIN BR 390.0 6.0 EXAMPL~E S ~COMPAR~TrVE~
Example 5 wa~ carried out in ~he same manner as Example 3, using the following compounds and amoun~s:
Grams ~t. %
Isopropanol 1917.5 29.5 Methyl cellosolve1917.5 29.5 Dibu~yl phthalate130.0 2.0 Joncryl 67 780.0 12.0 CHLOROSTAIN OR 1755.0 27.0 The resulting ink is a control ink using only CHLOROSTAIN OR
without the u~e of any CHLO~OSTAIN 8R.
Example 6 was carried out in the same manner as Example 3, using the following compounds and amounts:
Gram~~to S
Isopropanol 2405.0 37.0 Methyl cello301ve2405.0 37.0 Dibutyl phthalate130.0 2.0 Joncryl 67 780.0 12 . O
CHLOROSTAIN BR 780.0 12 . O
From Table 2, it can be seen that when the inks were imaged before being soaked, complete water washout only occurred in Example 5, which contains only CHLOROSTAIN OR, with CHLOROST~IN BR
being absent. From Table 1, when the same inks were soaked before 20~
1 imaging, Examples 3~ 4 and 6 gave acceptable results. Compaxative Examples 2 and 5 were the only inks showing complete water washout before 240 minutes.
~AKPL~ 7 S Example 7 was carried out in the same manner as Example 1, using the following compounds and amounts:
~c. %
Methyl carbitol 2~.5 Dibutyl phthalate 2.0 Isopropyl Alcohol 29.5 Joncryl 67 lZ.O
CHLOROSTAIN OR 15.0 CHLOROSTAIN BR 12.0 E~AMPLE 8 In a five gallon plastic bucket, 8.85 lbs. of methyl carbitol, 8.85 lbs. of isopropyl alcohol and 0.6 lbs. of dibutyl phthalate were mixed. The mixture wa~ stirred with an air driven stirrer. To this mixture, 3.6 lbs. of Joncryl 67 resin was added.
The mixture was stirred until the acrylic resin was dissolved, approximately 1 hour. Next, 4.5 lbs. of CHLOROSTAIN OR liquid was added and the mixture was stirred unt,il the liquid was completely dissolv~d, approximately 15 minutes. 3.6 lbs. of CHLOROSTAIN BR
solid was then added with stirring until it was dis~olved, approximately 30 m~nutes.
The resulting ink was printed on 24# OCR bond paper and 99#
TAG paper. Strip~ were then cu~ and half of the strip was activated using diluted household bleach and a cotton swab. The ~trips were allowed to dry for one half hour. The strips were ~hen placed in llO~F wa~er and allowed to soak. A strip was 2~3~2~3-419 1 removed from the beaker at 5, 15, 30, 60, 120 and 240 minutes and allowed to dry. Each strip was reactivated with diluted bleach on the half that was not activated prior to the hot water soak. The results compare the water re-~istance of the imaged and unimaged ink. See Tables 3 and 4.
The quan~ities used in Example 8 reprQ~ent the Pollowing percent~:
Pounds ~t. ~
I~opropyl alcohol3.5 29.5 Methyl carbitol 8.5 29.5 Dibutyl phth~late0.6 2.0 Joncryl 67 3.6 12.0 CHLOROSTAIN OR 4.5 15.0 CHLOROSTAIN ~R 3.6 12.0 As can be seen in Table~ 3 and 4, the ink was not suseeptible to water washout in either the imaged or ~nimaged states.
~xampl~ 9 The following ingredien~s were dissolved by mixing:
Foral 65 (~lycerol ester of ~ynthetic24 8.3 resin (Hercule~) Methyl carbitol 118 40.7 I~opropyl alcohol llB 40.7 Chlorostain BR 30 10.3 The solution was hand coated onto 204 Xerographic paper using a smooth rod. The samples ~ere dried and ta~ted 8~ bePore.
~XAMPLE 10 The following ingredients were dissolved by mixing:
. . ., ~ ~., ~
2~8~7 1 GRAMS %
Epon 1002 (epoxy resin) (shell) 24 13.9 Methyl carbitol 118 68.6 Chlorostain BR 30 17.4 The solution was hand coated on o 20# Xerographic paper using a smoo~h rod. The sampleq were dried and tested as before.
~xam~le 11 The following ingredients were dissolved by mixing:
GRA~S %
Parez 613 (melamine formaldehyde resin) (American Cyanamid) 24 13.9 Methyl carbitol 118 68.6 Chlorostain BR 30 17.4 The solution was hand coated onto 20# Xero~raphic paper using a smooth rod. The samples were dried and tested as before.
ExamPle 12 The following ingredients were dissolved by mixing:
GRAMS %
Mowilith S0 (Polyvinyl acetate) (Hoechst Chemical) 24 8.3 Methyl carbitol 118 40.7 Isopropyl alcohol 118 40.7 Chlorostain BR 30 10.3 The solution w~s hand coated onto 20# Xerographic paper using a smooth rod. The sample-c were dried snd tested as before.
E~am~le 13 The following ingredient~ were dissolved by mixing:
G~MS %
Polypale ester 10 (glycerol ester of synthetic resin~ (Hercules) 24 8.3 Methyl carbitol 118 40.7 Isopropyl alcohol 118 40.7 Chlorostain BR 30 10.3 20~
1 Not all of the resin dissolved in 24 hours. The clear liquid was decanted, Chlorostain BR added, dissolved and coated.
The ~olution was hand coated onto 20# Xerographic paper using a smooth rod. The samples were dried and tested a~ before.
x~me~_14 The following ingredients were dissolved by mixing:
GRAMS
Pental~n 802 A (phenolic-modified pentaerythxitol ester of syn~hetic resin) (Hercules) 12 7.5 Methyl carbitol 118 73.8 Chlorostain BR 30 18.8 Not all of the resin dissolved in 24 hours. The clear liquid was decanted, Chlorostain BR added, dissolved and coat~d.
The solution was hand coated onto 20~ Xerographic paper using a smooth rod. The samples were dried and tested as before.
It can be seen from Table 5 that the inks made by Examples 9-14 are not leached from the test paper until at least 15 minutes (Exs. 9, 11 and 12), and in some cases are not leached from the paper even after soaking in water for 30 minutes. On the other hand, the ink made by Example 2, using a mixture of Chlorostain BR, 30~ HCl and tap water, was leached out of the test paper before 5 minu~es.
Other ~mbodiments of the invention will be apparent to those skilled in the ar~ from consideration of the specification and practice of the invention disclosed herein. I~ is intendsd that the specifica~ion and example~ be con~idered aR exemplary only with a true scope and spirit of the invention being indicated by the following claims.
SDI~I U 110' W08~ 2~ 9L9~
_ __ ~_ _~ __ __ __ __ ~ sal~ ~ 13' ~0' ilO~ 120' 2~0 _ __ __ __ ~_ __ __ _~
~u a ~ ~R ~113S ~ ~ ~ ~
_ __ _. ._ ~ __ __ ~a~ ~ ~ ~ ~ a~ ~ ~ n~c _ __ __ __ __ __ __ __ ~il~YU 4 1~ S~ ~rOtlg ~SO~ t~G~la r~s L~
.
~8 ~ ~ ~ ~o~ ~o~ ~ ~ ao~
- - - - - - - -~ - -. - - - -~ ~ a~ Da~ D~ ~ ~C liUB a~
~v- - - - - - l~ - - ~ - - - - ~ - - -S~ ~S 110 ~ --~-----~ ----S~ ~L ~' 1~'~O' ~0' ~0' a40~
_ . . _ ~ __ ~
~r~ a ~ D~ a~n~ D~ s~ D~ ~
_- . . - _ ~ __ __ __ ~u ~ ~ ~ ~ ~ - ~ ~ ~
~ ~ ~ L~ ~S ~a~ L~ LSC~ L~r - - - - - ~- - ~ ~ - - - -I~LI~ 3 ~ 111~ ~t 1~1, 1101111 11 __ _ __ . ._ .
~ ~ D~Jt IU~I: 11~ ~a~ ~U21C i~lllt D~C
_ __ __ __ es~_:, , __ __ __ 20~8~
SOA~ TI~E AT 110 F BEFORE I~AGING ~IT~I BLEACI~
I _ . .__ _ ~ :_ A__ _ _, IPAPER INITI~L ¦ 5 ' 15 ' 30 ~ 60 ' 12 0 ' 2 40 ' I . ._ I .. . __ . _ _ .__ ¦2 4# OCR D~e ¦ DARR DARl~ DAR$ DAR~ D~EUC DABR
~ -- _ . . __ ~= _ ~ ._ ¦99# TAC ¦ DARR DARR DARK DARR DARR DARl~ DAR~
i~ ~ . _ --SOA.K TI~ AT 110 ~ AFrE:R I~G:~NG WITEI BL~C~
_ _ _ _ -----~ ... _ . ~----- ~-- r ---~
PAPER INITIAL 5 ' 15 ' 30 ' 50 ' 120 ' 240 _ _ ~ . _ ,,, __ . I
24# OCR DARK DJU~C D~R~ D~RR DARIC DJ~RR DARX l .. = .. _ .. =_ . . -9 9# T~C ¦ D~ D~ DIU~Y DJ~RK ¦ DARR ¦ DAR~ DARK l . .1 ... ~F_.~ .~ ", _ .. 1 , ~ -8iL7 TABL~
SO~X TI~E AT 110 F BEFO~E I~AGING ~ITH BLEACH
r Ink ¦ Initlal ¦ 5 Minutes ¦ 15 Minutes ¦ 30 Minutes - , -_ ..
E~ample 9 d-rk dark none none ¦
E~ample 10 darkdsrk dark li~ht .. __ _ ...... _.
Esamp 1 e 11 dark llght none r.one . _ Exampla 12 dark llght none none E~ample 13 dark dnrk dark llght ... _ ._ ...... __ . __ E~amlpe 14 darkdark dark dark . _ _ E~ample 2 DarkNone Non~ None SOAR TI~E AT 110'' F AFTER r~AGING ~IT~ BLEACH
Ink ¦ Inltlal ¦ 5 ~inutes ¦ 15 Mlnutes ¦ 30 Mlnutes -- __ ~
Example 9 Dark¦ Dark ¦ Dark Dark == . _ -------~
Example 10 Dark ¦ D4rk Dark ¦ Dsrk .. ,~ _-__ _ E~ample 11 D-rk ¦ Dark Dark Dark ~ - . '- I= _ ~
Example 12 Dsrk Dsrk Dark Dark . ......... . ~ _ - ---- _ ... = .=-------- . , Example 13 D~rk Dark ¦ Dark ¦ Dark . ~ _ 'I
E~amlpe 14 D~rk Dark ¦ Dark Dsrk __ _ - ~ 'I
Esampl~ 2 Dark Dark ¦ Dnrk ¦ Dark .~. ~ ~_, ~, . . .~ . . _ . ._ ~ - _ ~
Claims (52)
1. A security composition for use in an ink formulation comprising a resin, and a diphenyl guanidine compound.
2. The security composition according to claim 1, wherein said resin is an acrylic resin.
3. The security composition according to claim 1, further comprising a benzothiazole compound.
4. The security composition according to claim 2, wherein said acrylic resin is present in an amount of about 12.0% by weight, and said diphenyl guanidine compound is present in an amount of from about 12% to 21% by weight.
5. The security composition according to claim 3, wherein said benzothiazole compound is present in an amount of about 0-21%
by weight.
by weight.
6. The security composition according to claim 2, wherein said acrylic resin is JONCRYL 67.
7. The security composition according to claim 3, wherein said benzothiazole compound is CHLOROSTAIN OR.
8. The security composition according to claim 1, wherein said diphenyl guanidine compound is CHLOROSTAIN BR.
9. A leach resistant ink composition comprising a resin, a diphenyl guanidine compound, a glycol ether and a plasticizer.
10. The leach resistant ink of claim 9, wherein said resin is an acrylic resin.
11. The leach resistant ink composition according to claim 9, further comprising a benzothiazole compound.
12. The leach resistant ink composition according to claim 9, further comprising a solvent.
13. The leach resistant ink composition according to claim 10, wherein said acrylic resin is present in an amount of about 1200% by weight, and said diphenyl guanidine compound is present in an amount of from about 12% to 21% by weight.
14. The leach resistant ink composition according to claim 11, wherein said benzothiazole compound is present in an amount of about to 0-21% by weight.
15. The leach resistant ink composition according to claim 9, wherein said glycol ether is present in an amount of about 29 to 59% by weight.
16. The leach resistant ink composition according to claim 9, wherein said plasticizer compound is present in an amount from about 0 to 2% by weight.
17. The leach resistant ink composition according to claim 12, wherein said solvent is present in an amount from about 0 to 37% by weight.
18. The leach resistant ink composition according to claim 10, wherein said acrylic resin is JONCRYL 67.
19. The leach resistant ink composition according to claim 11, wherein said benzothiazole compound is CHLOROSTAIN OR.
20. The leach resistant ink composition according to claim 9, wherein said glycol ether is selected from methyl cellosolve and methyl carbitol.
21. The leach resistant ink composition according to claim 20, wherein the glycol ether is methyl carbitol.
22. The leach resistant ink composition according to claim 19, wherein said plasticizer compound is selected from diethylene glycol, diethylene glycol monoethyl ether, diethyl phthalate, dibutyl phthalate, methyl phthalate, triethanolamine, triethyl citrate, tributoxyethyl phosphate, o,p-toluene ethyl sulfonamide, o,p-toluene sulfonamide and methyl phthalyl ethyl glycolate.
23. The leach resistant ink composition according to claim 22, wherein said plasticizer compound is selected from dibutyl phthalate, diethyl phthalate and methyl phthalate.
24. The leach resistant ink composition according to claim 23, wherein the plasticizer is dibutyl phthalate.
25. The leach resistant ink composition according to claim 12, wherein said solvent is an alcohol.
26. The leach resistant ink composition according to claim 25, wherein said solvent is isopropanol.
27. The leach resistant ink composition according to claim 9, wherein said diphenyl guanidine compound is CHLOROSTAIN BR.
28. A leach resistant ink composition comprising, about 29-59% by weight of a glycol ether compound, about 1-3% by weight of a plasticizer, about 8-15% by weight of an acrylic resin, about 15-21% by weight of a benzothiazole compound, and about 5-21% by weight of a diphenyl guanidine compound.
29. The leach resistant ink composition according to claim 28, wherein the glycol ether is methyl carbitol.
30. The leach resistant ink composition according to claim 28, wherein the plasticizer is dibutyl phthalate.
31. The leach resistant ink composition according to claim 28, wherein the acrylic resin is JONCRYL 67.
32. The leach resistant ink composition according to claim 28, wherein the benzothiazole compound is CHLOROSTAIN OR.
33. The leach resistant ink composition according to claim 28, wherein the diphenyl guanidine compound is CHLOROSTAIN BR.
34. A document resistant to alteration by oxidizing agents comprising a substrate and a leach resistant ink composition applied thereto, said ink composition comprising diphenyl guanidine, a resin, a glycol ether and a plasticizer.
35. The document of claim 34, wherein said resin is an acrylic resin.
36. The document according to claim 34, wherein the ink composition further comprises a benzothiazole compound.
37. The document according to claim 34, wherein the ink composition further comprising a solvent.
38. The document according to claim 35, wherein said acrylic resin is present in an amount of about 12.0% by weight, and said diphenyl guanidine compound is present in an amount of from about 12% to 21% by weight.
39. The leach resistant ink composition according to claim 36, wherein said benzothiazole compound is present in an amount of about to 0-21% by weight.
40. The document according to claim 34, wherein said glycol ether is present in an amount of about 29 to 59% by weight.
41. The document according to claim 34, wherein said plasticizer compound is present in an amount from about 1 to 3% by weight.
42. The document according to claim 37, wherein said solvent is present in an amount from about 0 to 37% by weight.
43. The document according to claim 35, wherein said acrylic resin is JONCRYL 67.
44. The document according to claim 36, wherein said benzothiazole compound is CHLOROSTAIN OR.
45. The document according to claim 34, wherein said glycol ether is selected from methyl cellosolve and methyl carbitol.
46. The document according to claim 45, wherein the glycol ether is methyl carbitol.
47. The document according to claim 34, wherein said plasticizer compound is selected from diethylene glycol, diethylene glycol monoethyl ether, diethyl phthalate, dibutyl phthalate, methyl phthalate, triethanolamine, triethyl citrate, tributoxyethyl phosphate, o,p-toluene ethyl sulfonamide, o,p-toluene sulfonamide and methyl phthalyl ethyl glycolate.
48. The document according to claim 47, wherein said plasticizer compound is selected from dibutyl phthalate, diethyl phthalate and methyl phthalate.
49. The document according to claim 48, wherein the plasticizer is dibutyl phthalate.
50. The document according to claim 37, wherein said solvent is an alcohol.
51. The document according to claim 50, wherein said solvent is isopropanol.
52. The document according to claim 34, wherein said diphenyl guanidine is CHLOROSTAIN BR.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/810,132 | 1991-12-19 | ||
| US07/810,132 US5304587A (en) | 1991-12-19 | 1991-12-19 | Water resistant security ink composition |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2085817A1 true CA2085817A1 (en) | 1993-06-20 |
Family
ID=25203088
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002085817A Abandoned CA2085817A1 (en) | 1991-12-19 | 1992-12-18 | Water resistant security ink composition |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US5304587A (en) |
| EP (1) | EP0547786B1 (en) |
| JP (1) | JPH0791493B2 (en) |
| AU (1) | AU658035B2 (en) |
| CA (1) | CA2085817A1 (en) |
| DE (1) | DE69209798T2 (en) |
| MX (1) | MX9207356A (en) |
| NZ (1) | NZ245401A (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5498283A (en) * | 1994-08-23 | 1996-03-12 | Scitex Digital Printing, Inc. | Waterfast security inks |
| DE19634466C2 (en) * | 1996-08-27 | 2001-07-05 | Mitsubishi Hitec Paper Bielefe | Sheets of paper for use in a carbon copy set |
| US5720801A (en) * | 1996-11-06 | 1998-02-24 | Nadan; Wendy | Water resistant security ink composition |
| US5891228A (en) * | 1997-01-08 | 1999-04-06 | Markem Corporation | Hot melt jet ink composition |
| US6686054B2 (en) * | 1998-04-22 | 2004-02-03 | Sri International | Method and composition for the sizing of paper using azetidinium and/or guanidine polymers |
| US6197880B1 (en) | 1998-04-22 | 2001-03-06 | Sri International | Method and composition for coating pre-sized paper using azetidinium and/or guanidine polymers |
| US6291023B1 (en) | 1998-04-22 | 2001-09-18 | Sri International | Method and composition for textile printing |
| US6712894B2 (en) | 2001-05-09 | 2004-03-30 | Cabot Corporation | Method of producing secure images using inks comprising modified pigment particles |
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| US8070186B2 (en) | 2006-05-31 | 2011-12-06 | Cabot Corporation | Printable reflective features formed from multiple inks and processes for making them |
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| US8790459B2 (en) * | 2006-05-31 | 2014-07-29 | Cabot Corporation | Colored reflective features and inks and processes for making them |
| US9533523B2 (en) | 2006-05-31 | 2017-01-03 | Sicpa Holding Sa | Reflective features with co-planar elements and processes for making them |
| US20070281177A1 (en) * | 2006-05-31 | 2007-12-06 | Cabot Corporation | Colored Reflective Features And Inks And Processes For Making Them |
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| JP6503744B2 (en) * | 2015-01-14 | 2019-04-24 | 凸版印刷株式会社 | Form |
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| DE545441C (en) * | 1928-11-16 | 1932-02-29 | I G Farbenindustrie Akt Ges | Process for the preparation of neutral vinyl polymers |
| US1839995A (en) * | 1929-08-22 | 1932-01-05 | Todd Co Inc | Safety paper and method of making the same |
| US1911774A (en) * | 1931-01-29 | 1933-05-30 | Todd Co Inc | Safety paper |
| US2767154A (en) * | 1951-07-04 | 1956-10-16 | Degussa | Method of producing pigmented lacquers and the like |
| GB1108555A (en) * | 1964-07-09 | 1968-04-03 | Dunlop Co Ltd | Improvements relating to playballs |
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-
1991
- 1991-12-19 US US07/810,132 patent/US5304587A/en not_active Expired - Lifetime
-
1992
- 1992-11-23 DE DE69209798T patent/DE69209798T2/en not_active Expired - Fee Related
- 1992-11-23 EP EP92310687A patent/EP0547786B1/en not_active Expired - Lifetime
- 1992-12-08 NZ NZ245401A patent/NZ245401A/en unknown
- 1992-12-17 MX MX9207356A patent/MX9207356A/en not_active IP Right Cessation
- 1992-12-17 AU AU30214/92A patent/AU658035B2/en not_active Ceased
- 1992-12-18 CA CA002085817A patent/CA2085817A1/en not_active Abandoned
- 1992-12-21 JP JP4356361A patent/JPH0791493B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| MX9207356A (en) | 1993-07-01 |
| NZ245401A (en) | 1995-08-28 |
| US5304587A (en) | 1994-04-19 |
| EP0547786A1 (en) | 1993-06-23 |
| AU3021492A (en) | 1993-06-24 |
| DE69209798D1 (en) | 1996-05-15 |
| JPH0791493B2 (en) | 1995-10-04 |
| EP0547786B1 (en) | 1996-04-10 |
| DE69209798T2 (en) | 1996-09-19 |
| JPH05247389A (en) | 1993-09-24 |
| AU658035B2 (en) | 1995-03-30 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| EEER | Examination request | ||
| FZDE | Discontinued |