CA1148356A - Sensitized record sheet - Google Patents
Sensitized record sheetInfo
- Publication number
- CA1148356A CA1148356A CA000337270A CA337270A CA1148356A CA 1148356 A CA1148356 A CA 1148356A CA 000337270 A CA000337270 A CA 000337270A CA 337270 A CA337270 A CA 337270A CA 1148356 A CA1148356 A CA 1148356A
- Authority
- CA
- Canada
- Prior art keywords
- record sheet
- sensitized record
- sensitized
- fraction
- biphenyl
- 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
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
Landscapes
- Color Printing (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
Theodore Maierson Docket 2444 CIP
Abstract of the Disclosure A sensitized record sheet which develops useful color when and where an acidic reactant material is applied thereto.
The record sheet bears, on a surface thereof, a low-tack resin-based ink comprising a solvent, a resin and a colorless, chromogenic dye-precursor such as Crystal Violet Lactone, and optionally a zinc salt catalyst. The solvent includes a relatively volatile fraction, a relatively non-volatile or plasticizing fraction, and optionally a bodying fraction.
Abstract of the Disclosure A sensitized record sheet which develops useful color when and where an acidic reactant material is applied thereto.
The record sheet bears, on a surface thereof, a low-tack resin-based ink comprising a solvent, a resin and a colorless, chromogenic dye-precursor such as Crystal Violet Lactone, and optionally a zinc salt catalyst. The solvent includes a relatively volatile fraction, a relatively non-volatile or plasticizing fraction, and optionally a bodying fraction.
Description
Docket 2444 CIP
33~
. SENSITIZED RECORD SHEET
Background_of the Invent~on This invention is related to an acid-colorable sensitize record sheet for use in chemical copy systems. The record sheet of this invention bears on at least one sur:Eace thereof a film of :~
. a low-~ack ink which is substantially color~less but is acid : ~ colorable. In use, acidic materi~l is applied to the record ~!0 sheet in a mark-f~rming pattern, thereby causing color to appear . when and where the acidic materi~l is applied thereto.
The colorless, acid-colorable~ low-tac~ ink of this invention comprises a basic, colorless, chromogen;c dye-precursor, ;: capable of developing a distinctive color by chemical reaction with an acid.
Exemplary of the colorless, chromogen;c dye-precursors useful herein are Crystal Violet ~actone (CVL), p-~oluenesul~inate ~ salt of Michlerl~ Hydrol or 4,4i-bis (diethylaminoj benzhydrol, :~ ¦ben~oyl leuco methylene blue (BLMB), Indolyl Red (3,3-phthalidylidene-bis-~(N-ethyl-2~methylindole), Malachlte Green ;:
¦Lactone, 8'-methoxybenzoindolinospiro-pyran, Rhodamine L~c~one, . .
¦and mixtures thereof.
¦ Exemplary o~ the acids useful in coloring ~he colorless, :
::: ¦chromogenic dye-precursors of this invention are acidic clays such .i ¦as attapulgite, kaolin, and acid-treated Silton clay, and organi : ¦acids such as carbo~ylic acids and phenols, particularly phenolic I
I;
.~heodore ~ c~rson Docket 2444 CIP ~ 5~
resins such as the novalak resins and certain metal salts thereof, such as zinc novolaks.
In use, the sensitized record sheet of this invention is colored by application thereto of an acid material, containing one or more of the acids of the type described above. The acid can be applied to the sensitized record sheet of this invention in the form of a liquid solu~ion or suspension, or in dry form as a loose powder or as a powder suspended in a matrix material such as a wax. To make a primary record, the acid material can be applied in the form of an ink from a pen, brush~ spray or type font, or by use of an acidic crayon. Either a primary record or a copy can be made on the sensitized record sheet of this ; inv~ntion by application of acidic material to a sensitized surface of the record sheet, for instance, by markin~-pressure-release of the acidic material from the under-side of an ; oversheet. Such oversheets~may have an acidic coa~ing on the underside, which coating may contain acidic powder in a wax base oran acidic solution, present as droplets, isolated in a dried emu1si film or s the core mater~l1 in microcapsules.
33~
. SENSITIZED RECORD SHEET
Background_of the Invent~on This invention is related to an acid-colorable sensitize record sheet for use in chemical copy systems. The record sheet of this invention bears on at least one sur:Eace thereof a film of :~
. a low-~ack ink which is substantially color~less but is acid : ~ colorable. In use, acidic materi~l is applied to the record ~!0 sheet in a mark-f~rming pattern, thereby causing color to appear . when and where the acidic materi~l is applied thereto.
The colorless, acid-colorable~ low-tac~ ink of this invention comprises a basic, colorless, chromogen;c dye-precursor, ;: capable of developing a distinctive color by chemical reaction with an acid.
Exemplary of the colorless, chromogen;c dye-precursors useful herein are Crystal Violet ~actone (CVL), p-~oluenesul~inate ~ salt of Michlerl~ Hydrol or 4,4i-bis (diethylaminoj benzhydrol, :~ ¦ben~oyl leuco methylene blue (BLMB), Indolyl Red (3,3-phthalidylidene-bis-~(N-ethyl-2~methylindole), Malachlte Green ;:
¦Lactone, 8'-methoxybenzoindolinospiro-pyran, Rhodamine L~c~one, . .
¦and mixtures thereof.
¦ Exemplary o~ the acids useful in coloring ~he colorless, :
::: ¦chromogenic dye-precursors of this invention are acidic clays such .i ¦as attapulgite, kaolin, and acid-treated Silton clay, and organi : ¦acids such as carbo~ylic acids and phenols, particularly phenolic I
I;
.~heodore ~ c~rson Docket 2444 CIP ~ 5~
resins such as the novalak resins and certain metal salts thereof, such as zinc novolaks.
In use, the sensitized record sheet of this invention is colored by application thereto of an acid material, containing one or more of the acids of the type described above. The acid can be applied to the sensitized record sheet of this invention in the form of a liquid solu~ion or suspension, or in dry form as a loose powder or as a powder suspended in a matrix material such as a wax. To make a primary record, the acid material can be applied in the form of an ink from a pen, brush~ spray or type font, or by use of an acidic crayon. Either a primary record or a copy can be made on the sensitized record sheet of this ; inv~ntion by application of acidic material to a sensitized surface of the record sheet, for instance, by markin~-pressure-release of the acidic material from the under-side of an ; oversheet. Such oversheets~may have an acidic coa~ing on the underside, which coating may contain acidic powder in a wax base oran acidic solution, present as droplets, isolated in a dried emu1si film or s the core mater~l1 in microcapsules.
-2-: ~
';~ , 11 . '' ' '`
' Docket 2444 CIP
835~;
Preferably the sensi~ized record sheet of this invention is used as a receiving sheet, mated with a pressure-responsive transfer oversheet. Such receiving sheets are known in ~he art as CF sheets (coated face); and such trans~er sheets are known as CB sheets (coated back).
The combination of an acidic CB transfer sheet and a basic chromogenic CF receiving sheet is the reverse o~ the conventional commercial carbonless copy paper record system. The - transfer coating of commercial CB sheets offers a protective structure (such as microcapsules, dried emulsion films or wax films) to isolate the colorless~ chromogenic dye-precursor compounds from the efects of light and air which may induce undesired colora~ion o~ the dye-precursor. The use of chromogenic dyerprecursors on CF receiving sheet surfaces o~fers many advantages, but has been avoided in commercial practice because it is dif~icult, and has been previously impractical, to stabilize such a chromogenic CF surface against accidental coloration, particularly by ultraviolet light. The low-tack ink and r~ecord sheet of this invention overcomes the problem of unintended coloration of the dye-precursor.
The advantages of the sensitized record sheet of this invention over the conventional aqueous-coated CB sheet, having the chromogenic dye-precursor present as microencapsulated solution droplets, include the following: more efficient use of costly chromogenic dye-precursors; selective application of reactant~ only in required ar~as, aqueous coating methods _3_ ~, . .
: : ~ , ............................ ... . . .
: ': ' Theodore ~laierson Docket 2444 CIP 1~48356 un-needed, thus saving the energy necessary to dry the aqueous coats; wider range of su~strate papers available particularly low-weight papers which cannot be aqueous coated; rapid stabilization of the ink coat on the paper surface, giving a polymer film which is available for immediate reactivity;
produces no dusting, which is a common problem in aqueous coated systems; and the ink film can be applied by press-printing methods, thus avoiding the expense of a separate coating step.
This Invention The sensitiæed record sheet of this invention bears a low-tack ink on a surface thereof. The low-tack ink contains a solvent, (including a plasticizer), a resin and a colorless chromogenic dye-precursor. Preferably,the solvent further contains a bodying agent, and the ink further contains a zinc salt catalyst.
lS The solvent is an organic solvent, pre~erably being largely an aromatic hydrocarbon solvent. The 901vent must be a solvent for the colorless, chromogenic dye-precursor. The solvent must be a mixe~d solvent, being volatile in part and relatively non-volatile in part. The solvent must have sufficiently low vapor pressure to permit use of the ink on multiple roll ink feed devices with little loss of liquid volume by evaporation so as to avoid premature setting of the ink within the ink train. When the lnk is spread in a thin film as on a paper sheet substrate, the solvent should evaporate in part to give a more rigid, low-tack film. But the solvent must be relatively non-volatile in part so as to not completely evaporate from the substrate but rather remain thereon to serve as a plasticizer for the applied resin film. The solvent, and indeed all o~ the other comp~nents of the ink, must -4~
: ~ ~
~ ck~t ~
4~356 be compatible with the colorless chromogenic dye-precursor, that is, not react with the dye-precursor to generate color. Exemplar of the more volatile fraction of the solvents of use herein is the preferred mixed aromatic solvent: 70-80% monoisopropyl S biphenyl and 20-30% diisopropyl biphenyl. Other relatively volatile solvents, which may be used alone or mixed or as diluents with the preferred relatively volatile solvent, are high boiling kerosene, butyl ben20ate, benzylbenzoate, dimethylphthala~e, isophorone, cyclohexanone, and alkylated naphthalene.
The relatively non-volatile or plasticizing fraction of the solvent must be sufficien~ly high boiling to not substan-tially evaporate under ambient conditions and to thus become a permanent part of the applied ink film. Exemplary of ~he relat~vely non-volatile or plasticizing fraction solvents of use herein is the preerred mixed aromat~c liquid; 5-20% diisopropyl ; biphenyl, 30-60% triisopropyl biphenyl, and 10-40% tetraisopropyl biphenyl. Other useful plastici~ing fraction solvents which may ~; be used alone or mixed or as diluents wlth ~he preferred plasticizing ~raction solvents are dioctylphth31ate, dibutylphthalate, butylbenzylphthalate, halogenated terphenyl, tricresylphosphate, benzophenone, and dicyclohexlphthalate. A
particularly useful plasticizing fraction is a 1:1 mixture of benzophenone and dicyclohexlphthalate.
The preferred solvent combination o~ relatively high boiling and low boiling fractions described above is preferred as giving good dye æolvency and being non-migrating, non-toxic, and compati~le with printing press materials.
~ Resins, use~ul as the base o~ the ink of this invention, ; ¦ should have a low acid number (preferably less than 1.0~ and ~ ~ . .. , ;
Docket ~4 ,1 ~
a softening point in the range of about 80 C. to about 105 C.
Preferred are hydrocarbon resins such as poly-alpha-methlstyrene and polyalkyl resin. Useful poly-alpha-methylstyrene resins are the Kris~alex resins such as Kristalex 1085 and 3100 (Hercules Inc.). Useful polyalkyl resins include Wingtac 95 (Goodyear Chemical Company). Rosin esters may also be used as the resin herein.
The combination of resin and solvent [and plasticize~
here described generally lacks sufficient viscosity to be used convPniently on a printing press, such as a le~ter press~ without ~he addition of a viscos ity regulator or bodying agent as part of the solvent. Fatty alcohols have been found to be partic:ularly useful as the bodying fraction of the solvent. Preferred is a mixture of ~b~ut 65%-75% stearyl alcohol and about 25%-35% cetyl alcohol.
As the artisan will appreciate 9 less viscous inks are ~r particularly useful for flexographic and gravure pri~ting. The reduced viscosity can be achieved by using less bodying agent and[or more volatile diluent for flexo and gravure inks than is ~- 0 used for letterpress inks.
It has been found that various catalys~s or activators can be added to the ink of this invention to enhance the reactivit o~ the colorless, chromogenic dye-precursors and give more rapid ; ~ and intense color development in use, without destabilizing the ,; ink to premature and undesired color developments during storage and handling. Preferred are zinc aliphatic carboxylic acid salts r or zinc cycloaliphatic carboxylic acid salts such as zinc octoate and zinc neo-decanoate. The selected zin^ salt may also be a zinc resinate, having a zinc content of about 8 tO about 1(~/~ an acid:
O number of about -15 to about -l9,-and a softening point in ~Trademark -6-.
l ~)OCk~L ~ ~4'~
~ 3 ~ 6 the range of about 82C. to about 100C. The use of the zinc ca~alyst in the ink of this invention is preferred, although ~he ink and sensitized record sheets of this invention perform quite satisfactorily wi~hout the zinc catalyst.
The ink of this invention may be formulated as follows:
Solvent 33-70%
Dye-precursor 2-11%
Resin 30-50%
Zinc salt 0.2-5%
The 33_70V/o solvent of the above formulation is 20-35% of a more volatile fraction, 10-25% o a relatively non-volatile fraction and 3-10% of a atty alcohol bodying agent, based Oll the weigh~
of the total formulation. As noted above, the fatty alcohol is not essential to the perEormance of the ink and sensitized record material o this invention and can be omitted. All percents used herein are percents by weight.
Useful and preferred embodiments of this invention are set out in the following Examples:
,~ Example l A preferred ink was made by mixing the following:
28.19 parts of mixed 70-80% monoisopropyl biphenyl and 20-30% diisopropyl biphenyl volatile solvent fraction 13.89 parts of plastici~ing solvent fraction~ which is 5-20%
diisopropyl biphenyl, :30 60% triisoprophyl biphenyl and 10-40%
; tetraisopropylbiphenyl . , ~- . , . - . ;. -, ~ , ;
; 6.62 parts of a 30:70 cetyl alcohol-stearyl alcohol mixture which is the bodying fraction of the solvent 5.38 parts of CVL
0.30 parts of Indolyl. ~ed ; 43.62 parts of poly-alpha-methylstyrene resin (Kristalex 1085) ;~ 2,00 parts of zinc oc~oate ' ~ ~ . . .. ... ............. .
.L~ S~
A similar ink to that of Example l was prepared by substituting the same amount of polyalkyl resin (Wingtac 95) for the poly-alpha-methylstyrene resin of that Example. Mix-tures of the two resins were also quite satisfactory.
A similar ink to that of Example 1 was prepared by substituting the same amount of zinc neo-decanoate for the zinc octoate of that Example.
Another preferred ink was made by mixing the following:
30.0 parts of the volatile solvent fraction of Example l 14.2 parts of a 1:1 mixture of benzophenone and dicyclohexyl-phthalate as the plasticizing solvent fraction, 5.9 parts of the fatty alcohol bodying fraction of the sol-vent of Example l.
4.8 parts of ~-toluenesulfinate salt of Michler's Hydrol 45.0 parts of poly-alpha-methyl strene resin (Kristalex 3100).
In addition to serving as a bodying agent in this Ex-ample, the mixture of cetyl alcohol and stearyl alcohols in-; hibits heat-induced color deve]opment in the dyestuff of this Example, which dyestuff tends to develop a blue color on heating in the absence of the bodying agent.
~; The inks of this invention were applied to various base paper stocks to give a "dry" ink weight in the range of about 0.1 to 0.5 lb./ream of 500 sheets (17 x 22 inches).
For most common paper stocks, application in the range of 0.2 to 0.3 lb./ream was found to be dry to the touch, non-off-~; setting and satisfactory for acid-activated print production.
Paper stocks .
.:
' ' -8- ~
,.~, ,.
:i ~ Docket 24 4CIP 1~48356 of about lO to 20 lb./ream were generally used as the base stock.
Although much heavier papers could also be used.
Application of the exemplified inks to the paper stock ¦ was preferably made by letterpress printing, including rubber 5 , plate printing and dry-offset.
It will be appreciated that by these means a sheet may be evenly printed in its entirety, to ~ive over-all sensitivityj or be spot printed to give sensitivity only in desired areas. The latte-r method is economical of materials and is particularly useful in the manufacture of business forms.
The sensitized record sheets of this invention instantly produced permanent dark blue to blue-black marks when and where treated with an acidi.c marker.
; Subst,ràte stocks, for preparation of the sensitized record sheets of this invention by appl1cation thereto of the low-tack ink of this invention, are preferably paper, but may include other ~iber, such as glass fibers and polyethylene fibers ~nown in the synthetic "paper" art. Acidic pigments and clay . filler may produce a low order coloration on contact with the ink of this invention~ and should therefore be avoided in choosing ¦ a suitable aper subscrate for usF herein.
' ~ . .
~ . . ~
1 : 9 . ~1 ` .
: ` . :
';~ , 11 . '' ' '`
' Docket 2444 CIP
835~;
Preferably the sensi~ized record sheet of this invention is used as a receiving sheet, mated with a pressure-responsive transfer oversheet. Such receiving sheets are known in ~he art as CF sheets (coated face); and such trans~er sheets are known as CB sheets (coated back).
The combination of an acidic CB transfer sheet and a basic chromogenic CF receiving sheet is the reverse o~ the conventional commercial carbonless copy paper record system. The - transfer coating of commercial CB sheets offers a protective structure (such as microcapsules, dried emulsion films or wax films) to isolate the colorless~ chromogenic dye-precursor compounds from the efects of light and air which may induce undesired colora~ion o~ the dye-precursor. The use of chromogenic dyerprecursors on CF receiving sheet surfaces o~fers many advantages, but has been avoided in commercial practice because it is dif~icult, and has been previously impractical, to stabilize such a chromogenic CF surface against accidental coloration, particularly by ultraviolet light. The low-tack ink and r~ecord sheet of this invention overcomes the problem of unintended coloration of the dye-precursor.
The advantages of the sensitized record sheet of this invention over the conventional aqueous-coated CB sheet, having the chromogenic dye-precursor present as microencapsulated solution droplets, include the following: more efficient use of costly chromogenic dye-precursors; selective application of reactant~ only in required ar~as, aqueous coating methods _3_ ~, . .
: : ~ , ............................ ... . . .
: ': ' Theodore ~laierson Docket 2444 CIP 1~48356 un-needed, thus saving the energy necessary to dry the aqueous coats; wider range of su~strate papers available particularly low-weight papers which cannot be aqueous coated; rapid stabilization of the ink coat on the paper surface, giving a polymer film which is available for immediate reactivity;
produces no dusting, which is a common problem in aqueous coated systems; and the ink film can be applied by press-printing methods, thus avoiding the expense of a separate coating step.
This Invention The sensitiæed record sheet of this invention bears a low-tack ink on a surface thereof. The low-tack ink contains a solvent, (including a plasticizer), a resin and a colorless chromogenic dye-precursor. Preferably,the solvent further contains a bodying agent, and the ink further contains a zinc salt catalyst.
lS The solvent is an organic solvent, pre~erably being largely an aromatic hydrocarbon solvent. The 901vent must be a solvent for the colorless, chromogenic dye-precursor. The solvent must be a mixe~d solvent, being volatile in part and relatively non-volatile in part. The solvent must have sufficiently low vapor pressure to permit use of the ink on multiple roll ink feed devices with little loss of liquid volume by evaporation so as to avoid premature setting of the ink within the ink train. When the lnk is spread in a thin film as on a paper sheet substrate, the solvent should evaporate in part to give a more rigid, low-tack film. But the solvent must be relatively non-volatile in part so as to not completely evaporate from the substrate but rather remain thereon to serve as a plasticizer for the applied resin film. The solvent, and indeed all o~ the other comp~nents of the ink, must -4~
: ~ ~
~ ck~t ~
4~356 be compatible with the colorless chromogenic dye-precursor, that is, not react with the dye-precursor to generate color. Exemplar of the more volatile fraction of the solvents of use herein is the preferred mixed aromatic solvent: 70-80% monoisopropyl S biphenyl and 20-30% diisopropyl biphenyl. Other relatively volatile solvents, which may be used alone or mixed or as diluents with the preferred relatively volatile solvent, are high boiling kerosene, butyl ben20ate, benzylbenzoate, dimethylphthala~e, isophorone, cyclohexanone, and alkylated naphthalene.
The relatively non-volatile or plasticizing fraction of the solvent must be sufficien~ly high boiling to not substan-tially evaporate under ambient conditions and to thus become a permanent part of the applied ink film. Exemplary of ~he relat~vely non-volatile or plasticizing fraction solvents of use herein is the preerred mixed aromat~c liquid; 5-20% diisopropyl ; biphenyl, 30-60% triisopropyl biphenyl, and 10-40% tetraisopropyl biphenyl. Other useful plastici~ing fraction solvents which may ~; be used alone or mixed or as diluents wlth ~he preferred plasticizing ~raction solvents are dioctylphth31ate, dibutylphthalate, butylbenzylphthalate, halogenated terphenyl, tricresylphosphate, benzophenone, and dicyclohexlphthalate. A
particularly useful plasticizing fraction is a 1:1 mixture of benzophenone and dicyclohexlphthalate.
The preferred solvent combination o~ relatively high boiling and low boiling fractions described above is preferred as giving good dye æolvency and being non-migrating, non-toxic, and compati~le with printing press materials.
~ Resins, use~ul as the base o~ the ink of this invention, ; ¦ should have a low acid number (preferably less than 1.0~ and ~ ~ . .. , ;
Docket ~4 ,1 ~
a softening point in the range of about 80 C. to about 105 C.
Preferred are hydrocarbon resins such as poly-alpha-methlstyrene and polyalkyl resin. Useful poly-alpha-methylstyrene resins are the Kris~alex resins such as Kristalex 1085 and 3100 (Hercules Inc.). Useful polyalkyl resins include Wingtac 95 (Goodyear Chemical Company). Rosin esters may also be used as the resin herein.
The combination of resin and solvent [and plasticize~
here described generally lacks sufficient viscosity to be used convPniently on a printing press, such as a le~ter press~ without ~he addition of a viscos ity regulator or bodying agent as part of the solvent. Fatty alcohols have been found to be partic:ularly useful as the bodying fraction of the solvent. Preferred is a mixture of ~b~ut 65%-75% stearyl alcohol and about 25%-35% cetyl alcohol.
As the artisan will appreciate 9 less viscous inks are ~r particularly useful for flexographic and gravure pri~ting. The reduced viscosity can be achieved by using less bodying agent and[or more volatile diluent for flexo and gravure inks than is ~- 0 used for letterpress inks.
It has been found that various catalys~s or activators can be added to the ink of this invention to enhance the reactivit o~ the colorless, chromogenic dye-precursors and give more rapid ; ~ and intense color development in use, without destabilizing the ,; ink to premature and undesired color developments during storage and handling. Preferred are zinc aliphatic carboxylic acid salts r or zinc cycloaliphatic carboxylic acid salts such as zinc octoate and zinc neo-decanoate. The selected zin^ salt may also be a zinc resinate, having a zinc content of about 8 tO about 1(~/~ an acid:
O number of about -15 to about -l9,-and a softening point in ~Trademark -6-.
l ~)OCk~L ~ ~4'~
~ 3 ~ 6 the range of about 82C. to about 100C. The use of the zinc ca~alyst in the ink of this invention is preferred, although ~he ink and sensitized record sheets of this invention perform quite satisfactorily wi~hout the zinc catalyst.
The ink of this invention may be formulated as follows:
Solvent 33-70%
Dye-precursor 2-11%
Resin 30-50%
Zinc salt 0.2-5%
The 33_70V/o solvent of the above formulation is 20-35% of a more volatile fraction, 10-25% o a relatively non-volatile fraction and 3-10% of a atty alcohol bodying agent, based Oll the weigh~
of the total formulation. As noted above, the fatty alcohol is not essential to the perEormance of the ink and sensitized record material o this invention and can be omitted. All percents used herein are percents by weight.
Useful and preferred embodiments of this invention are set out in the following Examples:
,~ Example l A preferred ink was made by mixing the following:
28.19 parts of mixed 70-80% monoisopropyl biphenyl and 20-30% diisopropyl biphenyl volatile solvent fraction 13.89 parts of plastici~ing solvent fraction~ which is 5-20%
diisopropyl biphenyl, :30 60% triisoprophyl biphenyl and 10-40%
; tetraisopropylbiphenyl . , ~- . , . - . ;. -, ~ , ;
; 6.62 parts of a 30:70 cetyl alcohol-stearyl alcohol mixture which is the bodying fraction of the solvent 5.38 parts of CVL
0.30 parts of Indolyl. ~ed ; 43.62 parts of poly-alpha-methylstyrene resin (Kristalex 1085) ;~ 2,00 parts of zinc oc~oate ' ~ ~ . . .. ... ............. .
.L~ S~
A similar ink to that of Example l was prepared by substituting the same amount of polyalkyl resin (Wingtac 95) for the poly-alpha-methylstyrene resin of that Example. Mix-tures of the two resins were also quite satisfactory.
A similar ink to that of Example 1 was prepared by substituting the same amount of zinc neo-decanoate for the zinc octoate of that Example.
Another preferred ink was made by mixing the following:
30.0 parts of the volatile solvent fraction of Example l 14.2 parts of a 1:1 mixture of benzophenone and dicyclohexyl-phthalate as the plasticizing solvent fraction, 5.9 parts of the fatty alcohol bodying fraction of the sol-vent of Example l.
4.8 parts of ~-toluenesulfinate salt of Michler's Hydrol 45.0 parts of poly-alpha-methyl strene resin (Kristalex 3100).
In addition to serving as a bodying agent in this Ex-ample, the mixture of cetyl alcohol and stearyl alcohols in-; hibits heat-induced color deve]opment in the dyestuff of this Example, which dyestuff tends to develop a blue color on heating in the absence of the bodying agent.
~; The inks of this invention were applied to various base paper stocks to give a "dry" ink weight in the range of about 0.1 to 0.5 lb./ream of 500 sheets (17 x 22 inches).
For most common paper stocks, application in the range of 0.2 to 0.3 lb./ream was found to be dry to the touch, non-off-~; setting and satisfactory for acid-activated print production.
Paper stocks .
.:
' ' -8- ~
,.~, ,.
:i ~ Docket 24 4CIP 1~48356 of about lO to 20 lb./ream were generally used as the base stock.
Although much heavier papers could also be used.
Application of the exemplified inks to the paper stock ¦ was preferably made by letterpress printing, including rubber 5 , plate printing and dry-offset.
It will be appreciated that by these means a sheet may be evenly printed in its entirety, to ~ive over-all sensitivityj or be spot printed to give sensitivity only in desired areas. The latte-r method is economical of materials and is particularly useful in the manufacture of business forms.
The sensitized record sheets of this invention instantly produced permanent dark blue to blue-black marks when and where treated with an acidi.c marker.
; Subst,ràte stocks, for preparation of the sensitized record sheets of this invention by appl1cation thereto of the low-tack ink of this invention, are preferably paper, but may include other ~iber, such as glass fibers and polyethylene fibers ~nown in the synthetic "paper" art. Acidic pigments and clay . filler may produce a low order coloration on contact with the ink of this invention~ and should therefore be avoided in choosing ¦ a suitable aper subscrate for usF herein.
' ~ . .
~ . . ~
1 : 9 . ~1 ` .
: ` . :
Claims (18)
1. A sensitized record sheet which develops useful color when and where an acidic reactant material is applied thereto, bearing on a surface thereof a low-tack ink consisting essentially of an organic solvent solution of a colorless, chromogenic dye-precursor, and a hydrocarbon resin of an acid number in the range of 0 to 25 and having a softening point in the range of about 80°C to about 105°C., wherein the organic solvent is a mixture of a low volatile fraction having a boiling range of about 280°C. to 325°C. and a plasticizing fraction having a melting point above 20°C.
2. The sensitized record sheet of Claim 1, wherein the volatile fraction of the organic solvent is a mixture of monoisopropyl biphenyl and diisopropyl biphenyl.
3. The sensitized record sheet of Claim 2, wherein the volatile fraction of the organic solvent is about 70 to about 80% monoisopropyl biphenyl and about 20 to about 30% diisopropyl biphenyl.
4. The sensitized record sheet of Claim 1, wherein the plasticizing fraction is a polyisopropyl biphenyl of about 30 to about 60% triisopropyl biphenyl and about 10 to about 40% tetraisopropyl biphenyl.
5. The sensitized record sheet of Claim 1, wherein the plasticizing fraction is a 1:1 mixture of benzophenone and dicyclohexylphthalate.
Theodore Maierson Docket 2444 CIP
Theodore Maierson Docket 2444 CIP
6. The sensitized record sheet of Claim l, wherein the chromogenic dye-precursor comprises Crystal Violet Lactone.
7. The sensitized record sheet of Claim 1, wherein the hydrocarbon resin has an acid number of less than about 1Ø
S. The sensitized record sheet of Claim 7 wherein the hydrocarbon resin is poly-alpha- methylstyrene .
9. The sensitized record sheet of Claim l wherein the solvent further comprises a fatty alcohol bodying agent.
10. The sensitized record sheet of Claim 9 wherein the fatty alcohol bodying agent is a mixture of stearyl alcohol and cetyl alcohol.
11. The sensitized record sheet of Claim 10, wherein the fatty alcohol bodying agent is about 70% stearyl alcohol and about 30% cetyl alcohol.
12. The sensitized record sheet of Claim 1, wherein the chromogenic dye-precursor comprises p-toluenesulfinate salt of Michler's Hydrol.
13. The sensitized record sheet of Claim 7 wherein the hydrocarbon resin is polyalkyl resin.
14. The sensitized record sheet of Claim 1, wherein the record sheet is paper and the low-tack ink comprises about 20 to 35% volatile organic solvent fraction, about 2 to about 11%
colorless, chromogenic dye-precursor, about 10 to about 25%
polyisopropyl biphenyl plasticizing solvent fraction, and about 30 to about 50% hydrocarbon resin.
colorless, chromogenic dye-precursor, about 10 to about 25%
polyisopropyl biphenyl plasticizing solvent fraction, and about 30 to about 50% hydrocarbon resin.
The sensitized record sheet of Claim 14 wherein the solvent further comprises about 3 to about 10% fatty alcohol bodying agent.
16. The sensitized record sheet of Claim 1, wherein the low-tack ink further comprises an effective amount of a catalyst which is a zinc salt of an aliphalic or cycloaliphatic carboxylic acid.
17. The sensitized record sheet of Claim 16, wherein the amount of the catalyst is about 0.2 to about 5%.
18. The sensitized record sheet of Claim 1$, wherein the ink further comprises about 2% of an activator selected from the group consisting of zinc resinate, zinc octoate and zinc neo-decanoate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US96813078A | 1978-12-11 | 1978-12-11 | |
| US968,130 | 1978-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1148356A true CA1148356A (en) | 1983-06-21 |
Family
ID=25513782
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000337270A Expired CA1148356A (en) | 1978-12-11 | 1979-10-10 | Sensitized record sheet |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1148356A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601690A1 (en) * | 1992-12-02 | 1994-06-15 | Koch Industries, Inc. | Solvent for use in carbonless paper, comprising diisopropylbiphenyl and triisopropylbiphenyl, and products utilising the same |
-
1979
- 1979-10-10 CA CA000337270A patent/CA1148356A/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0601690A1 (en) * | 1992-12-02 | 1994-06-15 | Koch Industries, Inc. | Solvent for use in carbonless paper, comprising diisopropylbiphenyl and triisopropylbiphenyl, and products utilising the same |
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| Date | Code | Title | Description |
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| MKEX | Expiry |