CA1139560A - Pressure sensitive mark-recording systems - Google Patents
Pressure sensitive mark-recording systemsInfo
- Publication number
- CA1139560A CA1139560A CA000341757A CA341757A CA1139560A CA 1139560 A CA1139560 A CA 1139560A CA 000341757 A CA000341757 A CA 000341757A CA 341757 A CA341757 A CA 341757A CA 1139560 A CA1139560 A CA 1139560A
- Authority
- CA
- Canada
- Prior art keywords
- phenol
- promoter
- solution according
- radical
- alpha
- 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
- B41M5/165—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 characterised by the use of microcapsules; Special solvents for incorporating the ingredients
- B41M5/1655—Solvents
Abstract
IMPROVEMENTS RELATING TO PRESSURE SENSITIVE
MARK-RECORDING SYSTEMS
Abstract of the Disclosure Solutions useful in pressure sensitive mark-recording systems comprise a chromogen dissolved in a liquid solvent containing a hydrocarbon which is in part benzenoid. Also dissolved in the solvent is a promoter which is an alkylated, aralkylated or cyclo-alkylated phenol or is a compound containing an alkylated, aralkylated or cycloalkylated hydroxyphenol radical.
MARK-RECORDING SYSTEMS
Abstract of the Disclosure Solutions useful in pressure sensitive mark-recording systems comprise a chromogen dissolved in a liquid solvent containing a hydrocarbon which is in part benzenoid. Also dissolved in the solvent is a promoter which is an alkylated, aralkylated or cyclo-alkylated phenol or is a compound containing an alkylated, aralkylated or cycloalkylated hydroxyphenol radical.
Description
~3-21-4569A CN :
':
. .
. .
-- t --I - - , :
- ..
~MPROVE~lENTS RELATING TO P~ESSURE SENSITIVE
~`~RK-RECORDING SYSTEMS
- . ' . . ..
.This invention relates to solutions ~hich are ...
use~ul in the ~roduction of pressuxe-sen~i.t:ive ma~k-recording systems and to systems thlls producedO
The most familiar form o~ pressl~e-sensitive mark-recording system is the so-called carbonle~Qs copyi~g : paper which comprises a t~vo-.sheet ~7stem i~ vhich the . under sur8lace of the top sheet has a coati3-~g o~ micro~
capsules of a solution o~ a colourless chromosen3 while the upper surlace o~ ;he lower (receiver) sheet has an 10 absorbent coating includin~5 a sensitizin~ agent for the .
chromogen. When a markinD instru~ent is applied to the .
: top sheet, the microcapsules are locally ruptured, . . thereby releasing the chromogen solution f3~0m the affected microcapsules to react with the underlying sensitizing a~ent a~d orm coloured marks on the receiver ..
sheet corresponding to the marks applied to the top sheet~ .
A successful carbonless copying paper s~rstem n.eeds to meet a number of criteria For examplè, the marks on the receiver sheet should develop rapidly to a legible intensity of colour, and a le~ible mark should :.
persis-t for as long as the sheet is required -to ~e kept~
~hether the various criteria are met depends on a number of factors including tlle nature of the solvent, the sensitizing agent and the chromogen, and many different materials of each category have been proposed.
i~l3~S~
We have now found that improvements are achieved in respect of the initial intensity of colour of the mark and -its durability by including in the system certain phenolic compounds.
A solution of the invention comprises a liquid solvent comprising an aromatic hydxocarbon in which at least half the carbon atoms are benzenoid carbon atoms, and, aissolved in the solvent, a chromogen and a compound (hereinafter referred to as.a promoter) which is an alkylated, aralkylated or 10 cycloalkylated phenol or which contains an alkylated, aralkylated or cycloalkylated hydroxyphenyl radical in its molecule, the structure of the phenol or radical being such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of at least four carbon 15 atoms or by an aralk~l or cycloalkyl group, and the solvent having a low volatility consistent with its use as a chromogen solvent in a system of the invention.
A pressure-sensitive mark-recording system of the invention comprises ~a) sheet material, (b) promoted mark-20 forming components supported by the sheet material and - arranged in j-uxtaposition but in unreactive condition, the said components comprising (i) a-chromogen (ii) a sensitizing agent fo~ the ch~omogen which produces a colour from the chromogen when brought into contact with the chromogen in the 25 presence of a sol~ent and (iii) a promoter as deEined above, and (c) the said soivent, which is a ]i~uid comprising an aromatic hydrocarbon in which at least half the carbon atoms are benzenoid carbon atoms, and in which solvent both the chromogen and the promoter are soluble, supported by the 30 sheet material but separated from the sensitizing agent by a physical barrier which is rupturable on the application : of a marking instrumentto the sheet material.
; The chromogens, sensitizing agents and the aromatic hydrocarbons useful in the p~esent invention are,in general, : 35 materials conventionally employed in the art, and are more fully described below.
5~ .
.
- 3 - , .
In the promoter, the or each phenol nucleus may contain ...
from one to three-alkyl, aralkyl or cycloalkyl (including -alkylcycloalkyl) groups, and pre~erably contains two or ...
three such yroups, each of such groups preferably having ...
5 up to 12 carbon atoms, with the proviso indicated above ..
regarding occupancy of. at least one o~ the positions ortho .
to the hydroxy group. An alkyl group occupying such a ..
position is preferably an alkyl group of ~rom 4 to 12 ..
carbon atoms, especially a tertiary alkyl group, ~or ..
10 example a t-butyl, t-amyl, 1,1,3,3-tetramethylbutyl or ..
1,1,3-trimethylhexyl group. Alkyl substituents in other ....
positions can have straight or branched chains, and usually contain from 1 to 12 carbon atoms,examples being methyl, . .
ethyl, isopropyl, n-hexyl, 2-ethy].hexyl, nonyl, decyl, and 15 the tertiary alkyl groups named above. An alkyl group in ..
such other position is often preferably an alkyl group containing from one to three carbon atoms, e.g. methyl, .
ethyl, or isopropyl, for example where the alkyl group ...
_ concerned is a third alkyl group in a di-tertiary alkyl ..
20 phenol, in a diaralkylated phenol or in a dicycloalkyl phenol, or where the alkyl group is presen- in an ortho-tertiary alkyIated, aralkylated or cycloalkylated hydroxy- .
phenyl nucleus that is linked to other atoms in the molecule .
of ~.he promoter. :.:
An aralkyl substituent in a promoter molecule is ..
preferably a benzyl, alpha-methylbenzyl or alpha, alpha-dimethylbenzyl group. The last two are especially preferred where the substituent occupies a position ortho to a hydroxyl group. A cycloalkyl group occupying such a .-.
30 position is preferably an alpha-alkyl cycloalkyl group, ......
for example an alpha-methylcyclohexyl or alpha-ethylcyclo- .
hexyl group. .
....
,.....
, , . .
Pre~erred promoters are mononuclear phenols, substituted in the manner definedi compounds containing two hydroxyphenyl radicals, each substituted in the manner defined, and linked, preferably ~t the 2- or.4- positions, 5 through a sulphur atom or through an alkylene or alkylidene group, usually a Cl_4 alkylene o:r alkylidene group; and compounds having the general formula ~ A-(CH2)pC0~ mR
where A represents a hydroxyphenyl radica~ substituted in the 10 manner defined, preferably linked at-the 2- or 4-position to the (CH2)p radical, p is an integer of ~rom 1 to 4, m.is an integer of from l to 4 and R represents a radical derived by the loss of m hydrogen atoms from an alkane o~ the formula C H2n + 2 where n is an integer o~ from 1 to 24, preferably 15 of from m to 24.
Specific examples of promote^s that are alkylated, aralkylated or cycloalkylated mono-nuclear phenols are ortho (alpha-methylbenzyl)phenol, 2,4-di(alpha-methylbenzyl)phenol,
':
. .
. .
-- t --I - - , :
- ..
~MPROVE~lENTS RELATING TO P~ESSURE SENSITIVE
~`~RK-RECORDING SYSTEMS
- . ' . . ..
.This invention relates to solutions ~hich are ...
use~ul in the ~roduction of pressuxe-sen~i.t:ive ma~k-recording systems and to systems thlls producedO
The most familiar form o~ pressl~e-sensitive mark-recording system is the so-called carbonle~Qs copyi~g : paper which comprises a t~vo-.sheet ~7stem i~ vhich the . under sur8lace of the top sheet has a coati3-~g o~ micro~
capsules of a solution o~ a colourless chromosen3 while the upper surlace o~ ;he lower (receiver) sheet has an 10 absorbent coating includin~5 a sensitizin~ agent for the .
chromogen. When a markinD instru~ent is applied to the .
: top sheet, the microcapsules are locally ruptured, . . thereby releasing the chromogen solution f3~0m the affected microcapsules to react with the underlying sensitizing a~ent a~d orm coloured marks on the receiver ..
sheet corresponding to the marks applied to the top sheet~ .
A successful carbonless copying paper s~rstem n.eeds to meet a number of criteria For examplè, the marks on the receiver sheet should develop rapidly to a legible intensity of colour, and a le~ible mark should :.
persis-t for as long as the sheet is required -to ~e kept~
~hether the various criteria are met depends on a number of factors including tlle nature of the solvent, the sensitizing agent and the chromogen, and many different materials of each category have been proposed.
i~l3~S~
We have now found that improvements are achieved in respect of the initial intensity of colour of the mark and -its durability by including in the system certain phenolic compounds.
A solution of the invention comprises a liquid solvent comprising an aromatic hydxocarbon in which at least half the carbon atoms are benzenoid carbon atoms, and, aissolved in the solvent, a chromogen and a compound (hereinafter referred to as.a promoter) which is an alkylated, aralkylated or 10 cycloalkylated phenol or which contains an alkylated, aralkylated or cycloalkylated hydroxyphenyl radical in its molecule, the structure of the phenol or radical being such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of at least four carbon 15 atoms or by an aralk~l or cycloalkyl group, and the solvent having a low volatility consistent with its use as a chromogen solvent in a system of the invention.
A pressure-sensitive mark-recording system of the invention comprises ~a) sheet material, (b) promoted mark-20 forming components supported by the sheet material and - arranged in j-uxtaposition but in unreactive condition, the said components comprising (i) a-chromogen (ii) a sensitizing agent fo~ the ch~omogen which produces a colour from the chromogen when brought into contact with the chromogen in the 25 presence of a sol~ent and (iii) a promoter as deEined above, and (c) the said soivent, which is a ]i~uid comprising an aromatic hydrocarbon in which at least half the carbon atoms are benzenoid carbon atoms, and in which solvent both the chromogen and the promoter are soluble, supported by the 30 sheet material but separated from the sensitizing agent by a physical barrier which is rupturable on the application : of a marking instrumentto the sheet material.
; The chromogens, sensitizing agents and the aromatic hydrocarbons useful in the p~esent invention are,in general, : 35 materials conventionally employed in the art, and are more fully described below.
5~ .
.
- 3 - , .
In the promoter, the or each phenol nucleus may contain ...
from one to three-alkyl, aralkyl or cycloalkyl (including -alkylcycloalkyl) groups, and pre~erably contains two or ...
three such yroups, each of such groups preferably having ...
5 up to 12 carbon atoms, with the proviso indicated above ..
regarding occupancy of. at least one o~ the positions ortho .
to the hydroxy group. An alkyl group occupying such a ..
position is preferably an alkyl group of ~rom 4 to 12 ..
carbon atoms, especially a tertiary alkyl group, ~or ..
10 example a t-butyl, t-amyl, 1,1,3,3-tetramethylbutyl or ..
1,1,3-trimethylhexyl group. Alkyl substituents in other ....
positions can have straight or branched chains, and usually contain from 1 to 12 carbon atoms,examples being methyl, . .
ethyl, isopropyl, n-hexyl, 2-ethy].hexyl, nonyl, decyl, and 15 the tertiary alkyl groups named above. An alkyl group in ..
such other position is often preferably an alkyl group containing from one to three carbon atoms, e.g. methyl, .
ethyl, or isopropyl, for example where the alkyl group ...
_ concerned is a third alkyl group in a di-tertiary alkyl ..
20 phenol, in a diaralkylated phenol or in a dicycloalkyl phenol, or where the alkyl group is presen- in an ortho-tertiary alkyIated, aralkylated or cycloalkylated hydroxy- .
phenyl nucleus that is linked to other atoms in the molecule .
of ~.he promoter. :.:
An aralkyl substituent in a promoter molecule is ..
preferably a benzyl, alpha-methylbenzyl or alpha, alpha-dimethylbenzyl group. The last two are especially preferred where the substituent occupies a position ortho to a hydroxyl group. A cycloalkyl group occupying such a .-.
30 position is preferably an alpha-alkyl cycloalkyl group, ......
for example an alpha-methylcyclohexyl or alpha-ethylcyclo- .
hexyl group. .
....
,.....
, , . .
Pre~erred promoters are mononuclear phenols, substituted in the manner definedi compounds containing two hydroxyphenyl radicals, each substituted in the manner defined, and linked, preferably ~t the 2- or.4- positions, 5 through a sulphur atom or through an alkylene or alkylidene group, usually a Cl_4 alkylene o:r alkylidene group; and compounds having the general formula ~ A-(CH2)pC0~ mR
where A represents a hydroxyphenyl radica~ substituted in the 10 manner defined, preferably linked at-the 2- or 4-position to the (CH2)p radical, p is an integer of ~rom 1 to 4, m.is an integer of from l to 4 and R represents a radical derived by the loss of m hydrogen atoms from an alkane o~ the formula C H2n + 2 where n is an integer o~ from 1 to 24, preferably 15 of from m to 24.
Specific examples of promote^s that are alkylated, aralkylated or cycloalkylated mono-nuclear phenols are ortho (alpha-methylbenzyl)phenol, 2,4-di(alpha-methylbenzyl)phenol,
2,6-di(alpha-methylbenzylphenol) and 2,4,6-tri(alpha-20 methylbenzyl)phenol and mixtures of these mono, di and tri(alpha-methylbenzYlated)phenols~ 2(alpha-methylbenzyl)-4-methylphenol, 2,6-di-t-butyl-4-methylphenol, 2,5-di-t-amyl-hydro~uinone, 4,6-di-nonyl-2-methylphenol, 2,4-dimethyl-6 (~-melhylcyclohexyl)phenol and 2~6-di(d-methylcyclohexyl)-4 25 methylphenol.
Examples o~ promoters containing two hydroxyphenyl radicals substituted and linked in the manner defined above are 4,4'-thiobis(2-t-~utyl-5-methylphenol), 4,4'-butylidene-bis(2-t-butyl-5-methylphenol), 2,2'-methylenebis(4-methyl-30.6-t-butylphenol), 2,2'-methylenebis(4-ethyl`6-t-butylphenol)~
and bisr2-hydroxy-3(~-methylcyclohexyl)-5-methylphenyl~
methane.
Examples of compounds having the general formula [A-(CH2)pCOO] mR
35 are octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl~methane.
Such promoters are co~ercially available materials.
The amount of the promoter used in a solution o the _invention can be, for example, from 0.05 to 10% by weight of the solvent, but i9 preferably from 0.1 to 3%. The :
5 optimum will vary with the particular solvent and promoter used, but is often in the range 0.5 to 2æ by weight of the solvent.
In addition to improving the initial intensity and durability of the mark, the presence of the promoter has 10 been found to increase the solubility of the chromogen in the solvent. This effect could be used to increase the concentration o the chromogen in the solvent and thus obtain darker marks, but is mainly of interest in that it helps to avoid precipitation of the chromogen when the 15 latter is used at conventional concentrations and the - -solution or system is stored at low temperatures.
The aromatic hydrocarbons suitable for use in the present invention can be single compounds, but are often mixtures of individual compounds, the aromatic hydrocarbon 20 being such that at least half the carbon atoms in the _ compound or mixture ar2 benzenoid carbon atoms. Aromatic hydrocarbons which can be used as, or as components of, -the solvent in this invention include partially hydrogenatea terphenyls, for example hexahydroterphenyls and dodeca-hydroterphenyls. As normally produced, materials of this type are mixtures containing in various proportions, ~ully hydrogenated terphenyls, partially hydrogenated terphenyls, and terphenyl itself. The terphenyl which is partially hydrogenated in obtaining such mixtures is itsel~ a mixture -30 of isomers. Other hydrocarbons include benzylated and a]pha-methylbenzylated alkylbenzene~, e-g- mono- and dibenzyl ethyl-benzene and mono(alpha-methylbenzyl)toluene, alkylnaphthalenes, e.g. dipropylnaphthalene and mono-alpha or -beta~2-hexyl) naphthalene, alkylbiphenyls, e.g. mono- and diisopropyl-35 biphenyls.
The solvent can be an aromatic hydrocarbon ~providedthe hydrocarbon is a liquid at room temperature) or a mixture of aromatic hydrocarbons, or an aromatic hydrocarbon or mixture together with a diluent, a diluent being an inert liquid miscible with the aromatic hydrocarbon(s). Examples of suitable diluents include mineral and vegetable oils, 5 such as kerosene, paraf~in oil, castor oil, soybean oil, corn oil and (long-chain alkylated)benzenes, for example (C7-C16 alkylated)benzenes. The d:iluent in a solvent o~
the invention unctions to alter physical properties of the solvent, for instance viscosity or vapour pressure, where 10 such alteration may be desired for optimum handling or processing. The solvent preferably con~ains at least 50%
by weight of aromatic hydrocarbon but in some instances, the aromatic hydrocarbon may be dilute~ with up to, for example,
Examples o~ promoters containing two hydroxyphenyl radicals substituted and linked in the manner defined above are 4,4'-thiobis(2-t-~utyl-5-methylphenol), 4,4'-butylidene-bis(2-t-butyl-5-methylphenol), 2,2'-methylenebis(4-methyl-30.6-t-butylphenol), 2,2'-methylenebis(4-ethyl`6-t-butylphenol)~
and bisr2-hydroxy-3(~-methylcyclohexyl)-5-methylphenyl~
methane.
Examples of compounds having the general formula [A-(CH2)pCOO] mR
35 are octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate and tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyl-oxymethyl~methane.
Such promoters are co~ercially available materials.
The amount of the promoter used in a solution o the _invention can be, for example, from 0.05 to 10% by weight of the solvent, but i9 preferably from 0.1 to 3%. The :
5 optimum will vary with the particular solvent and promoter used, but is often in the range 0.5 to 2æ by weight of the solvent.
In addition to improving the initial intensity and durability of the mark, the presence of the promoter has 10 been found to increase the solubility of the chromogen in the solvent. This effect could be used to increase the concentration o the chromogen in the solvent and thus obtain darker marks, but is mainly of interest in that it helps to avoid precipitation of the chromogen when the 15 latter is used at conventional concentrations and the - -solution or system is stored at low temperatures.
The aromatic hydrocarbons suitable for use in the present invention can be single compounds, but are often mixtures of individual compounds, the aromatic hydrocarbon 20 being such that at least half the carbon atoms in the _ compound or mixture ar2 benzenoid carbon atoms. Aromatic hydrocarbons which can be used as, or as components of, -the solvent in this invention include partially hydrogenatea terphenyls, for example hexahydroterphenyls and dodeca-hydroterphenyls. As normally produced, materials of this type are mixtures containing in various proportions, ~ully hydrogenated terphenyls, partially hydrogenated terphenyls, and terphenyl itself. The terphenyl which is partially hydrogenated in obtaining such mixtures is itsel~ a mixture -30 of isomers. Other hydrocarbons include benzylated and a]pha-methylbenzylated alkylbenzene~, e-g- mono- and dibenzyl ethyl-benzene and mono(alpha-methylbenzyl)toluene, alkylnaphthalenes, e.g. dipropylnaphthalene and mono-alpha or -beta~2-hexyl) naphthalene, alkylbiphenyls, e.g. mono- and diisopropyl-35 biphenyls.
The solvent can be an aromatic hydrocarbon ~providedthe hydrocarbon is a liquid at room temperature) or a mixture of aromatic hydrocarbons, or an aromatic hydrocarbon or mixture together with a diluent, a diluent being an inert liquid miscible with the aromatic hydrocarbon(s). Examples of suitable diluents include mineral and vegetable oils, 5 such as kerosene, paraf~in oil, castor oil, soybean oil, corn oil and (long-chain alkylated)benzenes, for example (C7-C16 alkylated)benzenes. The d:iluent in a solvent o~
the invention unctions to alter physical properties of the solvent, for instance viscosity or vapour pressure, where 10 such alteration may be desired for optimum handling or processing. The solvent preferably con~ains at least 50%
by weight of aromatic hydrocarbon but in some instances, the aromatic hydrocarbon may be dilute~ with up to, for example,
3 times its own weight of diluent. For rapid development of 15 print intensi-ty, the solvent is preferably one having a viscosity in the range 5 to 15 centiso~es at 38C.
The chromogen used in the presentinvention is usually an aromatic compound containing a double bond system which is converted to a more highly polarized conjugated and 20 coloured form when reacted with an acidic sensitizing material. A-particularly preLerred class o~ chromogens includes compounds of the phthalide type, for instance crystal violet lactone which is 3,3-bis(p-dimethylamino-phenyi)-6-dimethylaminonaphthalide, and malachite green 25 lactone which is 3~3-bistp-dimethylaminophenyl)phthalide~
Other phthalide-derived chromogens include 3,3-bis(p-dipropylaminophenyl)phthalide, 3,3-bis(p-methylaminophenyl) phthalide, 3-(substituted-phenyl)-3-(indole-3-yl)-phthalides such as 3-(p-dimethylaminopheryl)-3-(1,~-dimethylindol-3-30 yl)phthalide, 3,3-bis(methylindol-3-yl)-phthalides such as 3,3-bis(1,2-dimethylindol-3-yl)phthalide, 3-(phenyl)-3-(heterocyclic-substituted) .
11 13~ 0 phthalides such as 3-(p-dimethylaminophenyl)-3-(1-methyl -pyrr-2-yl) 6-dimethylaminophthalide, indole and carbazole-substituted phthalides such as 3,3-bis(1,2- ..
- dimethylindol-3-yl)-5-dimethylaminophthalide and 3,3-bis (9-ethylcarbazol-3-yl)-5-dimethylaminophthalide7 and substituted indole phthalides such as 3-(1,3-dimethyl~
indol-3-yl)-3-(2-meth~rlindol-3-yl)-phthalide~
Other chromogens which can be u~ed in the present invention include 3-dialkylamino-6-alkyl-7-alkylaminO-10 fluorans, 3-dialkylamino-7-dia~.]-.ylan~i.nofluorans and- ..
3-methyl-2,2'-spirobi(benzo/f7chromene) An auxiliary colouring agent can be employed ~Yith the above chromogens. For e~arnpleycr~stal violet lactone (CVL) is usually used in conjunction \Yith be~oyl leuco -methylene blue (BLh~). The colouring agent compleme~ts the chromogen bacause on contact wi1h the sensiti2ing agent the CVL produces an i~edi.ate dark blue colouration~ but the colour tellds to fade over a period .-of timeO The BL.~.IB when in contact ~vith the sensitizing ;:
agent produces a somewhat pale initial colour, but the colbur gradually intensifies by oxidation of the dye~ :.
--The sensitizing agent used in a system o~ the present invention can be~ for e~ample; an acid clay, for instance an attapulgite or bentonite clay, or an acidic ..
organic polymer, for example a phenol-aldehyde polymer or a partially or wholly h~drolysed styrene/maleic .:
anhydride or eihylene/maleic anhydride polymer.
Part-cularly good results are obtained in the present invention using an acid clay as the sensitizing agentO
A system of the present invention can be prepared according to well Xnown conventional procedures t~hich are adequately described in the literature~
~lthough a preferred e~.bodiment of this invention comprises a two-sheet system tvherein the sensiti~in~ agen-t is carried by one sheet and a m~rl;ing fluid comprising a solu-tion of the invention is carried by a second sheet, 3~ 5~
s the invention is not limited to such systems aloneD
The only essential requirement is that the chromogen and the-sensitizing agent be maintained in a separate or unreactive.condition until pressure is applied to the system, and that upon the a~plication of pressure the chromogen and the sensitizlng age~t are brought into reactive con-tact in the presence of the solvent and o~
the promoter. Thus it is possible to have the chromo~en and sensitizin~ agent present in a dry and unreactive 10 state on a common c~rrier and to have a solution of the promoter in the solvent.carried on a separate shee~
whereupon the application o pressure would release the solution into the chro~ogen/sensitizing agent mixture and promote localized reaction and colour development Obviously, many other arrangements, configurætions and relationships OI the solven+ and the promoted mar~
forming materials ~vith respPct to their encapsulation and location on the supportin~ sheet or webs can be envisaged, and such arran~e~ents are within. the scope of the present invention. For example, it is possible to coat a sinDle paper or supportmember with all the components of this system to form a single sel-E-contained unit ~hich can be marked by th~ move~ent o a stylus or other pressure-imparting me~ns upon the ~5 sur~ace of the paperO Such papers are particularly useful for use in inkless recording instrumentsO
Solutions of Lhe invention were evaluated by the following technlque :
A soluLion of a blend of equal parts by we-ght o~
CVL and BL~B in the solvenL ~Yas preparedO ~ por-tion of this solution was used ~s the control, and in other portions there ~Yere dissolved the promoters to be evaluatedO To estimate pri~t intensity, a plate eng~raved with a p~ttern of dots ~as coated with sufficiellt OI the solution to gi~e a co~ting lS microns in thickness, usinC~ a doctor ~lade. A carriage-supported roller ~ ~3q561~ , ~
having a paper sheet coated ~Yith an acid clay sensitizing .. :
agent wrapped round the roller ~vas then moved slowly ....
across the solution-coated plate under constant pressure.
Colour developed on the paper. The paper was removed 5 from the roller, and the intensity o~ colour was measured using a Macbeth RD 51~ reflectometer calibra-ted against a "perfect white" of 0.07 units of optical density and ...
a "perfect black" of 1-78 units of optical density, using ..
standard "perfect ~vhite" and "perfect hlack" plates ..
10 supplied by the manufacturer. A.fter the i.nitial rea~ing, ..
the paper was transPerred to a humidi~ied oven, and.was removed at intervals for further colour ~ntensity ~ .
measurements. . .
To obt~in the results shown in the Tahles below5 the ..
15 colour intensity ~Yas measured each time at 20 diIferent .:
points on the paper surface and the ~alues were averagedo The figures in the column headed "Standardized" are values of the average colour irltensity on .a scale on which the a~erage i~litial colou.~ inten~ity o~ the control is 100.
20 The results glven.in Table 1 were obtained usin~ a ..
. solution containing 2.94% by weight of the blend o~ CVL
and BLMB alld l.9~o hy wei~]lt of the promoter in a solvent -- consisting of a mix~ure of 7 parts by ~Yeight o~ h~drogena-ted terphenyls obtained by ~he hydrogenation of terphenyl with 25 approxima-tely 4~,~0 of the amount o~ hydrogen required for .-.
complete hydrogenation, and 3 parts by ~eight of a (C9-Cll al~yl)benzeneD The oven was held at 75C~ and 60~o relative hum dity. The promoters used ~Yere as follows:
Mixture ol mono- and di(~-meth~lbenz~lated)phenol ..
30 ~ - 4,6-di~onyl-2-~ethylphenol C - Tetrakis~3-(3,5-di-t-butyl-4-hydroxypllen.yl) propionyl)oxymethy~methane ....
D - Octadecyl 3-(3,~-di-t-butyl-4-hydroxyphenyl) ...
propionate .
. . .
. .
. :
. .
:.
S~ , -- 10~ ,. ......
_ Table 1 I~ltial Intensity Intensity after 4S hours in oven Promo~er . _ Direct Standardized Direct Standardized . ...... _ ':,'.
A 0.63 1120 5 0054 96~4 :.. ' B 0.67 119~6 0.53 94L 6 C 0.60 107.1 0.54 96.4 D 0.64 114 D 2 0 53* 94 r 6* ..
None 0.56 100.0 0.44 ----.-- T - ''' After 20 hours in oven The results given in Table ~I were obtained using a solution containin~ 2.97qo by weight of the blend of CVL and BL~IB and 0.96% by weight of the promo-ter i~ a solvent consistin~ o~ a mi~ture of 7 parts by weight of hydrogenated terphenyls obtained by the hydrogenation of terphenyl with approximately 40% of the amount OI hydrogen required for complete hydrogenation, and 3 parts by ~eight of kero~ene~ The oven W2S held at 70 C. and 50~c relative hu~idity~ -- Table II
Initial Intensi y ~Intensity after 96 hours - I - i~ oven Promoter ~
Direct ~Standaràized Direct Standardized . . .__.................................. .. :-B j 0064 11004 0~36 62 D
C ~ 0 D 63 10806 0031 5304 None ~ 0058 100 0024 41~4 The improvements obtained in the presence of the - promoter, both in respect of initial colour intensity and persistence o~ colour durin~ accelerated storage, are apparent from the above resultsD
The efIects of varying the proportions of CVL and BL~IB in the blend in the presence and absence of promoter were investi~ated, with the results 5ho~Yn in Table III. The solvent was the same mixture as that 35 used to ob~ain the results of Table II, and the oven .
was maint~ined at 75 C. and 60% relative humidity.
Table ~II
.
. .... _ _ ..
Percent by weight in solution ;CVL 1.5 1051~5 1~5 1~0 l~0 B~ 1.5 1~5l~0 0~5 1~0 1~0 , Promoter B 01.0 1~0 l~,0 0 l~0 ___ .. ._. :',' Time (Hours) D rect I~ tensit~
~ ~ -. --------I ' ''' 0 0,61 0.65 0066 0~7~0.61 0.64 :
23 0.50 0~53 0059 0~56~Sl 0057 .
00~8 O.SS 0.53 0O5~ _ 0.47 .
47 0.50 0.5~ 0O55 0~5500~4 0~51 :
54 0047 0~54 0.~5 0,580~43 0.55 .
126 ~5 0051 00~9 00520~41 0,51 .
156 0.4~ 0054 0050 0.5~ _ OOS0 These results demonstrate the improvement o~tainable -- by the addition of the promoter, and tha~ when using a :
solution containing a promoter, the amounts of chromogen and auxiliary colouring a~ent can be reduced ~Yhile maintaining good print-intensity and dura~ilit~, :
The cor.cen~ra~ion of the chromogen in a solution o*
the invention is usually 0075 - 2% by weight of the solu-tion. Where both a ohromogen and an auxiliary colo~lring agent are used, their proportions by weight may be, for example, from 40:60 to 80:20~ and are 25 pre~erably uithin the range 50:50 -to 75:25.
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. . .
. .
.
. . .
. . .
. .
. . .
The chromogen used in the presentinvention is usually an aromatic compound containing a double bond system which is converted to a more highly polarized conjugated and 20 coloured form when reacted with an acidic sensitizing material. A-particularly preLerred class o~ chromogens includes compounds of the phthalide type, for instance crystal violet lactone which is 3,3-bis(p-dimethylamino-phenyi)-6-dimethylaminonaphthalide, and malachite green 25 lactone which is 3~3-bistp-dimethylaminophenyl)phthalide~
Other phthalide-derived chromogens include 3,3-bis(p-dipropylaminophenyl)phthalide, 3,3-bis(p-methylaminophenyl) phthalide, 3-(substituted-phenyl)-3-(indole-3-yl)-phthalides such as 3-(p-dimethylaminopheryl)-3-(1,~-dimethylindol-3-30 yl)phthalide, 3,3-bis(methylindol-3-yl)-phthalides such as 3,3-bis(1,2-dimethylindol-3-yl)phthalide, 3-(phenyl)-3-(heterocyclic-substituted) .
11 13~ 0 phthalides such as 3-(p-dimethylaminophenyl)-3-(1-methyl -pyrr-2-yl) 6-dimethylaminophthalide, indole and carbazole-substituted phthalides such as 3,3-bis(1,2- ..
- dimethylindol-3-yl)-5-dimethylaminophthalide and 3,3-bis (9-ethylcarbazol-3-yl)-5-dimethylaminophthalide7 and substituted indole phthalides such as 3-(1,3-dimethyl~
indol-3-yl)-3-(2-meth~rlindol-3-yl)-phthalide~
Other chromogens which can be u~ed in the present invention include 3-dialkylamino-6-alkyl-7-alkylaminO-10 fluorans, 3-dialkylamino-7-dia~.]-.ylan~i.nofluorans and- ..
3-methyl-2,2'-spirobi(benzo/f7chromene) An auxiliary colouring agent can be employed ~Yith the above chromogens. For e~arnpleycr~stal violet lactone (CVL) is usually used in conjunction \Yith be~oyl leuco -methylene blue (BLh~). The colouring agent compleme~ts the chromogen bacause on contact wi1h the sensiti2ing agent the CVL produces an i~edi.ate dark blue colouration~ but the colour tellds to fade over a period .-of timeO The BL.~.IB when in contact ~vith the sensitizing ;:
agent produces a somewhat pale initial colour, but the colbur gradually intensifies by oxidation of the dye~ :.
--The sensitizing agent used in a system o~ the present invention can be~ for e~ample; an acid clay, for instance an attapulgite or bentonite clay, or an acidic ..
organic polymer, for example a phenol-aldehyde polymer or a partially or wholly h~drolysed styrene/maleic .:
anhydride or eihylene/maleic anhydride polymer.
Part-cularly good results are obtained in the present invention using an acid clay as the sensitizing agentO
A system of the present invention can be prepared according to well Xnown conventional procedures t~hich are adequately described in the literature~
~lthough a preferred e~.bodiment of this invention comprises a two-sheet system tvherein the sensiti~in~ agen-t is carried by one sheet and a m~rl;ing fluid comprising a solu-tion of the invention is carried by a second sheet, 3~ 5~
s the invention is not limited to such systems aloneD
The only essential requirement is that the chromogen and the-sensitizing agent be maintained in a separate or unreactive.condition until pressure is applied to the system, and that upon the a~plication of pressure the chromogen and the sensitizlng age~t are brought into reactive con-tact in the presence of the solvent and o~
the promoter. Thus it is possible to have the chromo~en and sensitizin~ agent present in a dry and unreactive 10 state on a common c~rrier and to have a solution of the promoter in the solvent.carried on a separate shee~
whereupon the application o pressure would release the solution into the chro~ogen/sensitizing agent mixture and promote localized reaction and colour development Obviously, many other arrangements, configurætions and relationships OI the solven+ and the promoted mar~
forming materials ~vith respPct to their encapsulation and location on the supportin~ sheet or webs can be envisaged, and such arran~e~ents are within. the scope of the present invention. For example, it is possible to coat a sinDle paper or supportmember with all the components of this system to form a single sel-E-contained unit ~hich can be marked by th~ move~ent o a stylus or other pressure-imparting me~ns upon the ~5 sur~ace of the paperO Such papers are particularly useful for use in inkless recording instrumentsO
Solutions of Lhe invention were evaluated by the following technlque :
A soluLion of a blend of equal parts by we-ght o~
CVL and BL~B in the solvenL ~Yas preparedO ~ por-tion of this solution was used ~s the control, and in other portions there ~Yere dissolved the promoters to be evaluatedO To estimate pri~t intensity, a plate eng~raved with a p~ttern of dots ~as coated with sufficiellt OI the solution to gi~e a co~ting lS microns in thickness, usinC~ a doctor ~lade. A carriage-supported roller ~ ~3q561~ , ~
having a paper sheet coated ~Yith an acid clay sensitizing .. :
agent wrapped round the roller ~vas then moved slowly ....
across the solution-coated plate under constant pressure.
Colour developed on the paper. The paper was removed 5 from the roller, and the intensity o~ colour was measured using a Macbeth RD 51~ reflectometer calibra-ted against a "perfect white" of 0.07 units of optical density and ...
a "perfect black" of 1-78 units of optical density, using ..
standard "perfect ~vhite" and "perfect hlack" plates ..
10 supplied by the manufacturer. A.fter the i.nitial rea~ing, ..
the paper was transPerred to a humidi~ied oven, and.was removed at intervals for further colour ~ntensity ~ .
measurements. . .
To obt~in the results shown in the Tahles below5 the ..
15 colour intensity ~Yas measured each time at 20 diIferent .:
points on the paper surface and the ~alues were averagedo The figures in the column headed "Standardized" are values of the average colour irltensity on .a scale on which the a~erage i~litial colou.~ inten~ity o~ the control is 100.
20 The results glven.in Table 1 were obtained usin~ a ..
. solution containing 2.94% by weight of the blend o~ CVL
and BLMB alld l.9~o hy wei~]lt of the promoter in a solvent -- consisting of a mix~ure of 7 parts by ~Yeight o~ h~drogena-ted terphenyls obtained by ~he hydrogenation of terphenyl with 25 approxima-tely 4~,~0 of the amount o~ hydrogen required for .-.
complete hydrogenation, and 3 parts by ~eight of a (C9-Cll al~yl)benzeneD The oven was held at 75C~ and 60~o relative hum dity. The promoters used ~Yere as follows:
Mixture ol mono- and di(~-meth~lbenz~lated)phenol ..
30 ~ - 4,6-di~onyl-2-~ethylphenol C - Tetrakis~3-(3,5-di-t-butyl-4-hydroxypllen.yl) propionyl)oxymethy~methane ....
D - Octadecyl 3-(3,~-di-t-butyl-4-hydroxyphenyl) ...
propionate .
. . .
. .
. :
. .
:.
S~ , -- 10~ ,. ......
_ Table 1 I~ltial Intensity Intensity after 4S hours in oven Promo~er . _ Direct Standardized Direct Standardized . ...... _ ':,'.
A 0.63 1120 5 0054 96~4 :.. ' B 0.67 119~6 0.53 94L 6 C 0.60 107.1 0.54 96.4 D 0.64 114 D 2 0 53* 94 r 6* ..
None 0.56 100.0 0.44 ----.-- T - ''' After 20 hours in oven The results given in Table ~I were obtained using a solution containin~ 2.97qo by weight of the blend of CVL and BL~IB and 0.96% by weight of the promo-ter i~ a solvent consistin~ o~ a mi~ture of 7 parts by weight of hydrogenated terphenyls obtained by the hydrogenation of terphenyl with approximately 40% of the amount OI hydrogen required for complete hydrogenation, and 3 parts by ~eight of kero~ene~ The oven W2S held at 70 C. and 50~c relative hu~idity~ -- Table II
Initial Intensi y ~Intensity after 96 hours - I - i~ oven Promoter ~
Direct ~Standaràized Direct Standardized . . .__.................................. .. :-B j 0064 11004 0~36 62 D
C ~ 0 D 63 10806 0031 5304 None ~ 0058 100 0024 41~4 The improvements obtained in the presence of the - promoter, both in respect of initial colour intensity and persistence o~ colour durin~ accelerated storage, are apparent from the above resultsD
The efIects of varying the proportions of CVL and BL~IB in the blend in the presence and absence of promoter were investi~ated, with the results 5ho~Yn in Table III. The solvent was the same mixture as that 35 used to ob~ain the results of Table II, and the oven .
was maint~ined at 75 C. and 60% relative humidity.
Table ~II
.
. .... _ _ ..
Percent by weight in solution ;CVL 1.5 1051~5 1~5 1~0 l~0 B~ 1.5 1~5l~0 0~5 1~0 1~0 , Promoter B 01.0 1~0 l~,0 0 l~0 ___ .. ._. :',' Time (Hours) D rect I~ tensit~
~ ~ -. --------I ' ''' 0 0,61 0.65 0066 0~7~0.61 0.64 :
23 0.50 0~53 0059 0~56~Sl 0057 .
00~8 O.SS 0.53 0O5~ _ 0.47 .
47 0.50 0.5~ 0O55 0~5500~4 0~51 :
54 0047 0~54 0.~5 0,580~43 0.55 .
126 ~5 0051 00~9 00520~41 0,51 .
156 0.4~ 0054 0050 0.5~ _ OOS0 These results demonstrate the improvement o~tainable -- by the addition of the promoter, and tha~ when using a :
solution containing a promoter, the amounts of chromogen and auxiliary colouring a~ent can be reduced ~Yhile maintaining good print-intensity and dura~ilit~, :
The cor.cen~ra~ion of the chromogen in a solution o*
the invention is usually 0075 - 2% by weight of the solu-tion. Where both a ohromogen and an auxiliary colo~lring agent are used, their proportions by weight may be, for example, from 40:60 to 80:20~ and are 25 pre~erably uithin the range 50:50 -to 75:25.
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. . .
. .
.
. . .
. . .
. .
. . .
Claims (19)
1. A solution for use in a pressure sensitive mark-recording system, the said solution comprising a chromogen dissolved in a liquid solvent comprising an aromatic hydro-carbon in which at least half the carbon atoms are benzenoid carbon atoms, characterized in that there is also dissolved in the solvent a promoter which is a compound that is an alkylated, aralkylated or cycloalkylated phenol or which contains an alkylated, aralkylated or cycloalkylated hydroxy-phenyl radical in its molecule, the structure of the phenol or radical being such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of at least four carbon atoms or by an aralkyl or cycloalkyl group.
2. A solution according to claim 1 in which the promoter is a mononuclear phenol; a compound containing two hydroxy-phenyl radicals linked at the 2- or 4-position through a sulphur atom or through an alkylene or alkylidene group;
or a compound having the general formula [A-(CH2)pCOOlmR
where A represents a hydroxphenyl radical linked at the 2-or 4-position to the (CH2)p radical, p is an integer of from 1 to 4, m is an integer of from 1 to 4 and R represents a radical derived by the loss of m hydrogen atoms from an alkane of the formula CnH2n + 2 where n is an integer of from 1 to 24.
or a compound having the general formula [A-(CH2)pCOOlmR
where A represents a hydroxphenyl radical linked at the 2-or 4-position to the (CH2)p radical, p is an integer of from 1 to 4, m is an integer of from 1 to 4 and R represents a radical derived by the loss of m hydrogen atoms from an alkane of the formula CnH2n + 2 where n is an integer of from 1 to 24.
3. A solution according to claim 1 in which the structure of the phenol or radical is such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of from 4 to 12 carbon atoms, an alpha-alkyl benzyl group or an alpha-alkyl cyclohexyl group.
4. A solution according to claim 2 in which the structure of the phenol or radical is such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of from 4 to 12 carbon atoms, an alpha-alkyl benzyl group or an alpha-alkyl cyclohexyl group.
5. A solution according to claim 1 in which the promoter is alpha-methylbenzylated phenol containing a mixture of ortho(alpha-methylbenzyl)phenol and 2,4-di(alpha-methylbenzyl) phenol and/or 2,6-di(alpha-methylbenzyl)phenol.
6. A solution according to claim 1 in which the promoter is 4,6-dinonyl-2-methyl phenol.
7. A solution according to claim 1 wherein the phenol or radical contains two or three alkyl, aralkyl or cycloalkyl substituent groups and the structure of the phenol or radical is such that at least one of the positions ortho to the hydroxyl group is occupied by a tertiary alkyl group of from 4 to 12 carbon atoms or by an alpha-methylcyclohexyl group and at least one other position in the nucleus of the phenol or radical is occupied by an alkyl group of from one to three carbon atoms.
8. A solution according to claim 1 wherein the promoter is 2,6-di-t-butyl-4-methylphenol, 2,4-dimethyl-6(alpha-methylcyclohexyl]phenol, 2,6-di-(alpha-methylcyclohexyl)-4-methylphenol, 4,4'-thiobis(2-t-butyl-5-methylphenol), 4,4'-butylidene-bis(2-t-butyl-5-methylphenol), 2,2'-methylenebis (4-methyl-6-t-butylphenol), 2,2'-methylenebis(4-ethyl-6-t-butylphenol), or bis[2-hydroxy-3(alpha-methylcyclohexyl)-5-methylphenyl]methane.
9. A solution according to claim 1 wherein the promoter is a compound having the general formula [A-(CH2)pCOO]mR
where A represents a hydroxphenyl radical linked at the 4-position to the (CH2)p radical and having a tertiary alkyl group of from 4 to 12 carbon atoms in at least one of the 3-and 5-positions, and R represents a radical derived by the loss of m hydrogen atoms from an alkane of the formula CnH2n + 2 where n is an integer of from m to 24.
where A represents a hydroxphenyl radical linked at the 4-position to the (CH2)p radical and having a tertiary alkyl group of from 4 to 12 carbon atoms in at least one of the 3-and 5-positions, and R represents a radical derived by the loss of m hydrogen atoms from an alkane of the formula CnH2n + 2 where n is an integer of from m to 24.
10. A solution according to claim 1 wherein the promoter is octadecyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate or tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionyloxy-methyl]methane.
11. A solution according to claim 1, 2 or 3, in which the amount of the promoter is from 0.1 to 3% by weight of the solvent.
12. A solution according to claim 4, 5 or 6, in which the amount of the promoter is from 0.1 to 3% by weight of the solvent.
13. A solution according to claim 7, 8 or 9, in which.
the amount of the promoter is from 0.1 to 3% by weight of the solvent.
the amount of the promoter is from 0.1 to 3% by weight of the solvent.
14. A solution according to claim 10, in which the amount of the promoter is from 0.1 to 3% by weigh of the solvent.
15. A solution according to claim 1, 2 or 3, in which the chromogen is crystal violet lactone (CVL), and the solution also contains benzoyl leuco methylene blue (BLMB) as an auxiliary colouring agent, the proportions of CVL and BLMB being from 40:60 to 75:25 by weight.
16. A solution according to claim 4, 5 or 6, in which the chromogen is crystal violet lactone (CVL), and the solution also contains benzoyl leuco methylene blue (BLMB) as an auxiliary colouring agent, the proportions of CVL and BLMB being from 40:60 to 75:25 by weight.
17. A solution according to claim 7, 8 or 9, in which.
the chromogen is crystal violet lactone (CVL), and the solution also contains benzoyl leuco methylene blue (BLMB) as an auxiliary colouring agent, the proportions of CVL and BLMB being from 40:60 to 75:25 by weight.
the chromogen is crystal violet lactone (CVL), and the solution also contains benzoyl leuco methylene blue (BLMB) as an auxiliary colouring agent, the proportions of CVL and BLMB being from 40:60 to 75:25 by weight.
18. A solution according to claim 10, in which the chromogen is crystal violet lactone (CVL), and the solution also contains benzoyl leuco methylene blue (BLMB) as an auxiliary colouring agent, the proportions of CVL and BLMB being from 40:60 to 75:25 by weight.
19. A pressure-sensitive mark-recording system comprising (a) sheet material, (b) mark-forming components supported by the sheet material and arranged in juxtaposition but in unreactive condition, the said components comprising (i) a chromogen, (ii) a sensitizing agent for the chromogen which produces a colour from the chromogen when brought into contact with the chromogen in the presence of a solvent, and (c) the said solvent, being a solvent comprising an aromatic hydrocarbon in which at least half the carbon atoms are benzenoid carbon atoms, supported by the sheet material but separated from the sensitizing agent by a physical barrier which is rupturable on the application of a marking instrument to the sheet material, characterized in that the sheet material also supports a promoter which is an alkylated, aralkylated or cycloalkylated phenol or a compound which contains an alkylated, aralkylated or cycloalkylated hydroxyphenyl radical in its molecule, the structure of the phenol or radical being such that at least one of the positions ortho to the hydroxyl group is occupied by an alkyl group of at least four carbon atoms or by an aralkyl or cycloalkyl group, the promoter being soluble in the solvent, and the location of the promoter in the system being such that it is present when the chromogen is brought into contact with the sensitizing agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB7848222 | 1978-12-13 | ||
| GB48222/78 | 1978-12-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1139560A true CA1139560A (en) | 1983-01-18 |
Family
ID=10501684
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000341757A Expired CA1139560A (en) | 1978-12-13 | 1979-12-12 | Pressure sensitive mark-recording systems |
Country Status (3)
| Country | Link |
|---|---|
| EP (1) | EP0012579B1 (en) |
| CA (1) | CA1139560A (en) |
| DE (1) | DE2965775D1 (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4275905A (en) * | 1978-12-29 | 1981-06-30 | Appleton Papers Inc. | Pressure-sensitive record material |
| US4372582A (en) * | 1981-03-30 | 1983-02-08 | Minnesota Mining And Manufacturing Company | Stabilizer for electron doner-acceptor carbonless copying systems |
| US4489336A (en) * | 1981-06-05 | 1984-12-18 | Kanzaki Paper Manufacturing Co., Ltd. | Pressure sensitive manifold paper |
| FR2637291B1 (en) * | 1988-09-30 | 1993-04-23 | Atochem | NOVEL COMPOSITION, ITS APPLICATION AS AN ELECTRICAL INSULATOR AND A MANUFACTURING METHOD THEREOF |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB873702A (en) * | 1958-08-26 | 1961-07-26 | Caribonum Ltd | Improvements in or relating to manifolding |
| US3996405A (en) * | 1973-01-24 | 1976-12-07 | Ncr Corporation | Pressure-sensitive record material |
| US4093278A (en) * | 1976-12-27 | 1978-06-06 | Monsanto Company | Dye solvents for pressure-sensitive copying systems |
-
1979
- 1979-12-07 EP EP19790302817 patent/EP0012579B1/en not_active Expired
- 1979-12-07 DE DE7979302817T patent/DE2965775D1/en not_active Expired
- 1979-12-12 CA CA000341757A patent/CA1139560A/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| DE2965775D1 (en) | 1983-07-28 |
| EP0012579A2 (en) | 1980-06-25 |
| EP0012579B1 (en) | 1983-06-22 |
| EP0012579A3 (en) | 1980-10-15 |
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