CA1095656A - Capillary type ink - Google Patents
Capillary type inkInfo
- Publication number
- CA1095656A CA1095656A CA316,261A CA316261A CA1095656A CA 1095656 A CA1095656 A CA 1095656A CA 316261 A CA316261 A CA 316261A CA 1095656 A CA1095656 A CA 1095656A
- Authority
- CA
- Canada
- Prior art keywords
- ink
- writing
- ink composition
- quaternary ammonium
- weight
- 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
Landscapes
- Pens And Brushes (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
ABSTRACT
Ink compositions for use in capillary type writing instruments containing quaternary ammonium of the formula:
RCH2N(CH3)3+X-wherein R is -CH2OH or -COOH, and X is -OH, -Cl, -Br, or -I.
These ink compositions, when used in capillary type writing instruments, allow rejuvenation of writing points which have dried out from exposure to the atmosphere.
Ink compositions for use in capillary type writing instruments containing quaternary ammonium of the formula:
RCH2N(CH3)3+X-wherein R is -CH2OH or -COOH, and X is -OH, -Cl, -Br, or -I.
These ink compositions, when used in capillary type writing instruments, allow rejuvenation of writing points which have dried out from exposure to the atmosphere.
Description
1~95656 I~
. I,.
I . CAPILLARY TYPF,_INK
¦ BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to an ink for use in capillary type writin~ instruments, and more particularly, to aqueous ink co~positions promoting rejuvenation after the writing tip o~ a capillary type writing nstrument has dried out from exposure ¦ to the atmosphere.
l Description of the Prior ~rt ¦-¦ A problem frequently encountered by people who use ¦ capillary type writing instruments is writing point dryout.
¦ Capillary type writing instruments include those pens or marking devices which have fiber, felt, or porous plastic type writing ¦ points which deliver ink from a reservoir to the writing point I5 ¦ by means of ca~illary action. The in~s used in capillary type I writing instruments ~ave generally been of two types: 1) water I ~ based inks containing water soluble dyes~ (the inks of the ¦ present invention), and 2) inks which contain organic solvents l and dyes which are soluble in an organic medium.
Capillary type writing instruments employ a variety of types of fiber, felt, and porous plastic writing points.
Felt i~ a fabric of natural and/or synthetic fibers worl~ed together by pressure, heat, or chemical action without weaving or knitting. The fibers tend to be arranged in a random fashion.
When felt is used as a writing point, the ink is conveyed through the interstices between the individual fibers by capillary action.
A second major type of writing point is made by bonding together a bundle of parallel strands of either natural ...
., I ~ I
1~)95656 - or synthetic fibers (e.g. polyvinyl chloride, polyethylene, or polyamide polymers) to form capillary pathways between the bundles leading to the writing point. U.S. Patent 3,558,392 is an example of such a point. The fibrous point is made by setting a bundle of parallel strands of synthetic fibers in a desired relation by drawing the bundle through a heat-setting zone to establish dimensions in cross-section of the final object and to create longitudinally extending channels. The strength of the point is subsequently increased by immersion in a dilute resin solution followed by heating to evaporate the solvent and cure the resin. Depending on the denier of the fibers of the particular yarn which is used to form the writing point, a number of cannels will be formed having average or mean transverse dimensions of from 1 x 1 mils. to 3 x 6 mils. Channels of 1.5 to 3 mils. in one transverse direction and between 3 and 6 mils. in another direction are representative of the most desirable channel sizes. Thus, the capillary channels are typically between 4.5 and 18 sq.
mils. in cross-sectional area.
An example of another type of writing point is described in U.S. Patent 3,778,495. The point described there is an elongated unitary writing element made by extruding and melt-drawing a polymer (e.g. acrylic, acetal, polyamide, or polyester polymers) and then reforming the internal portions of the extruded body by a compressive drawing operation to obtain channels of a desired size. The writing point thus formed has a longitudinally extending, axialj ink-conveying channel and circumaxial, spaced, ink-conveying channels, the axial channel having a cross-sectional area equivalent to a circle with a diameter between two and four mils. The enlarged circumaxial bm~
~1 lOg5656 inl~-conveying channels have an oblong cross-sectional shape approximately 1 to 3 mils. wide and 3 to 5 mils. in a radial direction. The circumaxial ink-conveying channels are connected to the axial channel by capillary channels having diameters of between 0.4 mils. and 1.0 mils. The longi~udinal channels of the rods serve to deliver ink to the writing point by ~eans of capillary action.
In each of the above cases, the ink is fed from a reservoir to the writing surface by means of the writing point.
The reservoir which ~eeds the writing point may be either a container of liquid ink or a bundle of fibers saturated with ink. Either will perform equally in capillary writing instru-ments since dryout is attributable to changes occuring at the writing tip rather than inside the pen.
A problem with capillary type writing instruments is that when exposed to the atmosphere, as when left uncapped for a period of time, the water in the ink may evaporate so as to change the composition of the ink and make it more viscous.
The capillaries within the tip of the writing instrument will then ~ecome clogged so that the written line produced becomes irregular. If left uncapped long enough, the composit on o~
the ink at the tip may be so changed that it will not flow at all through the capillaries of the tip, writing becomes im-possible, and the instrument must be discarded.
. I,.
I . CAPILLARY TYPF,_INK
¦ BACKGROUND OF THE INVENTION
Field of the Invention This invention relates to an ink for use in capillary type writin~ instruments, and more particularly, to aqueous ink co~positions promoting rejuvenation after the writing tip o~ a capillary type writing nstrument has dried out from exposure ¦ to the atmosphere.
l Description of the Prior ~rt ¦-¦ A problem frequently encountered by people who use ¦ capillary type writing instruments is writing point dryout.
¦ Capillary type writing instruments include those pens or marking devices which have fiber, felt, or porous plastic type writing ¦ points which deliver ink from a reservoir to the writing point I5 ¦ by means of ca~illary action. The in~s used in capillary type I writing instruments ~ave generally been of two types: 1) water I ~ based inks containing water soluble dyes~ (the inks of the ¦ present invention), and 2) inks which contain organic solvents l and dyes which are soluble in an organic medium.
Capillary type writing instruments employ a variety of types of fiber, felt, and porous plastic writing points.
Felt i~ a fabric of natural and/or synthetic fibers worl~ed together by pressure, heat, or chemical action without weaving or knitting. The fibers tend to be arranged in a random fashion.
When felt is used as a writing point, the ink is conveyed through the interstices between the individual fibers by capillary action.
A second major type of writing point is made by bonding together a bundle of parallel strands of either natural ...
., I ~ I
1~)95656 - or synthetic fibers (e.g. polyvinyl chloride, polyethylene, or polyamide polymers) to form capillary pathways between the bundles leading to the writing point. U.S. Patent 3,558,392 is an example of such a point. The fibrous point is made by setting a bundle of parallel strands of synthetic fibers in a desired relation by drawing the bundle through a heat-setting zone to establish dimensions in cross-section of the final object and to create longitudinally extending channels. The strength of the point is subsequently increased by immersion in a dilute resin solution followed by heating to evaporate the solvent and cure the resin. Depending on the denier of the fibers of the particular yarn which is used to form the writing point, a number of cannels will be formed having average or mean transverse dimensions of from 1 x 1 mils. to 3 x 6 mils. Channels of 1.5 to 3 mils. in one transverse direction and between 3 and 6 mils. in another direction are representative of the most desirable channel sizes. Thus, the capillary channels are typically between 4.5 and 18 sq.
mils. in cross-sectional area.
An example of another type of writing point is described in U.S. Patent 3,778,495. The point described there is an elongated unitary writing element made by extruding and melt-drawing a polymer (e.g. acrylic, acetal, polyamide, or polyester polymers) and then reforming the internal portions of the extruded body by a compressive drawing operation to obtain channels of a desired size. The writing point thus formed has a longitudinally extending, axialj ink-conveying channel and circumaxial, spaced, ink-conveying channels, the axial channel having a cross-sectional area equivalent to a circle with a diameter between two and four mils. The enlarged circumaxial bm~
~1 lOg5656 inl~-conveying channels have an oblong cross-sectional shape approximately 1 to 3 mils. wide and 3 to 5 mils. in a radial direction. The circumaxial ink-conveying channels are connected to the axial channel by capillary channels having diameters of between 0.4 mils. and 1.0 mils. The longi~udinal channels of the rods serve to deliver ink to the writing point by ~eans of capillary action.
In each of the above cases, the ink is fed from a reservoir to the writing surface by means of the writing point.
The reservoir which ~eeds the writing point may be either a container of liquid ink or a bundle of fibers saturated with ink. Either will perform equally in capillary writing instru-ments since dryout is attributable to changes occuring at the writing tip rather than inside the pen.
A problem with capillary type writing instruments is that when exposed to the atmosphere, as when left uncapped for a period of time, the water in the ink may evaporate so as to change the composition of the ink and make it more viscous.
The capillaries within the tip of the writing instrument will then ~ecome clogged so that the written line produced becomes irregular. If left uncapped long enough, the composit on o~
the ink at the tip may be so changed that it will not flow at all through the capillaries of the tip, writing becomes im-possible, and the instrument must be discarded.
2~ Attempts have been made to retard the rate at which water based inks dry out by adding humectant materials such as ethylene glycol, propylene glycol, and other higher molecular weight polyhydroxy compounds such as those described in U.S.
¦~ Patent 3, ,045. However, such materials tend to increase ' ~ 13i95656 the viscosity of the ink to such an extent that it will not flow freely through the capillaries of capillary type writing instruments, Furthermore, the selective evaporation of the more volatile constituents of the ink may cause ~he inks to be thickened at the exposed tip of the instrument by the less volatile polyhydroxy compounds which remain. If additional polyhydroxy compound is used in the ink formulation, the gains from increased humectancy are lost to the increasing viscosity.
In an attempt to solve the point dryout problem, U.S. Patent 3,519,443, describes inks formulated with formamide as a solvent to reduce the rate of point dryout. Forma~ide is somewhat toxic. This constitutes a disadvantage since capillary ' type writing instruments containing water-based inks may be used by children. In addition, formamide is suggested for use at concentrations fro~ 10% to 100% o~ the total solvent content of the ink, levels at which a disagreeable odor may be -produced.
In spite of the above attempts to reduce point dryout, ¦ problems still exist. Therefore, a need exists for ink com-~20 positions which not only reduce the rate of dryout, but allow rejuvenation even after dryout has occurred.
SUMMARY_OF THE IN~ENTION
The present invention comprises an ink composition adapted for use in a capillary type ~itin~ instrument com-prising an aqueous solùtion containing:
(a) from about 0.5% to about 15% by weight of a water soluble dye; and (b) from about 1% to about 25% of a quaternary ammonium com-pound ot he ~ormula:
. RC1~2N (C~ ) X I .
wherein --R is -CH2OH or -CO~H, and 1 X is -OH, -Cl, -Br, or -I.
¦ DETAILED DESCRIP~ION OF THE INVENTION
Satisfactory operation of capillary type writing instruments is dependent upon a steady capillary flow of ink to the point which engages the paper or other writing surface.
¦ Thus, the ink used must be sufficiently fluid to assure free I and continuous flow through the capillary passages from the I reservoir to the writing tip. Conversely, problems can occur ¦ if the ink is too thin. ~eathering (i.e. laterial wicking of ¦ the ink into the paper from the written line), and strike 1 through (i.e. penetration of the ink to the back of the paper), ¦ are common problems when ink viscosity is too low. To make ¦ sure that the writing point is supplied a suitable amount of in~, the inks should be formulated to have a viscosity below 50 centipoises at 20C and, more preferably, a viscosity in the range between 2 and 5 centipoises.
In its simplest form, the present invention comprises an aqueous solution of a water soluble dye and a compound of the formula:
RCH2N(CH3)3 X
wherein R is -CH2OH or -COOH, and X is -OH, -C1, -Br, or -I.
_5_ . ,, I
. ' I .
P~eferred quaternary a~monium compounds according _ to the invention are:
(~-hydroxyethyl)trimethylammonium chloride, ~IOCH2CH2N(CH3)3 Cl and carboxymethyltrimethylammonium hydroxide, HOOCCH2N(CH3)3 OH
The quaternary ammonium co~pound may be present in the composition from 1% to 25% by ~eight, preferably from 5% to 15%.
While an aqueous solution of a water soluble ink and a quaternary ammonium compound produce an acceptable ink, it is preferred to include at least one polyhydric alcohol in the ink formulation.
I , ............ ~.................................... .
Polyhydric alcohols are used in the present invention to increase the viscosity of the ink thereby improving the characteristics of the line produced by the writing instrument and reducing strike through and eathering.
Polyhydric alcohols use~ul in the invention include al~ylene glycols (e.g., ethylene glycol, propylene glycol, and butylene glycol), polyalkylene glycols (e.g., diethylene glycol and tripropylene glycol), mono- and di-al~yl ethers of poly-hydric alcohols (e.g., ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol butyl ether~ and trihydric alcohols (e.g., glycerin). The preferred alcoho~s ~ are glycerin and ethylene glycol, and mixtures thereof.
1~95656 The total amount of polyhydric alcohol employed in the compositions of the invention may be varied within wide lil.lits as dictated by the viscosity considerations of the composition as discussed above. As will be appreciated by those skilled in the art, the amount of polyhydric alcohol employed depends in part on the molecular weight of the parti- ¦
cular alcohol employed, since viscosity is generally direct~y proportional to molecular weight. In general, the polyhydric alcohol component of the invention constitutes from lV/o to 50%
by weight of the composition.
While any of the water soluble dyes typically used in ink formulations may be employed in producing inks in accordance with the present invention, acid dyes are preferred due to their high tinctorial strength. Such acid dyes possess one or more sulfonate groups attached to an aromatic nucleus, . . . . ;.- .
and can be classified according to their chemical structure into ten different categories: nitro, nitroso, monoazo, monoazo (metalized), disazo, triphenylmethane, xanthene, anthraquinone, azine, and quinoline. The amount of dye used will, of course, vary with the nature and color of the ink to be produced and may constitute from about 0.5% to 15% by weight o the total ink composition.
If desired, it is also possible to add other optional ingredients typically used in water based inks such as corrosion inhibitors (e.~., benzotriazole) and preservatives (e.g., methyl parasept).
The inks can be produced by the simple operation of mixing and dissolving the ingredients in any suitable way, but it is preferred that the ink componen~s (with the exception ~7~
. .
. ' ~9 S~ 5 6 of a quaternary ammonium com~ound of the present invention) be I held at 55C with constant stirring for ~wo hours after their ¦ initial mixing. I~en the ink cools to room temperature, a ¦ quaternary ammonium compound of the present invention is intro- ¦
¦ duced with stirring and the ink formula~ion is then filtered.
I The filtered ink is incorporated in any of the con-ventional capillary writin~ instrument types described above, by well known procedures. For exampleJ the ink may be injected into the end of the reservoir opposite the writing point in a previously assembled porous point pen by means of a syringe.
An alternate procedure, described in U.S. Patent 3J581,378J
i8 to first saturate a fibrous reservoir with inkJ followed by insertion into the-barrel of the porous point pen.
The inks of the present invention are designed for ¦ use in capillary type: writin~ instruments where the writing ¦ point may be acc~idently allowed to dry out (e.g. J by leaving ¦ the writing ~oint uncapped for a perio~ of time). Should that occur, the instrument may be rejuvenatedJ rather than being discarded as would be the case with pens containing prior art 1 inks. Rejuvenation is accomplished by recapping the ~riting point and allowing the instrument to equilibrate for a few hours, after which the writing point will have regained its ability to produce a written line, In order to illustrate typical and preferred in~
compositions embodying the present inventionJ the following examples are included:
EXl~LE I
Six percent by weight of a dye known as Color Index Acid Green 16 (C.I. #44025), 2% by weight of a dye Icnown as 0951i56 Color Index Acid ~ellow 11 (C.I. ~18820), 1% by weig~lt benæo-triazole, 0,2% methyl parasept, 5% glycerin, and 12.5% ethylene I glycol were mixed and dissolved in 73~3~O by weight OL water.
¦ The solution was held at 55C, with constant stirring for two ¦ hours. After the ink was cooled, 10% by weight of (~-hydroxy-ethyl)trimethylammonium chloride was dissolved in the cooled solution. The ink formulation was then filtered and charged ¦ into capillary type writing instruments having writing tips l formed of closely packed polyester fiber strands. Each pen -¦ was tested to make sure it would produce a written line, afterwhich the uncapped pens were placed in a dessicator containing a saturated solution of MgC12 6H20 to maintain a R.H. of approximately 33%.
l Pens removed from the dessicator our, seven, and ¦ fourteen days later would not produce a written line since l their writing points had dried out. However, when the pens ¦ were recapped and allowed to equilibrate for a few hours, the ; ¦ ability to ~ite had been restored in all cases.
I EX~LF. II
1 Ingredi nt /O by Weig,ht Color Index Acid Blue 9 (C.I. ~42090) 7.0 benzotriazole l.0 methyl parasept 0.2 glycerin 5.0 ethylene glycol 12.5 water q.s. to lO0 1~ -9- '.1 . .
Procedure: The above ingredien~s are combined and heated to 55 C for two hours with constant stirring. The solution is allo~Jed to cool to room tempera~ure, at which time 10% by weight of carboxymethyltrimethylammonium hydroxide is added with stirring. The ink formulation is then filtered and charged into capillary type writing instruments having writing tips formed by closely packed polyester fiber strands.
EXAMPLE III
Ingredient ~/O by Wei~ht Color Index Acid Red 73 (C.I. #27290) 8.0 benzotriazole 1.0 methyl parasept 0.2 glycerin 5.0 ethylene glycol 12.5 water q,s. to 100 Procedure: The above ingredients are combined and heated to 55C for two hours with constant stirring. The solution is allowed to cool to room temperature, at which time 10% by weight of (~-hydroxyethyl)trimethylammoniu~ chloride is added wlth stirring. After filtering, the ink formulation is charged into capillary type writing instruments having ~riting tips formed of closely packed polyester fiber strands.
EX~PLE IV
Ingredient % by Weight Color Index Acid Blue 9 (C.I, #42090) 7.0 benzotriazole 1.0 methyl parasept 0.2 water q.s. to 100 .' ...... , 1, ' ' .
1~95656 !
l I
Proce(lure: The above ingredients are combined and heated to 55 C for two hours with constant stirring. The solution is allowed to cool to room temperatur~, at which time 15% by j weight of carboxymethyltrimethyla~monium hydroxide is added I with stirring. The ink formula~ion is then filtered and charged into capillary type writing instruments having writing tips formed by extruding, melt-drawing, and compressively drawing polyamide.
¦ The pens containing the ink compositions set forth I in Examples II, III, and IV can be rejuvenated after their ' writing points have dried out, by cappin~ for a few hours.
~ At that time, their abiiity to produce a written line will have ¦ been restored.
What is claimed is:
¦~ Patent 3, ,045. However, such materials tend to increase ' ~ 13i95656 the viscosity of the ink to such an extent that it will not flow freely through the capillaries of capillary type writing instruments, Furthermore, the selective evaporation of the more volatile constituents of the ink may cause ~he inks to be thickened at the exposed tip of the instrument by the less volatile polyhydroxy compounds which remain. If additional polyhydroxy compound is used in the ink formulation, the gains from increased humectancy are lost to the increasing viscosity.
In an attempt to solve the point dryout problem, U.S. Patent 3,519,443, describes inks formulated with formamide as a solvent to reduce the rate of point dryout. Forma~ide is somewhat toxic. This constitutes a disadvantage since capillary ' type writing instruments containing water-based inks may be used by children. In addition, formamide is suggested for use at concentrations fro~ 10% to 100% o~ the total solvent content of the ink, levels at which a disagreeable odor may be -produced.
In spite of the above attempts to reduce point dryout, ¦ problems still exist. Therefore, a need exists for ink com-~20 positions which not only reduce the rate of dryout, but allow rejuvenation even after dryout has occurred.
SUMMARY_OF THE IN~ENTION
The present invention comprises an ink composition adapted for use in a capillary type ~itin~ instrument com-prising an aqueous solùtion containing:
(a) from about 0.5% to about 15% by weight of a water soluble dye; and (b) from about 1% to about 25% of a quaternary ammonium com-pound ot he ~ormula:
. RC1~2N (C~ ) X I .
wherein --R is -CH2OH or -CO~H, and 1 X is -OH, -Cl, -Br, or -I.
¦ DETAILED DESCRIP~ION OF THE INVENTION
Satisfactory operation of capillary type writing instruments is dependent upon a steady capillary flow of ink to the point which engages the paper or other writing surface.
¦ Thus, the ink used must be sufficiently fluid to assure free I and continuous flow through the capillary passages from the I reservoir to the writing tip. Conversely, problems can occur ¦ if the ink is too thin. ~eathering (i.e. laterial wicking of ¦ the ink into the paper from the written line), and strike 1 through (i.e. penetration of the ink to the back of the paper), ¦ are common problems when ink viscosity is too low. To make ¦ sure that the writing point is supplied a suitable amount of in~, the inks should be formulated to have a viscosity below 50 centipoises at 20C and, more preferably, a viscosity in the range between 2 and 5 centipoises.
In its simplest form, the present invention comprises an aqueous solution of a water soluble dye and a compound of the formula:
RCH2N(CH3)3 X
wherein R is -CH2OH or -COOH, and X is -OH, -C1, -Br, or -I.
_5_ . ,, I
. ' I .
P~eferred quaternary a~monium compounds according _ to the invention are:
(~-hydroxyethyl)trimethylammonium chloride, ~IOCH2CH2N(CH3)3 Cl and carboxymethyltrimethylammonium hydroxide, HOOCCH2N(CH3)3 OH
The quaternary ammonium co~pound may be present in the composition from 1% to 25% by ~eight, preferably from 5% to 15%.
While an aqueous solution of a water soluble ink and a quaternary ammonium compound produce an acceptable ink, it is preferred to include at least one polyhydric alcohol in the ink formulation.
I , ............ ~.................................... .
Polyhydric alcohols are used in the present invention to increase the viscosity of the ink thereby improving the characteristics of the line produced by the writing instrument and reducing strike through and eathering.
Polyhydric alcohols use~ul in the invention include al~ylene glycols (e.g., ethylene glycol, propylene glycol, and butylene glycol), polyalkylene glycols (e.g., diethylene glycol and tripropylene glycol), mono- and di-al~yl ethers of poly-hydric alcohols (e.g., ethylene glycol methyl ether, ethylene glycol ethyl ether, and ethylene glycol butyl ether~ and trihydric alcohols (e.g., glycerin). The preferred alcoho~s ~ are glycerin and ethylene glycol, and mixtures thereof.
1~95656 The total amount of polyhydric alcohol employed in the compositions of the invention may be varied within wide lil.lits as dictated by the viscosity considerations of the composition as discussed above. As will be appreciated by those skilled in the art, the amount of polyhydric alcohol employed depends in part on the molecular weight of the parti- ¦
cular alcohol employed, since viscosity is generally direct~y proportional to molecular weight. In general, the polyhydric alcohol component of the invention constitutes from lV/o to 50%
by weight of the composition.
While any of the water soluble dyes typically used in ink formulations may be employed in producing inks in accordance with the present invention, acid dyes are preferred due to their high tinctorial strength. Such acid dyes possess one or more sulfonate groups attached to an aromatic nucleus, . . . . ;.- .
and can be classified according to their chemical structure into ten different categories: nitro, nitroso, monoazo, monoazo (metalized), disazo, triphenylmethane, xanthene, anthraquinone, azine, and quinoline. The amount of dye used will, of course, vary with the nature and color of the ink to be produced and may constitute from about 0.5% to 15% by weight o the total ink composition.
If desired, it is also possible to add other optional ingredients typically used in water based inks such as corrosion inhibitors (e.~., benzotriazole) and preservatives (e.g., methyl parasept).
The inks can be produced by the simple operation of mixing and dissolving the ingredients in any suitable way, but it is preferred that the ink componen~s (with the exception ~7~
. .
. ' ~9 S~ 5 6 of a quaternary ammonium com~ound of the present invention) be I held at 55C with constant stirring for ~wo hours after their ¦ initial mixing. I~en the ink cools to room temperature, a ¦ quaternary ammonium compound of the present invention is intro- ¦
¦ duced with stirring and the ink formula~ion is then filtered.
I The filtered ink is incorporated in any of the con-ventional capillary writin~ instrument types described above, by well known procedures. For exampleJ the ink may be injected into the end of the reservoir opposite the writing point in a previously assembled porous point pen by means of a syringe.
An alternate procedure, described in U.S. Patent 3J581,378J
i8 to first saturate a fibrous reservoir with inkJ followed by insertion into the-barrel of the porous point pen.
The inks of the present invention are designed for ¦ use in capillary type: writin~ instruments where the writing ¦ point may be acc~idently allowed to dry out (e.g. J by leaving ¦ the writing ~oint uncapped for a perio~ of time). Should that occur, the instrument may be rejuvenatedJ rather than being discarded as would be the case with pens containing prior art 1 inks. Rejuvenation is accomplished by recapping the ~riting point and allowing the instrument to equilibrate for a few hours, after which the writing point will have regained its ability to produce a written line, In order to illustrate typical and preferred in~
compositions embodying the present inventionJ the following examples are included:
EXl~LE I
Six percent by weight of a dye known as Color Index Acid Green 16 (C.I. #44025), 2% by weight of a dye Icnown as 0951i56 Color Index Acid ~ellow 11 (C.I. ~18820), 1% by weig~lt benæo-triazole, 0,2% methyl parasept, 5% glycerin, and 12.5% ethylene I glycol were mixed and dissolved in 73~3~O by weight OL water.
¦ The solution was held at 55C, with constant stirring for two ¦ hours. After the ink was cooled, 10% by weight of (~-hydroxy-ethyl)trimethylammonium chloride was dissolved in the cooled solution. The ink formulation was then filtered and charged ¦ into capillary type writing instruments having writing tips l formed of closely packed polyester fiber strands. Each pen -¦ was tested to make sure it would produce a written line, afterwhich the uncapped pens were placed in a dessicator containing a saturated solution of MgC12 6H20 to maintain a R.H. of approximately 33%.
l Pens removed from the dessicator our, seven, and ¦ fourteen days later would not produce a written line since l their writing points had dried out. However, when the pens ¦ were recapped and allowed to equilibrate for a few hours, the ; ¦ ability to ~ite had been restored in all cases.
I EX~LF. II
1 Ingredi nt /O by Weig,ht Color Index Acid Blue 9 (C.I. ~42090) 7.0 benzotriazole l.0 methyl parasept 0.2 glycerin 5.0 ethylene glycol 12.5 water q.s. to lO0 1~ -9- '.1 . .
Procedure: The above ingredien~s are combined and heated to 55 C for two hours with constant stirring. The solution is allo~Jed to cool to room tempera~ure, at which time 10% by weight of carboxymethyltrimethylammonium hydroxide is added with stirring. The ink formulation is then filtered and charged into capillary type writing instruments having writing tips formed by closely packed polyester fiber strands.
EXAMPLE III
Ingredient ~/O by Wei~ht Color Index Acid Red 73 (C.I. #27290) 8.0 benzotriazole 1.0 methyl parasept 0.2 glycerin 5.0 ethylene glycol 12.5 water q,s. to 100 Procedure: The above ingredients are combined and heated to 55C for two hours with constant stirring. The solution is allowed to cool to room temperature, at which time 10% by weight of (~-hydroxyethyl)trimethylammoniu~ chloride is added wlth stirring. After filtering, the ink formulation is charged into capillary type writing instruments having ~riting tips formed of closely packed polyester fiber strands.
EX~PLE IV
Ingredient % by Weight Color Index Acid Blue 9 (C.I, #42090) 7.0 benzotriazole 1.0 methyl parasept 0.2 water q.s. to 100 .' ...... , 1, ' ' .
1~95656 !
l I
Proce(lure: The above ingredients are combined and heated to 55 C for two hours with constant stirring. The solution is allowed to cool to room temperatur~, at which time 15% by j weight of carboxymethyltrimethyla~monium hydroxide is added I with stirring. The ink formula~ion is then filtered and charged into capillary type writing instruments having writing tips formed by extruding, melt-drawing, and compressively drawing polyamide.
¦ The pens containing the ink compositions set forth I in Examples II, III, and IV can be rejuvenated after their ' writing points have dried out, by cappin~ for a few hours.
~ At that time, their abiiity to produce a written line will have ¦ been restored.
What is claimed is:
Claims (8)
1. An ink composition adapted for use in capillary type writing instrument comprising an aqueous solution contain-ing:
(a) from about 1.5% to 15% by weight of a water soluble dye; and (b) from about 1% to about 25% of a quaternary ammonium compound of the formula RCH2N(CH3)3+X-wherein R is -CH2OH or -COOH, and X is -OH, -Cl, -Br, or -I.
(a) from about 1.5% to 15% by weight of a water soluble dye; and (b) from about 1% to about 25% of a quaternary ammonium compound of the formula RCH2N(CH3)3+X-wherein R is -CH2OH or -COOH, and X is -OH, -Cl, -Br, or -I.
2. The ink composition as claimed in Claim 1 in which the percent by weight of said quaternary ammonium compound is from about 5 to about 15.
3. The ink composition as claimed in Claim 1 in which said quaternary ammonium compound is (.alpha.-hydroxyethyl)tri-methylammonium chloride.
4. The ink composition as claimed in Claim 1 in which said quaternary ammonium compound is carboxymethyltrimethyl-ammonium hydroxide.
5. The ink composition as claimed in Claim 1, further including from about 1% to about 50% by weight of a water soluble polyhydric alcohol.
6. The ink composition as claimed in Claim 5 in which said alcohol is glycerin.
7. The ink composition as claimed in Claim 5 in which said alcohol is ethylene glycol.
8. A writing system comprising a capillary type writing instrument charged with an aqueous solution containing:
(a) from about 0.5% to about 15% by weight of a water soluble dye; and (b) from about 1% to about 25% of a quaternary ammonium compound of the formula RCH2N(CH3)3+X-wherein R is -CH2OH or -COOH, and X is -OH, -Cl, -Br, or -I.
(a) from about 0.5% to about 15% by weight of a water soluble dye; and (b) from about 1% to about 25% of a quaternary ammonium compound of the formula RCH2N(CH3)3+X-wherein R is -CH2OH or -COOH, and X is -OH, -Cl, -Br, or -I.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA316,261A CA1095656A (en) | 1978-11-15 | 1978-11-15 | Capillary type ink |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA316,261A CA1095656A (en) | 1978-11-15 | 1978-11-15 | Capillary type ink |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1095656A true CA1095656A (en) | 1981-02-17 |
Family
ID=4112952
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA316,261A Expired CA1095656A (en) | 1978-11-15 | 1978-11-15 | Capillary type ink |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1095656A (en) |
-
1978
- 1978-11-15 CA CA316,261A patent/CA1095656A/en not_active Expired
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2376123C (en) | Oil-based ballpoint pen ink composition and oil-based ballpoint pen | |
| DE3207116A1 (en) | OVERPRESSURE PEN PEN TYPE WRITER AND INK FOR SUCH A WRITER | |
| DE1769498C3 (en) | Ink for recorders | |
| DE69506954T2 (en) | Fluorescent ink composition for marker pens | |
| DE602005001225T2 (en) | Water-based inkjet ink for ink-jet printing, ink cartridge containing the ink and ink-jet printing method | |
| US7011466B2 (en) | Writing implement | |
| JPH01304163A (en) | Water-base fluorescent ink for writing utensil | |
| US4171983A (en) | Capillary type ink | |
| CA1095656A (en) | Capillary type ink | |
| US3519443A (en) | Capillary type ink and instruments using the same | |
| US6644880B2 (en) | Writing article whose writing tip includes a drying retardant and process for the manufacture of such a tip | |
| US4202652A (en) | Capillary type ink | |
| KR100470618B1 (en) | Writing utensil | |
| JP3163465B2 (en) | Water-based ink for direct liquid writing instruments | |
| JPH08157765A (en) | Oil-base ink composition for ball-point | |
| CA1142304A (en) | Capillary type ink | |
| JP3995418B2 (en) | Firing colored pencil lead and method for producing the same | |
| JP2003176438A (en) | Ink composition for oil-based marking pen | |
| DD144574A5 (en) | METHOD FOR PRODUCING HYDROPHILIC SYNTHESIS FIBERS AND FAEDES | |
| JP3707893B2 (en) | Firing colored pencil lead and method for producing the same | |
| JPS6225184A (en) | Oily ink | |
| JP7291486B2 (en) | Retractable padding type marking pen and core used for it | |
| JP4518629B2 (en) | Writing instrument with excellent cap-off performance | |
| JPS6138222B2 (en) | ||
| JP3671308B2 (en) | Water-based ink composition for marking pens |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |