GB2187469A - Recording liquid containing water soluble dyes - Google Patents
Recording liquid containing water soluble dyes Download PDFInfo
- Publication number
- GB2187469A GB2187469A GB08701481A GB8701481A GB2187469A GB 2187469 A GB2187469 A GB 2187469A GB 08701481 A GB08701481 A GB 08701481A GB 8701481 A GB8701481 A GB 8701481A GB 2187469 A GB2187469 A GB 2187469A
- Authority
- GB
- United Kingdom
- Prior art keywords
- dyes
- recording
- water
- recording liquid
- soluble
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/16—Writing inks
- C09D11/17—Writing inks characterised by colouring agents
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/32—Inkjet printing inks characterised by colouring agents
- C09D11/328—Inkjet printing inks characterised by colouring agents characterised by dyes
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Inks, Pencil-Leads, Or Crayons (AREA)
Abstract
A recording liquid containing a plurality of water-soluble dyes is provided in which the water-soluble dyes give a tone satisfying the following formula (I) and has a chromatographic characteristic satisfying the following formula (II): 0</= 2ROOT ( DELTA a*)<2> + ( DELTA b*)<2></= 10 (I> 0</= DELTA Rf</=0.2 (II> wherein (I), DELTA a* and DELTA b* represent respectively a difference in a* and b* between any two dyes selected from said plurality of dyes in perception chromaticity indexes, and DELTA Rf represents a difference of flow rate Rf in paper chromatography between any two dyes selected from said plurality of dyes. A recording method using the recording liquid is also provided, which is useful for recording onto a recording medium containing a cellulose fiber exposed at the surface of the recording medium.
Description
SPECIFICATION
Recording liquid and recording method using the same Background of the invention Field of the invention
The present invention relates to a recording liquid (hereinafter referred to as an ink) for recording on a recording medium (e.g. a paper, a resin film) by means of inkjet recording ora writing tool (e.g. afountain pen, a felt pen), as well as to a recording method using the recording liquid.
Description ofthe invention
Inkjet recording is a recording method wherein an ink is ejected by an appropriate ejecting mechanism to form ink droplets and a partorall of the droplets are aliowed to deposit on a recording medium such asa paperorthe like to conduct recording. As the ink used in inkjet recording, there are known and being used inks obtained by dissolving or dispersing various water-soluble dyes or pigments in wateror a liquid medium consisting of water and a water-soluble organic solvent.
Similar inks may be usedforwriting tools such as fountain pens, felt pens, ball pens and the like.
As the recording medium on which recording is made with the above inks, there are being used paper, converted paper, su rface-treated plastic films, etc.
Such inks should have properties of water resistance, light resistance, storage stability (no precipitate formation during storage) and the like.
A number ofwater-soluble dyes for these inks are known. Two or more of water-soluble dyes are used in combination when desired ink properties cannot be achieved with a single dye.
The use of at least two water-soluble dyes in combination gives desired properties to the ink. However, it has happened frequently that when such an ink is used for recording on general office use paper such as a notebook, a reporting paper, a copying paper, a letter paper and the like, as compared with the case where an ink containing a single dye is used, the peripheral areas of inkdots get blurred and the recorded image becomes unclear as a whole.
The present inventor made extensive research on the cause of the above phenomenon, and found thatthe recorded image becomes unclear as a whole when a plurality of dyes used in combination exhibit different tones and moreover havethe different affinityfor cellulosefiberof recording paperfrom each other.
That is, when a dye with higher affinity and a dye with lower affinity is used in combination, they causefine separation from each other on the cellulose of the paper and the different tones of individual dyes appear separately on the paper, making the image unclear.
Summary of the invention
An object of the present invention is to provide a recording liquid which has remedied the above mentioned drawbacks ofthe prior art and can give a recorded image offine color and excellent clearness particularly on papers whose fibers are exposed at the surface (e.g. a reporting paper, a copying paper), as well as a recording method using said recording liquid.
According to one aspect of the present invention, there is provided a recording liquid containing a plurality of water-soluble dyes, characterized in that said water-soluble dyes give a tone satisfying the following formula (I) and have a chromatographic characteristic satisfying the following formula (11):
OARf0.2 (II) In the formula (I), ha* and Ab* represent respectively a difference of a* orb* between any two dyes selected from said plurality of dyes in ClE-L*a*b*, and ARfrepresentsa difference of flow rate Rf in paper chromatography between any two dyes selected from said plurality of dyes.
According to another aspect ofthe present invention, there is also provided a recording method wherein recording is conducted by depositing droplets of a recording liquid onto a recording medium, the recording liquid contains a plurality of water-soluble dyes; thatthe water-soluble dyes give a tone satisfying thefollow- ing formula (I) and have a chromatographic characteristic satisfying the following formula (ill); and that the recording material contains a cellulose fiber exposed at the surface of the recording medium.
OARf=0.2 (11) Detailed description of the preferred embodiments
The present invention will be described in more detail.
The ink of the present invention generally comprises at leasttwo water-soluble dyes, a liquid medium for dissolving or dispersing these dyes and, as necessary, appropriate additives. The water-soluble dyes are required to have similar tones and similar chromatographic characteristics.
In the present invention, the tone of a dye is represented by the a* and b* of the dye defined by the CIE 1976 (L*, a*, b*) space.
In the present invention, the chromatographic characteristic of a dye is represented by a flow rate ofthe dye measured using the following paper chromatography procedure. The object of the present invention can be achieved by combined use of dyes which are similar to each other in this flow rate.
The flow rate of a water-soluble dye is measured asfollows.
A dye is dissolved in a water/diethylene glycol (55/45 by volume) mixed solvent at a concentration of 5% by weight two prepare a testsolution.2,ut ofthis test solution is charged to the lower end of a piece offilter paper [Toyo Filter Paper No. 50 (trade name), manufactured by Toyo Roshi K.K.]. Then, development is effected for a predetermined length of time according to an ordinary method by using the above mixed solvent as a developer. Thereafter, the development distance A ofthe developer from the charge point as well as the flow distance B ofthe dye from the charge point is measured, and their ratio B/A (= Rf) is calculated. This Rf is defined as the flow rate ofthe dye.
The present inventor investigated the chromatographic characteristics of various water-soluble dyes on the basis of the flow rate defined above, and found that when two or more water-soluble dyes having a difference offlow rate of greater than 0.2 are used in combination to prepare an ink and recording is made with the ink on a recording material of paper type, the image obtained is always blurred at the peripheries and accordingly unclear.
The afore-mentioned difference offlow rates refers to the one between the two dyes used or the ones between the highest and the lowestflow rates among three of more dyes used in combination.
The study by the present inventor on various combinations of a number of dyes revealed that a clear image having a desired tone can be formed only when the dyes having similartones and similarchromatographic characteristics, i.e., the dyes satisfying both of the formulas (I) and (II) shown above are used in combination.
Acombination of dyeswhich are similarto each other only in tone or in chromatographiccharacteristicis incapable of giving a fully satisfactory image.
A plurality of water-soluble dyes used in combination in the present invention may be any water-soluble dyes used in conventional inks. The examples are acid dyes such as
C.I.Acid Black 24 ( a*=2.0, b*=2.0, Rf=0.93)
C.l.Acid Black 26 ( 2.3 4.8 0.90) C.l.AcidBlack 52::1 ( 4.2 4.7 0.97)
C.l.Acid Black 107 ( 0.6 3.4 0.85) C.l.AcidBlack 110 ( a*=4.4, b*=11.9, Rf=0.86) 139 ( 4.1 5.3 0.90)
C.l.AcidYellow 23 ( -4.2 42.7 0.90) 29 ( 2.0 42.4 0.82) 38 ( 3.7 43.4 0.85) 65 ( 0.4 49.2 0.85) C.l.Acid Red 27 ( 31.0 5.0 0.91) 35 ( 51.4 8.0 0.95) 42 ( 40.1 7.6 0.93) " 106 ( 43.9 5.2 0.99) 122 ( 53.3 8.7 0.98) 131 ( 37.8 19.8 0.96) 145 ( 39.2 21.0 0.92) 161 ( 40.7 3.7 0.86) 276 ( 51.8 9.5 0.74) 128 ( 33.8 1.6 0.68), and direct dyes such as
C.l.DirectBlack 19 ( a*=0.6, b*=-0.8, Rf=0.77) 154 ( 0.7 1.1 0.72)
C.l.Directyellow 12 ( 15.2 31.8 0.87) 86 ( - 4.6 59.7 0.82) 142 ( -10.4 57.4 0.76)
C.l.DirectBlue 86 ( -17.8 -28.5 0.86) 199 ( -15.94 -32.97 0.84)
The dyes for combination is selected from the above dyes and mixed such that the tones and chromatographic characteristics of the combined dyes satisfy the Formuia (I) and (II). The water-soluble dyes used in the present invention are not limited to those enumerated above, but any dyes may be used as long as their color tones and the chromatographic characteristics are close to each other.
These water-soluble dyes are used in the present invention in a total amount of ordinarily about 0.5to 30% by weight, more preferably about 1 to 10% by weight based on the ink.
The solvent used in the ink of the present invention iswaterora mixed solvent comprising water and a water-soluble organic solvent. A mixed solvent is particularly preferred which contains, as thewater-soluble organic solvent, a polyhydric alcohol effective for retarding the inkdrying.
As water, deionized water is preferred to ordinary water containing various ions.
Asthe water-soluble organic solvent used together with water, there may be mentioned, for example, alkyl alcohols of 1 to 4 carbon atoms such as methyl alcohol, ethyi alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, sec-butyl alcohol, tert-butyl alcohol, isobutyl alcohol and the like; am ides such as di methylformamide, dimethylacetamide and the like; ketones or ketoalcohols such as acetone, diacetone alcohol and the like; ethers such as tetrahydrofuran, dioxane and the like; polyalkylene glycols such as a polyethylene glycol, a polypropylene glycol and the like; alkylene glycols having 2 to 6 carbon atoms such as ethylene glycol, propylene glycol, butylene glycol,triethylene glycol, 1 ,2,6-hexanetriol, thiodiglycol, hexylene glycol, diethylene glycol and the like; lower alkyl ethers of polyhydric alcohols such as glycerine, ethylene glycol methyl (or ethyl) ether, diethylene glycol methyl (or ethyl) ether, triethylene glycol monomethyl (or monoethyl) ether and the like; N-methyl-2-pyrrolidone; 1 ,3-dimethyl-2-imidazolidinone; and so forth. Of these, polyhydric alcohols (e.g. diethylene glycol) and lower alkyl ethers of polyhydric alcohols [e.g.
triethylene glycol monomethyl (or monoethyl) ether] are preferred.
The content of the water-soluble organic solvent in the ink is ordinarily Oto 95 by weight, preferably 1 Oto 80 by weight, more preferably 20 to 50 % by weight based on the total weight ofthe ink.
The content of water in the ink may vary widely depending upon the type and composition ofthewater- soluble organic solvent, and the properties ofthe ink. It is ordinarily 10to 90% byweight, preferably 10to70 % by weight, more preferably 20 to 70 % by weight based on the total weight of the ink.
The ink of the present invention is basically constituted as described above. The ink may further contain, as necessary, conventionally known additives such as a dispersant, a surfactant, a viscosity-controlling agent, a surface tension-controlling agent and the like.
These additives include, for example, viscosity-controlling agents such as a polyvinyl alcohol, a cellulose, a water-soluble resin and the like; surfactants ofcationic, anionic or nonionictype; surface tension-controlling agents such as diethanol amine, triethanol amine and the like; buffer solutions as a pH-controlling agent; and antiseptics.
Further, a resistivity-adjusting agent such as lithium chloride, ammonium chloride, sodium chloride and other inorganic salts may be added to an ink formulation which is electrified in the ink jet printing process.
When the inkofthe present invention is used in such inkjet recording as the ink is ejected by the action of thermal energy, the ink may be controlled in thermal properties (e.g. specific heat, thermal expansion coefficient, thermal conductivity).
The drawbacks ofthe prior art are sufficiently remedied in the ink of the present invention as describes above. Therefore, when the present ink is used for recording on various recording materials, for example, those of papertype whose cellulose is exposed at the surface, by means of ink jet recording or an ordinary writing tool, a mixed tone of the two or more water-soluble dyes contained in the ink can be reproduced on the recording materials in such an extent that the reproduced tone has no practical problem. Hence, a clear, high contrast, high quality image of excellent light resistance and water resistance can be obtained not only in ordinary recording using a black ink of the present invention but also in full color recording using a plurality of color inks of the present invention.
In preparation of conventional inks, attention has been paid only to color mixing between the water soluble dyes to be jointly used in the inks. As a result, a desired color tone of ink has been achieved but it has been difficult to reproduce it on recording materials, particularly those whose cellulose are exposed atthe surface. In contrast, in preparation of the present ink, in addition to the color mixing between the dyes to be jointly used in the ink, a new criterion of chromatographic characteristics of these dyes has been employed.
This has sufficiently removed the drawbacks of the prior art.
The present invention will be described more specifically below byway of Examples, Comparative Examples and Application Example. Parts or % in the following is on weight basis unless otherwise specified.
Examples l to 5and Comparative Examples l to 2: The components of the following composition were stirred to dissolve the water-soluble dyes. The resulting solution was filtered to remove the insolubles, whereby five inks of the present invention and two inks of
Comparative Examples were prepared.
The values in parentheses given to each dye refer to the tone and flow rate of the dye.
Example 1
C.l.Acid Black 107 2.5 parts (a*=0.6, b*=3.4, Rf=0.85)
C.l.Acid Black 24 2.5 parts (a*=2.0, b*=2.0, Rf=0.93)
Diethylene glycol 30 parts
Deionized water 65 parts
Example 2 C.l.Acid Yellow 29 2.5 parts (a*=2.0, b*=42.4, Rf=0.82) C.l.Acid Yellow 38 2.5 parts (a* =3.7, b*=43.4 Rf=0.85)
Diethylene glycol 30 parts
Deionized water 65 parts
Example 3 C.l.Acid Red 106 2.5 parts (a*=43.9, b*=5.2, Rf=0.99) C.l.Acid Red 161 2.5 parts (a*=42.7, b*=3.7, Rf=0.86)
Diethylene glycol 30 parts
Deionized water 65 parts
Example 4 C.l.Acid Red 145 2.5 parts (a*=39.2, b*=21.0, Rf=0.92)
C.l.Acid Red 131 2.5 parts (a*=37.8, b*=19.8, Rf=0.96)
Diethylene glycol 30 parts
Deionized water 65 parts
Example 5
C.l.Acid Black 26 2.0 parts (a*=2.3, b*=4.8, Rf=0.90) C.l.Acid Black 52:1 1.5 parts (a*=4.2, b*=4.7, Rf=0.97) C.l.Acid Black 139 1.5 parts (a*=4.1, b*=5.3, Rf=0.90)
Diethylene glycol 30 parts
Deionized water 65 parts
Comparative Example 1
C.I.Acid Black 24 2.5 parts (a*=2.0, b*=2.0, Rf=0.93) C.l.Acid Black 110 2.5 parts (a*=4.4, b*=11.9, Rf=0.86)
Diethylene glycol 30 parts
Deionized water 65 parts
Comparative Example 2 ClAcid Black24 2.5 parts (a*=2.0, b*=2.0, Rf=0.93)
C.l.Acid Black 26 2.5 parts (a*=0.7, b*=1.1, Rf=0.72)
Diethylene glycol 30 parts
Deionized water 65 parts
Using the above prepared inks of Examples and Comparative Examples, recording was conducted on the following various recording materials by means of a recording apparatus of on-demand type recording head (PJ-1 210, manufactured by CANON K.K.) wherein inks were to be discharged by a piezo vibrator. With the inks ofthe present invention, there was no separation of water-soluble dyes from each other on the recording materials; ink tones could be reproduced; and clear images of excellent color could be obtained. Meanwhile, with the inks of Comparative Examples, inktones could not be reproduced and unclearimageswereob- tained.
Recording materials
(1) Ginwa (trade name) (high quality paper, manufactured by Sanyo-kokusaku Pulp Co., Ltd.)
(2) Seven Star (trade name) (high quality paper, manufactured by Hokuetsu Paper Mills, Ltd.)
(3) Hakubotan (trade name) (medium quality paper, manufactured by Honshu Paper Co., Ltd.)
(4) Toyo Roshi No.4 (trade name) (non-sized paper, manufactured by Toyo Roshi K.K.)
Each of the inks of Examples and Comparative Examples was charged into a felt pen and recording was conducted on papers with these pens. In the case of the inks of the present invention, no color separation on paper occurred and clear images of the same tones as those of the inks were obtained. In the case of the inks of Comparative Examples, separation of dyes from each other occurred on the papers; the inktonescould not be reproduced; and the images were unclear.
Claims (7)
1. A recording liquid containing a plurality of water-soluble dyes, said water-soluble dyes giving a tone satisfying the following formula (I) and having a chromatographic characteristic satisfying thefollowing formula (ill):
OARf0.2 (II) wherein (I), Aa* and Ab* represent respectively a difference in a* and by between any two dyes selected from said plurality of dyes in ClE-L*a*b*, and ARf represents a difference of Rfvalue in paperchromatography between any two dyes selected from said plurality of dyes.
2. A recording liquid according to Claim 1, wherein the content of the dyes is in the range of from 0.5 to 30 % by weight based on the total weight of the recording liquid.
3. A recording liquid according to Claim 1, wherein said recording liquid further contains water and a water-soluble organic solvent as liquid media for dissolving or dispersing the dyes.
4. A recording method wherein recording is conducted by depositing droplets of a recording liquid onto a recording medium, said recording liquid containing a plurality ofwater-soluble dyes; the water-soluble dyes giving a tone satisfying the following formula (I) and having a chromatographic characteristic satisfying the following formula (ill); and the recording medium containing a cellulose fiber exposed at the surface of the recording material:
0 =' ARf =' 0.2 (Il) wherein (I), ha* and Ab* represent respectively a difference of a* orb* between any two dyes selected from said plurality of dyes in ClE-L*a*b*, and ARf represents a difference of Rf value in paperchromatography between any two dyes selected from said plurality of dyes.
5. A recording method according to Claim 4, wherein the content of the dyes in the recording liquid is in the range offrom 0.5 to 30 % byweight based on the totalweightofthe recording liquid.
6. A recording method according to Claim 4, wherein the recording liquid contains water and a water soluble organic solvent as liquid media for dissolving ordispersing the dyes.
7. An ink, substantially as described with reference to any of Examples 1 to 5.
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61013893A JPS62172075A (en) | 1986-01-27 | 1986-01-27 | Recording liquid |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| GB8701481D0 GB8701481D0 (en) | 1987-02-25 |
| GB2187469A true GB2187469A (en) | 1987-09-09 |
| GB2187469B GB2187469B (en) | 1989-12-06 |
Family
ID=11845860
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| GB8701481A Expired GB2187469B (en) | 1986-01-27 | 1987-01-23 | Recording liquid and recording method using the same |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JPS62172075A (en) |
| DE (1) | DE3702340A1 (en) |
| GB (1) | GB2187469B (en) |
| HK (1) | HK69691A (en) |
| SG (1) | SG88891G (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3371264A4 (en) * | 2015-11-06 | 2018-09-12 | Ricoh Company, Ltd. | Ink set, ink stored container, inkjet printing method, and inkjet printing apparatus |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19600989B8 (en) * | 1995-01-13 | 2005-07-21 | Fuji Photo Film Co., Ltd., Minami-Ashigara | Method and apparatus for ink jet recording |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4505749A (en) * | 1983-06-24 | 1985-03-19 | Canon Kabushiki Kaisha | Method of forming color images |
-
1986
- 1986-01-27 JP JP61013893A patent/JPS62172075A/en active Pending
-
1987
- 1987-01-23 GB GB8701481A patent/GB2187469B/en not_active Expired
- 1987-01-27 DE DE19873702340 patent/DE3702340A1/en active Granted
-
1991
- 1991-08-29 HK HK69691A patent/HK69691A/en not_active IP Right Cessation
- 1991-10-22 SG SG88891A patent/SG88891G/en unknown
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4505749A (en) * | 1983-06-24 | 1985-03-19 | Canon Kabushiki Kaisha | Method of forming color images |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3371264A4 (en) * | 2015-11-06 | 2018-09-12 | Ricoh Company, Ltd. | Ink set, ink stored container, inkjet printing method, and inkjet printing apparatus |
| US10563077B2 (en) | 2015-11-06 | 2020-02-18 | Ricoh Company, Ltd. | Ink set, ink stored container, inkjet printing method, and inkjet printing apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62172075A (en) | 1987-07-29 |
| DE3702340A1 (en) | 1987-07-30 |
| DE3702340C2 (en) | 1988-06-30 |
| GB8701481D0 (en) | 1987-02-25 |
| HK69691A (en) | 1991-09-06 |
| GB2187469B (en) | 1989-12-06 |
| SG88891G (en) | 1991-11-22 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PE20 | Patent expired after termination of 20 years |
Effective date: 20070122 |