CA1073727A - Electrosensitive recording member with electrically conductive, light coloured intermediate and white, electrically destructable surface layers - Google Patents
Electrosensitive recording member with electrically conductive, light coloured intermediate and white, electrically destructable surface layersInfo
- Publication number
- CA1073727A CA1073727A CA235,465A CA235465A CA1073727A CA 1073727 A CA1073727 A CA 1073727A CA 235465 A CA235465 A CA 235465A CA 1073727 A CA1073727 A CA 1073727A
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- Prior art keywords
- layer
- intermediate layer
- white
- discharge
- color
- Prior art date
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Abstract
ABSTRACT OF THE DISCLOSURE
An electro-sensitive recording member includes a substrate on which there is disposed an electrically conductive, light colored intermediate layer comprising a pigment and a binder. The color of the intermediate layer is convertible to a darker color in response to the application of an electrical current or discharge thereto.
Disposed directly on the intermediate layer is a white surface layer that is no greater than approximately 10 microns thick and which is capable of being destroyed by application of an electrical current or discharge thereto to expose the intermediate layer. Electric current is selectively applied to the recording member by a stylus, and the electric current or discharge destroys the white surface layer to selectively expose the intermediate layer in accordance with an image to be recorded, the image resulting from the color contrast between the exposed and non-exposed portions of the intermediate layer.
An electro-sensitive recording member includes a substrate on which there is disposed an electrically conductive, light colored intermediate layer comprising a pigment and a binder. The color of the intermediate layer is convertible to a darker color in response to the application of an electrical current or discharge thereto.
Disposed directly on the intermediate layer is a white surface layer that is no greater than approximately 10 microns thick and which is capable of being destroyed by application of an electrical current or discharge thereto to expose the intermediate layer. Electric current is selectively applied to the recording member by a stylus, and the electric current or discharge destroys the white surface layer to selectively expose the intermediate layer in accordance with an image to be recorded, the image resulting from the color contrast between the exposed and non-exposed portions of the intermediate layer.
Description
.~ ~
B~C~I<C ROlJND Ol~ Tl 11~ INVI NTION
v 1. ~ielcl of tllc lnvention.
!¦ ~his invention rclates tO an electrosensitive medium which can form a visible image directly from an electric signal.
B~C~I<C ROlJND Ol~ Tl 11~ INVI NTION
v 1. ~ielcl of tllc lnvention.
!¦ ~his invention rclates tO an electrosensitive medium which can form a visible image directly from an electric signal.
2. Discussion of the Prior Art.
I .. . . . . . . ___ A variery of recording media are known which form a visible image directly frorn an electric signal but they have various drawbacks.
For example, in one known recording method, recording is effected by subjecting a conductive solution or an electrolyte impregnated in a paper sheet to electrolysis in response to an electric signal. In this method various difficulties have been experienced including (a) great variations in recording characteristics due to the water content of the paper sheet, (b) wear of the electrodes, tc) fading of picture images, and (d) discoloration of the recorc3ing paper sheet and the like.
¦ In order to eliminate these difficulties, a variety of dry type - . electrolytic recording media, as disclosed in Japanese Patent Publication INO. 38-22341, have been developed. However, none of this prior ar~
recording media is satisfactory in that they invariably contain a large - amount of a metal vxide or a metal sulfide in the coloring layer of the 20 recording shee~ so that wear of the recording stylus is accelerated due to the substantial hardness of the coloring layer. Further, a metal oxide or a metal sulfide which permits easy color development will have its own ~¦color and therefore is not suitable for coating on a recording shee~ since the latter has imparted thcreto the particlllar color of the metal oxiclc or s~llfide used. Also, a rccording ~:heet using a ~vhite metal o~;icle has clra~vbacl~s I
I ~ .
~ ' ~
.
.. . . ', '' . ~
I .. . . . . . . ___ A variery of recording media are known which form a visible image directly frorn an electric signal but they have various drawbacks.
For example, in one known recording method, recording is effected by subjecting a conductive solution or an electrolyte impregnated in a paper sheet to electrolysis in response to an electric signal. In this method various difficulties have been experienced including (a) great variations in recording characteristics due to the water content of the paper sheet, (b) wear of the electrodes, tc) fading of picture images, and (d) discoloration of the recorc3ing paper sheet and the like.
¦ In order to eliminate these difficulties, a variety of dry type - . electrolytic recording media, as disclosed in Japanese Patent Publication INO. 38-22341, have been developed. However, none of this prior ar~
recording media is satisfactory in that they invariably contain a large - amount of a metal vxide or a metal sulfide in the coloring layer of the 20 recording shee~ so that wear of the recording stylus is accelerated due to the substantial hardness of the coloring layer. Further, a metal oxide or a metal sulfide which permits easy color development will have its own ~¦color and therefore is not suitable for coating on a recording shee~ since the latter has imparted thcreto the particlllar color of the metal oxiclc or s~llfide used. Also, a rccording ~:heet using a ~vhite metal o~;icle has clra~vbacl~s I
I ~ .
~ ' ~
.
.. . . ', '' . ~
3'~
1'~ ' . .
in tllat it is susceptibl~ to non-uniform lecorcling and ~owere~ image dcnsit~
because of its increascd ~lectrical resistance.
There has also been used in another embodimellt of the prior art il an electrosensitive medium comprising (a) an under]ayer of carbon or some ¦~ other dark colored conductive material coated with a bmder on (b) a substrate or a supporting means, (c) a white surf~ce layer being disposed on the dark colored layer. With such a recording medium,portions of the white surface layer are burnt and removed by sparking to form a picture image by means of the contrast between the non-sparked white surface layer and the dark colored underlayer. However the burning operation produces a bad odor, smoke and ashes to the potentially extreme discomfort of the operator.
Moreover, the white surface layer must have a thickness as large as 10 to ~ 20 microns in order to conceal the-color of dark colored underlayer with ¦ the result that the recording medium suffers from lowered recording ¦ sensi~ivity in addition to the difficulties mentioned above. llence, application of high voltage is necessitated which tends to disintegrate the dark colored underlayer into powder ~ereby causing recording failure because of deposition of the powder on the recording stylus. Further, the powder deposited on the recording stylus is transferred again onto the white surface layer in the form of a so-called "tail". ~lso, a portion of the powc3er is directly dropped onto the white sulface layer ~vithout depositing on dle recorcling stylus and spoils marginal portions of the picture image.
An example of pr-ior art which overcornes these difficulties is found in Japancse Patcnt Publicatioll No. ~4-31998 wherc thcre is clisclosed a recording menlber comprising a base layer such as a paper sheet, a colorcd -3~
~ l'' . .
lQ~3 7Z ~
layer dispose~ on the base, a thin me-talli.c layer disposed on the colored layer and a white surface layer whi.ch can be very thin. However, the recording medium disclosed in this patent publication is disadvantageous in that it causes accelerated abrasive wear to the recording stylus. Thus, it cannot be practically used for stylus-scanning type recording due to tone variations. Therefore, the recording medium of the above Japanese patent publication has been excIusiveiy used for the d~t matrix type recording.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention there is provided an electrosensitive recording member comprising: a substrate; an electrically conductive, light : colored intermediate layer disposed on said substrate, said intermediate layer comprising a pigment and a binder, `
the color of said intermediate layer being convertible to a darker color in response to the application of an electrical current or discharge thereto; and a white surface layer disposed directly on said intermediate layer, said white surface layer being no greater than approximately 10 microns thick and being capable of being destroyed by application of an electrical current or discharge thereto to expose said.
intermediate layer, said electrically conductive layer being more electrically conductive than said white surface layer.
In accordance with another aspect of this invention there is provided a recording method comprising the steps of selectively applying electric current or discharge to an : electro-sensitive member comprising a substrate; an elec-trically conductive, light colored intermediate layer dis-posed on said substrate, said intermediate layer comprising ; a pigment and a binder, the color of said intermediate layer being convertible to a darker color in response to ,:; ~ , .
, ~ 3'~Z~
the application of said electrical current or discharge thereto; and a white sur~ace layer disposed directly on said intermediate layer, said white surface layer being no ~reater than approximately 10 microns thick and ~eing capable of being destroyed by application of an electrical current or discharge thereto to expose said intermediate :
layer; said electric current or discharge destroying said white surface layer to selectively expose said intermediate layer in accordance with an image to be recorded, said image resulting from the color contrast between the ex-posed and non-exposed portions of the intermediate layer, said electric current being selectively applied to said recording member by a stylus having a small contact area with said white layer, said electric current passing through said intermediate layer to a counter electrode in contact with said white layer, the contact area of said counter electrode with said white layer being substantially greater than the said contact area of said stylus with said white layer so that the white layer is not destroyed 20 as current passes back to said counter electrode from said : : !
inter~nediate layer through said white layer. ~:
This invention will be more apparent from a ' 4a 073'7Z'7 reacling of the follo~ving speci~ic~tit)n ancl claims taken with the drawing.
¦I BRII'F DESCRIIJrlON O~ l ITE DR~WING
j Figure l is a diagrammatic sectional view of an illustrative, basic embodiment of a recording medium according to the invention.
F~gu~e 2 is a diagrammatic sectional view of an illustrative, modified embodiment according to the invention.
Figure 3 is a diagrammatic view of an illust-ative application of the recording medium according to the invention.
DETAILED DESCRIPrION OF ~HE PREFERRED EMBODIMENTS
_ Figure l is a diagrammatic view of a basic embodiment of a ;
recording member according to the invention, the recording member comprising ~a) a whi~e surface layer 1 formed from a white pigment of zinc oxide, titanium oxide or the like and a binder, ~b) a conductive, intermediate layer 2 formed from a conductive zinc oxide, vanadium pentoxide or the like which produces a color in response to an electric signal and a blnder, and (c~ a support body or substrate 3 comprising a paper sheet, plastic film or the like.
;` Details of the respective layers are as follows. The whi~e surface layer I has close rela~ion with the whiteness of the recording member per se and serves to raise the contrast of the image portinns as well as to enhance the quality of the picture images. As ~or the white surface layer l, ma~erials may be used which have been used ~n conventional electrosensitive paper, for example, a pigment such as zinc oxide, titanium oxide1 tin oxide, aluminum o~idc, zinc, copper, copper rhodanide, lead rhodanide, thiosulfatc, basic lead carbonate, manganese carbonate, lead stearate, ,1 ~,, . . - -S-' ' . ' .
.
3'~2'~J
lead phthalate, manganese phthalate or the like, a metal and a metal oxide or a mixture thereo~ in the form of a mixture with a binder such as of a polyester resin, epoxy resin, melamine resin, phenol resin, urea resin, Glyptal resin, sulfonamide copolycondensation resin based on a alkyd resin, alcohol soluble phenolformaldehyde resin, polystyrene derivative, polyether, polystyrene, polymethacrylate, polyvinyl alcohol, vinyl acetate, shellac, casein or the like. The mixture is - applied on a substrate in a thickness less than 10 microns and preferably less than 5 microns.
The conductive, intermediate layer 2 functions as a current path and at the same time serves to provide or produce a color for the formation of the picture image. The conductive layer 2 may comprise any of the conventional electrolytic recording materials including metal oxides such as zinc oxide, titanium dioxide, lead oxide, nickel oxide, cadmium oxide, silver oxide, mercury oxide, lead carbonate and the like, metal sulfide such as zinc sulfide, cadmium sulfide and the like, or color developing agents such as a metallic acid and its alkali metal salt or alkaline earth metal salt or ammonium salt, in the form of a mixture with a binder such as polyacrylamide, polyvinylbenzyltrimethyl-ammonium chloride, styrene-maleic anhydride copolymer, polyvinyl alcohol, polyacrylic acid, cellulose derivative, acrylic resin, nylon resin, styrene resin or the like. In order to increase the conductivity, the mixture may have added thereto a powder of a metal~such as aluminum, zinc or copper or of a metal compound such as a metal sulfide.
The support or substrate 3 serves to retain the aforementioned white surface layer 1 and the intermediate conductive layer ~ and may be formed from a shee~ of paper, . ' :`
. . . ~ . . .
:~V~3'~
plastic film, metal foil or the like which is capable of retainirlg the afore-mentioned two layers 1 and 2 thereon.
Referring now to Figure 2, which shows a modified embodiment according to the present invention, white surfac2 layer 1 and support 3 have the same construction as .in Figure 1. However, the colorable conductive layer 2' responsive to an electric signal has a higher electrical resistance value than the conductive, intermediate layer 2 and includes a conductive layer 4 formed by vapor deposition of ~_luminum or from powder of a metal which will impart conductivity thereto.
The electrosensitive members of Figures 1 or 2 may be employed in a conventional recording process such as shown in Figure 3, using a stylus 5 Gf tungsten, iridium, silver, copper, stainless steel or the like on the surface of the recording medium and a counter or return electrode 6 with a large surface area, so that, upon application of a DC or AC
voltage across the stylus 5 and the counter electrode 6, the white surface layer portion immediately beneath the stylus 5 is destroyed and at the same time the conductive, intermediate ; 20 layer 2 is exposed or uncovered to provide or produce a color. ~:
. Further, conductive layer 2 acts as a current path between stylus 5 and counter electrode 6.
In accordance with one aspect of the invention, conductive, intermediate layer 2 is of a liyht color such as light grey, light yellow, light pink or the like. The density of intermediate layer 2 is no greater than approximately .
0.5 and preferably about 0.2. The color of intermediate layer 2 is lighter than that employed in the conductive underlayers of known electrosensitive mediums. Thus, the white ..
. 30 surface layer does not have to be very thick to conceal the conductive underlayer and may thus be extremely thin.
~ 7 -'--' I' - ~ ~
rtlll'r, bcl~l OClOlS, SlllOke nnc~ b-lrnt ashes are produecd in only an ~xtremely small or imp~rccptil)le amounc and the electric power for burning , the white sllrfacc la5~cr 1 is rcduced a considerable degree thus substantially i lessening the possil~ility of spoiling the marginal portions of the picture image because of dcstructioll of thc conductive, intermediate layer 2.
Furthermore, since the electrosensitive member of the present invention has increased whiteness as compared with conventional dry type electrolytic recording media, it becomes possible to employ a coloring agent which has a substantial density variation but which has been difficult to use in conventional dry type recording media due to their inferior whiteness In addition, it now IS possible to hold the abrasive wear of stylus 5 to a lesser amount as compared with known dry type electrolytic recording media and to a degree as in the conven~ional electrosensitive media.
The present invention wlll be illustrated more particuiarly by wa~
of Examples.
¦~ An acetylbutylcellulose solution containing 10~ zinc oxide was coated ¦l on a commercially available electrolytic colored, recording paper sheet A` ¦ (KT~ Paperj a product of ~okushu Seichi) in a thickness of 5 microns by means of a bar coated and brushing to form a white surface layer 1 thereon.
The recording papcr sheet originally had a yellowish grey color and a density of 0.18 but the apparent whiteness thereof was increased by the white surface layer 1 which had a density of 0. 08 where density is defined as in "ASA Pf-J2 . ]7 - 195S".
~hc coatecl, recordin~ pape1 sheet was moullt:ed on a Toshaf~x and ~r~ ~e m ~ r~/i! , -8- . .
. ,.. ----_.. ,. ,.. , ... ... , .. ...... . .,.. , , .. , ; ... ..
, . .. .. . . . . .
l~/3'7Z~
i subjccted to a rccordill~, procedurc with a linc densi~y of lO l. /mm ~o obtain a picture image having a density of 0. 8. Burning odors were procluced only in a slight amount as compared with the known electrosensitive paper during i a recording operation, with almost no smok~ or burnt ash~s.: There was obtained a satisfactory record which had improved whiteness and no spoilage of the marginal portions of the picture image.
30 parts by weight of molybdic acid, lO0 parts by weight of finely powdered copper were added to an aqueous solution of 12 parts by weight .polyvinylbenzyltrimethyl-ammonium chloride and agitated for two days in a ball mlll. The resultant mixture was coated on a quality paper sheet in a thickness of about 30 microns to obtain a colored conductive layer 2. An acetylbutylcellulose solution containing 10% titanium dioxide and 2% silver powder was coated on the colored conduct~ve layer 2 by means of a bar coater in a thickness of about 4 microns and by means of brushing, to obtain j a white surface Iayer 1. The colored conductive layer 2 had a reddish ¦ yellow color but after being covered with white surface layer 1, it had a ¦ satisfactory whiteness .
~ The resultant recording paper was mounted on a ~oshafax for recording with a line density of 20 l. /mm to obtain a record of 1. 0 in . density. Burning odors, smoke and aslles were produced only in an ignorable amount during the recording operation as compared with the known electro-sensitive paper. ~he resultant picture image had no spoila~e of rhe margin . and was clear and satisfactory in contrast.
~ . ' ' .
. , . ~.
',, .11 , ~73'~Z7 , The prcscnt invclltic~n llas bccn Iler~in cl~scribcd by way of .
.' particular examples ho~vcvcr, it should be unclerstood that not only .
the clectrols~tic coloring ma~eri~ls but also coloring materials which j, produce a color in responsc to an electric current or voltage may be used in coloring conductive l~ye~ 2 of the recording medium of the invention.
. ' ' . ~ ' .
~, , ;- . .
1'~ ' . .
in tllat it is susceptibl~ to non-uniform lecorcling and ~owere~ image dcnsit~
because of its increascd ~lectrical resistance.
There has also been used in another embodimellt of the prior art il an electrosensitive medium comprising (a) an under]ayer of carbon or some ¦~ other dark colored conductive material coated with a bmder on (b) a substrate or a supporting means, (c) a white surf~ce layer being disposed on the dark colored layer. With such a recording medium,portions of the white surface layer are burnt and removed by sparking to form a picture image by means of the contrast between the non-sparked white surface layer and the dark colored underlayer. However the burning operation produces a bad odor, smoke and ashes to the potentially extreme discomfort of the operator.
Moreover, the white surface layer must have a thickness as large as 10 to ~ 20 microns in order to conceal the-color of dark colored underlayer with ¦ the result that the recording medium suffers from lowered recording ¦ sensi~ivity in addition to the difficulties mentioned above. llence, application of high voltage is necessitated which tends to disintegrate the dark colored underlayer into powder ~ereby causing recording failure because of deposition of the powder on the recording stylus. Further, the powder deposited on the recording stylus is transferred again onto the white surface layer in the form of a so-called "tail". ~lso, a portion of the powc3er is directly dropped onto the white sulface layer ~vithout depositing on dle recorcling stylus and spoils marginal portions of the picture image.
An example of pr-ior art which overcornes these difficulties is found in Japancse Patcnt Publicatioll No. ~4-31998 wherc thcre is clisclosed a recording menlber comprising a base layer such as a paper sheet, a colorcd -3~
~ l'' . .
lQ~3 7Z ~
layer dispose~ on the base, a thin me-talli.c layer disposed on the colored layer and a white surface layer whi.ch can be very thin. However, the recording medium disclosed in this patent publication is disadvantageous in that it causes accelerated abrasive wear to the recording stylus. Thus, it cannot be practically used for stylus-scanning type recording due to tone variations. Therefore, the recording medium of the above Japanese patent publication has been excIusiveiy used for the d~t matrix type recording.
SUMMARY OF THE INVENTION
In accordance with one aspect of this invention there is provided an electrosensitive recording member comprising: a substrate; an electrically conductive, light : colored intermediate layer disposed on said substrate, said intermediate layer comprising a pigment and a binder, `
the color of said intermediate layer being convertible to a darker color in response to the application of an electrical current or discharge thereto; and a white surface layer disposed directly on said intermediate layer, said white surface layer being no greater than approximately 10 microns thick and being capable of being destroyed by application of an electrical current or discharge thereto to expose said.
intermediate layer, said electrically conductive layer being more electrically conductive than said white surface layer.
In accordance with another aspect of this invention there is provided a recording method comprising the steps of selectively applying electric current or discharge to an : electro-sensitive member comprising a substrate; an elec-trically conductive, light colored intermediate layer dis-posed on said substrate, said intermediate layer comprising ; a pigment and a binder, the color of said intermediate layer being convertible to a darker color in response to ,:; ~ , .
, ~ 3'~Z~
the application of said electrical current or discharge thereto; and a white sur~ace layer disposed directly on said intermediate layer, said white surface layer being no ~reater than approximately 10 microns thick and ~eing capable of being destroyed by application of an electrical current or discharge thereto to expose said intermediate :
layer; said electric current or discharge destroying said white surface layer to selectively expose said intermediate layer in accordance with an image to be recorded, said image resulting from the color contrast between the ex-posed and non-exposed portions of the intermediate layer, said electric current being selectively applied to said recording member by a stylus having a small contact area with said white layer, said electric current passing through said intermediate layer to a counter electrode in contact with said white layer, the contact area of said counter electrode with said white layer being substantially greater than the said contact area of said stylus with said white layer so that the white layer is not destroyed 20 as current passes back to said counter electrode from said : : !
inter~nediate layer through said white layer. ~:
This invention will be more apparent from a ' 4a 073'7Z'7 reacling of the follo~ving speci~ic~tit)n ancl claims taken with the drawing.
¦I BRII'F DESCRIIJrlON O~ l ITE DR~WING
j Figure l is a diagrammatic sectional view of an illustrative, basic embodiment of a recording medium according to the invention.
F~gu~e 2 is a diagrammatic sectional view of an illustrative, modified embodiment according to the invention.
Figure 3 is a diagrammatic view of an illust-ative application of the recording medium according to the invention.
DETAILED DESCRIPrION OF ~HE PREFERRED EMBODIMENTS
_ Figure l is a diagrammatic view of a basic embodiment of a ;
recording member according to the invention, the recording member comprising ~a) a whi~e surface layer 1 formed from a white pigment of zinc oxide, titanium oxide or the like and a binder, ~b) a conductive, intermediate layer 2 formed from a conductive zinc oxide, vanadium pentoxide or the like which produces a color in response to an electric signal and a blnder, and (c~ a support body or substrate 3 comprising a paper sheet, plastic film or the like.
;` Details of the respective layers are as follows. The whi~e surface layer I has close rela~ion with the whiteness of the recording member per se and serves to raise the contrast of the image portinns as well as to enhance the quality of the picture images. As ~or the white surface layer l, ma~erials may be used which have been used ~n conventional electrosensitive paper, for example, a pigment such as zinc oxide, titanium oxide1 tin oxide, aluminum o~idc, zinc, copper, copper rhodanide, lead rhodanide, thiosulfatc, basic lead carbonate, manganese carbonate, lead stearate, ,1 ~,, . . - -S-' ' . ' .
.
3'~2'~J
lead phthalate, manganese phthalate or the like, a metal and a metal oxide or a mixture thereo~ in the form of a mixture with a binder such as of a polyester resin, epoxy resin, melamine resin, phenol resin, urea resin, Glyptal resin, sulfonamide copolycondensation resin based on a alkyd resin, alcohol soluble phenolformaldehyde resin, polystyrene derivative, polyether, polystyrene, polymethacrylate, polyvinyl alcohol, vinyl acetate, shellac, casein or the like. The mixture is - applied on a substrate in a thickness less than 10 microns and preferably less than 5 microns.
The conductive, intermediate layer 2 functions as a current path and at the same time serves to provide or produce a color for the formation of the picture image. The conductive layer 2 may comprise any of the conventional electrolytic recording materials including metal oxides such as zinc oxide, titanium dioxide, lead oxide, nickel oxide, cadmium oxide, silver oxide, mercury oxide, lead carbonate and the like, metal sulfide such as zinc sulfide, cadmium sulfide and the like, or color developing agents such as a metallic acid and its alkali metal salt or alkaline earth metal salt or ammonium salt, in the form of a mixture with a binder such as polyacrylamide, polyvinylbenzyltrimethyl-ammonium chloride, styrene-maleic anhydride copolymer, polyvinyl alcohol, polyacrylic acid, cellulose derivative, acrylic resin, nylon resin, styrene resin or the like. In order to increase the conductivity, the mixture may have added thereto a powder of a metal~such as aluminum, zinc or copper or of a metal compound such as a metal sulfide.
The support or substrate 3 serves to retain the aforementioned white surface layer 1 and the intermediate conductive layer ~ and may be formed from a shee~ of paper, . ' :`
. . . ~ . . .
:~V~3'~
plastic film, metal foil or the like which is capable of retainirlg the afore-mentioned two layers 1 and 2 thereon.
Referring now to Figure 2, which shows a modified embodiment according to the present invention, white surfac2 layer 1 and support 3 have the same construction as .in Figure 1. However, the colorable conductive layer 2' responsive to an electric signal has a higher electrical resistance value than the conductive, intermediate layer 2 and includes a conductive layer 4 formed by vapor deposition of ~_luminum or from powder of a metal which will impart conductivity thereto.
The electrosensitive members of Figures 1 or 2 may be employed in a conventional recording process such as shown in Figure 3, using a stylus 5 Gf tungsten, iridium, silver, copper, stainless steel or the like on the surface of the recording medium and a counter or return electrode 6 with a large surface area, so that, upon application of a DC or AC
voltage across the stylus 5 and the counter electrode 6, the white surface layer portion immediately beneath the stylus 5 is destroyed and at the same time the conductive, intermediate ; 20 layer 2 is exposed or uncovered to provide or produce a color. ~:
. Further, conductive layer 2 acts as a current path between stylus 5 and counter electrode 6.
In accordance with one aspect of the invention, conductive, intermediate layer 2 is of a liyht color such as light grey, light yellow, light pink or the like. The density of intermediate layer 2 is no greater than approximately .
0.5 and preferably about 0.2. The color of intermediate layer 2 is lighter than that employed in the conductive underlayers of known electrosensitive mediums. Thus, the white ..
. 30 surface layer does not have to be very thick to conceal the conductive underlayer and may thus be extremely thin.
~ 7 -'--' I' - ~ ~
rtlll'r, bcl~l OClOlS, SlllOke nnc~ b-lrnt ashes are produecd in only an ~xtremely small or imp~rccptil)le amounc and the electric power for burning , the white sllrfacc la5~cr 1 is rcduced a considerable degree thus substantially i lessening the possil~ility of spoiling the marginal portions of the picture image because of dcstructioll of thc conductive, intermediate layer 2.
Furthermore, since the electrosensitive member of the present invention has increased whiteness as compared with conventional dry type electrolytic recording media, it becomes possible to employ a coloring agent which has a substantial density variation but which has been difficult to use in conventional dry type recording media due to their inferior whiteness In addition, it now IS possible to hold the abrasive wear of stylus 5 to a lesser amount as compared with known dry type electrolytic recording media and to a degree as in the conven~ional electrosensitive media.
The present invention wlll be illustrated more particuiarly by wa~
of Examples.
¦~ An acetylbutylcellulose solution containing 10~ zinc oxide was coated ¦l on a commercially available electrolytic colored, recording paper sheet A` ¦ (KT~ Paperj a product of ~okushu Seichi) in a thickness of 5 microns by means of a bar coated and brushing to form a white surface layer 1 thereon.
The recording papcr sheet originally had a yellowish grey color and a density of 0.18 but the apparent whiteness thereof was increased by the white surface layer 1 which had a density of 0. 08 where density is defined as in "ASA Pf-J2 . ]7 - 195S".
~hc coatecl, recordin~ pape1 sheet was moullt:ed on a Toshaf~x and ~r~ ~e m ~ r~/i! , -8- . .
. ,.. ----_.. ,. ,.. , ... ... , .. ...... . .,.. , , .. , ; ... ..
, . .. .. . . . . .
l~/3'7Z~
i subjccted to a rccordill~, procedurc with a linc densi~y of lO l. /mm ~o obtain a picture image having a density of 0. 8. Burning odors were procluced only in a slight amount as compared with the known electrosensitive paper during i a recording operation, with almost no smok~ or burnt ash~s.: There was obtained a satisfactory record which had improved whiteness and no spoilage of the marginal portions of the picture image.
30 parts by weight of molybdic acid, lO0 parts by weight of finely powdered copper were added to an aqueous solution of 12 parts by weight .polyvinylbenzyltrimethyl-ammonium chloride and agitated for two days in a ball mlll. The resultant mixture was coated on a quality paper sheet in a thickness of about 30 microns to obtain a colored conductive layer 2. An acetylbutylcellulose solution containing 10% titanium dioxide and 2% silver powder was coated on the colored conduct~ve layer 2 by means of a bar coater in a thickness of about 4 microns and by means of brushing, to obtain j a white surface Iayer 1. The colored conductive layer 2 had a reddish ¦ yellow color but after being covered with white surface layer 1, it had a ¦ satisfactory whiteness .
~ The resultant recording paper was mounted on a ~oshafax for recording with a line density of 20 l. /mm to obtain a record of 1. 0 in . density. Burning odors, smoke and aslles were produced only in an ignorable amount during the recording operation as compared with the known electro-sensitive paper. ~he resultant picture image had no spoila~e of rhe margin . and was clear and satisfactory in contrast.
~ . ' ' .
. , . ~.
',, .11 , ~73'~Z7 , The prcscnt invclltic~n llas bccn Iler~in cl~scribcd by way of .
.' particular examples ho~vcvcr, it should be unclerstood that not only .
the clectrols~tic coloring ma~eri~ls but also coloring materials which j, produce a color in responsc to an electric current or voltage may be used in coloring conductive l~ye~ 2 of the recording medium of the invention.
. ' ' . ~ ' .
~, , ;- . .
Claims (4)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. An electrosensitive recording member comprising:
a substrate; an electrically conductive, light colored intermediate layer disposed on said substrate, said inter-mediate layer comprising a pigment and a binder, the color of said intermediate layer being convertible to a darker color in response to the application of an electrical current or discharge thereto; and a white surface layer disposed directly on said intermediate layer, said white surface layer being no greater than approximately 10 microns thick and being capable of being destroyed by application of an electrical current or discharge thereto to expose said intermediate layer, said electrically con-ductive layer being more electrically conductive than said white surface layer.
a substrate; an electrically conductive, light colored intermediate layer disposed on said substrate, said inter-mediate layer comprising a pigment and a binder, the color of said intermediate layer being convertible to a darker color in response to the application of an electrical current or discharge thereto; and a white surface layer disposed directly on said intermediate layer, said white surface layer being no greater than approximately 10 microns thick and being capable of being destroyed by application of an electrical current or discharge thereto to expose said intermediate layer, said electrically con-ductive layer being more electrically conductive than said white surface layer.
2. A member as in Claim l where the thickness of said white layer is no greater than approximately 5 microns.
3. A member as in Claim 2 where said intermediate layer comprises two further layers, the first of said further layers being electrical conductive and disposed on said substrate and the second of said further layers being light colored, the color thereof being convertible to a darker color in response to the application of an electrical current or discharge thereto, said second layer being disposed on said first layer.
4. A recording method comprising the steps of selectively applying electric current or discharge to an electro-sensitive member comprising a substrate; an elec-trically conductive, light colored intermediate layer dis-posed on said substrate, said intermediate layer comprising a pigment and a binder, the color of said intermediate layer being convertible to a darker color in response to the application of said electrical current or discharge thereto; and a white surface layer disposed directly on said intermediate layer, said white surface layer being no greater than approximately 10 microns thick and being capable of being destroyed by application of an electrical current or discharge thereto to expose said intermediate layer; said electric current or discharge destroying said white surface layer to selectively expose said intermediate layer in accordance with an image to be recorded, said image resulting from the color contrast between the ex-posed and non-exposed portions of the intermediate layer, said electric current being selectively applied to said recording member by a stylus having a small contact area with said white layer, said electric current passing through said intermediate layer to a counter electrode in contact with said white layer, the contact area of said counter electrode with said white layer being substantially greater than the said contact area of said stylus with said white layer so that the white layer is not destroyed as current passes back to said counter electrode from said intermediate layer through said white layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA235,465A CA1073727A (en) | 1975-09-15 | 1975-09-15 | Electrosensitive recording member with electrically conductive, light coloured intermediate and white, electrically destructable surface layers |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA235,465A CA1073727A (en) | 1975-09-15 | 1975-09-15 | Electrosensitive recording member with electrically conductive, light coloured intermediate and white, electrically destructable surface layers |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1073727A true CA1073727A (en) | 1980-03-18 |
Family
ID=4104049
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA235,465A Expired CA1073727A (en) | 1975-09-15 | 1975-09-15 | Electrosensitive recording member with electrically conductive, light coloured intermediate and white, electrically destructable surface layers |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1073727A (en) |
-
1975
- 1975-09-15 CA CA235,465A patent/CA1073727A/en not_active Expired
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |