CA1099102A - Recording sheet and color developer therefor - Google Patents
Recording sheet and color developer thereforInfo
- Publication number
- CA1099102A CA1099102A CA342,905A CA342905A CA1099102A CA 1099102 A CA1099102 A CA 1099102A CA 342905 A CA342905 A CA 342905A CA 1099102 A CA1099102 A CA 1099102A
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- CA
- Canada
- Prior art keywords
- acid
- salicylic
- color
- color developer
- parts
- 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.)
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Abstract
ABSTRACT OF THE DISCLOSURE
This invention discloses a novel recording sheet which comprises a support and a color developer layer coated on the support. The layer comprises an inorganic pigment and a color developer which is capable of forming a distinct color when contacted with a color former. The color developer is a metal-lic compound of an aromatic carboxylic acid. The defects of the prior art including fogging, low color developing ability are overcome with the new recording sheet.
This invention discloses a novel recording sheet which comprises a support and a color developer layer coated on the support. The layer comprises an inorganic pigment and a color developer which is capable of forming a distinct color when contacted with a color former. The color developer is a metal-lic compound of an aromatic carboxylic acid. The defects of the prior art including fogging, low color developing ability are overcome with the new recording sheet.
Description
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I This is a clivisional application of pa-tent applica-tion serial number 125,694 filed on October 21, 1971.
The present invention relates to a recordiny sheet and a color- developer thereEore, and more particularly to a record-ing shee-t having coated thereon, a novel color developer layer which contains an inorganic pigment and a novel color developer for the recording sheet.
There have been known recording sheets utiliziny a color reaction of a colorless oryanic compound (hereinafter, 1~ referred to "color former") and an adsorbent material capable of forming a distinct color when contacted wi-th the color former.
As the recording sheets using the phenomenon, a pressure-sensitive recording sheet (USP 2,505,470, USP 2,505,489, USP
I This is a clivisional application of pa-tent applica-tion serial number 125,694 filed on October 21, 1971.
The present invention relates to a recordiny sheet and a color- developer thereEore, and more particularly to a record-ing shee-t having coated thereon, a novel color developer layer which contains an inorganic pigment and a novel color developer for the recording sheet.
There have been known recording sheets utiliziny a color reaction of a colorless oryanic compound (hereinafter, 1~ referred to "color former") and an adsorbent material capable of forming a distinct color when contacted wi-th the color former.
As the recording sheets using the phenomenon, a pressure-sensitive recording sheet (USP 2,505,470, USP 2,505,489, USP
2,550,471, USP 2,548,366, USP 2,712,507, USP 2,730,456, USP
2,730,457, USP 3,418,250, e-tc.) and a heat-sensitive recording sheet have been well known. Further, it has been known a printiny method, that an ink containing the color former is applied to the color developer sheet through a medium such as stencil or not.
In all cases, the above phenomenon of the color reac-7 0 tion between the color former and the color developer are utilizedunder pressure with a pen or stylus, under heat, etc.
The color former may be dissolved in a solvent such as chlorinated diphenyl, chlorinated paraffine or other organic solvent. The solution may be dispersed in a binder and/or may be microencapsulated, and then coated on a support such as paper, plastic film, resin-coated paper, etc.
In case of heat-sensitive recording sheet, the color former may be coaked on the support together with a thermofusible material such as acetoanilide which is melted under heating to dissolve the color former.
-1- ~
f~l 1 On -the other hand, the color developer is dissolved or dispersed in water or an oryanic solvent together with a hinder such as styrene-bu-tadiene rubber latex and then coa-ted on or mpregnated into a base support before or directly before record-ng .
The color former and color developer may be coated on the same surface or opposite surEaces of support, or the di~fer-ent supports.
Usually, after the color developer is coated on the support, a desensitizer is locally coated thereon in order that unnecessary surface portion is prevented from the color formatlon (USP 2,777,780). Another embodimen-t of the prevention of color formation is to locally coat the color developer on the support or the coated layer of color former without using the desensiti-~er.
~ s the above described color developerj there are clays such as acid clay, active clay, attapulgite, zeolite, bentonite, etc., phenol resins (USP 3,516,845; USP 3,540,911) and organic compounds such as succinic acid, tannic acid, gallic acid or phenol compound (USP 3,244,548) are known. Such organic compound is not practically employed for the reason that -the color develop-ing ability of color developer sheet which is a support having coated thereon the color developer is very low and the color developed on the sheet is low in ligh-t resistance although the compound can be very easily handled in manufacturing the color developer sheet.
Further, in case where the above color developer is locally coated on a support to form a color developer sheet, if large amour.t thereoE (7-10 g per 1 m of the support) is coated,
2,730,457, USP 3,418,250, e-tc.) and a heat-sensitive recording sheet have been well known. Further, it has been known a printiny method, that an ink containing the color former is applied to the color developer sheet through a medium such as stencil or not.
In all cases, the above phenomenon of the color reac-7 0 tion between the color former and the color developer are utilizedunder pressure with a pen or stylus, under heat, etc.
The color former may be dissolved in a solvent such as chlorinated diphenyl, chlorinated paraffine or other organic solvent. The solution may be dispersed in a binder and/or may be microencapsulated, and then coated on a support such as paper, plastic film, resin-coated paper, etc.
In case of heat-sensitive recording sheet, the color former may be coaked on the support together with a thermofusible material such as acetoanilide which is melted under heating to dissolve the color former.
-1- ~
f~l 1 On -the other hand, the color developer is dissolved or dispersed in water or an oryanic solvent together with a hinder such as styrene-bu-tadiene rubber latex and then coa-ted on or mpregnated into a base support before or directly before record-ng .
The color former and color developer may be coated on the same surface or opposite surEaces of support, or the di~fer-ent supports.
Usually, after the color developer is coated on the support, a desensitizer is locally coated thereon in order that unnecessary surface portion is prevented from the color formatlon (USP 2,777,780). Another embodimen-t of the prevention of color formation is to locally coat the color developer on the support or the coated layer of color former without using the desensiti-~er.
~ s the above described color developerj there are clays such as acid clay, active clay, attapulgite, zeolite, bentonite, etc., phenol resins (USP 3,516,845; USP 3,540,911) and organic compounds such as succinic acid, tannic acid, gallic acid or phenol compound (USP 3,244,548) are known. Such organic compound is not practically employed for the reason that -the color develop-ing ability of color developer sheet which is a support having coated thereon the color developer is very low and the color developed on the sheet is low in ligh-t resistance although the compound can be very easily handled in manufacturing the color developer sheet.
Further, in case where the above color developer is locally coated on a support to form a color developer sheet, if large amour.t thereoE (7-10 g per 1 m of the support) is coated,
3~
the color developer sheet cannot form sufficient color when con-tacted with the color former. As the result, local coating ~2-1 method is limi-ted.
In this case, slnce locally coa-ted por-tion of the color developer sheet is thicker than the other por-tion, the color former coated on another support, when contacted with the color developer sheet, is locally pressurized to form unpreferable color (hereinafter, referred to "fog").
The inventors have found tha-t all defec-ts of the color developer sheet and ink can be comple-tely removed by using a me~allic compound of an arornatic carboxylic acld. That is, the inventors have found that the color developer composed of a metal-lic compound of an aromatic carboxylic acid is far stronger in color developing ability than aromatic carboxylic acid or metallic compound, and that the color formed on the color former sheet is stronger in light resistance.
To this end, in one of its aspec-ts, the invention pro-vides a recording sheet comprising: (a) a support; (b) a co-! lor developer layer coated on said support, said color developer layer containing an inorganic pigment and a color developer cap-able of forming a distinct color when contacted with a color former, said ~olor- developer being a metallic co-mpound of an aromatic carboxylic acid.
The metal compound of aromatic carboxylic acid used in the color developer of the invention can be prepared by reacting an alkali metal salt of aromatic carboxylic acid and a water-soluble metal salt in a solvent in which both are soluble. In this case, -the ratio of the alkali metal salt and water-soluble me-tal salt is not particularly limited, but a molar ratio of 1:1 is preferable. The alkali metal salt of aromatic carboxylic acid used in the above reaction can be prepared by conventional synthe-tic methods. For example, it may be prepared by reacting an aromatic carboxylic acid with an alkali metal hydroxide or carbona-te.
1 The aroma-tic carboxylic acid used in -the present inven-tion includes, for example, benzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-toluic acid, m-toluic acid, p-toluic acidl o-bromobenzoic acid, m-bromo-benzoic acid, p-bromobenzoic acid, o-iodobenzoic acid, m-iodo-benzoic acid, p-iodobenzoic acid, 4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,3-~dichlorobenzoic acid, 2,4-dichlorobenzoic ~0 - 3a -1 acid, p-isopropylbenzoic acid, 2,5-dinitrobenzoic acid, 3,~-dinitrobenzoic acid, 3,5-dinitrobenzoic acid r p~ tert-butylbenzoic acid, N-phenyl-antranillic acid, ~-methyl-3-nitrobenzoic acid,
the color developer sheet cannot form sufficient color when con-tacted with the color former. As the result, local coating ~2-1 method is limi-ted.
In this case, slnce locally coa-ted por-tion of the color developer sheet is thicker than the other por-tion, the color former coated on another support, when contacted with the color developer sheet, is locally pressurized to form unpreferable color (hereinafter, referred to "fog").
The inventors have found tha-t all defec-ts of the color developer sheet and ink can be comple-tely removed by using a me~allic compound of an arornatic carboxylic acld. That is, the inventors have found that the color developer composed of a metal-lic compound of an aromatic carboxylic acid is far stronger in color developing ability than aromatic carboxylic acid or metallic compound, and that the color formed on the color former sheet is stronger in light resistance.
To this end, in one of its aspec-ts, the invention pro-vides a recording sheet comprising: (a) a support; (b) a co-! lor developer layer coated on said support, said color developer layer containing an inorganic pigment and a color developer cap-able of forming a distinct color when contacted with a color former, said ~olor- developer being a metallic co-mpound of an aromatic carboxylic acid.
The metal compound of aromatic carboxylic acid used in the color developer of the invention can be prepared by reacting an alkali metal salt of aromatic carboxylic acid and a water-soluble metal salt in a solvent in which both are soluble. In this case, -the ratio of the alkali metal salt and water-soluble me-tal salt is not particularly limited, but a molar ratio of 1:1 is preferable. The alkali metal salt of aromatic carboxylic acid used in the above reaction can be prepared by conventional synthe-tic methods. For example, it may be prepared by reacting an aromatic carboxylic acid with an alkali metal hydroxide or carbona-te.
1 The aroma-tic carboxylic acid used in -the present inven-tion includes, for example, benzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitrobenzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-toluic acid, m-toluic acid, p-toluic acidl o-bromobenzoic acid, m-bromo-benzoic acid, p-bromobenzoic acid, o-iodobenzoic acid, m-iodo-benzoic acid, p-iodobenzoic acid, 4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,3-~dichlorobenzoic acid, 2,4-dichlorobenzoic ~0 - 3a -1 acid, p-isopropylbenzoic acid, 2,5-dinitrobenzoic acid, 3,~-dinitrobenzoic acid, 3,5-dinitrobenzoic acid r p~ tert-butylbenzoic acid, N-phenyl-antranillic acid, ~-methyl-3-nitrobenzoic acid,
4-acetyl-benzoic acid, salicylic acid, 5-tert-bu-tyl-salicylic acid, 3-phenyl-salicylic acid, 3-methyl-5-tert-butyl-salicylic acid, 3,5-di-tert-butyl-salicylic acid, 3,5-di-tert-amyl-salicylic acid, 3-cyclohexyl-salicylic acid, 5-cyclohexyl-salicylic acid, 3-methyl-5-isoamyl-salicylic acid, 5-isoamyl-salicylic acid, 3,5-di-sec-butyl-salicylic acid, 5-nonyl-salicylic acid, 3-methyl-5-lauryl-salicylic acid, m-hydroxy-benzoic acid, p-hydroxybenzoic acid, 3,5-dinitrosalicylic acid, 2-hydroxyl-3-methyl-benzoic acid, 2,~-cresotinic acid, 2,5-cresotinic acid, 2,3-cresotinic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxybenzoic acid, l-naphthoic acid, 2-naphthoic acid, l-hydroxyl-2-naphthoic acid, 2-hydroxyl-3-naphthoic acid, 2-hydroxyl-l-naphthoic acid, 5,5'-me-thylene-salicylic acid, thiosalicylic acid, -trimellitic anhydride, anacardic acid, benzoic anhydride, 2-carboxybenzaldehyde, diphenic acid, etc. ~bove all, aroma-tic carboxylic acid having at least one hydroxyl group in the structure, especially ortho position, are effective.
As metals of metal salts to be reacted with alkali metal salts of carboxylic acids, there are the group Ib metals such as copper, silver, etc., the group IIa metals such as magnesium, calciumr etc., the group IIb metals such as zinc, cadmium, mercury r etc. r the group IIIb metals such as aluminum, gallium, etc. r the group IVb metals such as tin, lead, etc., the group VIa metals such as chromiumr molybdenumr etc. r the group VIIa metals such as manganese, etc., the group VIII metals such as 3~
cobal-tr nickel, etc., and the like. Among these, those wherein zinc, tin~aluminum or nickel is used, are especiall~ effective.
In using them in the reaction, they are used in the form of inorganic salt thereof such as chloride, sulfate, nitrate, etc~, or in the form of organic sal-t thereof such as oxalate, acetate, etc. These metal salts or alkali metal sal-ts of the aromatic carboxylic acid exhib:i-t almost no color-developiny abili-ty when used separately, but, when these reaction products is coated onto a support, me-tal salts of carboxylic acids show the following excellent color-developing ability.
The metal salt of the aroma-tic carboxylic acid which is prepared by the reaction between the alkall metal salt of the aromatic carboxylic acid and a water-soluble metal salt may be used as the reaction mix-ture or, more preferably, after -the separation and the puriEication.
Further, -Eor the purposes of increasing color developing ability and light resistance, an inorganic pigmen-t may be added to the color developer. The inorganic pigmen-t contains aluminum silicate, zinc silicate, lead silicate, tin silicate, colloidal hydrated aluminum silicate, zeolite, bentonite, kaolinite active clay, acid clay, talc and the like. An amount of inorganic pigment has no critical value, for example, more than 1 part by weight, preferably 5 parts by weight per 100 parts by weight of the metal compound of the aromatic carboxylic acid.
The color developer of the invention can be prepared by dissolving or dispersing the metal compound of aromatic carboxylic acid in water or an organic solvent such as methanol, ethanol, butanol, ethyl acetate, butyl acetate, benz.ene, toluene acetone, tetrahydrofuran or methylene chloride. Water and organic solvent may be mixed. Preferable solvent is capable oE dissolving the _30 organic carboxylic acid. In case of adding the inorganic pigment, 1 it may be dispersed ln water, -the organLc solvent, the solution or the dispersion. ~ concen-tration can be decided according to the conventional manner.
Thus prepared solution or dispersion can be coated on a suppor-t, if necessary, -toge-ther with a binder such as gum arabic, ethyl cellulose, s-tyrene-butadiene copolymer, nitro-cellulose, styrene-butadiene latex, methylmethacrylate-butadiene latex, etc. An amount o~ the binder can be easily decided by one skilled in the art. It should be noted tha-t the coated layer 1~ of color developer can be maintained on the support even if the binder is not present in the layer.
An amount of the color developer coating composition is not specifically limited to obtain sufficient color. For example, it is more than 0.1 g/m2, preferably 0.5 - 5 g/m . The upper limi-t of coating amount is not limited in a poin-t of color developing activity, and the above range is only due to economical reason.
The color developer composition on a support can be coated on a support by all kinds of coating method because the present invention is basically characterized by using the metallic compound of the aromatic carboxylic acid.
As another embodiment for preparing a color developer composition, the binder is dissolved in the organic solvent and a plasticizer is added and then the metallic compound of aromatic carboxylic acid is dissolved or dispersed in the resulting solution.
The plasticizer may contain esters of phosphoric acid, phthalic acid, adipic acid or sebatic acid (e.g tributyl phos-phate, dibutyl phthalate, dioctyl phthalate, butyl adipate, dibutyl sebacate): hydrocarbon such as chlorinated paraffin; and 1 glycerine of unsaturated Ea-t-ty acid sueh as castor oll.
In -this case, for the purpose oE stabilizing the color developer composition which may be used as a coating ink, an alkali metal salt o-E organic acid, or an alkali may be added to the composition. The alkali metal salt of organic acid is, for example, lithium salt, sodium salt or potassiu~ salt or butyric acid, caprylic acid, palmitic aeid, oleic acid, linoleie aeid, linolenic aeid, benzoic aeid, and the like. The alkali - are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silica-te, borax and conventional alkali compound. An amount o~ the alkali is 0.01 - 1 parts by weight per 1 par-t by ~eight of metal compound of aromatic carboxylic acid.
Each component is dissolved or dispersed by means of ball mill or sand mill. Thus prepared eolor developer ink can be loeally applied to a support.
A eolor developer sheet and eolor developer of the inven-tion ean be used in combination with conventional color former such as crystal violet laetone, benzoyl leuco methylene ~ blue, malachite green lactone, rhodamine B lactam, fluoranes (USP 3,501,331; USP 3,514,310; USP 3,514,311; USP 3,540,911), spiropyrans (USP 3,293,060), a mixture thereof and the like.
The modification of the invention can be easily earried out by one skilled in the art in aeeordanee with eonventional information, technique and the like.
The color formers for pressure-sensitive copying paper are ordinarily employed in eombination in order to secure the instantaneous color forming property and light fastness of colored image. For example, a eombination of instantaneous 3~
eolor forming crystal viole-t, lactone or 3-methyl-2,2'-spirobi ,,,r~
-I [benzo(f)]-chromene as a primary color former and benzoyl leucome-thylene blue having an excellent li~ht fastness has been most well known, however, the colored image obtained by contacting the combination of color formers with an aromatic carboxylic acid tends to disappear, when it is allowed to stand in a room or is exposed to sunlight, since crystal viole-t or chromene fades be-fore benzoyl leuco-methylene blue is color formed.
~owever, such a defect AS described above is removed in the present invention, since, on -the color developer sheet using a metallic compound of aromatic carboxylic acid and crystal violet lactone or chromene is strong in light fastness and does not fade before benzoyl leuco methylene blue is color formed.
This will be clear from the light-fastness of crystal violet lactone in the below described Examples.
Comparing with the conventional clay-coated paper, the color developer sheet of the present inven-tion has the following advantages:
The conventional clay-coated pap~r tends to be decreased in sensitivity of clay, when being allowed to stand in air, because of adsorbing materials in air on the active point of clay. That is, the color developing ability of color developer sheet is remarkably lowered with time.
In the color developer sheet of the present inven~ion, such de-Eect has been improved. And, in case of manufacturing a color developer sheet in accordance with the present invention, sufficient color developing ability and other properties necessary to the color developer sheet for pressure sensitive paper can be satisfied with smaller coating amount than in the conventional clay paper. That is, the amount of color developer of the present invention to be coated is sufficient with 0.1 to 5 g/rn2 ~9~2 1 while in the conventioncll clay paper the amount to be coated is 7 to 10 g/m . Thus, -the color developer sheet is possible to make a size spray coa-ting by means a machine from that it can do with a small amount and that the physical proper-ties oE liquid can be freely varied different from clay, and results in a remarkable effect not only on performance but also on product:ion.
Furthermore, the color developer of the present invention can ~ive the similar color developing ability with smaller amount (abou-t 2 g/m2) of it to be coated if a natural or synthe-tic high molecular substance or a water repellant is previously coated on the surface of paper.
The present invention will be illustrated using a pressure-sensltive recording paper with the following Examples.
The effect of the color developer sheet of the present invention was confirmed with the following color former sheet~
Microcapsules containing a color former is manufac-tured, for example, according -to the specification of U.S. Patent No. 2,800,457, as follows:
10 parts by weight of acid-treated pig skin gelatin and -~ 10 parts by weight of gum arabic were dissolved in 400 parts by weight of water at 40C and 0.2 part by weigh-t of Turkey red oil was added thereto as an emulsifier, and 40 parts by weight of color former oil were emulsifled and dispersed therein.
The color former oil is 2~ of crystal violet lactone or 3-dibenzylamino-7-diethylaminofluoran~ dissolved in an oil con-sisting of 4 parts by weight of chlorinated diphenyl and 1 part by weight of kerosene. The emulsification was s-topped when the size of oil droplet became to 5 microns on an average. Water at 40C was addea thereto to 900 parts by weight in total and the stirring was continued. At this time attention must be paid I so that the li~uid temperature does not lower to below 40C.
Next, 10% acetic acid was added -thereto to adjust the pH of sys-tem to ~.0 to 4.2 and to cause coacervation. ~he stirring was further continued and, aEter 20 minutes, the system was cooled with ice to gelate a coacerva-te ~ilm deposited around an oil droplet. When the li~uid temperature became to 20C, 7 parts by weight of 37% formaldehyde were added thereto and at 10~, 10~ aqueous solution of caustic soda was added to adjust the pH to 9. At this time, addition of caustic soda must be carried out with sufficient attention.
The liquid ternperature was raised to 50C by heat under stirring for 20 minutes. The microcapsule thus ob-tained was controlled to 30C and thereafter was coated on 40 g/m2 paper in 6 g/m2 as solid content and dried. Also in case o~ other color Eormer the recording paper was manu~actured in the same manner as described ab'ove.
The alkali metal salt of aromatic carboxyli~ acid used for the production of the developing sheet o~ the invention is prepared by reacting an aromatic carboxylic acid with an alkali ~ me-tal hydroxide or carbonate. An example of the procedure is as follows: 30 g of sodium hydroxide is dissolved in 300 ml o~
water, to which 100 g of salicylic acid is then added with agitation. The ayitation is continued for a while to dissolve the salicylic acid comple-tely and then the solution is evaporated to dryness to obtain 110 g o~ sodium salicylate.
` Sodium salts and potassium salts of aromatic carboxylic acid may similarly be prepared to that mentioned above~
The following examples are to illustrate the invention in more detail without limiting the same.
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~ 10 -1 Example 1 0.69 g equivalent of the sodiwm salt of aromatic carboxylic acid obtained b~ the above mentloned procedure was dissolved in 150 ml of warm water. On the other hand, 0.6 g equivalent of the sulfate was dissolved in 150 ml of warm water and added to the above mentioned aqueous solution of sodium aromatic carboxylate with agitation. After a while, the metal compound of aromatic carboxylic acid was precipitated. It was then filtered and washed with water several times to obtain the same.
10 g of the following binder was then dissolved in 300 ml of the solvent, in which 70 g of the resulting aromatic carboxylic acid and 30 g of the inorganic pigment were dispersed or dissolved. The so obtained solution was applied to an original paper of 50 g/m2 to give a coating of 3 g/m2 by means of a coating rod, followed by drying.
Example 2 0.1 g equivalent of the sodium salt of aromatic carboxylic acid obtained by the above mentioned procedure and 10 g of gum arabic were dissolved in 150 ml of water. On the other -~ hand, 0.1 g equivalent of the water-soluble metal salt was dissolved in 150 ml of warm water and added thereto with agitation.
~hen the stirring was continued for a while, fine crystals deposited. 50 g of the following inorganic pigment was dis-persed in the resulting dispersion and applied to an original paper of 50 g/m2 to give a coating of 4 g/m2 by means of a coating rod followed by drying.
Comparative Example 1 7 g of the binder was dissolved in 300 ml of the solvent, in which 70 g of the aromatic carboxylic acid was dispersed.
~ The resulting dispersion was applied to an original paper of 1 50 g/m2 to give a coating of 2.1 g/m2 by means of a coating rod followed by drying.
Comparative Example 2 0.1 g equivalent of the sodium salt of aromatic carboxylic acid and 7 g of gum arabic were dissolved in 150 ml of warm watcr, to which 0.1 g equivalent of the water-soluble metal salt dissolved in 150 ml of warm water was added with stirring. When the stirring was continued for a while, fine crys-tals deposited.
The resulting dispersion was applied to an original paper of 50 g/m2 to give a coating of 3 g~m2 by means of a coating rod, followed by drying.
Comparative Test 1 On the developing sheets of Examples 1 and 2, and Com^
parative ~xamples 1 and 2 were contacted with microcapsule sheets containing crystal violet lactone and pressurized under a load of 600 kg/cm . After allowed to stand in the dark for a day and night, the reflective absorption spectrum at ~00 - 700 m~ was measured, the extinction fac-tor at its absorption maximum (which will hereinafter be referred to as "density") being defined as "fresh density". After further exposed to the sunlight for 1 : 2 hours, the reflective absorption spectrum on the developed surface was measured to give its density. From the foregoing results, a value of light resistance defined by the following relation was obtained.
- Density of color images after exposed to sunlight Light resistance (%) = x 100 Fresh density of color images These results are shown in Table 1.
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rd ~ O ~ ~ ~ o rd O
u~ U rn ~ rn ,~ 4~ U u~N U~ N U rd U ~ u~
. ~ , ,~
r~I U I U
v ,1r~ rd rr) rd ~ I rd~ U ~ U
r-l U O X ,l X ~l U O O O O
>1 0 0 U N r~ r-l Or~ ~ ~d S r~ ,~ N
D U U ~
rd U = = = = = = = _ ,4 rd = I a) = I rd = I rd r u~ rd O,Qr~l ~ r~l ~
r,~ _ = = : = r r~ ~ o ,~ ~ r~ . ~r Ln _ 3 0 C mparative Test 2 The similar -tests to Compara-tive Test 1 were carried out using a microcapsule sheet containing 3-dibenzylamino-7-diethyl-aminofluoran -to obtain the results as shown in Table 2.
No. Example Aromatic Water- Inor- Sol- Binder Fresh Light re-or Com- carboxy- soluble ganic vent den-. sistance parative lic acid metal pigment si-ty after ex-Example salt posed for 2 hrs (%)_ 1 1 sali- zinc colloi-e~ha- ethyl 0.66 86.5 cylic sulfate dal alu- nol cellu-acid minumlose silicate hydrate ~ " 0.50 73.6 2 " ~ tin zeolite etha- " 0.72 77.5 sulfate nol:
water 3:1 " 1~ " 0.45 51.5 3 " " tin bento- etha- " 0 61 82 0 sulfate nite nol 1. , ____ 1~ " 0.53 52.0 4 " " " zinc " " 0.63 84.0 Si ~ icate ~0 " " " kaolin " " 0.65 78.5 6 " " " zinc oxide" " 0.64 79.5 calcium ben- S R 71.2 carbonate zene " " ---- " " 0.51 42.3 1 8 2 sali- manga- colloi- water gum 0 4 2 cylic nese dal alu- arabic 3 8 .0 acid sulfate minum silicate hydrate ~ -- " " 0.23 60.0 9 `' " cobalt zinc vinyl 0.32 97.2 alcohol " " --~- " " 0.24 85.0 10 " " chromiUmzinc si " gum 0.42 98.2 licate arabic " " ---- " " 0.36 96.0 11 " sulefadate kaolin " " 0.35 30.3 ~ ' " 0.23 23.5 12 I~ ., copper kaolin " " 0.45 52.6 " " ____ ~ " 0.30 43.0 13 " benzoiczinc dal alu- " " 0.32 31.5 acld sulfate mlllUm Sl-licate - hydrate " " ---- " " 0.28 22.0 14 " o-chloro-zinc kaolin " " 0.46 32.0 benzoicchloride ~0 acid - " " ___ ~ 0.30 22.6 " 2-hydroXY- alUmi~ kaolin butyl nitro-l-naphtholc num acetate cellu-0.48 47.0 acid chloride lose " " __~ 0.37 32.6 16 " 2-hydroxy- cke1 kaolin etha- ethyl 3-naphthoic snulfate nol cellu-0.45 91.2 " ____ ~ 0.35 ~9.0 Comparative Test 3 The similar tests to Comparative Test 1 were carried out using a microcapsule sheet containing 3-methyl-2,2'-spirobi[benzo(f)]
chromene as a color former to obtain the results as mentioned in 1 in Table 3.
TA~LE 3 No. Example Aromatic Water- Inor~ Sol- Binder Fresh Light re-or Com- carboxy- soluble ganic vent den- sistance parative lic acid metal pigment sity after ex-Example salt posed for _ _ hrs ( 50 ) 1 1 salicy- ~inc colloi- etha- ethyl lic sulfate dal alu- nol cellu- 0.71 76.1 acid minu~m lose silicate " t, hydrate " " 0.53 vanished 2 " " tin zeolite ethanol:
sulfate 3 1 0.41 47.5 ~ ---- " " 0.32 vanished 3 " " " bento- etha-nite nol " 0.51 41.6 ---- " " 0.34 Yanished silicate 0.~5 38.5 " " " kaolin " " 0.60 52.6 6 " " ll colloi- ll ~.72 108.5 dal alu-minum si--licate - hydrate In the case of using the developing sheet of No. 6, exposure to the sunlight was further carried out for 10 hours to obtain a light resistance o~ 81.0~.
As is evident from Tables 1 to 3, the developing sheet of the invention exhibits, when stacked on a color former-containing microcapsule sheet and pressed, more excellent developing capacity than ~hen a metal compound of aromatic carboxylic acid alone is used, and its developed color matter has a sufficient light resistance. Similar results were obtained regarding other color formers.
_30 1 Example 3 0.6 g equivalent of potassium salicylate prepared by the method above mentioned was dissolved in 150 ml of warm water to prepare aqueous potassium salicylate solution. 0.6 g equivalent of zinc sulfate was dissolved in 150 ml of warm water, then added to the aqueous sodium salicylate solution under stirring.
Immediately, white crystals were separated out. The resulting crystals were filtrated out and washed several times with water to obtain 90 g of white solid. 1 g of ethyl cellulose was -l dissolved in 200 ml of the solvent and to this solution, was added 50 y of the previously prepared white solid to dissolve.
The resulting solution was coated onto a base paper of 50 g/m2 so that the solid ingredient thereof was coated at the thickness of 3 g/m , then dried.
Example 4 0.3 gram~equival~nt of the sodium salt of the aromatic carboxylic acid obtained in Example 3 and 10 g of the binder was dissolved in 150 ml of warm water, then 0.3 gram-equivalent of the metal salt dissolved in 150 ml o ~warm water was added -~ thereto under stirring. After stirring for a while, the liquid became emulsified due to the formation of fine crystals. This solution wherein said crystals were dispersed, was coated onto a base paper of 50 g/m with coating rod so that the solid ingredient was coated at the thickness of 4 g/m2.
Comparative test 4 Microcapsule sheet containing crystal violet lactone was superposed on the color developer sheet prepared by Examples 3 and 4 and pressurized under the load pressure of 600 Kg/cm2.
After leaving the sheet for a day in dark, the absorption spectrum of the color images ln the visible region was measured, 1 and the absorbance (hereinafter referred to as "density") at the maximum absorption was defined as "fresh density"~
In addit.ion, after the irradiation with sunlight for 1 hour, the absorption spectrum of the color images surface in the visible region was measured to determine its density. From the above result, the light resistance value was determined. The results thereof are shown in Table 4. The light resistance value is defined by the following formula;
The density of colored images -10 Light resistance after the irradiat:ion with sunlight x 100 value (~) Fresh density of colored images .. . .. .
No. Exam- Aromatic Metal Solvent Binder Fresh Light resis-ple carboxy- Salt density tance value lic acid . after the irradiation with sun-light for 1 hour 1 3 Salicylic Zinc sulEth 1 cellu- 1-07 91.5 2 " ~ Ethanol lose :water (3:1) " 0.95 85.5 3 4 " Manga-nese sul-arabic 0.56 75.9 fate Water " Cobalt Water0.68 67.5 sulfate ' " Tin sul- Water " 0.86 79.3 fate 6 " ~ Nickel Water " 0.82 84.8 - sulfate " 1- ChromiUm Water 0.64 97.8 sulfate 8 " " LeadWater " 0.39 51.0 sulfate 9 " " CopperWater " 0.70 66.7 sulfate _30 " Benzoic sulfater 0.61 63.0 1 11 4 o-Chloro ZincWater Gum 0 64 56 0 benzoic sulfate arabic acid `
12 " 2-E-Iydroxy- z.
1 naphth nc Water " 0.89 73.5 OlC aCld 13 " Tin Water 1.10 80.0 chloride 14 ~ ~, sulfate ter 0.83 95.0 15 " 2 ELydrOxy- Aluminum oic acid su fa Water `' 0.81 67.9 16 " Salicylic ~70 acid " Water " 0.77 72.0 17 `' 2-Hydroxy- Manga-3-naphthoic nese Water " 0.63 94.5 acid sulfate 18 " 5-tert-butyl z. polyvinYl 1 12 90 3 salicylic chlorideWater alcohol acid 19 " 3,5-di- ~- Water " 0.95 85.2 tert-butyl salicylic acid " 3-phenyl " Water " 0.90 69.5 salicylic acid 21 " 3-methyl-5- ~, Water Styrene- 0.94 76.8 tert-butyl butadiene salicylic latex acid 22 " 5-cyclo- " Water " 0.97 74.9 hexyl sali-cylic- acid 23 " 3,5-di- " Water " 0.89 71.4 tert-amyl salicylic acid 24 3 3-methyl- I~ EthanolEthyl 0.93 72.3
As metals of metal salts to be reacted with alkali metal salts of carboxylic acids, there are the group Ib metals such as copper, silver, etc., the group IIa metals such as magnesium, calciumr etc., the group IIb metals such as zinc, cadmium, mercury r etc. r the group IIIb metals such as aluminum, gallium, etc. r the group IVb metals such as tin, lead, etc., the group VIa metals such as chromiumr molybdenumr etc. r the group VIIa metals such as manganese, etc., the group VIII metals such as 3~
cobal-tr nickel, etc., and the like. Among these, those wherein zinc, tin~aluminum or nickel is used, are especiall~ effective.
In using them in the reaction, they are used in the form of inorganic salt thereof such as chloride, sulfate, nitrate, etc~, or in the form of organic sal-t thereof such as oxalate, acetate, etc. These metal salts or alkali metal sal-ts of the aromatic carboxylic acid exhib:i-t almost no color-developiny abili-ty when used separately, but, when these reaction products is coated onto a support, me-tal salts of carboxylic acids show the following excellent color-developing ability.
The metal salt of the aroma-tic carboxylic acid which is prepared by the reaction between the alkall metal salt of the aromatic carboxylic acid and a water-soluble metal salt may be used as the reaction mix-ture or, more preferably, after -the separation and the puriEication.
Further, -Eor the purposes of increasing color developing ability and light resistance, an inorganic pigmen-t may be added to the color developer. The inorganic pigmen-t contains aluminum silicate, zinc silicate, lead silicate, tin silicate, colloidal hydrated aluminum silicate, zeolite, bentonite, kaolinite active clay, acid clay, talc and the like. An amount of inorganic pigment has no critical value, for example, more than 1 part by weight, preferably 5 parts by weight per 100 parts by weight of the metal compound of the aromatic carboxylic acid.
The color developer of the invention can be prepared by dissolving or dispersing the metal compound of aromatic carboxylic acid in water or an organic solvent such as methanol, ethanol, butanol, ethyl acetate, butyl acetate, benz.ene, toluene acetone, tetrahydrofuran or methylene chloride. Water and organic solvent may be mixed. Preferable solvent is capable oE dissolving the _30 organic carboxylic acid. In case of adding the inorganic pigment, 1 it may be dispersed ln water, -the organLc solvent, the solution or the dispersion. ~ concen-tration can be decided according to the conventional manner.
Thus prepared solution or dispersion can be coated on a suppor-t, if necessary, -toge-ther with a binder such as gum arabic, ethyl cellulose, s-tyrene-butadiene copolymer, nitro-cellulose, styrene-butadiene latex, methylmethacrylate-butadiene latex, etc. An amount o~ the binder can be easily decided by one skilled in the art. It should be noted tha-t the coated layer 1~ of color developer can be maintained on the support even if the binder is not present in the layer.
An amount of the color developer coating composition is not specifically limited to obtain sufficient color. For example, it is more than 0.1 g/m2, preferably 0.5 - 5 g/m . The upper limi-t of coating amount is not limited in a poin-t of color developing activity, and the above range is only due to economical reason.
The color developer composition on a support can be coated on a support by all kinds of coating method because the present invention is basically characterized by using the metallic compound of the aromatic carboxylic acid.
As another embodiment for preparing a color developer composition, the binder is dissolved in the organic solvent and a plasticizer is added and then the metallic compound of aromatic carboxylic acid is dissolved or dispersed in the resulting solution.
The plasticizer may contain esters of phosphoric acid, phthalic acid, adipic acid or sebatic acid (e.g tributyl phos-phate, dibutyl phthalate, dioctyl phthalate, butyl adipate, dibutyl sebacate): hydrocarbon such as chlorinated paraffin; and 1 glycerine of unsaturated Ea-t-ty acid sueh as castor oll.
In -this case, for the purpose oE stabilizing the color developer composition which may be used as a coating ink, an alkali metal salt o-E organic acid, or an alkali may be added to the composition. The alkali metal salt of organic acid is, for example, lithium salt, sodium salt or potassiu~ salt or butyric acid, caprylic acid, palmitic aeid, oleic acid, linoleie aeid, linolenic aeid, benzoic aeid, and the like. The alkali - are, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silica-te, borax and conventional alkali compound. An amount o~ the alkali is 0.01 - 1 parts by weight per 1 par-t by ~eight of metal compound of aromatic carboxylic acid.
Each component is dissolved or dispersed by means of ball mill or sand mill. Thus prepared eolor developer ink can be loeally applied to a support.
A eolor developer sheet and eolor developer of the inven-tion ean be used in combination with conventional color former such as crystal violet laetone, benzoyl leuco methylene ~ blue, malachite green lactone, rhodamine B lactam, fluoranes (USP 3,501,331; USP 3,514,310; USP 3,514,311; USP 3,540,911), spiropyrans (USP 3,293,060), a mixture thereof and the like.
The modification of the invention can be easily earried out by one skilled in the art in aeeordanee with eonventional information, technique and the like.
The color formers for pressure-sensitive copying paper are ordinarily employed in eombination in order to secure the instantaneous color forming property and light fastness of colored image. For example, a eombination of instantaneous 3~
eolor forming crystal viole-t, lactone or 3-methyl-2,2'-spirobi ,,,r~
-I [benzo(f)]-chromene as a primary color former and benzoyl leucome-thylene blue having an excellent li~ht fastness has been most well known, however, the colored image obtained by contacting the combination of color formers with an aromatic carboxylic acid tends to disappear, when it is allowed to stand in a room or is exposed to sunlight, since crystal viole-t or chromene fades be-fore benzoyl leuco-methylene blue is color formed.
~owever, such a defect AS described above is removed in the present invention, since, on -the color developer sheet using a metallic compound of aromatic carboxylic acid and crystal violet lactone or chromene is strong in light fastness and does not fade before benzoyl leuco methylene blue is color formed.
This will be clear from the light-fastness of crystal violet lactone in the below described Examples.
Comparing with the conventional clay-coated paper, the color developer sheet of the present inven-tion has the following advantages:
The conventional clay-coated pap~r tends to be decreased in sensitivity of clay, when being allowed to stand in air, because of adsorbing materials in air on the active point of clay. That is, the color developing ability of color developer sheet is remarkably lowered with time.
In the color developer sheet of the present inven~ion, such de-Eect has been improved. And, in case of manufacturing a color developer sheet in accordance with the present invention, sufficient color developing ability and other properties necessary to the color developer sheet for pressure sensitive paper can be satisfied with smaller coating amount than in the conventional clay paper. That is, the amount of color developer of the present invention to be coated is sufficient with 0.1 to 5 g/rn2 ~9~2 1 while in the conventioncll clay paper the amount to be coated is 7 to 10 g/m . Thus, -the color developer sheet is possible to make a size spray coa-ting by means a machine from that it can do with a small amount and that the physical proper-ties oE liquid can be freely varied different from clay, and results in a remarkable effect not only on performance but also on product:ion.
Furthermore, the color developer of the present invention can ~ive the similar color developing ability with smaller amount (abou-t 2 g/m2) of it to be coated if a natural or synthe-tic high molecular substance or a water repellant is previously coated on the surface of paper.
The present invention will be illustrated using a pressure-sensltive recording paper with the following Examples.
The effect of the color developer sheet of the present invention was confirmed with the following color former sheet~
Microcapsules containing a color former is manufac-tured, for example, according -to the specification of U.S. Patent No. 2,800,457, as follows:
10 parts by weight of acid-treated pig skin gelatin and -~ 10 parts by weight of gum arabic were dissolved in 400 parts by weight of water at 40C and 0.2 part by weigh-t of Turkey red oil was added thereto as an emulsifier, and 40 parts by weight of color former oil were emulsifled and dispersed therein.
The color former oil is 2~ of crystal violet lactone or 3-dibenzylamino-7-diethylaminofluoran~ dissolved in an oil con-sisting of 4 parts by weight of chlorinated diphenyl and 1 part by weight of kerosene. The emulsification was s-topped when the size of oil droplet became to 5 microns on an average. Water at 40C was addea thereto to 900 parts by weight in total and the stirring was continued. At this time attention must be paid I so that the li~uid temperature does not lower to below 40C.
Next, 10% acetic acid was added -thereto to adjust the pH of sys-tem to ~.0 to 4.2 and to cause coacervation. ~he stirring was further continued and, aEter 20 minutes, the system was cooled with ice to gelate a coacerva-te ~ilm deposited around an oil droplet. When the li~uid temperature became to 20C, 7 parts by weight of 37% formaldehyde were added thereto and at 10~, 10~ aqueous solution of caustic soda was added to adjust the pH to 9. At this time, addition of caustic soda must be carried out with sufficient attention.
The liquid ternperature was raised to 50C by heat under stirring for 20 minutes. The microcapsule thus ob-tained was controlled to 30C and thereafter was coated on 40 g/m2 paper in 6 g/m2 as solid content and dried. Also in case o~ other color Eormer the recording paper was manu~actured in the same manner as described ab'ove.
The alkali metal salt of aromatic carboxyli~ acid used for the production of the developing sheet o~ the invention is prepared by reacting an aromatic carboxylic acid with an alkali ~ me-tal hydroxide or carbonate. An example of the procedure is as follows: 30 g of sodium hydroxide is dissolved in 300 ml o~
water, to which 100 g of salicylic acid is then added with agitation. The ayitation is continued for a while to dissolve the salicylic acid comple-tely and then the solution is evaporated to dryness to obtain 110 g o~ sodium salicylate.
` Sodium salts and potassium salts of aromatic carboxylic acid may similarly be prepared to that mentioned above~
The following examples are to illustrate the invention in more detail without limiting the same.
_3~
~ 10 -1 Example 1 0.69 g equivalent of the sodiwm salt of aromatic carboxylic acid obtained b~ the above mentloned procedure was dissolved in 150 ml of warm water. On the other hand, 0.6 g equivalent of the sulfate was dissolved in 150 ml of warm water and added to the above mentioned aqueous solution of sodium aromatic carboxylate with agitation. After a while, the metal compound of aromatic carboxylic acid was precipitated. It was then filtered and washed with water several times to obtain the same.
10 g of the following binder was then dissolved in 300 ml of the solvent, in which 70 g of the resulting aromatic carboxylic acid and 30 g of the inorganic pigment were dispersed or dissolved. The so obtained solution was applied to an original paper of 50 g/m2 to give a coating of 3 g/m2 by means of a coating rod, followed by drying.
Example 2 0.1 g equivalent of the sodium salt of aromatic carboxylic acid obtained by the above mentioned procedure and 10 g of gum arabic were dissolved in 150 ml of water. On the other -~ hand, 0.1 g equivalent of the water-soluble metal salt was dissolved in 150 ml of warm water and added thereto with agitation.
~hen the stirring was continued for a while, fine crystals deposited. 50 g of the following inorganic pigment was dis-persed in the resulting dispersion and applied to an original paper of 50 g/m2 to give a coating of 4 g/m2 by means of a coating rod followed by drying.
Comparative Example 1 7 g of the binder was dissolved in 300 ml of the solvent, in which 70 g of the aromatic carboxylic acid was dispersed.
~ The resulting dispersion was applied to an original paper of 1 50 g/m2 to give a coating of 2.1 g/m2 by means of a coating rod followed by drying.
Comparative Example 2 0.1 g equivalent of the sodium salt of aromatic carboxylic acid and 7 g of gum arabic were dissolved in 150 ml of warm watcr, to which 0.1 g equivalent of the water-soluble metal salt dissolved in 150 ml of warm water was added with stirring. When the stirring was continued for a while, fine crys-tals deposited.
The resulting dispersion was applied to an original paper of 50 g/m2 to give a coating of 3 g~m2 by means of a coating rod, followed by drying.
Comparative Test 1 On the developing sheets of Examples 1 and 2, and Com^
parative ~xamples 1 and 2 were contacted with microcapsule sheets containing crystal violet lactone and pressurized under a load of 600 kg/cm . After allowed to stand in the dark for a day and night, the reflective absorption spectrum at ~00 - 700 m~ was measured, the extinction fac-tor at its absorption maximum (which will hereinafter be referred to as "density") being defined as "fresh density". After further exposed to the sunlight for 1 : 2 hours, the reflective absorption spectrum on the developed surface was measured to give its density. From the foregoing results, a value of light resistance defined by the following relation was obtained.
- Density of color images after exposed to sunlight Light resistance (%) = x 100 Fresh density of color images These results are shown in Table 1.
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rd ~ O ~ ~ ~ o rd O
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r,~ _ = = : = r r~ ~ o ,~ ~ r~ . ~r Ln _ 3 0 C mparative Test 2 The similar -tests to Compara-tive Test 1 were carried out using a microcapsule sheet containing 3-dibenzylamino-7-diethyl-aminofluoran -to obtain the results as shown in Table 2.
No. Example Aromatic Water- Inor- Sol- Binder Fresh Light re-or Com- carboxy- soluble ganic vent den-. sistance parative lic acid metal pigment si-ty after ex-Example salt posed for 2 hrs (%)_ 1 1 sali- zinc colloi-e~ha- ethyl 0.66 86.5 cylic sulfate dal alu- nol cellu-acid minumlose silicate hydrate ~ " 0.50 73.6 2 " ~ tin zeolite etha- " 0.72 77.5 sulfate nol:
water 3:1 " 1~ " 0.45 51.5 3 " " tin bento- etha- " 0 61 82 0 sulfate nite nol 1. , ____ 1~ " 0.53 52.0 4 " " " zinc " " 0.63 84.0 Si ~ icate ~0 " " " kaolin " " 0.65 78.5 6 " " " zinc oxide" " 0.64 79.5 calcium ben- S R 71.2 carbonate zene " " ---- " " 0.51 42.3 1 8 2 sali- manga- colloi- water gum 0 4 2 cylic nese dal alu- arabic 3 8 .0 acid sulfate minum silicate hydrate ~ -- " " 0.23 60.0 9 `' " cobalt zinc vinyl 0.32 97.2 alcohol " " --~- " " 0.24 85.0 10 " " chromiUmzinc si " gum 0.42 98.2 licate arabic " " ---- " " 0.36 96.0 11 " sulefadate kaolin " " 0.35 30.3 ~ ' " 0.23 23.5 12 I~ ., copper kaolin " " 0.45 52.6 " " ____ ~ " 0.30 43.0 13 " benzoiczinc dal alu- " " 0.32 31.5 acld sulfate mlllUm Sl-licate - hydrate " " ---- " " 0.28 22.0 14 " o-chloro-zinc kaolin " " 0.46 32.0 benzoicchloride ~0 acid - " " ___ ~ 0.30 22.6 " 2-hydroXY- alUmi~ kaolin butyl nitro-l-naphtholc num acetate cellu-0.48 47.0 acid chloride lose " " __~ 0.37 32.6 16 " 2-hydroxy- cke1 kaolin etha- ethyl 3-naphthoic snulfate nol cellu-0.45 91.2 " ____ ~ 0.35 ~9.0 Comparative Test 3 The similar tests to Comparative Test 1 were carried out using a microcapsule sheet containing 3-methyl-2,2'-spirobi[benzo(f)]
chromene as a color former to obtain the results as mentioned in 1 in Table 3.
TA~LE 3 No. Example Aromatic Water- Inor~ Sol- Binder Fresh Light re-or Com- carboxy- soluble ganic vent den- sistance parative lic acid metal pigment sity after ex-Example salt posed for _ _ hrs ( 50 ) 1 1 salicy- ~inc colloi- etha- ethyl lic sulfate dal alu- nol cellu- 0.71 76.1 acid minu~m lose silicate " t, hydrate " " 0.53 vanished 2 " " tin zeolite ethanol:
sulfate 3 1 0.41 47.5 ~ ---- " " 0.32 vanished 3 " " " bento- etha-nite nol " 0.51 41.6 ---- " " 0.34 Yanished silicate 0.~5 38.5 " " " kaolin " " 0.60 52.6 6 " " ll colloi- ll ~.72 108.5 dal alu-minum si--licate - hydrate In the case of using the developing sheet of No. 6, exposure to the sunlight was further carried out for 10 hours to obtain a light resistance o~ 81.0~.
As is evident from Tables 1 to 3, the developing sheet of the invention exhibits, when stacked on a color former-containing microcapsule sheet and pressed, more excellent developing capacity than ~hen a metal compound of aromatic carboxylic acid alone is used, and its developed color matter has a sufficient light resistance. Similar results were obtained regarding other color formers.
_30 1 Example 3 0.6 g equivalent of potassium salicylate prepared by the method above mentioned was dissolved in 150 ml of warm water to prepare aqueous potassium salicylate solution. 0.6 g equivalent of zinc sulfate was dissolved in 150 ml of warm water, then added to the aqueous sodium salicylate solution under stirring.
Immediately, white crystals were separated out. The resulting crystals were filtrated out and washed several times with water to obtain 90 g of white solid. 1 g of ethyl cellulose was -l dissolved in 200 ml of the solvent and to this solution, was added 50 y of the previously prepared white solid to dissolve.
The resulting solution was coated onto a base paper of 50 g/m2 so that the solid ingredient thereof was coated at the thickness of 3 g/m , then dried.
Example 4 0.3 gram~equival~nt of the sodium salt of the aromatic carboxylic acid obtained in Example 3 and 10 g of the binder was dissolved in 150 ml of warm water, then 0.3 gram-equivalent of the metal salt dissolved in 150 ml o ~warm water was added -~ thereto under stirring. After stirring for a while, the liquid became emulsified due to the formation of fine crystals. This solution wherein said crystals were dispersed, was coated onto a base paper of 50 g/m with coating rod so that the solid ingredient was coated at the thickness of 4 g/m2.
Comparative test 4 Microcapsule sheet containing crystal violet lactone was superposed on the color developer sheet prepared by Examples 3 and 4 and pressurized under the load pressure of 600 Kg/cm2.
After leaving the sheet for a day in dark, the absorption spectrum of the color images ln the visible region was measured, 1 and the absorbance (hereinafter referred to as "density") at the maximum absorption was defined as "fresh density"~
In addit.ion, after the irradiation with sunlight for 1 hour, the absorption spectrum of the color images surface in the visible region was measured to determine its density. From the above result, the light resistance value was determined. The results thereof are shown in Table 4. The light resistance value is defined by the following formula;
The density of colored images -10 Light resistance after the irradiat:ion with sunlight x 100 value (~) Fresh density of colored images .. . .. .
No. Exam- Aromatic Metal Solvent Binder Fresh Light resis-ple carboxy- Salt density tance value lic acid . after the irradiation with sun-light for 1 hour 1 3 Salicylic Zinc sulEth 1 cellu- 1-07 91.5 2 " ~ Ethanol lose :water (3:1) " 0.95 85.5 3 4 " Manga-nese sul-arabic 0.56 75.9 fate Water " Cobalt Water0.68 67.5 sulfate ' " Tin sul- Water " 0.86 79.3 fate 6 " ~ Nickel Water " 0.82 84.8 - sulfate " 1- ChromiUm Water 0.64 97.8 sulfate 8 " " LeadWater " 0.39 51.0 sulfate 9 " " CopperWater " 0.70 66.7 sulfate _30 " Benzoic sulfater 0.61 63.0 1 11 4 o-Chloro ZincWater Gum 0 64 56 0 benzoic sulfate arabic acid `
12 " 2-E-Iydroxy- z.
1 naphth nc Water " 0.89 73.5 OlC aCld 13 " Tin Water 1.10 80.0 chloride 14 ~ ~, sulfate ter 0.83 95.0 15 " 2 ELydrOxy- Aluminum oic acid su fa Water `' 0.81 67.9 16 " Salicylic ~70 acid " Water " 0.77 72.0 17 `' 2-Hydroxy- Manga-3-naphthoic nese Water " 0.63 94.5 acid sulfate 18 " 5-tert-butyl z. polyvinYl 1 12 90 3 salicylic chlorideWater alcohol acid 19 " 3,5-di- ~- Water " 0.95 85.2 tert-butyl salicylic acid " 3-phenyl " Water " 0.90 69.5 salicylic acid 21 " 3-methyl-5- ~, Water Styrene- 0.94 76.8 tert-butyl butadiene salicylic latex acid 22 " 5-cyclo- " Water " 0.97 74.9 hexyl sali-cylic- acid 23 " 3,5-di- " Water " 0.89 71.4 tert-amyl salicylic acid 24 3 3-methyl- I~ EthanolEthyl 0.93 72.3
5-isoamyl cellu-salicylic lose acid " 5-isoamyl " Methyl " 0.92 71.1 salicylic isobutyl 3~ acid ketone 1 26 3 5-tert- Tin Methanol E.thyl 0.91 67.7 bu-tyl sulfate cellu-salicylic lose acid 27 " 5-te.rt- Nickel Methanol E-thyl 0.91 71.7 butyl sulfate cellu-salicylic lose acid 28 " 3,5 di- Zinc Acetone " 0.92 70.5 -tert-butyl sulfa-te salicylic acid 29 " 3-cyclohexyl salicylic. Copper n-butyl- ll 0.71 69 2 acid sulfate acetate 3n salicylic Mangane~ benzene " 0.60 61.2 acld fate 31 " 3,5-di Zinc toluene " 0.91 59.6 sec-butyl sulfate salicylic acid 32 " 5-nonyl- Zinc benzene " 0.90 71.3 saliCYlic chloride acid Comparative test 5 The test described in the above color-developing test 3 was carried out using microcapsule-coated sheet containing 3-dibenzyl-~0 amino-7-dimethylaminofluoran. The results are shown in Table 5 _30 ~ 21 No. Exam Aroma- Metal salt Solvent Binder Fresh Light re-ple tic densi- sistance carbo- ty value after xylic the irra-acid diation with sun-. . . . ................. . . ligOh-trfor 1 3 Salicylic Zinc Ethanol Ethyl 0.75 86.8 acid sulfate cellu-lose _ .
2 .. .. ,- Ethanol ~,0.60 82,5 :water (3:1) . _ . . ...
3 4 ,l Manganese Water Gum0.45 80.0 sulfate arabic _ . . .. .
4 ll ., Cobalt .. .. 0.48 92.5 sulfate . _ .. __ .. ,. Tin ll ,. 0.80 70.5 . sulfate _ . . . .. .. .,
2 .. .. ,- Ethanol ~,0.60 82,5 :water (3:1) . _ . . ...
3 4 ,l Manganese Water Gum0.45 80.0 sulfate arabic _ . . .. .
4 ll ., Cobalt .. .. 0.48 92.5 sulfate . _ .. __ .. ,. Tin ll ,. 0.80 70.5 . sulfate _ . . . .. .. .,
6 .- .. Nickel ,l ,l 0.79 90.5 su a.e .. .... . .. ..
7 .l ,l Chromiwn ,l .l 0.72 98.0 sulfate ~0 . . ~_ _ .
8 .- ,l Lead ,l " 0.44 51.3 sulfate . . .... .. _.
9 ll ll Copper I~ - 0.61 71.5 sulfate . .......... . _ .- Benzoic Zinc .. .. 0.56 50.2 acid sulfate . .. . . . . ._~
11 .. o-Chloro-~ l~ 'l l~ 0.59 54.5 benzoic acid . . _ .
12 .- 2-Hydroxy- Zinc .- ll 0.73 79.4 l-naphth- chloride oic acid _30 _ l _ _ _ - 22 w I 13 ¦ 4 2-Hydroxy~ Tin 'l " 0-81 79.0 l-naphth~ chloride oic acid __ _ . _ _ 14 I. " Nickel ,l ,l 0.70 94.5 sulfate _ _ _ _ _ 15 ,l 2-Hydroxy- Aluminum 3-naphth- sulfate ,l ,l 0.67 66.2 oie aeid _ ~ ___ 16,l Salicylic ,l .. " 0.73 67.5 _ _ _ 17., 2-Hydroxy- Manganese ll ll 0.57 92.3 3-naphth- sulfate oie acid . . _.
18 4 5-ter-t- Zine Water polyvinylo 76 72 4 butyl sali ehloride alcohol .
eylie acid _ . l . _ 19 ll 3,5-di-tert " ll ll 0 75 68 3 butyl sali, .
eylie aeid _ _ _ ., 3-phenyl .l .l .- 0.65 67.2 salieylie aeid .
. 21 ., 3-methyl~ ll 11 btytraednie- 0.78 70.2 salieylie ene la-te .20 aeid . l _ .
22 ., 5-eyelo- ll ll ll 0.79 68.8 salieylie . aeid .
23 .l 3,5-di- .l .l 'l 0.73 66.3 -tert-amyl salicylic _ . _ 24 3 3-methyl- " Ethanol Ethyl 0 76 70.0 5-isoamyl eellu-salieylic lose acld _ _ _ ' / . .
ll 5-isoamyl " fMethyl ll 0.75 68.1 _ salieylie liso- .
aeid Ibutyl _ . Iketone _ .
1 26 3 5-tert Tin Methanol Ethyl 0.73 65~6 butyl sulfate cellu-aeid 109 e ... . . .~ ._._ _._ 27 " ., Nickel sulfate ll ll 0.62 66.9 ._ _ .. . __ _ 28 ,l butyl sulnfCate Acetone ,l0.70 67.1 aeid _ . _ , . . . ~_ . . _ _ __ . .
29 ll 3-cyclo~ Copper n-butyl- ll 0.61 65.5 hexyl sulfate acetate aeid . _. .. _ . _ .. _ . . .. ,__ 30 3 3-phenyl Manganese Benzene Ethyl 0.51 58.0 salicylic sulfate cellu-_ acid lose _ 31 ll 3,5-di-' 2ine sec-but~l- sulfate Toluene ll 0.71 56.3 . . saildcylic ........ .. . __ . . _ .. ~ . . . ~
32 O 5-nonyl- Zinc Benzene .l 0.61 62.0 aeid ehloride It can be understood from Tables 4 and 5 that, when contacted with a color-former-containing capsule sheet under pressure, the color developer shee-t of this invention shows suffieient eolor density and the light resistance of the color image formed.
In addition, the color image formed on the color developer sheet ha`s~resistance to the "wetting with water". Especially, when 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, etc.
are used, the color image formed did not disappear at all when wetted with water.
~30 Similar results were obtained about the other color formers.
1 Example 5 100 parts by weight (hereinafter, "part" means "part by weight") of potassium salic~late prepared in the abGve-described manner was dissolved in 150 parts of hot water, and into the solution was added with stirring 60 parts of stannous chloride dissolved in 150 parts of hot water, whereby stannous salicylate was immediately precipitated as whité crystals. The crystals were filtered out, washed several times with water, and then dried to obtain 100 parts of stannous salicylate as solids.
40 parts of nitrocellulose was dissolved in a mixture of 15 parts of butyl acetate, 80 parts of isopropanol and 60 parts of butanol to give a homogeneous solution, into which 120 parts of above-described solid stannous salicylate was mixed and totally dissolved or dispersed by a ball mill to obtain a developer ink as a white suspension. The ink was diluted with a 1: 1 mixture of ethyl acetate and ethanol to give a viscosity of about 0.7 poises and printed by a flexographic printing process to give 3 g/m2 of dried coating film.
Example 6 100 parts of sodium 2-hydroxy-3-naphthoic acld was dissolved into 150 parts of hot water and into the solution was added with stirring ao parts of zinc chloride dissolved in lS0 parts of water, whereby zinc 2-hydroxy-3-naphthoate was immediately precipitated as crystals~ The resulting mixture was concentrated to a total weight of 200 parts. Into a mixture of 15 parts of dioctyl phthalater 120 parts of ethyl acetate, 100 parts of isopropanol and 80 parts of methanol was dissolved 50 parts of ethyl cellulose to give a homogeneous solution to which were added 200 parts of the above-described concentrate and 50 parts ~ of kaolin and completely dissolved or dispersed in a ball mill to ) obtain a developing ink in the form of a suspension. The ir;k was diluted with a 1 : 1 mixture of ethyl acetate and ethanol to give a viscosity of about 0.7 poise and printed by a flexo-graphic printing process to give 3 g/m of dried coating film.
Example 7 100 parts of sodium o-chlorobenæoic acid obtained by the aforementioned method was dissolved in 150 parts of hot water and into the solution was added with stirring a solution of 100 parts of nickel sulfate in 150 parts of hot water, whereby crystals of nickel o-chlorobenzoic acid were immediately preci-pitated, the precipitate filtered out, washed several times withwater and dried to obtain 80 parts of solid nickel o-chlorobenzoic acid. Into a mixture of butyl adipate, ethyl acetate, 20 parts of methyl ethyl ketone and toluol was dissolved 8 parts of vinyl chloride-vinyl acetate copolymer to obtain a homogeneous solution into which 20 parts of the above-described nickel o-chlorobenzoic acid and 10 parts of aluminum silicate hydrate (Trade Mark, "Osmos N", manufactured by Shiraishi Kogyo) were mixed followed by homogeneous dissolution or dispersion in a ball mill to obtain a developer ink. The ink was diluted with toluene to give a viscosity of about 1 poise and sub~ected to a gravure printing process to give 3 g/m2 of dried coating film.
Example 8 100 parts of sodium 2-hydroxy-1-naphthoate prepared by -the above method was dissolved in 150 parts of warm water and into the solution was added with stirring a solution of 60 parts of aluminum sulfate in 150 parts of warm water whereby crystals o~
aluminum 2-hydroxy-1-naphthoate were immediately precipitated.
The precipitate was filtered out, washed several times with _30 water and dried to obtain 70 parts of solid aluminum 2-hydroxy~l-1 naphthoate.
Into a mixture of 2 parts of castor oil 20 parts of toluene 20 parts of ethyl acetate and 20 parts of n-hexane was dissolved 8 parts of nitro cellulose to obtain a homogeneous solution. Into the solution was mixed 20 parts of the above-described aluminum 2-hydroxy-l~naphthoate and 7 parts of silicon oxide (Trade Mark "Siloide") followed by homogeneously dissolving or dispersing by a ball mill to obtain a developer ink. The resulting ink was diluted with xylol to give a viscosity of about 1 poise and subjected to a gravure printing process to give about 2 g/m2 of dried coating film.
Example 9 ~ 0 parts of sodium anacardate prepared according to the aforemen-tioned method was dissolved in 150 parts of hot water and into the solution was added with stirring a solution of 20 parts of zinc sulfate in 150 parts of hot water to obtain zinc anacardate. The mixture was concentrated to a total weight of 200 parts and then mixed with a mixture of 40 parts of ethyl cellulose, 70 parts of ethyl cellulose, 150 parts of ethanol and .20 40 parts of titanium oxide followed by completely dissolving or dispersing by a ball mill to afford a developer ink in the form of an emulsion. The ink was diluted with ethanol to give a viscosity of about 1 poise and subjected to a flexographic printing process to give about 3 g/m2 of dried coating film.
Comparative test 6 The above-described paper coated with microcapsules _ containing crystal violet lactone was piled on each of the surfaces printed with each color developer ink in the Examples and pressurized under pressure load of 600 kg/~ to form color images~ After allowed to stand in the dark for an hour, the - 27 ~
1 spectral absorpt.ion curve was measured within the wave length ranging from 400 to 700 m~, the density at the absorption maximum was defined as fresh density.
After further irradiating sunlight for 1 hour and for 3 hours, the spectral absorption curve of the color images was measured and its light resistance was calculated according to the following equation.
Density at the absorption maximum Light resistance (%) _aft.e,r,irradiation of sunlight x 100 Fresh density at the absorption - maximum The results are summarized in the following Table 6.
... ~ ................ . _ . . _ . . .... .
Fresh density Light resistance Light resistance (~) (%) after 1 hour after 3 hours irradiation of irradiation of sunlight sunlight ... _ .. _ . . . . . .. _ . _ . _ _ ... .. . .
Example 5 0.75 82 70 6 0.91 87 79 7 0.86 89 ~5 8 0.89 84 78 20 9 0.73 80 71 .. . _ ............. .. _ ~ . . ..... _ From the Table 6, it is evident that the developer inks of the present invention are superior in their deve~oping ability and light resistance even in the case of thin printed layer of 3 g/m .
Comparative test _ A paper coated with microcapsules containing 3-methyl-2,2'~
spirobi (ben~o[f]chromene) was placed on each of the sur~aces printed with the color developer ink in the above-described -30 Examples, and its fresh density and light resistance were measured ~ ~ 9 ~
1 in the same manner as described above in Comparative test 6.
Fresh density Light resistance Light resistance (~) - ~%~ after 1 hour after 3 hours irradiatlon of irradiation of sunlight sunlight Example 5 0.70 70 62 6 0.85 73 65 7 0.73 91 87 8 0~82 79 66 9 0.69 68 58 .... ~
As apparent from the numerical values in the above described Table 7, the paper surfaces printed with the developer inks of the present invention show an excellent devel.oping ability also for the color former sheet containing 3-methyl-2,2'-spirobi(benzo[f]chromene). Furthermore, the paper surface printed with the ink containing aluminum silicate hydrate (Osmos N) was remarkably improved in the light resistance of the color developed image of 3-methyl-2,2'-spirobi(benzo[f]chromene).
.20 Although the disclosure describes and illustrates a preferred embodiment of the invention, it is to be understood the invention is not restricted to this particular embodiment.
_30 ~ 29 -
11 .. o-Chloro-~ l~ 'l l~ 0.59 54.5 benzoic acid . . _ .
12 .- 2-Hydroxy- Zinc .- ll 0.73 79.4 l-naphth- chloride oic acid _30 _ l _ _ _ - 22 w I 13 ¦ 4 2-Hydroxy~ Tin 'l " 0-81 79.0 l-naphth~ chloride oic acid __ _ . _ _ 14 I. " Nickel ,l ,l 0.70 94.5 sulfate _ _ _ _ _ 15 ,l 2-Hydroxy- Aluminum 3-naphth- sulfate ,l ,l 0.67 66.2 oie aeid _ ~ ___ 16,l Salicylic ,l .. " 0.73 67.5 _ _ _ 17., 2-Hydroxy- Manganese ll ll 0.57 92.3 3-naphth- sulfate oie acid . . _.
18 4 5-ter-t- Zine Water polyvinylo 76 72 4 butyl sali ehloride alcohol .
eylie acid _ . l . _ 19 ll 3,5-di-tert " ll ll 0 75 68 3 butyl sali, .
eylie aeid _ _ _ ., 3-phenyl .l .l .- 0.65 67.2 salieylie aeid .
. 21 ., 3-methyl~ ll 11 btytraednie- 0.78 70.2 salieylie ene la-te .20 aeid . l _ .
22 ., 5-eyelo- ll ll ll 0.79 68.8 salieylie . aeid .
23 .l 3,5-di- .l .l 'l 0.73 66.3 -tert-amyl salicylic _ . _ 24 3 3-methyl- " Ethanol Ethyl 0 76 70.0 5-isoamyl eellu-salieylic lose acld _ _ _ ' / . .
ll 5-isoamyl " fMethyl ll 0.75 68.1 _ salieylie liso- .
aeid Ibutyl _ . Iketone _ .
1 26 3 5-tert Tin Methanol Ethyl 0.73 65~6 butyl sulfate cellu-aeid 109 e ... . . .~ ._._ _._ 27 " ., Nickel sulfate ll ll 0.62 66.9 ._ _ .. . __ _ 28 ,l butyl sulnfCate Acetone ,l0.70 67.1 aeid _ . _ , . . . ~_ . . _ _ __ . .
29 ll 3-cyclo~ Copper n-butyl- ll 0.61 65.5 hexyl sulfate acetate aeid . _. .. _ . _ .. _ . . .. ,__ 30 3 3-phenyl Manganese Benzene Ethyl 0.51 58.0 salicylic sulfate cellu-_ acid lose _ 31 ll 3,5-di-' 2ine sec-but~l- sulfate Toluene ll 0.71 56.3 . . saildcylic ........ .. . __ . . _ .. ~ . . . ~
32 O 5-nonyl- Zinc Benzene .l 0.61 62.0 aeid ehloride It can be understood from Tables 4 and 5 that, when contacted with a color-former-containing capsule sheet under pressure, the color developer shee-t of this invention shows suffieient eolor density and the light resistance of the color image formed.
In addition, the color image formed on the color developer sheet ha`s~resistance to the "wetting with water". Especially, when 2-hydroxy-1-naphthoic acid, 2-hydroxy-3-naphthoic acid, etc.
are used, the color image formed did not disappear at all when wetted with water.
~30 Similar results were obtained about the other color formers.
1 Example 5 100 parts by weight (hereinafter, "part" means "part by weight") of potassium salic~late prepared in the abGve-described manner was dissolved in 150 parts of hot water, and into the solution was added with stirring 60 parts of stannous chloride dissolved in 150 parts of hot water, whereby stannous salicylate was immediately precipitated as whité crystals. The crystals were filtered out, washed several times with water, and then dried to obtain 100 parts of stannous salicylate as solids.
40 parts of nitrocellulose was dissolved in a mixture of 15 parts of butyl acetate, 80 parts of isopropanol and 60 parts of butanol to give a homogeneous solution, into which 120 parts of above-described solid stannous salicylate was mixed and totally dissolved or dispersed by a ball mill to obtain a developer ink as a white suspension. The ink was diluted with a 1: 1 mixture of ethyl acetate and ethanol to give a viscosity of about 0.7 poises and printed by a flexographic printing process to give 3 g/m2 of dried coating film.
Example 6 100 parts of sodium 2-hydroxy-3-naphthoic acld was dissolved into 150 parts of hot water and into the solution was added with stirring ao parts of zinc chloride dissolved in lS0 parts of water, whereby zinc 2-hydroxy-3-naphthoate was immediately precipitated as crystals~ The resulting mixture was concentrated to a total weight of 200 parts. Into a mixture of 15 parts of dioctyl phthalater 120 parts of ethyl acetate, 100 parts of isopropanol and 80 parts of methanol was dissolved 50 parts of ethyl cellulose to give a homogeneous solution to which were added 200 parts of the above-described concentrate and 50 parts ~ of kaolin and completely dissolved or dispersed in a ball mill to ) obtain a developing ink in the form of a suspension. The ir;k was diluted with a 1 : 1 mixture of ethyl acetate and ethanol to give a viscosity of about 0.7 poise and printed by a flexo-graphic printing process to give 3 g/m of dried coating film.
Example 7 100 parts of sodium o-chlorobenæoic acid obtained by the aforementioned method was dissolved in 150 parts of hot water and into the solution was added with stirring a solution of 100 parts of nickel sulfate in 150 parts of hot water, whereby crystals of nickel o-chlorobenzoic acid were immediately preci-pitated, the precipitate filtered out, washed several times withwater and dried to obtain 80 parts of solid nickel o-chlorobenzoic acid. Into a mixture of butyl adipate, ethyl acetate, 20 parts of methyl ethyl ketone and toluol was dissolved 8 parts of vinyl chloride-vinyl acetate copolymer to obtain a homogeneous solution into which 20 parts of the above-described nickel o-chlorobenzoic acid and 10 parts of aluminum silicate hydrate (Trade Mark, "Osmos N", manufactured by Shiraishi Kogyo) were mixed followed by homogeneous dissolution or dispersion in a ball mill to obtain a developer ink. The ink was diluted with toluene to give a viscosity of about 1 poise and sub~ected to a gravure printing process to give 3 g/m2 of dried coating film.
Example 8 100 parts of sodium 2-hydroxy-1-naphthoate prepared by -the above method was dissolved in 150 parts of warm water and into the solution was added with stirring a solution of 60 parts of aluminum sulfate in 150 parts of warm water whereby crystals o~
aluminum 2-hydroxy-1-naphthoate were immediately precipitated.
The precipitate was filtered out, washed several times with _30 water and dried to obtain 70 parts of solid aluminum 2-hydroxy~l-1 naphthoate.
Into a mixture of 2 parts of castor oil 20 parts of toluene 20 parts of ethyl acetate and 20 parts of n-hexane was dissolved 8 parts of nitro cellulose to obtain a homogeneous solution. Into the solution was mixed 20 parts of the above-described aluminum 2-hydroxy-l~naphthoate and 7 parts of silicon oxide (Trade Mark "Siloide") followed by homogeneously dissolving or dispersing by a ball mill to obtain a developer ink. The resulting ink was diluted with xylol to give a viscosity of about 1 poise and subjected to a gravure printing process to give about 2 g/m2 of dried coating film.
Example 9 ~ 0 parts of sodium anacardate prepared according to the aforemen-tioned method was dissolved in 150 parts of hot water and into the solution was added with stirring a solution of 20 parts of zinc sulfate in 150 parts of hot water to obtain zinc anacardate. The mixture was concentrated to a total weight of 200 parts and then mixed with a mixture of 40 parts of ethyl cellulose, 70 parts of ethyl cellulose, 150 parts of ethanol and .20 40 parts of titanium oxide followed by completely dissolving or dispersing by a ball mill to afford a developer ink in the form of an emulsion. The ink was diluted with ethanol to give a viscosity of about 1 poise and subjected to a flexographic printing process to give about 3 g/m2 of dried coating film.
Comparative test 6 The above-described paper coated with microcapsules _ containing crystal violet lactone was piled on each of the surfaces printed with each color developer ink in the Examples and pressurized under pressure load of 600 kg/~ to form color images~ After allowed to stand in the dark for an hour, the - 27 ~
1 spectral absorpt.ion curve was measured within the wave length ranging from 400 to 700 m~, the density at the absorption maximum was defined as fresh density.
After further irradiating sunlight for 1 hour and for 3 hours, the spectral absorption curve of the color images was measured and its light resistance was calculated according to the following equation.
Density at the absorption maximum Light resistance (%) _aft.e,r,irradiation of sunlight x 100 Fresh density at the absorption - maximum The results are summarized in the following Table 6.
... ~ ................ . _ . . _ . . .... .
Fresh density Light resistance Light resistance (~) (%) after 1 hour after 3 hours irradiation of irradiation of sunlight sunlight ... _ .. _ . . . . . .. _ . _ . _ _ ... .. . .
Example 5 0.75 82 70 6 0.91 87 79 7 0.86 89 ~5 8 0.89 84 78 20 9 0.73 80 71 .. . _ ............. .. _ ~ . . ..... _ From the Table 6, it is evident that the developer inks of the present invention are superior in their deve~oping ability and light resistance even in the case of thin printed layer of 3 g/m .
Comparative test _ A paper coated with microcapsules containing 3-methyl-2,2'~
spirobi (ben~o[f]chromene) was placed on each of the sur~aces printed with the color developer ink in the above-described -30 Examples, and its fresh density and light resistance were measured ~ ~ 9 ~
1 in the same manner as described above in Comparative test 6.
Fresh density Light resistance Light resistance (~) - ~%~ after 1 hour after 3 hours irradiatlon of irradiation of sunlight sunlight Example 5 0.70 70 62 6 0.85 73 65 7 0.73 91 87 8 0~82 79 66 9 0.69 68 58 .... ~
As apparent from the numerical values in the above described Table 7, the paper surfaces printed with the developer inks of the present invention show an excellent devel.oping ability also for the color former sheet containing 3-methyl-2,2'-spirobi(benzo[f]chromene). Furthermore, the paper surface printed with the ink containing aluminum silicate hydrate (Osmos N) was remarkably improved in the light resistance of the color developed image of 3-methyl-2,2'-spirobi(benzo[f]chromene).
.20 Although the disclosure describes and illustrates a preferred embodiment of the invention, it is to be understood the invention is not restricted to this particular embodiment.
_30 ~ 29 -
Claims (5)
1. A recording sheet- comprising:
(a) a support;
(b) a color developer layer coated on said support, said color developer layer containing an inorganic pigment and a color developer capable of forming a distinct color when con-tacted with a color former, said color developer being a metal-lic compound of an aromatic carboxylic acid.
(a) a support;
(b) a color developer layer coated on said support, said color developer layer containing an inorganic pigment and a color developer capable of forming a distinct color when con-tacted with a color former, said color developer being a metal-lic compound of an aromatic carboxylic acid.
2, A recording sheet as claimed in claim 1 wherein said aromatic carboxylic acid contains at least one hydroxyl group.
3. A recording sheet as claimed in claim 1 wherein said aromatic carboxylic acid is selected from the group consisting of benzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid , p-nitro-benzoic acid, o-chlorobenzoic acid, m-chlorobenzoic acid, p-chlorobenzoic acid, o-toluic acid, m-toluic acid, p-toluic acid, o-bromobenzoic acid, m-bromobenzoic acid, p-bromobenzoic acid, o-iodobenzoic acid, m-iodobenzoic acid, p-iodobenzoic acid, 4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2, 3-dichlorobenzoic acid, 2, 4-dichlorobenzoic acid, p-iospropyl-benzoic acid, 2,5-dinitrobenzoic acid, 3,4-dinitrobenzoic acid, 3,5-dinitrobenzoic acid, p-tert-butylbenzoic acid, N-phenyl, antranillic acid, 4-methyl-3-nitrobenzoic acid, 4-acetyl-benzoic acid, salicylic acid, 5-tert-butyl-salicylic acid, 3-phenyl-salicylic acid, 3-methyl-5-tert-butyl-salicylic acid, 3,5-di-tert-butyl-salicylic acid, 3,5-ditert-amyl-salicylic acid, 3-cyclo-hexyl-salicylic acid, 5-cyclohexyl-salicylic acid, 3-methyl-5-isoamyl-salicylic acid, 5-isoamyl-salicylic acid, 3,5-di-sec-butyl-salicylic acid, 5-nonyl-salicylic acid, 3-methyl-5-lauryl-salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 3, 5-dinitrosalicylic acid, 2-hyclroxyl-3-methyl-benzoic acid, 2,4-cresotinic acid, 2,5-cresotinic acid, 2,3-cresotinic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, 2,6-dihydroxy-benzoic acid, 1-naphthoic acid, 2-naphthoic acid, 1-hydroxyl-2-naphthoic acid, 2-hydroxyl-3-naphthoic acid, 2-hydroxyl-1-naphthoic acid, 5,5'-methylene-salicylic acid, thiosalicylic acid, trimellitic anhydride, anacardic acid, benzoic anhydride, 2-carboxybenzaldehyde and diphenic acid.
4. A recording sheet as claimed in claim 1, 2 or 3 wherein said inorganic pigment contains a compound selected from the group consisting of aluminum silicate, zinc silicate, lead silicate, tin silicate, colloidal hydrated aluminum silicate, zeolite, bentonite, kaolinite active clay, acid clay and talc.
5. A recording sheet as claimed in claim 1, 2 or 3 wherein said inorganic pigment is present in an amount of about 5 parts by weight per 100 parts by weight of said metal compound of said aromatic carboxylic acid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CA342,905A CA1099102A (en) | 1970-10-23 | 1980-01-02 | Recording sheet and color developer therefor |
Applications Claiming Priority (8)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP93247/70 | 1970-10-23 | ||
| JP9324770A JPS5519190B1 (en) | 1970-10-23 | 1970-10-23 | |
| JP94874/70 | 1970-10-27 | ||
| JP45094874A JPS521327B1 (en) | 1970-10-27 | 1970-10-27 | |
| JP10987270 | 1970-12-10 | ||
| JP109872/70 | 1970-12-10 | ||
| CA125,694A CA1099099A (en) | 1970-10-23 | 1971-10-21 | Recording sheet and color developer therefor |
| CA342,905A CA1099102A (en) | 1970-10-23 | 1980-01-02 | Recording sheet and color developer therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1099102A true CA1099102A (en) | 1981-04-14 |
Family
ID=27507957
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA342,905A Expired CA1099102A (en) | 1970-10-23 | 1980-01-02 | Recording sheet and color developer therefor |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1099102A (en) |
-
1980
- 1980-01-02 CA CA342,905A patent/CA1099102A/en not_active Expired
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