US3871900A - Recording sheet - Google Patents

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Publication number
US3871900A
US3871900A US382224A US38222473A US3871900A US 3871900 A US3871900 A US 3871900A US 382224 A US382224 A US 382224A US 38222473 A US38222473 A US 38222473A US 3871900 A US3871900 A US 3871900A
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group
acid
alcohol
color
carbon atoms
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Takao Hayashi
Hajime Kato
Sadao Ishige
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/124—Duplicating or marking methods; Sheet materials for use therein using pressure to make a masked colour visible, e.g. to make a coloured support visible, to create an opaque or transparent pattern, or to form colour by uniting colour-forming components
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders

Definitions

  • ABSTRACT A recording sheet comprising a support having thereon a color developer layer capable of reacting with a color former to form color images, said color developer layer containing (1) a metal compound of an aromatic carboxylic acid and (2) at least one member selected from the group consisting of ethers and alcohols.
  • the present invention relates to a recording sheet, and more particularly to a recording sheet containing an improved color developer.
  • the above mentioned phenomenon of the color reaction between the color former and the color developer requires physical conditions such as pressure with a pen or with a key of a typewriter, heat, etc.
  • a pressure-sensitive copying paper may be obtained by dissolving a color former in a solvent such as chlorinated paraffin, alkylnaphthalene, alkylated diphenylethane, alkylated diphenylmethane, or the like, dispersing the resulting solution in a binder or microencapsulating the solution, and then the coating on a support such as paper, plastic film, etc.
  • a solvent such as chlorinated paraffin, alkylnaphthalene, alkylated diphenylethane, alkylated diphenylmethane, or the like
  • a heat-sensitive recording sheet may be obtained by coating 21 color former on a support together with a thermofusible material such as acetanilide.
  • thermofusible material means a material which is melted on heating to dissolve the color former.
  • the color former and color developer may be coated on the same surface or opposite surfaces of a support, or on different supports.
  • the color devcloper may be coated on or impregnated into a sup port as an ink.
  • clays such as acid clay, activated clay, attapulgite, zeolite, bentonite, etc.; organic acids such as succinic acid, tannic acid, gallic acid or phenol compounds, and acidic polymers such as phenol resins are known.
  • organic acids such as succinic acid, tannic acid, gallic acid or phenol compounds
  • acidic polymers such as phenol resins
  • a mixture of an aromatic carboxylic acid and a metal compound a metal compound of a polymer of an arcmatic carboxylic acid having at least one hydroxy group and an aldehyde; a metal compound of an aromatic carboxylic acid; a metal compound of a phenol compound having a pKa of not more than 8; and the like, are effective as a color developer.
  • a metal compound of an aromatic carbox ylic acid is particularly effective as a color developer. That is, a color developer sheet containing as a color developer a metal compound of an aromatic carboxylic acid has the following excellent properties in comparison with conventional color developer sheets.
  • the light fastness of the colored image on the color developer sheet is excellent.
  • a primary object of the present invention is to improve the color-developing ability of a color developer sheet containing a metal compound of an aromatic carboxylic acid.
  • Another object of the present invention is to simplify the steps for preparing a coating solution containing an aromatic carboxylic acid.
  • Further object of the present invention is to improve the coating characteristics of the coating solution containing an aromatic carboxylic acid.
  • Still afurther object of the present invention is to provide a color developer having the above-described advantages.
  • Still a further object of the present invention is to provide a recording sheet having the above-described advantages.
  • X is (CH ),,OR', -(CH ),,OH, [(CH ),,O],,H, [(CH ),,O],,R", an alkyl group (preferably, having up to l8 carbon atoms) or an alkenyl group (preferably, having up to 18 carbon atoms),
  • R is an alkyl group (preferably, having up to 10 carbon atoms), an aryl group (preferably, having up to carbon atoms) or an alkenyl group (preferably, having up to 10 carbon atoms),
  • R and R each is an alkyl group (preferably, having up to 18 carbon atoms), an aryl group (preferably, having up to 18 carbon atoms) or an alkenyl group (preferably, having up to 18 carbon atoms)
  • p is an integer of l to (preferably, 2 or 3)
  • q is an integer of 2 to 30.
  • ethers such as ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol dimethyl ether, 3-methoxybutyl acetate, ethylene glycol monoethyl ether, ethylene glycol diethyl ether, diethylene glycol acetate monoethyl ether, ethylene glycol diphenyl ether, ethylene glycol dimethyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monobenzyl ether, ethylene glycol monooctyl ether, ethylene glycol monododecyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether, polyoxyethylene cetyl alcohol ether, polyoxyethylene oleyl alcohol ether, polyoxyethylene stearyl alcohol ether, polyoxyethylene lau
  • the alcohols are preferably aliphatic alcohols having 1 to 18 carbon atoms, although other alcohols can be employed. Specific examples are alcohols such as nbutyl alcohol, n-amyl alcohol, n-hexyl alcohol, n-heptyl alcohol, n-octyl alcohol, n-nonyl alcohol, n-decyl alcohol, lauryl alcohol, myristyl alcohol, cetyl alcohol, stearyl alcohol, isobutyl alcohol, sec-butyl alcohol, isoamyl alcohol, tert-butyl alcohol, sec-butyl carbinol, diethyl carbinol, l-hexanol, 2-hexanol, 3-hexanol, cyclohexanol, 3-methyl-l-pentanol, 4-methyl-2-hexanol, allyl alcohol, -trans-crotyl alcohol, ciscrotyl alcohol, 2-methyl-3-buten-l
  • glycol ethers are particularly desirable and, of the alcohols, alcohols having 4 or more carbon atoms are particularly prefcrableThat is, when a glycol ether or an alcohol having 4 or more carbon atoms is used, the colordeveloping ability is markedly improved and, when they are used in combination, the color-developing ability is improved to an even greater extent.
  • water-immersion coloration of the color developer layer is depressed.
  • water-immersion coloration means the phenomenon of the coloring of the color former upon immersing in water the color developer layer in face-to-face contact with a color former layer followed by drying.
  • a suitable amount of the ethers and alcohols which can be used is from 10 to 250 parts by weight, preferably 50 to 150 parts by weight, per 100 parts by weight of the aromatic carboxylic acid.
  • the metal compound of the aromatic carboxylic acid to be used in the color developer sheet of the invention is the compound prepared by reacting an alkali metal salt, such as the sodium or potassium salt, of an aromatic carboxylic acid with a water-soluble metal salt in a solvent in which both are soluble.
  • an alkali metal salt such as the sodium or potassium salt
  • the alkali m'etalsalt of the aromatic vcarboxylic acid and the water-soluble metal salt may be reacted with each other in optional porportions, but preferably, they are reacted in gram equivalent amounts.
  • the metal compound of an aromatic carboxylic acid 5 is a salt of such an acid such as a zinc, tin, aluminum,
  • nickel, magnesium or calcium salt of an aromatic carboxylic acid and these salts can be obtained easily by stirring an aromatic carboxylic acid or an alkali metal salt thereofwith a metal hdyroxide, sulfate or nitrate in the presence of an alkali.
  • a metal hdyroxide, sulfate or nitrate in the presence of an alkali.
  • the pH value, temperature and pressure are not critical.
  • the aromatic carboxylic acid is preferably represented by the formula:
  • R may be the same or different and represents a hydrogen atom, a hydroxy group, a halogen atom such as chlorine, a nitro group, an alkyl group having 1 to 10 carbon atoms (preferably 3 to 6 carbon atoms), of which the total carbon atoms are less than 13, an aryl group such as phenyl group, an arylami no group such as anilino group, and an alicyclic group such as hexyl group, m is an integer of O to 7 and n is an integer of 0 to 5, and the aromatic carboxylic acid may be dimerized through the substituent R as a methylene group.
  • the most preferable compounds are those represented by the formula COOH wherein R is as defined above, n IS 1 or 2, and R is attached to the meta-position relative to thehydroxy group.
  • aromatic carboxylic acids having at least one hydroxyl group are especially effective and those having a hydroxyl group in the o-position, i.e., the aromatic carboxylic acids represented by the following formulae, are more effective.
  • the aromatic carboxylic acid used in the present invention includes, for example, benzoic acid, nitrobenzoic acid (any of mand p-derivatives may be used), chlorobenzoic acid (any of 0-, mand p-derivatives may be used), toluic acid (any of o-, mand pderivatives may be used), 4-methyl-3-nitrobenzoic acid, 2-chloro-4-nitrobenzoic acid, 2,3- dichlorobenzoic acid, 4-methyl-3-nitrobenzoic acid, 4-acetylbenzoic acid, 2,4-dihydroxybenzoic acid, 2,5- dihydroxybenzoic acid, l-naphthoic acid, 2-naphthoic acid, l-hydroxy-Z-naphthoic acid, 2-hydroxy-3- naphthoic acid, 2-hydroxy-l-naphthoic acid, thiosalicyclic acid, salicylic acid, 3,5-dinitrosalicyclic acid, 3-
  • metals which form the metal compound of the aromatic carboxylic acid used in this invention there can be mentioned metals of Group I B of the Periodic Table as, e.g., copper and silver; metals of Group II A as, e.g., magnesium and calcium; metals of Group II B, e.g. zinc, cadmium and mercury; metals of Group III B, e.g., aluminum and gallium; metals of Group IV A, e.g., tin and lead; metals of Group VI A, e.g., chromium and molybdenum; metals of Group Vll B, e.g., manganese; and metals of Group VIII such as cobalt and nickel.
  • metals of Group I B of the Periodic Table as, e.g., copper and silver
  • metals of Group II A as, e.g., magnesium and calcium
  • metals of Group II B e.g. zinc, cadmium and mercury
  • metals of Group III B e.g.
  • the chlorides, sulfates, nitrates or acetates of copper, zinc, aluminum, tin, nickel, etc. are particularly useful.
  • the color developer of the present invention may be provided on a support in various manners. Since the effects of the present invention are naturally produced when at least one or more of the ethers or alcohols are present in the color developer layer, the process for the production is not particularly limited. However, for the purpose of simplifying the step of preparing a coating solution containing an aromatic carboxylic acid, which is one object of the present invention, it is desirable to add at least one ether or alcohol before reacting the alkali metal salt of an aromatic carboxylic acid with the water-soluble metal salt. In addition, when a waterinsoluble ether or alcohol is used, it is necessary to add it before the reaction between the alkali metal salt of the aromatic carboxylic acid and the water-soluble metal salt occurs.
  • a water-soluble high molecular weight material such as water-soluble polyvinyl alcohol, methyl cellulose, hydroxymethyl cellulose, etc. as a viscosity reducing agent
  • a metal compound of an aromatic carboxylic acid having low viscosity and small particle size can be produced.
  • partially saponified polyvinyl alcohol having polymerization degree of not more'than 1000 is particularly effective.
  • the effects of the present invention are not decreased at all even when acidic resins such as phenolformaldehyde resins, metal oxides, metal hydroxides, clays or the chemically or physically treated embodiments thereof are incorporated in the color developer layer of the present invention.
  • acidic resins such as phenolformaldehyde resins, metal oxides, metal hydroxides, clays or the chemically or physically treated embodiments thereof are incorporated in the color developer layer of the present invention.
  • acid resins such as phenol-formaldehyde resin such as p-phenylphenol-formaldehyde resin, p-t-butylphenolformaldehyde resin, p-chlorophenol-formaldehyde resins, other color developers such as Japanese acid clay and active clay, attapulgite, inorganic pigments such as metal oxides and metal hydroxides or chemically or physically treated-products thereof.
  • acid resins such as phenol-formaldehyde resin such as p-phenylphenol-formaldehyde resin, p-t-butylphenolformaldehyde resin, p-chlorophenol-formaldehyde resins, other color developers such as Japanese acid clay and active clay, attapulgite, inorganic pigments such as metal oxides and metal hydroxides or chemically or physically treated-products thereof.
  • metal Zn, Mg and Al.
  • the Japanese acid clay, active clay or attapulgite is generally used in an amount not less than 1 wt%, preferably 20 to 2000 wt%, more preferably 500 to I000 wt% based on the metal compound of aromatic carboxylic acid, and the metal oxide or hydroxide is generally used in an amount of from about 20 to 400 wt%, preferably 50 to 200 wt% based on the metal compound of aromatic carboxylic acid.
  • binder material such as latexes, starches, gum arabic, carboxymethyl cellulose or casein.
  • the coating solution which is prepared as described above, may contain a binder such as latex, polyvinyl alcohol, maleic anhydride-styrene copolymer, starch and gum arabic. It is to be uderstood that all binders wellknown as film-forming materials can be used in the invention.
  • a binder such as latex, polyvinyl alcohol, maleic anhydride-styrene copolymer, starch and gum arabic. It is to be uderstood that all binders wellknown as film-forming materials can be used in the invention.
  • the binders can be classified into three groups i.e., (l) a water soluble or hydrophilic binder, for example, a natural compound such as proteins (e.g., gelatin, gum arabic, colloid albumin, casein), celluloses (e.g., carboxymethyl cellulose, hydroxyethyl cellulose), saccharoses (e.g., agar, sodium alginate, starch, carboxymethyl starch), and a synthetic compound such as polyvinyl alcohol, poly-N-vinylpyrrolidone, polyacrylate, polyacrylamide; (2) a water-dispersible binder, for example, latex such as styrenebutadiene copolymer latex, styrene-maleic anhydride copolymer latex; and (3) an organic solvent-soluble binder such nitrocellulose, ethyl cellulose or polyester.
  • a water soluble or hydrophilic binder for example, a natural compound such as proteins (e.g.
  • binders can be used in the form of solution or dispersion in a solvent in the invention, and the binder can be varied depending upon the type of the solvent.
  • the water-soluble or dispersible binder can be used in the aqueous solution or dispersion.
  • the metal compound of aromatic carboxylic acid can be coated without using the binder. It is to be noted that the 7 binder isoptional because it may not be necessary in case where the solvent is organic in nature.
  • the amountof these binders to be used varies depending upon'the kind thereof and the kind of additives used, but an amount offrom to 30 parts by weight per 100 parts by weight of solid ingredients contained in the coating solution generally is desirable.
  • the coating solution is applied to the support in general a minimum about of 0.1 g/m as the metal compound of the aromatic carboxylic acid. Generally from about 0.1 to 10 g/m preferably from 0.2 to 5 g/m is suitable. The upper limit of the coating amount is determined only by economic reasons, and the effects of the present invention are not dissipated even when a coating amount above the above-described range is used.
  • the recording sheet of the present invention may assume any form known in the art.
  • the color developer and color former may be provided on the same surface or opposite surfaces of a support, or on different supports.
  • the recording sheet of the present invention is characterized by the color developer, various conditions other than the aforesaid conditions, i.e., various optional additives to the color developer layer, the procedure of addition, the kind and form of color former which couples with the developer and the kind of solvent used, may be selected with ease based on common knowledge in the art.
  • the colordeveloping ability is markedly improved, the step for preparing a coating solution is simplified, and a coating solution having low viscosity and excellent coating characteristics are produced.
  • the nature of the low viscosity is a viscosity of the coating solution such that the coating amount is not more than 5 g/m when the coating solution is coated on a support using air knife coating of which air knife pressure is 2000 mmH O and of which coating speed is 400 m/min.
  • Microcapsule's containing a color former can be produced by various known processes. Typical of the capsule formation methods are those utilizing the coacervation of a'hydrophilic colloid sol as described in US. Pat; Nos. 2,800,457, 2,800,458, and typical of those utilizing interfacial polymerization are those described in' British Pat; Nos. 867,797, 950,443, 989,264 and 1,091,076. The color former is dissolved in a solvent and thenin microencapsulated.
  • any solvents which can be used are one or more of the natural or synthetic oils, for example, chlorinated biphenyls, chlorinated terphenyls, alkylated biphenyls, 'alkylated terphenyls, chlorinated paraffins, chlorinated naphthalenes, alkylated naphthalenes, kerosine, paraffin, naphthene oils and cotton seed oil.
  • oils for example, chlorinated biphenyls, chlorinated terphenyls, alkylated biphenyls, 'alkylated terphenyls, chlorinated paraffins, chlorinated naphthalenes, alkylated naphthalenes, kerosine, paraffin, naphthene oils and cotton seed oil.
  • the color former (which is an electron donating colorless organic compound capable of forming a distinct color when contacted with an electron accepting acid compound) is not particularly limited but examples thereof are: triarylmethane type compounds such as 3,3-bis( pdimethylaminophenyl)-6-dimethylaminophthalide, i.e., crystal violet lactone (which will hereinafter be referred to as CVL), 3,3-bis-(p-dimethylaminophenyl)phthalide, 3-(p-dimethylaminophenyl)-3-(1,2- dimethylindole-3-yl)phthalide, v 3-(pdimethylaminophenyl)-3-(2-methylindole-3- yl)phthalide, 3-(p-dimethylaminophenyl)-3-(2- phenylindole-3-yl)phthalide, 3,3-bis( 1,2- dimethylindole-3-yl)-5-dimethylaminophthalide, 3,3-
  • Coating may be carried out by any coating system, such as, air knife coating, blade coating, roll coating or by any known printing system.
  • coating system such as, air knife coating, blade coating, roll coating or by any known printing system.
  • the microcapsules were produced as follows according to US. Pat. No. 2,800,457.
  • the coating solution was coated on a 50 g/m paper temperature reached C, a sodium hydroxide in an amount of 2 g/m on a solids basis, followed by aqueous solution was added thereto to adjust the pH to drying,
  • the color developing ability was determined by an optical densitometer (reflectance 111400 to 700 my). The numerical value shows the color density at maximum.
  • microcapsule dispersion was adjusted to 30C and applied to a g/m paper in an amount of 6 g/m based on the amount of solid ingredients followed by drying.
  • EXAMPLE 1 0.1 Mol of S-tert-butylsalicylic acid was dissolved in a mixture of 0.1 mol of sodium hydroxide and 300 ml of water. To this solution were added 30 g ofa 10% polyvinyl alcohol (polymerization degree: about 500; saponification degree: about 87%) aqueous solution and an ether or alcohol as listed in the following table. Then, a solution prepared by dissolving 0.1 mol of zinc chloride in 100 cc of water was gradually added thereto under stirring. The resulting coating solution was coated on a 50 g/m paper in an amount of2 g/m based on the solid ingredients followed by drying. The viscosity of the coating solution was low, and the coating characteristics of the solution were good.
  • COMPARATIVE EXAMPLE 2 0.1 Mol of S-tert-butylsalicylic acid was dissolved in 0.1 mol of caustic soda and 300 ml of water. To this solution was added 30 g of a 10% polyvinyl alcohol aqueous solution. Then, asolution prepared by dissolving 0.7 mol of zinc chloride in 700 cc of water and a solution prepared by dissolving in 300 cc of water 0.3 mol of nickel sulfate were gradually added thereto under stirring. To this solution was added 20 g of a styrenemethyl methacrylate copolymer latex to prepare a coating solution.
  • the solution was then coated on a 50 g/m paper in an amount of 3 g/m on a solids basis, followed by drying.
  • EXAMPLE 4 0.1 M01 of 3,5-di-tert-butylsalicylic acid was dissolved in a mixture of 0.1 mol of sodium hydroxide and 300 ml of water. To this solution were added 50 g of a 10% polyvinyl alcohol (as described in Example 1 aqueous solution, g of agalmatolite and an ether or alcohol as shown in the following table. Then, a solution prepared by dissolving 0.15 mol of zinc chloride in 1000 ml of water was gradually added thereto under stirring. Furthermore, 50 g of a styrene-butadiene eopolymer latex was added thereto. The resulting coating solution was applied to a 50 g/m paper in an amount of 3 g/m on a solids basis. The viscosity of the solution was low, and the coating characteristics of the solution were good.
  • a 10% polyvinyl alcohol as described in Example 1 aqueous solution, g of agalmatolite and an
  • COMPARATIVE EXAMPLE 3 0.1 MOI of 3,S-di-tert-butysalicylic acid was dissolved in a mixture of 0.1 mol of sodium hydroxide and 300 ml of water. To this solution were added 50 g of a 10% polyvinyl alcohol (as described in Example 1) aqueous solution and 20 g of agalmatolite. Then, a solution prepared by dissolving 0.15 mol of zinc chloride in 1000 ml of water was gradually added thereto under stirring. Furthermore, 50 g of a styrene-butadiene eopolymer latex was added thereto.
  • the resulting coating solution was applied to a 50 g/m paper in an amount of 3 g/m on a solids basis.
  • the coating solution had a high .viscosity and contained many bubbles, and the particle size of the metal compound was large. Therefore, the solution was coated on the support after applying ultrasonic waves thereto.
  • styrene-butadiene latex 4 g was added thereto to prepare a coating solution.
  • the resulting coating solution was coated onto a 50 g/m paper in an amount of 3 g/m on a solids basis followed by drying.
  • COMPARATIVE EXAMPLE 4 5 Grams of activated clay was dispersed in 50 cc of water. To this was added 0.6 cc of 20% sodium hydroxide. Then, a solution prepared by dissolving 10 g of a 10% polyvinyl alcohol (as described in Example 1) aqueous solution and 0.012 mol of zinc sulfate in 10 cc of water was gradually added thereto under stirring. Furthermore, a solution prepared by dissolving 0.01 mol of 3,5-di-tert-butyl-salicylic acid and 0.01 mol of sodium hydroxide in 30 cc of water was gradually added thereto under stirring.
  • styrene-butadiene latex 4 g was added thereto to prepare a coating solution.
  • the resulting coating solution was coated on a 50 g/m paper in an amount of 3 g/m on a solids basis followed by drying.
  • the coating solution of the present m- EXAMPLE 6 vention was low in viscosity and the particle size of the metal salt of the aromatic carboxylic acid formed by the reaction was small.
  • water-immersion coloration was particularly small when n-octyl alcohol or n-hexyl alcohol was used.
  • n-butyl alcohol and diacetone alcohol also provided sufficient effects.
  • EXAMPLE 5 5 Grams of kaolin was dispersed in 50 cc of water. To this was added under stirring a solution prepared by dissolving 10 g of a 5% hydroxymethyl cellulose and 0.01 mol of tin sulfate in 10 cc of water. Furthermore, after adding thereto 3 g of diethylene glycol monobutyl ether, a solution prepared by dissolving 0.01 mol of 3,5-di-tert-amylsalicylic acid and 0.01 mol of potassium hydroxide in cc of water was gradually added thereto under stirring. After the completion of the addition, 3 g of a vinyl acetate-acrylate copolymer was added thereto to prepare a coating solution. The resulting coating solution was applied to a 50 g/m paper in an amount of 4 g/m as solids, followed by drying.
  • COMPARATIVE EXAMPLE 5 5 Grams of kaolin was dispersed in 50 cc of water. To this was added under stirring a solution prepared by dissolving 10 g of 5% hydroxymethyl cellulose and 0.01 mol of tin sulfate in 10 cc of water. Furthermore, 0.01 mol of 3,S-di-tert-amylsalicylic acid and 0.01 mol of potassium hydroxide were dissolved in 30 cc of water and gradually added thereto. After the completion of the addition, 4.3 g of vinyl aeetate-acrylate (1:1 molar ratio) copolymer was added thereto to prepare a coating solution. The resulting coating solution was applied to a 50 g/m paper in an amount of 4 g/m on a solids basis, followed by drying.
  • the step for preparing a coating solution was simplified and, in addition, the viscosity of the coating solution was so low that the coating solution had excellent coating characteristics.
  • the water-immersion coloration was also remarkably depressed and the commercial value of the resulting sheet was markedly improved. Additionally, the light fastness, and water resistance of the color image, the activity of the color developer sheet with the passage of time, and the like were not affected at all.
  • a recording sheet comprising a support having thereon a color developer layer capable of reacting with a color former to form color images, said color developer layer containing l a metal salt of an aromatic carboxylic acid and (2) at least one member selected from the group consisting of ethers and alcohols, said Ill B, Group IV A, Group VIA, Group VII B or Group VIII of the Periodic Table.
  • R may be the same or different and represents a hydrogen atom, a hydroxy group, a halogen atom, a nitro group, an alkyl group having 1 to 10 carbon atoms, the total carbon number in the Rs being less than 13, an aryl group, an arylamino group or an alicyclic group, m is an integer of O to 7 and n is an integer of to 5, or said aromatic carboxylic acid may be dimerized through the substituent R as a methylene group.
  • said color developer layer contains from l0 to 250 parts by weight of said ether and alcohol per 100 parts by weight of said aromatic carboxylic acid and wherein said color developer layer is present on said support at a level of at least O.l g/m as the metal salt of the aromatic carboxylic acid;
  • said ether is represented by the formula:
  • X is -(CH ),,OR, (CH ),,OH, [(CH ),,O],,H, [(CH ),,O],,R", an alkyl group having up to l8 carbon atoms or an alkenyl group having up to 18 carbon atoms
  • R is an alkyl group having up to 10 carbon atoms, an aryl group having up to [0 carbon atoms or an alkenyl group having up to II) carbon atoms
  • R and R" each is an alkyl group having up to 18 carbon atoms, an aryl group having up to l8 carbon atoms or an alkenyl group having up to l8 carbon atoms
  • p is an integer of l to 20 and q is an integer of 2 to 30
  • the alcohol is an aliphatic alcohol having from 1 to 18 carbon atoms.
  • said ether is a glycol ether.
  • said color developer layer contains from 10 to 250 parts by weight of said ether andalcohol per parts by weight of said aromatic carboxylic acid and wherein said color developer layer is present on said support a level of at least 0.1 g/m as the metal salt of the aromatic carboxylic acid.
  • X is (CH ),,OR, (CH ),,OH, [(CH ),,O],,H, [(CH ),,O],,R, an alkyl group having up to l8 carbon atoms or an alkenyl group having up to l8 carbon atoms
  • R is an alkyl group having up to 10 carbon atoms, an aryl group having up to 10 carbon atoms or an alkenyl group having up to 10 carbon atoms
  • R and R each is an alkyl group having up to 18 carbon atoms, an aryl group having up to 18 carbon atoms or an alkenyl group having up to 18 carbon atoms
  • p is an integer of l to 20 and q is an integer of 2 to 30.
  • aromatic carboxylic acid is selected from the group consisting of benzoic acid, nitrobcnzoic acid, chlorobenzoic acid, toluic acid, 4-methyl-3-nitroben2oic acid, 2- chloro-4-nitrobenzoic acid, 2,3-dichlorobenzoic acid, 4-methyl-3-nitrobcnzoic acid, 4-acetylbenzoic acid, 2,4-dihydroxybenzoic acid, 2,5-dihydroxybenzoic acid, l-napththoic acid, 2-naphthoic acid, l-hydroxy-2- naphthoic acid, 2-hydroxy-3-naphthoic acid, 2- hydroxy-l-naphthoic acid, thiosalicyclic acid, salicylic acid, 3,5-dinitrosalicylic acid, 3-methylsalicyclic acid,
  • phenylsalicylic acid 3-methyl-5-tert-butylsalicylic acid, 3,5-di-tert-butylsalicylic acid, 3,5-di-tertamylsalicylic acid, 3-cyclohexylsalicylic acid, 5-cyclohexylsalicylic acid and 3-methyl-5- isoamylsalicylic acid.
  • a pressure sensitive copying assembly comprising a color former layer on a first support and a color developer layer on a second support, said color developer layer and said color former layer being brought together at the time of pressure sensitive copying to permit color developer and color former to be brought into reactive contact to form a color image, said color developer layer containing (1) a metal salt of an aromatic carboxylic acid and (2) at least one member selected from the group consisting of ethers and alcohols, said component (I) and said component (2) being present at a porportion sufficient to increase the colordeveloping ability of said color developer and said color former.
  • a pressure sensitive copying assembly comprising a color former layer and a color developer layer carried on the same support, said color developer layer and said color former layer being in relationship such that at the time of pressure sensitive copying, color developer and color former are brought into reactive contact to form a color image.
  • Said color developer layer containing (l) a metal salt of an aromatic carboxylic acid and (2) at least one member selected from the group consisting of ethers and alcohols, said component (I) and said component (2) being present at a proportion sufficient to increase the color-developing ability of said color developer and said color former.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
US382224A 1972-07-28 1973-07-24 Recording sheet Expired - Lifetime US3871900A (en)

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JP7575872A JPS5318921B2 (es) 1972-07-28 1972-07-28

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US (1) US3871900A (es)
JP (1) JPS5318921B2 (es)
BE (1) BE802914A (es)
DE (1) DE2338288C2 (es)
ES (1) ES417280A1 (es)
GB (1) GB1445113A (es)

Cited By (14)

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US4124554A (en) * 1977-02-03 1978-11-07 Union Carbide Corporation Post-formed aqueous phenolic resin dispersions
US4239815A (en) * 1977-12-07 1980-12-16 Fuji Photo Film Co., Ltd. Method of producing recording sheets
US4269893A (en) * 1978-05-12 1981-05-26 Fuji Photo Film Co., Ltd. Recording material containing a novel color developer
US4303719A (en) * 1980-07-29 1981-12-01 Vassiliades Anthony E Chromogenic copy system
US4336067A (en) * 1977-09-06 1982-06-22 The Mead Corporation Hot melt chromogenic coating composition
US4372583A (en) * 1980-07-29 1983-02-08 Vassiliades Anthony E Chromogenic copy system and method
US4399188A (en) * 1980-04-10 1983-08-16 Jujo Paper Co., Ltd. Heat-sensitive recording sheet
EP0135901A2 (de) * 1983-09-16 1985-04-03 Jujo Paper Co., Ltd. Wärmeempfindliches Aufzeichnungsblatt
EP0189760A1 (en) * 1985-01-09 1986-08-06 Jujo Paper Co., Ltd. Thermosensitive recording sheet
US4687869A (en) * 1984-10-22 1987-08-18 Ciba-Geigy Corporation Metal salicylates, process for their preparation and use thereof as color developers in pressure-sensitive or heat-sensitive recording materials
US4745203A (en) * 1985-10-03 1988-05-17 Ciba-Geigy Corporation Process for the preparation of mixtures of metal salts of ring-substituted salicylic acid compounds
US4748259A (en) * 1985-10-03 1988-05-31 Ciba-Geigy Corporation Process for the preparation of mixtures of metal salts of ring-substituted salicylic acid compounds
US4859650A (en) * 1986-09-30 1989-08-22 Feldmuhle Aktiengesellschaft Pressure-sensitive recording material
US6180213B1 (en) * 1997-09-22 2001-01-30 Konica Corporation Heat sensitive planographic printing plate, its manufacturing method and image forming method employing the same

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Publication number Priority date Publication date Assignee Title
JPS5199321U (es) * 1975-02-06 1976-08-10
JPS5538733Y2 (es) * 1975-03-10 1980-09-10
JPS5640564Y2 (es) * 1975-08-29 1981-09-22
JPS5753685Y2 (es) * 1976-02-19 1982-11-20
JPS5489817A (en) * 1977-12-27 1979-07-17 Fuji Photo Film Co Ltd Recording material
JPS6054197B2 (ja) 1978-01-05 1985-11-29 富士写真フイルム株式会社 顕色インキ
JPS54156711A (en) * 1978-05-29 1979-12-11 Mishima Paper Co Ltd Pressureesensitive recording paper
JPS5534916A (en) * 1978-09-01 1980-03-11 Mitsubishi Paper Mills Ltd Pressure-sensible recording material
JPS5538826A (en) * 1978-09-11 1980-03-18 Fuji Photo Film Co Ltd Color-developing ink
JPS576795A (en) * 1980-06-17 1982-01-13 Tomoegawa Paper Co Ltd Thermo-sensitive recorder
JPS5748113U (es) * 1980-09-05 1982-03-17
DE3044119A1 (de) * 1980-11-24 1982-06-24 Basf Ag, 6700 Ludwigshafen Farbbildner entwickelnde beschichtungen
JPS5933369A (ja) * 1982-08-18 1984-02-23 Mitsubishi Paper Mills Ltd 顕色インキ
JPS59207284A (ja) * 1983-05-10 1984-11-24 Fuji Photo Film Co Ltd 感圧記録用顕色剤シ−トの製造方法
JPS61160293A (ja) * 1985-01-09 1986-07-19 Jujo Paper Co Ltd 感熱記録紙
JPS61185484A (ja) * 1985-02-13 1986-08-19 Jujo Paper Co Ltd 感熱記録紙
JP2595097Y2 (ja) * 1991-05-31 1999-05-24 スズキ株式会社 カウルトップガーニッシュの取付装置
KR100341502B1 (ko) * 1999-12-23 2002-06-21 이계안 자동차의 쿼터 글래스 고정구조
GB201505874D0 (en) 2015-04-07 2015-05-20 Greener Bryan And Active Device Dev Ltd Pressure imaging and indicating materials and devices

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US2663653A (en) * 1948-03-17 1953-12-22 Standard Register Co Manifold sheet and process of making same
US3346571A (en) * 1963-06-05 1967-10-10 Allied Chem 2-(omega-substituted vinylene)-3, 3-disubstituted-3h-indoles
US3632376A (en) * 1969-05-09 1972-01-04 Columbia Ribbon & Carbon Heat-stencil assembly
US3664858A (en) * 1970-02-18 1972-05-23 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3767449A (en) * 1970-09-28 1973-10-23 Fuji Photo Film Co Ltd Recording sheet
US3769062A (en) * 1970-07-08 1973-10-30 Fuji Photo Film Co Ltd Pressure-sensitive recording paper

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Publication number Priority date Publication date Assignee Title
US2663653A (en) * 1948-03-17 1953-12-22 Standard Register Co Manifold sheet and process of making same
US3346571A (en) * 1963-06-05 1967-10-10 Allied Chem 2-(omega-substituted vinylene)-3, 3-disubstituted-3h-indoles
US3632376A (en) * 1969-05-09 1972-01-04 Columbia Ribbon & Carbon Heat-stencil assembly
US3664858A (en) * 1970-02-18 1972-05-23 Minnesota Mining & Mfg Heat-sensitive copy-sheet
US3769062A (en) * 1970-07-08 1973-10-30 Fuji Photo Film Co Ltd Pressure-sensitive recording paper
US3767449A (en) * 1970-09-28 1973-10-23 Fuji Photo Film Co Ltd Recording sheet
US3772052A (en) * 1970-09-28 1973-11-13 Fuji Photo Film Co Ltd Recording sheet and color developer therefor

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4124554A (en) * 1977-02-03 1978-11-07 Union Carbide Corporation Post-formed aqueous phenolic resin dispersions
US4336067A (en) * 1977-09-06 1982-06-22 The Mead Corporation Hot melt chromogenic coating composition
US4239815A (en) * 1977-12-07 1980-12-16 Fuji Photo Film Co., Ltd. Method of producing recording sheets
US4269893A (en) * 1978-05-12 1981-05-26 Fuji Photo Film Co., Ltd. Recording material containing a novel color developer
US4399188A (en) * 1980-04-10 1983-08-16 Jujo Paper Co., Ltd. Heat-sensitive recording sheet
US4303719A (en) * 1980-07-29 1981-12-01 Vassiliades Anthony E Chromogenic copy system
US4372583A (en) * 1980-07-29 1983-02-08 Vassiliades Anthony E Chromogenic copy system and method
EP0135901A3 (en) * 1983-09-16 1986-05-14 Jujo Paper Co., Ltd. Heat-sensitive registration material
EP0135901A2 (de) * 1983-09-16 1985-04-03 Jujo Paper Co., Ltd. Wärmeempfindliches Aufzeichnungsblatt
US4591888A (en) * 1983-09-16 1986-05-27 Jujo Paper Co., Ltd. Heat-sensitive recording sheet
US4687869A (en) * 1984-10-22 1987-08-18 Ciba-Geigy Corporation Metal salicylates, process for their preparation and use thereof as color developers in pressure-sensitive or heat-sensitive recording materials
EP0189760A1 (en) * 1985-01-09 1986-08-06 Jujo Paper Co., Ltd. Thermosensitive recording sheet
US4721701A (en) * 1985-01-09 1988-01-26 Jujo Paper Co., Ltd. Thermosensitive recording sheet
US4745203A (en) * 1985-10-03 1988-05-17 Ciba-Geigy Corporation Process for the preparation of mixtures of metal salts of ring-substituted salicylic acid compounds
US4748259A (en) * 1985-10-03 1988-05-31 Ciba-Geigy Corporation Process for the preparation of mixtures of metal salts of ring-substituted salicylic acid compounds
US4859650A (en) * 1986-09-30 1989-08-22 Feldmuhle Aktiengesellschaft Pressure-sensitive recording material
US6180213B1 (en) * 1997-09-22 2001-01-30 Konica Corporation Heat sensitive planographic printing plate, its manufacturing method and image forming method employing the same

Also Published As

Publication number Publication date
JPS4934330A (es) 1974-03-29
BE802914A (fr) 1973-11-16
DE2338288A1 (de) 1974-02-07
DE2338288C2 (de) 1982-12-09
ES417280A1 (es) 1976-03-16
JPS5318921B2 (es) 1978-06-17
GB1445113A (en) 1976-08-04

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