EP0629511A2 - Matériau d'enregistrement - Google Patents

Matériau d'enregistrement Download PDF

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Publication number
EP0629511A2
EP0629511A2 EP94303938A EP94303938A EP0629511A2 EP 0629511 A2 EP0629511 A2 EP 0629511A2 EP 94303938 A EP94303938 A EP 94303938A EP 94303938 A EP94303938 A EP 94303938A EP 0629511 A2 EP0629511 A2 EP 0629511A2
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EP
European Patent Office
Prior art keywords
oil
color former
recording material
electron
developer
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Application number
EP94303938A
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German (de)
English (en)
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EP0629511A3 (fr
EP0629511B1 (fr
Inventor
Shojiro C/O Fuji Film Co. Ltd. Sano
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Publication of EP0629511A3 publication Critical patent/EP0629511A3/fr
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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
    • B41M5/165—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 characterised by the use of microcapsules; Special solvents for incorporating the ingredients
    • B41M5/1655—Solvents
    • 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
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
    • B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds

Definitions

  • the present invention relates to a recording material which is employable for a pressure sensitive material and a heat sensitive material.
  • Color former an electron-donating color former
  • developer an electron-accepting developer
  • the pressure sensitive material utilizes the mechanisms that the micro capsule containing the color former is ruptured by application of pressure to form a color image through the reaction of the color former with the developer.
  • the pressure sensitive recording material includes a no-carbon-paper-type recording material that a color former layer comprising a micro capsule containing a color former (hereinafter may be referred to as "color former layer”) and a developer layer containing an electron-accepting developer (hereinafter may be referred to as "developer layer”) are respectively formed on surfaces of separate supports or separate surfaces of one support and are in contact with each other to be used; and a self-coloring-type pressure sensitive recording material (e.g., pressing-type paper or self-contained paper) comprising a self-coloring layer having both the color former and the developer provided on one side surface of a support.
  • color former layer a color former layer comprising a micro capsule containing a color former
  • developer layer containing an electron-accepting developer
  • the no-carbon-paper-type recording material consists of a upper paper having a color former layer provided on one side surface of a support (which usually is paper sheet), an intermediate paper having a color former layer provided on one side surface of a support and a developer layer on another side surface of the support, and a lower paper having a developer layer provided on one side surface of a support.
  • the intermediate paper is usually used in the form of two or more sheets.
  • Such no-carbon-paper-type recording material is employed by bringing the color former into contact with the developer to form a colored image.
  • the self-coloring-type pressure sensitive recording material when pressure is applied to a surface having a self-coloring layer, a microcapsule in the layer is ruptured to form a color image on the self-coloring layer through the reaction of the color former with the developer. Therefore, the material is usually employed for writing or drawing an image such as a letter on a paper placed on the self-coloring layer with writing instruments or a typewriter, for directly printing a colored image on the self-coloring layer with a printer or a typewriter, or for printing a letter for OCR (optical character reader) on the self-coloring layer.
  • OCR optical character reader
  • a self-coloring-type pressure sensitive recording material using a upper paper having a self-coloring layer provided on one side surface of a support and a color former layer on another side surface of the support, in combination with an intermediate paper having a color former layer and developer layer and a lower paper having a developer layer is occasionally employed.
  • Types of the self-coloring layer of the self-coloring-type pressure sensitive recording material includes a two layers-type layer consisting of a color former layer containing a microcapsule containing a color former and a developer layer containing a developer which are superposed upon each other, and a one layer-type layer consisting of one layer containing a color former and a developer.
  • the heat sensitive recording materials containing a microcapsule are those having a heat sensitive layer which contains a microcapsule containing a color former and a developer, as described in Japanese Patent Provisional Publications No. 63(1988)-265682 and No. 1(1989)-105782.
  • Such recording material has the advantages that can be designed for OHP (over head projector) or multicolor type.
  • the microcapsule which is contained in the above recording materials, contains a color former dissolved in a solvent. It is necessary that such solvent is capable of dissolving the color former.
  • the solvents generally include kerosine, paraffin, naphthene oil, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, alkylated naphthalene, diaryl alkane and phthalic acid ester.
  • solvents generally give off ill smell. Some of them are harmful to living things so that they have the danger that bring out environmental pollution (e.g., poor working condition).
  • the recording material is prepared using such solvents or the recording material containing the solvents is used, the above problem occur.
  • Japanese Patent Provisional Publication No. 50(1975)-90409 describes a process for preparation of a pressure sensitive recording paper comprising the steps of dissolving a color former in an animal or vegetable oil heated at 105 to 260°C to prepare a color former solution, and forming a microcapsule layer containing the color former solution on support.
  • the animal or vegetable oils used in the process are natural edible materials mainly composed of triglyceride. Such oils have no ill smell and assured safety from the viewpoint of ecology, and further are available at low prices. Therefore, the oils are suitable for a solvent for the color former solution contained in the microcapsule.
  • the animal or vegetable oils generally do not have a sufficient dissolving power required for dissolving a color former and therefore it is difficult to increase a concentration of the color former in its solution.
  • a color former is dissolved in an animal or vegetable oil by heating the oil at a high temperature of 105 to 260°C.
  • heating brings about deterioration of quality of the oil due to oxidation, and the heated oil occasionally gives off ill smell.
  • the oil itself inhibits occasionally coloring of the color former (i.e., desensitizes the color former).
  • the present inventor has studied to find a color former that easily dissolves in glycerides such as vegetable or animal oils in high concentration at relatively low temperature.
  • finding of such color former enables the glycerides to use as a solvent for the color former solution contained in the microcapsule.
  • the invention resides in a recording material which contains both a microcapsule containing an electron-donating color former dissolved in a solvent and an electron-accepting developer; wherein the solvent comprises a glyceride and the electron-donating color former comprises a fluoran compound of the formula (I): in which R 1 represents an alkyl group of 1 to 4 carbon atoms, R 2 represents a branched alkyl group of 4 to 12 carbon atoms or a tetrahydrofurfuryl group, and each of R 3 and R 4 represents independently a hydrogen atom, a halogen atom or a methyl group, provided that R 1 differs from R 2 .
  • the solvent comprises a glyceride
  • the electron-donating color former comprises a fluoran compound of the formula (I): in which R 1 represents an alkyl group of 1 to 4 carbon atoms, R 2 represents a branched alkyl group of 4 to 12 carbon atoms or a tetrahydrofurfuryl group
  • the invention resides in a pressure sensitive recording material which contains both a pressure rupturable color former layer comprising a microcapsule which contains an electron-donating color former dissolved in a solvent and a developer layer comprising an electron-accepting developer; wherein the solvent comprises a glyceride and the electron-donating color former comprises a fluoran compound of the above formula (I).
  • a pressure sensitive recording material which comprises a upper paper comprising a paper sheet and a pressure rupturable color former layer provided on the paper sheet, and a lower paper comprising a paper sheet and a developer layer provided on the paper sheet, said color former layer comprising a microcapsule which contains an electron-donating color former dissolved in a solvent and said developer layer comprising an electron-accepting developer;
  • the solvent comprises a glyceride and the electron-donating color former comprises a fluoran compound of the formula (I).
  • the recording material of the invention employs glycerides as a solvent for dissolving the color former.
  • the glycerides generally give off no ill smell and are not harmful to living things. Therefore, they do not bring out poor working condition, and naturally do not environmental pollution.
  • the recording material shows coloring of high density due to use of the specific fluoran compound (color former) in combination with the glycerides because the fluoran compound is not desensitized by the glycerides.
  • the recording material of the invention is one that has assured safety and shows coloring of high density. Particularly, it is useful for a pressure sensitive recording material.
  • the recording material of the invention contains both a microcapsule containing an electron-donating color former dissolved in a solvent and an electron-accepting developer.
  • the recording material is not restricted in its form so long as it contains a microcapsule containing a color former dissolved in a solvent.
  • the heat sensitive recording material has the same structure as that shown in Fig. 3.
  • the self-coloring layer 14 corresponds to a heat sensitive layer.
  • the recording material of the invention is characterized by the use of the specific compound as the color former contained in the microcapsule and glyceride as the solvent for dissolving the color former.
  • the specific compound as the color former contained in the microcapsule and glyceride as the solvent for dissolving the color former.
  • Glyceride employed in the invention is used for dissolving the color former. Any natural glycerides and synthesis glycerides are employable in the invention. Further, any of triglycerides, diglycerides, monoglycerides and a mixture thereof are employable in the invention. It is preferred that the glyceride is mainly composed of triglyceride. The glyceride preferably is a ester of glycerin and saturated fatty acid.
  • Examples of the glycerides include 1-monocaprin, 1-monoundecanoin, 1-monolaurin, 1-monotridecanoin, 1-monomyristin, 1-monopentadecanoin, 1-monopalmitin, 1-monostearin, 1-monoolein, 1-monoelaidin, 1- monolinolenin, 1-monoarachin, 1-monobutyrin, 2-monocaprin, 2-monolaurin, 2-monomyristin, 2-monopaimi- tin, 2-monostearin,
  • 1,3-dicaprin 1,3-diundecanoin, 1,3-dilaurin, 1,3-ditridecanoin, 1,3-myristin, 1,3-pentadecanoin, 1,3-dipalmitin, 1,3-distearin, 1,3-diarachin, 1,2-dilaurin, 1,2-dimyristin, 1,2-dipalmitin, 1,2-distearin,
  • these glycerides may be synthesis glycerides or natural oil, it is convenience to use the natural oil.
  • Preferred examples of the natural oil include vegetable oils such as soybean oil, sesame oil, corn oil, rapeseed oil, cotton seed oil, olive oil, peanut oil, castor oil, palm oil, coconut oil, sunflower oil, camellia oil and palm kernel oil. These oils are employable singly or in combination.
  • hardened oil prepared by hydrogenation of unsaturated glyceride and epoxidated oil prepared by epoxidation of unsaturated bond of unsaturated glyceride are also employable as glyceride of the invention.
  • a conventional solvent mentioned previously is employable in the amount that the resultant recording material does not give off ill smell (not more than 30 weight % per glyceride), in combination of glyceride.
  • the color former employed in the invention is a fluoran compound of the formula (I) mentioned previously.
  • Examples of the alkyl group of 1 to 4 carbon atoms represented by R 1 include methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and tert-butyl. Preferred are methyl, ethyl, n-propyl and isopropyl. Particularly, ethyl is preferred.
  • Examples of the branched alkyl group of 4 to 12 carbon atoms represented by R 2 include isobutyl, sec-butyl, tert-butyl, isopentyl, sec-pentyl, tert-pentyl, isohexyl, 2-methylhexyl, 2-ethylhexyl and 2-ethyldecyl.
  • Preferred examples of the group represented by R 2 include isobutyl, sec-butyl, isopentyl, isohexyl, 2-methylhexyl, 2-ethylhexyl, 2-ethyldecyl and tetrahydrofurfuryl. Particularly, isobutyl and tetrahydrofurfuryl are preferred.
  • Preferred examples of the group represented by R 3 include hydrogen, chlorine and methyl. Particularly, methyl is preferred.
  • Preferred examples of the group represented by R 4 include hydrogen, chlorine and methyl. Particularly, hydrogen is preferred.
  • fluoran compound of the formula (I) include 2-anilino-3-methyl-6-N-ethyl-N-iso- butylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-isopentylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-isobutylaminofluoran, 2-anilino-3-methyl-6-N-methyl-N-isopentylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-isohexylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-(2-ethylhexyl)aminofluoran, 2-toluidino-3-methyl-6-N-ethyl-N-isobutylaminofluoran, 2-anilino-3-methyl-6-N-ethyl-N-(2-ethylde
  • the known color formers can be employed together with the fluoran compound for purpose of controlling tone.
  • the known color formers include triphenylmethanphthalide compounds, fluoran compounds other than the fluoran compounds of the invention, phenothiazine compounds, indolylphthalide compounds, leucoauramine compounds, rhodaminelactam compounds, triphenylmethan compounds, tria- zene compounds and spiropyran compounds.
  • the fluoran compound of the invention is preferably used in the amount of not less than 70 weight % based on the total amount of the used color formers to give an image of high coloring density.
  • the microcapsule containing the color former of the fluoran compound having the formula (I) is prepared by dissolving the color former in the solvent of the glyceride.
  • the fluoran compound is preferably dissolved in a solvent of the glyceride at a temperature of 80 to 100°C. In the case of a temperature lower than 80°C, the fluoran compound is not easily dissolved in the glyceride. In the case of a temperature higher than 100°C, the glyceride is occasionally deteriorated.
  • the fluoran compound of the formula (I) is contained in the solution of the color former in the amount of 3 to 8 % by weight based on the amount of the glyceride.
  • Color formers other than the fluoran compound of the formula (I) are dissolved in the glyceride at the temperature within the above range so long as in the amount of lower than 1 weight %. For dissolving these colorformers in the above amount (3 to 8 weight %), it is required to heat a mixture containing them to approx. 150°C.
  • microcapsule of the invention containing the color former dissolved in the solvent is prepared according to the known method such as an interfacial polymerization method, an internal polymerization method, a phase separation method, an external polymerization method or a coaservation method.
  • the shell material of the microcapsule water-insoluble or oil-insoluble polymers which is used in the conventional pressure sensitive material are employable.
  • the shell material is preferred to be polyurethane/polyurea resin having high resistance to heat-fogging.
  • the microcapsule dispersion forforming the shell of polyurethane/polyurea resin to incorporate the color former is prepared by, for example, the steps of dissolving a multi-functional isocyanate compound and a multi-functional hydroxyl compound (further UV absorbent if desired) in the solution prepared by dissolving the color former in glyceride as above, dispersing the resultant solution to a hydrophilic liquid, adding a multi-functional amine to the resultant dispersing solution, and coating the polyurethane/polyurea resin around a drop of the glyceride solution.
  • the multi-functional hydroxyl compound and the multi-functional amine may be used in combination as above, or either of them may be used.
  • the dispersing solution of the microcapsule prepared above is directly employed as a coating solution for forming the color former layer. Otherwise, the coating solution is prepared by adding further a binder and/or an agent for protecting a capsule to the dispersing solution.
  • the resultant coating solution is coated on the support according to a known coating method and the coated layer is dried.
  • the color former layer for the no-carbon-paper-type pressure sensitive recording material is formed.
  • the binder include a water-soluble binder and a latex binder and examples of the agent for protecting a capsule include powders of cellulose, powders of starch and talc.
  • materials of the support materials employed for the support of the conventional pressure sensitive recording material and the conventional heat sensitive recording material.
  • materials of the support include a paper made of pulp, a surface treated paper, a synthetic paper made of plastic and a plastic film.
  • the coated amount of the color former layer formed on the support after drying generally is in the range of 0.05 to 0.30 g/m 2 , and preferably is in the range of 0.08 to 0.20 g/m 2 .
  • Examples of the developer contained in the developer layer of the no-carbon-paper-type pressure sensitive recording material include clay materials such as acid clay, activated clay, attapulgite, zeolite, bentonite and kaolin, metal salts of aromatic carboxylic acids (e.g., salicylic acid derivatives), and a phenol formaldehyde resin.
  • the developer preferably is clay materials from the viewpoint of ecology.
  • a coating solution for forming the above developer layer is prepared according a known method.
  • the coating solution may further contain a binder.
  • the binder include natural or synthetic polymers such as styrene/butadiene copolymer latex, polyvinyl acetate latex, polyacrylate latex, polyvinyl alcohol, polyacrylic acid, maleic anhydride/styrene copolymer, starch, casein, carboxymethyl cellulose and methyl cellulose.
  • the developer layer is formed on the support utilizing a known coating method.
  • the coated amount of the developer layer formed on the support after drying generally is in the range of 0.1 to 4.0 g/m 2 , and preferably is in the range of 0.2 to 3.0 g/m 2 .
  • the no-carbon-paper-type pressure sensitive recording material according to the invention has a composition similar to a conventional one except for employing the fluoran compound of the formula (I) as colorformer and the glyceride as the solvent for dissolving the color former. Therefore, the no-carbon-paper-type pressure sensitive material of the invention can be prepared utilizing the known process.
  • the recording materials such as the self-coloring-type pressure sensitive recording material and the heat sensitive recording material described previously, they have a composition similar to conventional one except for employing the above specific compounds as color former and as the solvent for dissolving the color former which are contained in the microcapsule. Therefore, the recording materials can be prepared utilizing the known processes.
  • the above coating solution for forming a color former layer was so coated as to have 4.0 g/m 2 in terms of solid content using an air-knife coater, and dried to prepare the color former sheet.
  • This color former sheet scarcely gave off smell.
  • a mixture of 200 g of activated clay, 20 g of sodium carbonate, 8 g of magnesium oxide, 1 g of sodium hexametaphosphate, 20 g of 20 weight % sodium hydroxide and 500 g of water was dispersed by means of a cady mill.
  • 40 g (solid content) of a carboxyl-modified SBR (styrene butylene rubber) latex and 60 g of a starch aqueous solution (10 weight %) were added to prepare the coating solution "A" for forming a developer layer.
  • the above coating solution "A" for forming a developer layer was so coated as to have 6.0 g/m 2 in terms of solid content using an air-knife coater, and dried to prepare the developer sheet "A".
  • the resultant color former sheet was placed on the resultant developer sheet "A" in such a manner that the color former layer and the developer layer came into contact each other.
  • Load of 300 kg/cm 2 was applied to the resultant composite to form a developed image on the developer layer.
  • D density
  • Example 1 Procedures of Example 1 was repeated except for using the same amount of soybean oil instead of cotton seed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet scarcely gave off smell.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 1 Procedures of Example 1 was repeated except for using the same amount of corn oil instead of cotton seed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet scarcely gave off smell.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 1 Procedures of Example 1 was repeated except for using the same amount of epoxidated soybean oil instead of cotton seed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet scarcely gave off smell.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 1 Procedures of Example 1 was repeated except for using the same amount of 1,2-dilaurin instead of cotton seed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet scarcely gave off smell.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 1 Procedures of Example 1 was repeated except for using the same amount of 1-phenyl-1-xylylethane instead of cotton seed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet gave off a stimulative smell.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 1 Procedures of Example 1 was repeated except for using the oily solution prepared above instead of one of Example 1, to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 1 Procedures of Example 1 was repeated except for using the oily solution prepared above instead of one of Example 1, to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • Example 1 Using the resultant color former sheet and the developer sheet "A" prepared in the same manner as Example 1, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • a vessel having the emulsion therein was cooled from the outside with stirring the emulsion to set a colloid wall deposited on the oil drop to gel.
  • the temperature of the emulsion became 10°C with continuously stirring, 3.0 g of formaldehyde 37 % solution was added to the emulsion and further 40 g of 7 weight % aqueous solution of sodium salt of carboxymethyl-cellulose (etherification degree: 0.75) was added.
  • sodium hydroxide 10 weight % aqueous solution was dropwise added to the emulsion till the pH became 10, and the vessel having the emulsion therein was heated from the outside to raise its temperature to 40°C.
  • the emulsion was kept at this temperature for 1 hour to prepare a capsule solution containing the color former.
  • the coating solution for forming a color former layer which contains the microcapsule containing the color former was prepared.
  • the above coating solution for forming the color former layer was so coated as to have 4.5 g/m 2 in terms of solid content using an air-knife coater, and was dried to prepare the color former sheet.
  • This color former sheet scarcely gave off smell.
  • a mixture of 120 g of calcium carbonate, 20 g of zinc oxide, 5 g of zinc 3,5-bis(a-methylbenzyl)salicylate, 1 g of sodium hexametaphosphate and 200 g of water was subjected to atomization treatment using a sand mill to prepare a dispersing solution.
  • the above coating solution "B" for forming a developer layer was so coated as to have 4.5 g/m 2 in terms of solid content using an air-knife coater, and dried to prepare the developer sheet "B".
  • the obtained color former sheet was placed on the resultant developer sheet "B" in such a manner that the color former layer and the developer layer came into contact.
  • the evaluation of the developed color density was performed in the same manner as that of Example 1. The result is set forth in Table 1.
  • Example 6 Procedures of Example 6 was repeated except for using the same amount of triacetin instead of rapeseed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet gave off a stimulative smell.
  • Example 6 Using the resultant color former sheet and the developer sheet "B" prepared in the same manner as Example 6, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • Example 6 Procedures of Example 6 was repeated except for using the same amount of monoisopropylbiphenyl instead of rape-seed oil to prepare the coating solution for forming a color former layer and then to prepare the color forming sheet.
  • the resultant color former sheet gave off a stimulative smell.
  • Example 6 Using the resultant color former sheet and the developer sheet "B" prepared in the same manner as Example 6, the evaluation of the developed color density was performed in the same manner as Example 1. The result is set forth in Table 1.
  • any recording materials prepared in the Examples scarcely gave off smell. Further, these materials showed the color images of high color densities with combination of the developer sheets.
  • the recording materials of Comparison Examples 1 and 4 which used materials other than glyceride as a solvent gave off a stimulative smell to give unpleasant feeling to users, although they showed the color images of high color densities similar to those of Examples.
  • the color formers were little dissolved or were insoluble in the triglyceride and therefore the use of them did not result in formation of capsule, or merely resulted in formation of capsule which gave the color image of an extremely low density on the developer sheet.

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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)
EP94303938A 1993-06-01 1994-06-01 Matériau d'enregistrement Revoked EP0629511B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP156132/93 1993-06-01
JP15613293A JP3172332B2 (ja) 1993-06-01 1993-06-01 記録材料
JP15613293 1993-06-01

Publications (3)

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EP0629511A2 true EP0629511A2 (fr) 1994-12-21
EP0629511A3 EP0629511A3 (fr) 1996-01-10
EP0629511B1 EP0629511B1 (fr) 1999-12-01

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EP94303938A Revoked EP0629511B1 (fr) 1993-06-01 1994-06-01 Matériau d'enregistrement

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EP (1) EP0629511B1 (fr)
JP (1) JP3172332B2 (fr)
ES (1) ES2142376T3 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0718116A2 (fr) * 1994-12-19 1996-06-26 Fuji Photo Film Co., Ltd. Matériau d'enregistrement
FR2770450A1 (fr) * 1997-10-30 1999-05-07 Henkel Kgaa Utilisation de triglycerides alcoxyles
EP1564019A1 (fr) * 2004-02-17 2005-08-17 Sensient Imaging Technologies S.A. Feuille à copier et méthode pour créer ou augmenter la qualité de copie d'une feuille à copier
DE19717651B4 (de) * 1996-04-26 2006-04-13 Mitsubishi Paper Mills Limited Kohlenstoff-freies, druckempfindliches Kopierpapier und dessen Verwendung
WO2014076468A1 (fr) * 2012-11-14 2014-05-22 Active Device Development Limited Matériaux de formation de couleur, dispositifs d'enregistrement de contact et dispositifs d'enregistrement de pression

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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GB2220909A (en) * 1988-06-15 1990-01-24 Fuji Photo Film Co Ltd Manufacture of microcapsules for pressure-sensitive recording sheets
EP0520639A1 (fr) * 1991-06-18 1992-12-30 The Wiggins Teape Group Limited Compositions de solvant pour le papier de copie sensible à la pression

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Publication number Priority date Publication date Assignee Title
JPS5090409A (fr) * 1973-12-12 1975-07-19
US4583104A (en) * 1983-09-05 1986-04-15 Fuji Photo Film Co., Ltd. Recording materials
EP0176161A1 (fr) * 1984-08-24 1986-04-02 Taoka Chemical Co., Ltd Composés de fluorane, leur production et leur utilisation
GB2210701A (en) * 1987-10-02 1989-06-14 Fuji Photo Film Co Ltd A heat sensitive recording material
GB2220909A (en) * 1988-06-15 1990-01-24 Fuji Photo Film Co Ltd Manufacture of microcapsules for pressure-sensitive recording sheets
EP0520639A1 (fr) * 1991-06-18 1992-12-30 The Wiggins Teape Group Limited Compositions de solvant pour le papier de copie sensible à la pression

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0718116A2 (fr) * 1994-12-19 1996-06-26 Fuji Photo Film Co., Ltd. Matériau d'enregistrement
EP0718116A3 (fr) * 1994-12-19 1996-07-31 Fuji Photo Film Co Ltd
DE19717651B4 (de) * 1996-04-26 2006-04-13 Mitsubishi Paper Mills Limited Kohlenstoff-freies, druckempfindliches Kopierpapier und dessen Verwendung
FR2770450A1 (fr) * 1997-10-30 1999-05-07 Henkel Kgaa Utilisation de triglycerides alcoxyles
EP1564019A1 (fr) * 2004-02-17 2005-08-17 Sensient Imaging Technologies S.A. Feuille à copier et méthode pour créer ou augmenter la qualité de copie d'une feuille à copier
WO2014076468A1 (fr) * 2012-11-14 2014-05-22 Active Device Development Limited Matériaux de formation de couleur, dispositifs d'enregistrement de contact et dispositifs d'enregistrement de pression
US9604485B2 (en) 2012-11-14 2017-03-28 Active Device Development Limited Colour-forming materials, contact recording devices and pressure recording devices

Also Published As

Publication number Publication date
JPH06340169A (ja) 1994-12-13
EP0629511A3 (fr) 1996-01-10
EP0629511B1 (fr) 1999-12-01
ES2142376T3 (es) 2000-04-16
JP3172332B2 (ja) 2001-06-04

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