US3900217A - Pressure-sensitive copying paper - Google Patents

Pressure-sensitive copying paper Download PDF

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US3900217A
US3900217A US378105A US37810573A US3900217A US 3900217 A US3900217 A US 3900217A US 378105 A US378105 A US 378105A US 37810573 A US37810573 A US 37810573A US 3900217 A US3900217 A US 3900217A
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Prior art keywords
color
weight
phenothiazine
former
oil
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US378105A
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Inventor
Takao Hayashi
Hiroharu Matsukawa
Sadao Ishige
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Fujifilm Holdings Corp
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Fuji Photo Film Co Ltd
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Priority claimed from JP45051116A external-priority patent/JPS4843294B1/ja
Priority to CA115,054A priority Critical patent/CA944150A/en
Priority to GB2761171A priority patent/GB1338784A/en
Priority to FR7121285A priority patent/FR2096242A5/fr
Priority to DE2129467A priority patent/DE2129467B2/de
Priority to BE768496A priority patent/BE768496A/xx
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
Priority to US378105A priority patent/US3900217A/en
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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
    • B41M5/136—Organic colour formers, e.g. leuco dyes
    • 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

Definitions

  • This invention relates to a pressure-sensitive copying paper. More particularly, this invention relates to a method for preventing discoloration and fading of a color formed by a pressure-sensitive copying paper utilizing color reaction of color former and a solid acid substance.
  • a pressuresensitive copying paper is produced by utilizing microcapsules containing a solution of a substantially colorless organic compound (hereinafter, referred to as color former) and a material hereinafter, referred to as developer) which reacts in contact with the colorformer to form a distinctive color.
  • color former substantially colorless organic compound
  • developer material hereinafter, referred to as developer
  • both of these components are coated on the same support, or on different supports.
  • the developer examples include solid acid sub stances, for example, clay minerals such as acid clay, active clay, attapulgite, zeolite or bentonite; organic acids such as succinic acid, tannic acid, gallic acid or pentachlorophenol; phenol resins such as phenolformaldehyde (novolac type); and mixture thereof.
  • clay minerals such as acid clay, active clay, attapulgite, zeolite or bentonite
  • organic acids such as succinic acid, tannic acid, gallic acid or pentachlorophenol
  • phenol resins such as phenolformaldehyde (novolac type); and mixture thereof.
  • malachite green lactone which is 3,3-bis-(p-dimethylaminophenyl) phthalide
  • benzoyl leuco methylene blue crystal violet lactone which 3,3-bis(p-dimethylaminophenyl)-6- dimethylamino phthalide
  • Rhodamine B 3-dia1kylamino7-dialkylamino fluoranes
  • 3-methyl- 2,2'-spirobi benzo [f] chromene
  • a color-former sheet is prepared by coating microcapsules containing a colorformer on a support
  • a developer sheet is prepared by coating a developer on a support.
  • the pressuresensitive copying paper used in the present invention, is meant not only a combination of the color-former sheet and the developer sheet, but also a combination of a color-former and a developer coated together on a surface of a support.
  • the light resistance of a color obtained by the color reaction between a color-fomier and a developer depends mainly on the structure of the color. But the light resistance is affected by the developer. Clays such as acid clay are the most widely used developers. The light resistance of a color formed by use of such developer lactam,
  • microcapsule-coated paper i.e. colorformer sheet
  • microcapsule-coated paper i.e. colorformer sheet
  • crystal violet lactone has very poor resistance to light
  • the resulting color readily disappears on being allowed to stand indoors or on exposure to sunlight. Consequently, the color image formed becomes light blue formed from benzoyl leuco methylene blue, and reduces the commercial value of the copying paper produced.
  • 3.-diben zylamin o-7- diethylamino fluorane is used as the coupler.
  • All conventional pressure-sensitive copying paper causes the above defects because a combination of two-type color formers has been used; one type is a rapid-color former and the other type is a slow-color former, and no color-former having good properties to all conditions has been found.
  • an object of the invention is to provide a pressure-sensitive copying paper capable of forming color images of increased lightresistance and Without discoloration and fade.
  • the inventors have found that the above objects can be attained by incorporating a phenothiazine compound soluble in or miscible with an organic solvent for the color former into microcapsules.
  • Phenothiazine compound of the invention must give useful effects to color former and dye thereof under varied atmosphere such as temperature, humidity, sunlight, etc., so it must not form distinct color when contacted with solid acid substance. If it forms distinct color when contacted with solid acid substance, finally obtained color is different from the color formed by only color former because it is a mixed color of both. Accordingly, the color-forming phenothiazine compound such as 3,7-dimethylamino phenothiazine or 3,- 7 -dimethylamino l O-benzoylphenothiazine can not im-. prove the properties of color former or dye thereof.
  • phenothiazine compound I of the invention is defined as a substantially colorless contacted with asolid acid substance.
  • Preferred phenothiazine compound of the invention is represented by the formula,
  • n is O, l or 2; X, Y and Z each is a group having not smaller than O.5 of Hammett constant sigma).
  • an electron-attracting group has a positive value of the Hammett constant and an electron-donating group has a negative value of Hammett constant.
  • the substituents, X, Y and Z have Hammett constant of smaller than O.5 (that is, it is not preferred that the value is 0.6, O.7, 1.0, Hammett constant is generally applied to meta or parasubstituent, but the position thereof is not important in the invention, so long as the Hammett constant is satisfied with the critical value.
  • Z is a hydrogen atom; an alkyl group; an alkyl substituted with aryl, cyano, hydroxy, halogen, amino, alkoxy, alkoxycarbonyl or acyl group; an aryl group; an acyl group; an alkoxycarbonyl group and a formyl group.
  • the preferred substituents, X and Y each is a hydrogen atom, an alkyl group, a halogen atom, a nitro group, an acrylamino group, a hydroxyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an alkylsulfonylamino group and an arylsulfonylamino group.
  • all alkyl groups including an 'alkoxy, acyl, etc. have 1 to 18 carbon atoms, preferably 1 to 5 carbon atoms, and all aryl groups includes phenyl and naphthyl groups.
  • phenothiazine compounds of the invention are phenothiazine, IO-methylphenothiazine, l0-ethylphenothiazine, lO-octadecylphenothiazine, l0-allyl-phenothiazine, l0-benzylphenothiazine, l0-,Bcyanoethylphenothiazine, -[3- hydroxyethyl-phenothiazine, l O-B-chloroethylphenothiazine, lO-B-carboethoxy-phenothiazine, lO-acetyl-phenothiazine, lO-benzoyl-phenothiazine, lO-anisoyl-phenothiazine, l-hydroxyphenothiazine, lmethoxy-phenothiazine, 2-hydroxy-phenothiazine,
  • the phenothiazine compound can be incorporated into the solvent for the color former before or after the color former is dissolved in the solvent, and then the resulting solution is microencapsulated.
  • the phenothiazine compound can be also dissolved in the solvent and microencapsulated.
  • microcapsules are coated on a support such as a paper, a plastic sheet such as polypropylene or polyethylene terephthalate, or a resin-coated sheet such as polyethylene-laminated paper.
  • a pressure-sensitive copying paper of the invention includes an embodiment of a support having coated thereon a microcapsule layer, of which microcapsules contains the phenothiazine compound and the color former, and an embodiment of a support having coated thereon a microcapsule layer including microcapsules which contains the phenothiazine compound and microcapsules which contains the color former.
  • the pressure-sensitive copying paper may include an embodiment of combination with the above two embodiment.
  • microcapsules have about 1 to 500 microns and can be easily obtained by the well known methods disclosed in US. Pat. No. 2,800,457; 2,800,458; 3,429,827; 3,577,515; British Pat. No. 867,797; 989,264; 1,091,076, etc.
  • the phenothiazine compound and/or the color former can be advantageously dissolved in an organic solvent which is preferably immiscible with water.
  • the solvent has preferably a boiling point of higher than C.
  • natural and synthetic oils can be used singly or in combination.
  • an vegetable oil such as cotton seed oil, bean oil or castor oil
  • a synthetic oil such as chlorinated biphenyl, chlorinated terphenyl, alkylated biphenyl, alkylated terphenyl, chlorinated paraffin, chlorinated naphthalene, alkylated naphthalene, kerosene, paraffin or naphthene oil.
  • the color former is a colorless compound capable of forming a color dye when contacted with a solid acid substance. Therefore, the color former can be defined as a dye-precursor.
  • the color formers of the invention can contain those used in the color formation systems based on a reaction between electron-donor and electron-acceptor.
  • the kind of the color former to be used is not critical in this invention and all well-known color formers, for example, disclosed in US. Pat. Nos. 3,501,331; 3,514,310; 3,514,311; 3,540,911; 3,293,060 can be used.
  • Examples of the color former usable in this invention are triarylmethane compounds such as 3,3-bis(p-dimethylaminophenyl)-6- dimethylamino phthalide, i.e., Crystal Violet Lactone (which will be abbreviated as CVL), 3,3-bis(pdimethyl-aminophenyl) phthalide, i.e., malachite green lactone, 3-(p-dimethylaminophenyl)-3-( 1,2- dimethylindol-3-yl )phthalide, 3-( pdimethylaminophenyl )-3-( 2-methylindol-3 yl) phthalide, 3-( p-dimethylaminophenyl )-3-( Z-phenylindol- 3-yl) phthalide, 3,3-bis( 1,2-dimethylindol-3-yl)-5- dimethylaminophthalide, 3,3-bis( l ,2-dimethylindol-3
  • diethylaminofluoran 7-diethylamino-3-(dibenzylamino) fluoran 7-diethylamino-3- (methylbenzylamino) fluoran, 7-diethylamino-3- (chloroethyl-methylamino) fluoran and 7-diethylamino-3-(diethylamino) fluoran;
  • thiazine compounds such as benzoyl leucomethylene blue, and pnitrobenzyl leucomethylene blue
  • spiropyran compounds such as 3-methyl-spiro-dinaphthopyran, 3'ethyl-spiro-dinaphthopyran, 3,3 '-dichloro-spirodinaphthopyran, 3-benzyl-spiro-dinaphthopyran, 3- methyl-naphtho-( 3-methoxybenzo )-spiropyran and 3-propyl-spiro
  • an amount of color former is easily decided by one skilled in the art in relation to an amount of solid acid. Therefore, amounts of color former and solid acid substance are not important in the invention. But, an amount of phenothiazine compound is rather important.
  • the amount of the phenothiazine compound in the invention is about 10 to 200%, preferably to 100% by weight based on the total amount of the color former coated on the support.
  • the solid acid substance can include those mentioned before and those disclosed in U.S. Pat. Nos. 2,777,780; 3,427,180; 3,455,721; 3,466,185; 3,516,845; 3,540,914; 3,634,121; 3,466,256; 3,672,935; 3,682,680; U.S. Ser. Nos. 184,608 and 192,593, etc.
  • the solid acid substance is dissolved or dispersed and coated on such a support as mentioned above, if necessary, together with a wellknown binder such as gum arabic, gelatin, ethyl cellulose, styrene-butadiene copolymer, styrene-butadiene latex, nitrocellulose, methyl-methacrylatebutadiene latex, etc.
  • a wellknown binder such as gum arabic, gelatin, ethyl cellulose, styrene-butadiene copolymer, styrene-butadiene latex, nitrocellulose, methyl-methacrylatebutadiene latex, etc.
  • the solution or dispersion can be coated on the afore-mentioned microcapsule layer provided on a support. Further, it is coated on a support and then the aforementioned microcapsules can be coated thereon.
  • microcapsules and the solid acid substance can be coated by such the coating method as air knife coat ing method, a blade coating method, a roll coating method, and the like, and various printing methods.
  • EXAMPLE 1 Ten parts by weight of acid-treated pigskin gelatin and 10 parts of gum arabic were dissolved in 400 parts by weight of water at 40C. With the addition of 0.2 part by weight of Turkey red oil as an emulsifier, 40 parts by weight of a color-former oil was emulsified into the aqueous solution.
  • the color-former oil had been prepared by dissolving in an oil consisting of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene, 2% by weight, based on the oil, of crystal violet lactone, and then dissolving 2% by weight, based on the oil, of phenothiazine.
  • a 15% aqueous solution of sodium hydroxide was poured to adjust the pH to 9.
  • the addition of sodium hydroxide was performed with utmost care.
  • the mixture was heated for 20 minutes with stirring to raise the temperature to 50C.
  • the resulting capsule dispersion was coated on a base paper having; a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • EXAMPLE 2 To 40 parts by weight of color-former oil consisting of 2% by weight of crystal violet lactone dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was added 2% by weight, based on the oil, of ll0-ethylphenothiazine-5- oxide, and these were microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m and allowed to dry to form a color-former sheet.
  • EXAMPLE 3 To 40 parts by weight of a color-former oil consisting of 2% by weight of crystal violet lactone dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was added 2% by weight, based on the oil, 3-metlnoxy-phenothiazine, and these were microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former.
  • a color-former oil consisting of 2% by weight of crystal violet lactone dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was added 2% by weight, based on the oil, 3-metlnoxy-phenothiazine, and these were microencapsulated in the same manner as set forth in Example 1.
  • COMPARATIVE EXAMPLE 1 A color-former oil consisting of 4 parts by weight of chlorodiphenyl and 1 part of kerosene and 2% by weight of crystal violet lactone was microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a based paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • Example 1 Each of the color-former sheet obtained in Examples 1-3 and Comparative Example 1 was superposed on a test developer sheet, and a pressure of 600 Kg/cm was applied thereto to form a color.
  • the test developer sheet was prepared by the following procedure. Eight parts of 20% sodium hydroxide and a dispersing agent were added to 300 parts of water, and with stirring, parts by weight of acid clay was gradually added. After thorough stirring, the stirring was slowed down, and 20 parts by weight, calculated as solids content, of a styrene-butadiene latex was added gradually. The resulting coating solution was applied to a base paper having a unit weight of 40 g/m in an amount of 10 g/m as solids content, and allowed to dry.
  • the absorption spectrum curve (fresh 5 density designated by A) at a wavelength in the range of 700 to 380 mp. was measured.
  • the absorption spec trum curve of the color-former was also measured after irradiation of sunlight for one hour (density designated by B) and three hours (density designated by C), respectively.
  • the results obtained are shown in FIG. 1, I to IV, in which I refers to the coupler sheet of Example I, II refers to the sheet of Example 2, III refers to the sheet of Example 3, and IV refers to the sheet of Comparative Example 1.
  • the measurement of the absorption spectrum curves was performed by a Beckman spectrophotometer, Type DB.
  • the light resistance of crystal violet lactone was determined by the following formula, and the results are given in Table 1.
  • EXAMPLE 4 In parts by weight of a color-former oil, consisting of 2% by weight of 3-methyl-2,2spirobi(benzo [f] chromene) dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene, was dissolved 2% by weight, based on the oil, of phenothiazine, and these were microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color former sheet.
  • EXAMPLE 5 In 40 parts by weight of a color-former oil consisting of 2% by weight of 3-methyl-2,2-spirobi(benzo [f] chromene) dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of 3-methoxy phenothiazine, and these were microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • a color-former oil consisting of 2% by weight of 3-methyl-2,2-spirobi(benzo [f] chromene) dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of 3-meth
  • COMPARATIVE EXAMPLE 2 A coupler oil consisiting of 2% by weight of 3-methyl-2,2-spirobi(benzo [f] chromene) dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was microencapsulated in the same manner as set forth in Example The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • the light resistance of the color-former was determined in the same way as described in Comparative Test 1. The re- It is seen from the foregoing results that the light resistance of 3-methyl-2,2-spirobi(benzo [f] chromene) is improved and its color change considerably prevented, by the addition of phenothiazine and its derivatrves.
  • EXAMPLE 7 In 40 parts by weight of a color-former oil consisting of 2% by weight of 3-diethylamino fluorance-pnitroanilinolactam dissolved in an oil consisting of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of phenothiazine, and these were microencapsulated in the same manner as set forth in Example I. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • EXAMPLE 8 In 40 parts by weight of a color-former oil consisting of 2% by weight of 3-diethylamino fluorance pnitroanilide dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of 10-ethylphenothiazine-S-oxide, and these were micro-' encapsulated in the same manner as set forth in Example l. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • a color-former oil consisting of 2% by weight of 3-diethylamino fluorance pnitroanilide dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the
  • EXAMPLE 9 In 40 parts by weight of a color-former oi] consisting of 2% by weight of 3-diethylamino fluorane pnitroanilinolactam dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of 3-methoxyphenothiazine, and these were microencapsulated in the same manner as set forth in Example l The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • a color-former oi] consisting of 2% by weight of 3-diethylamino fluorane pnitroanilinolactam dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by
  • COMPARATIVE EXAMPLE 3 Forty parts by weight of a color-former oil consisting a 2% by weight of 3*diethylamino-fluorane pnitroanilinolactam dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and alllowed to dry to form a color-former sheet.
  • EXAMPLE 10 EXAMPLE 11 In 40 parts by weight of a color-former oil consisting of 2% by weight of 3-dibenzylamino-7- diethylaminofiuorane dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of lO-ethylphenothiazine-S-oxide, and these were microencapsulated in the same manner as set forth in Example 1. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m and allowed to dry to form a color-former sheet.
  • a color-former oil consisting of 2% by weight of 3-dibenzylamino-7- diethylaminofiuorane dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved
  • EXAMPLE 12 In 40 parts by weight of a color-former oil consisting of 5% by weight of 3-dibenzylamino-7- diethylaminofiuorane dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based on the oil, of 7-methoxy-phenothiazine, and these were microencapsulated in the same manner as set forth in Example I. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • a color-former oil consisting of 5% by weight of 3-dibenzylamino-7- diethylaminofiuorane dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was dissolved 2% by weight, based
  • COMPARATIVE EXAMPLE 4 Forty parts by weight of a color-former oil consisting of 2% by weight of 3-dibenzylamino-7- diethylaminofiuorane dissolved in an oil composed of 4 parts by weight of chlorodiphenyl and 1 part by weight of kerosene was microencapsulated in the same manner as set forth in Example I. The resulting microcapsule dispersion was coated on a base paper having a unit weight of 40 g/m in an amount of 6 g/m as solids content, and allowed to dry to form a color-former sheet.
  • COMPARATlVE TEST 4 Each of the color-former sheets obtained in Examples -12 and Comparative Example 4 was superposed on the test developer sheet described in Comparative Test 1, and a color was formed by applying a pressure of 600 Kglcm After allowing the color image to stand for one hour in a dark place, the absorption spectrum curve of the color image as a wavelength in the range of 700 to 380 mp. (fresh density designated by A) was measured. The absorption spectrum curve of the coupler was also measured after subjecting it to irradiation of sunlight for one hour (density designated by B) and three hours (density designated by C), respectively. The results are shown in FIG.
  • a pressure-sensitive copying paper comprising a support having coated thereon a layer of microcapsules containing a substantially. colorless electron donor 001- I or-forming compound capable of forming a distinct color when contacted with an electron acceptor solid acid, said layer containing a colorless phenothiazene compound incapable of forming a distinct color when contacted with the electron acceptor solid acid, the amount of said phenothiazene compound being 10 to 200% by weight based on the color former, said phenothiazene compound being represented by the formula,
  • n O, l or 2
  • X, Y and Z each is a hydrogen atom, an alkyl group, a halogen atom, a nitro group, an acylamino group, a hydroxyl group, an alkoxy group, an acyloxy group, an alkoxycarbonyl group, an alkylsulfonylamino group or an arylsulfonylamino group, said alkyl group and alkyls attached to the other substituents having 1 to 8 carbon atoms, and all aryl groups being phenyl or naphthyl groups.

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  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
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US378105A 1970-06-13 1973-07-11 Pressure-sensitive copying paper Expired - Lifetime US3900217A (en)

Priority Applications (6)

Application Number Priority Date Filing Date Title
CA115,054A CA944150A (en) 1970-06-13 1971-06-08 Pressure-sensitive copying paper
GB2761171A GB1338784A (en) 1970-06-13 1971-06-11 Colour former compositions for pressure-sensitive recording
FR7121285A FR2096242A5 (enrdf_load_stackoverflow) 1970-06-13 1971-06-11
DE2129467A DE2129467B2 (de) 1970-06-13 1971-06-14 Druckempfindliches Kopierpapier
BE768496A BE768496A (fr) 1970-06-13 1971-06-14 Papier a reproduire sensible a la pression
US378105A US3900217A (en) 1970-06-13 1973-07-11 Pressure-sensitive copying paper

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JP45051116A JPS4843294B1 (enrdf_load_stackoverflow) 1970-06-13 1970-06-13
US15283171A 1971-06-14 1971-06-14
US378105A US3900217A (en) 1970-06-13 1973-07-11 Pressure-sensitive copying paper

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BE (1) BE768496A (enrdf_load_stackoverflow)
CA (1) CA944150A (enrdf_load_stackoverflow)
DE (1) DE2129467B2 (enrdf_load_stackoverflow)
FR (1) FR2096242A5 (enrdf_load_stackoverflow)
GB (1) GB1338784A (enrdf_load_stackoverflow)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4132436A (en) * 1976-02-04 1979-01-02 Fuji Photo Film Co., Ltd. Recording material
US4379721A (en) * 1980-03-14 1983-04-12 Spezial-Papiermaschinenfabrik August Alfred Krupp Gmbh & Co. Pressure sensitive recording materials
US4549192A (en) * 1984-07-31 1985-10-22 The Hilton-Davis Chemical Co. Electrochromic marking systems
US4551740A (en) * 1984-07-31 1985-11-05 The Hilton-Davis Chemical Co. Electrochromic and marking systems
US4561001A (en) * 1984-07-31 1985-12-24 The Hilton-Davis Chemical Co. Electrochromic marking systems
US4570171A (en) * 1984-07-31 1986-02-11 The Hilton-Davis Chemical Co. Electrochromic marking systems

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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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US2915415A (en) * 1957-06-19 1959-12-01 Caribonum Ltd Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3427180A (en) * 1965-03-31 1969-02-11 Ncr Co Pressure-sensitive record system and compositions
US3501331A (en) * 1967-01-27 1970-03-17 Fuji Photo Film Co Ltd Pressure sensitive fluoran derivative containing copying paper
US3540909A (en) * 1967-01-30 1970-11-17 Ncr Co Pressure sensitive recording sheets employing 3,3-bis(phenylindol - 3-yl) phthalide
US3649649A (en) * 1967-07-10 1972-03-14 Nisso Kako Co Ltd Fluoran derivatives and preparation thereof
US3769062A (en) * 1970-07-08 1973-10-30 Fuji Photo Film Co Ltd Pressure-sensitive recording paper

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US2915415A (en) * 1957-06-19 1959-12-01 Caribonum Ltd Leucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3427180A (en) * 1965-03-31 1969-02-11 Ncr Co Pressure-sensitive record system and compositions
US3501331A (en) * 1967-01-27 1970-03-17 Fuji Photo Film Co Ltd Pressure sensitive fluoran derivative containing copying paper
US3540909A (en) * 1967-01-30 1970-11-17 Ncr Co Pressure sensitive recording sheets employing 3,3-bis(phenylindol - 3-yl) phthalide
US3649649A (en) * 1967-07-10 1972-03-14 Nisso Kako Co Ltd Fluoran derivatives and preparation thereof
US3769062A (en) * 1970-07-08 1973-10-30 Fuji Photo Film Co Ltd Pressure-sensitive recording paper

Cited By (6)

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Publication number Priority date Publication date Assignee Title
US4132436A (en) * 1976-02-04 1979-01-02 Fuji Photo Film Co., Ltd. Recording material
US4379721A (en) * 1980-03-14 1983-04-12 Spezial-Papiermaschinenfabrik August Alfred Krupp Gmbh & Co. Pressure sensitive recording materials
US4549192A (en) * 1984-07-31 1985-10-22 The Hilton-Davis Chemical Co. Electrochromic marking systems
US4551740A (en) * 1984-07-31 1985-11-05 The Hilton-Davis Chemical Co. Electrochromic and marking systems
US4561001A (en) * 1984-07-31 1985-12-24 The Hilton-Davis Chemical Co. Electrochromic marking systems
US4570171A (en) * 1984-07-31 1986-02-11 The Hilton-Davis Chemical Co. Electrochromic marking systems

Also Published As

Publication number Publication date
BE768496A (fr) 1971-11-03
CA944150A (en) 1974-03-26
DE2129467B2 (de) 1974-08-15
FR2096242A5 (enrdf_load_stackoverflow) 1972-02-11
DE2129467A1 (de) 1971-12-23
DE2129467C3 (enrdf_load_stackoverflow) 1975-04-03
GB1338784A (en) 1973-11-28

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