Classifications

• • 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
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B11/00—Diaryl- or thriarylmethane dyes
  • C09B11/04—Diaryl- or thriarylmethane dyes derived from triarylmethanes, i.e. central C-atom is substituted by amino, cyano, alkyl
  • C09B11/26—Triarylmethane dyes in which at least one of the aromatic nuclei is heterocyclic

Definitions

• a pressure-sensitive copying sheet comprising an adsorbent solid acid and a microencapsulated color former capable of forming a distinct color when reacted with said adsorbent solid acid coated on the same or different surface of support or supports, said microcapsules containing an organic solvent having dissolved therein as a color former at least one phthalide compound represented by the following formula:
• the present invention relates to a pressure-sensitive copying paper, more particularly to a pressure-sensitive copying paper having a microcapsule layer containing a novel phthalide compound as a color former.
• Pressure-sensitive copying papers generally comprise a transfer sheet having thereon a layer of fine capsules containing therein a solution of an electron donating colorless organic compound (hereinafter the organic compound is called the color former) in an organic solvent, and a receiving sheet, having thereon a layer of an electron-accepting solid.
• a suitable binder is usually present to contain the solid.
• Pressure-sensitive copying paper systems which consist of the aforesaid transfer sheet (hereinafter this sheet is called the upper sheet) and a receiving sheet (hereinafter this sheet is called the lower sheet) and an intermediate sheet (hereinafter this sheet is called the middle sheet).
• the middle sheet usually has coated, on opposite surfaces, a layer of microcapsules containing the color former solution and a layer of the solid acid and a binder.
• a recording sheet which may be prepared 2' by coating the above described microcapsu'les and the absorbent solid acid on the same surface of afsupport.
• solid acids are usually used, e.g. acid clay, attapulgite, zeolite, bentonite, kaolin, acid polymers such as phenolic resin and the like.
• organic solvents for dissol-w'ng the color former are ethylene glycol, chlorobenzene, and chlorodiphenyl.
• Crystal Violet Lactone has widely been used as a purple-color former. Although Crystal Violet Lactone is immediately colored purple-blue when it is brought into contact with an electron-accepting solid acid, it suffers from the following disadvantages: the color exhibits poor light fastness and the purple-blue vanishes upon contact with water.
• Benzoyl Leuco Methylene Blue has also been used as a blue-color former.
• the color former When the color former is brought into contact with an electron accepting solid acid, a blue color having good light fastness is formed but this color former has the disadvantage that it takes a long period of time to color.
• a pressure-sensitive copying paper containing as a color former the phthalide compound represented by the general formula I wherein R represents a hydrogen atom, a methyl group, an ethyl group, an acetyl group, or a benzyl group; R represents a methyl group, or an ethyl group; R represents a hydrogen atom, a methyl group, or an ethyl group; R represents a methyl group, or a phenyl group; X represents a methyl group, methoxy group, or an ethoxy group; Y represents a hydrogen atom, a chlorine atom, a bromine atom, or a dimethylamino group; and n is an integer from 1 to 4.
• An object of the present invention is, therefore, to provide pressure-sensitive copying papers containing as a color former the phthalide compound represented by the aforesaid general formula which is immediately colored when it is brought into contact with a solid acid to provide a stable purple or blue color having excellent light fastness and water resistance.
• An object of this invention is to provide pressure-sensitive copying papers which can be colored various colors by using the phthalide compound represented by the afore- I GO OH X I R1 ⁇ I R2 R4 Yn a COOH OH R
• the phthalide compound used in this invention represented by the general formula described above may be prepared by reacting the corresponding benzophenone carboxylic acid and an indole or the corresponding benzoylindole and an aromatic amine for 1-10 hours at a reaction temperature of 50130 C., in the presence of a condensing agent such as acetic anhydride or phosphorus oxychloride using, if necessary, a volatile inert organic solvent such as benzene, or chloro-benzene, pouring the reaction mixture in ice-cooled water or a dilute aqueous solution of an acid such as hydrochloric acid to hydrolyze the condensing agent, adding a volatile inert solvent such as benzene or chlorobenzene to extract the
• PRODUCTION EXAMPLE 1 A mixture of 2.0 g. of 1,2-dimethyl-3-(2'-carboxybenzoyl)-indole, 1.6 g. of N,N-diethyl-m-toluidine, and 14.3 g. of acetic anhydride was heated to 50-55 C. for hours, with stirring, to cause the reaction. The reaction mixture was poured in 400 g. of ice-water to hydrolyze the acetic anhydride, and after adding thereto 100 g. of benzene, the pH of the mixture was adjusted to 12 by adding an aqueous solution of sodium hydroxide.
• the benzene layer formed was recovered by decantation and after treating the benzene layer with activated carbon, benzene was distilled off under reduced pressure. Then, by recrystallizing the residue from petroleum ether, 2.0 g. of 3-(2- methyl-4'-diethylaminophenyl) 3 (1',2'-dimethylindol- 3-yl)-phthalide represented by the following formula was obtained as a white color former having a melting point of 180-182 C. When a benzene solution of the color former thus prepared was brought into contact with an acid cl ay layer coated on a paper; the color former immediately colored blue. j
• PRODUCTION-EXAMPLE 3 To 15 g. of monochlorobenzene were added 2.0 g. of 1,2-dimethyl-3-(2'-carboxybenzoyl)-indole and 1.1 g. of N-methyl-m-anisidine and then 1.6 g. of phosphorus oxychloride was further added to the mixture.
• the resultant mixture was heated to -105 C. for 2 hours with stirring to cause the reaction.
• the reaction mixture was poured in 400 g. of ice-waterto hydrolyze the phosphorus oxychloride, and after adding thereto 100 g. of monochlorobenzene, the pH of the mixture was adjusted to 12 by adding an aqueous solution of sodium hydroxide.
• the monochlorobenzene layer formed was recovered by decantation and after treating the monochlorobenzene layer with activated carbon, monochlorobenzene was distilled oil under reduced pressure. Then, by recrytallizing the residue from petroleum ether, 1.6 g.
• PRODUCTION EXAMPLE 4 5,6,7-tetrachlorophthalide represented by the following formula a I Y O CH3 as a liglit g reen'colori'former having a melting point of 2 51 253. C. When a benzene solution of the color former was brought into' contact -withan acid clay layer coated on paper, the color former immediately colored blue.
• PRODUCTION EXAMPLE 5 as a white color former having a melting point 193l94 C.
• a benzene solution of the color former was brought into contact with an acid; clay layer coated on a paper, the color former immediately colored violet-blue.
• PRODUCTION EXAMPLE 6 A mixtureof 1.2 g. of 1-methyl-2phenyl-3-(2-carboxy- 324f,5',6-tetrabromobenzoyl)-indole, 0.5 g. of N,N-diethyl-m-phenetidine, and 5.0 g. of acetic anhydride was heated to 80-85 C. for 3 hours, with stirring, to cause thereaction. Then, the reaction mixture wa treated as in Production Example 1 to provide 1.1 g.
• PRODUCTION EXAMPLE 7 .To .15 -g..of..monochlorobenzene were added 2.3 g. of
• reaction mixture was treated as in Production Example 3 to provide 1.6 g. of 3-(2'-ethoxy-4'-diethylaminophenyl) 3 (2' methylindol 3' yl)-phthalide represented by the following formula CgHs as a light-yellow color former having a melting point of 223-225 C.
• CgHs 3-(2'-ethoxy-4'-diethylaminophenyl) 3 (2' methylindol 3' yl)-phthalide represented by the following formula CgHs as a light-yellow color former having a melting point of 223-225 C.
• PRODUCTION EXAMPLE 8 A mixture of 2.0 g. of 1,2 dimethyl 3 (2' canboxybenzoyl)-indole, 1.2 g. of N-acetyl-N-methyl-m-anisidine, and 20.0 g. of acetic anhydride was heated to 90 C. for 2 hours, with stirring, to cause the reaction. The reaction mixture was then treated as in Production Example 1 to provide 2.0 g. of 3-(2'-methoxy-4-N-acetyl-N- methylamino-phenyl) 3 (1',2' dimethylindol 3' y1)- phthalide represented by the following formula as a white color former having a melting point of 245- 253 C. When a benzene solution of the color former was brought into contact with an acid clay layer coated on a paper, the color former immediately colored violetblue.
• PRODUCTION EXAMPLE 9 as a. light-yellow color formerhaving a melting, point of -l97 C.
• a benzene solution of the colorformer was brought into contact.with an acid. clay layer coated on a paper, the color former immediately colored violetblue.
• acid clay As the electron accepting solid acid, acid clay, attapulgite, zeolite, bentonite, kaolin, acid polymers such as phenolic resin etc. are used.
• the pressure-sensitive copying paper of this invention in which the phthalide compound represented by the aforesaid general formula is used as a color former is colorless or has a very faint yellow character before use, but when the pressure-sensitive copying paper subjected to localized pressure by, e.g., handwriting or typewriting, purple or blue coloring instantly occurs. Moreover, the color density of the color thus formed is high, and the light and water resistance thereof are excellent.
• a pressure-sensitive copying paper capable of providing various colors copying can be obtained unaccompanied by any adverse effect, such as; desensitization.
• Example 1 In 100 g. of trichlorodiphenyl there was dissolved 2.5 g. of 3-(2-methyl 4' diethylaminophenyl)-3-(1',2'-dimethylindol-3-yl)-phthalide, and then 20 g. of gum arabic and 160 g. of water were added to the solution at 50 C. followed by emulsification. To the emulsion were added 20 g. of acid-treated gelatin and 160 g. of water and thereafter the pH of the emulsion was adjusted to 5 by adding acetic acid while stirring. Then, 500 g.
• the color density of the color former thus formed was high. Moreover when the blue color former was placed for an extended period of time in a chamber free from the direct rays of the sun, no discoloring was observed. When it was exposed to the direct rays of the sun for an extended period of time, fading was scarcely observed. Furthermore, the color former thus colored exhibited excellent water resistance.
• Example 2 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 1.5 g. of 3- (2'-ethoxy 4' diethylaminophenyl)-3-(1,2'-dimethylindol-3'-yl) phthalide was used as the color former.
• the color former When the upper sheet was placed on the lower sheet so that the microcapsule layer was brought into intimate contact with the acid clay layer of the lower sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer thus pressed immediately colored violet-blue.
• the violet-blue color former Upon testing the violet-blue color former for light fastness, it was confirmed that the color former had sufficient stability for practical use.
• the violet-blue color former also was excellent in water resistance.
• Example 3 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 1.5 g. of 3- (2-methoxy- 4 methylaminophenyl)-3-(l',2-dimethylindol-3'-yl)-phthalide was used as the color former.
• the color former When the upper sheet was placed on the lower sheet so that the microcapsule layer was brought into intimate contact with the acid clay layer of the under sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer thus pressed immediately colored violet.
• the color former thus colored violet With respect to light fastness, it was confirmed that the violet color former had sufficient stability for practical use.
• Example 4 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 1.5 g. of 3- (2-methoxy 4 dimethylaminophenyl)-3-(1',2'-dimeth ylindol-3'-yl)-4,5,6,7-tetrachlorophthalide was used as the color former.
• the color former When the upper sheet was placed on the lower sheet so that the microcapsule layer was brought into intimate contact with the acid clay layer of the lower sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer thus pressed were immediately colored blue.
• the blue color former had suflicient stability for practical use.
• the blue color former was also excellent in water resistance.
• Example 5 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 1.5 g. of 3- (2-ethoxy 4' diethylaminophenyl)-3-(l',2dimethylindol-3-yl)-5-dimethylaminophthalide was used as the color former.
• the color former When the upper sheet was placed on the lower sheet so that the microcapsule layer of the upper sheet was brought into intimate contact with the acid clay layer of the lower sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer thus pressed immediately colored violet-blue.
• the violet-blue color former By testing the violet-blue color former with respect to light fastness, it was confirmed that the violet-blue color former violetblue had sufiicient stability for practical use.
• the violetblue color former was also excellent in water resistance.
• Example 6 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 2.0 g. of 3- (2'-ethoxy 4 diethylaminophenyl) 3 5 (Imethyl-2'- phenylindol-3'-yl)-4,5,6,7-tetrabromophthalide was used as the color former.
• the color former When the upper sheet was placed on the lower sheet so that the microcapsule layer of the upper sheet was brought into intimate contact with the acid clay layer of the lower sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer that pressed immediately colored blue.
• the colored color former also was excellent in water resistance.
• Example 7 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 2.0 g. of 3-(2'ethoxy-4'-diethylaminophenyl)-3 (2' methylindol- 3'-yl)-phthalide was used as the color former.
• the upper sheet was placed on the lower sheet so that the microcapsule layer of the upper sheet was brought into intimate contact with the acid clay layer of the lower sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer thus pressed immediately colored violet.
• the violet color former By testing the violet color former with respect to light fastness, it was confirmed that the colored color former had suflicient stability for practical use.
• Example 8 A colorless upper sheet was prepared following the same procedure as in Example 1 except that 2.0 g. of 3 (2' methoxy 4' N-acetyl-N-methylaminophenyl)-3- (1',2'-dimethylindol-3'-yl)-phthalide was used as the color former.
• the upper sheet was placed on the lower sheet so that the microcapsule layer of the upper sheet was brought into intimate contact with the acid clay layer of the lower sheet and localized pressure was applied thereto by handwriting, the areas of the acid clay layer thus pressed immediately colored violet-blue.
• the violet-blue color former By testing the violet-blue color former with respect to light fastness, it was confirmed that the colored color former had sulficient stability for practical use.
• Example 9 An upper sheet was prepared following the same procedure as in Example 1 except that 0.5 g. of 3-(2'-methoxy- 4 N methyl N benzylaminophenyl)-3-(1'-ethyl2'- phenylindol-3'-yl)-phthalide, 0.8 g. of o-hydroxybenzalacetophenone, 0.8 g. of Rhodamine B-Anilino-Lactam, 0.2 g. of Crystal Violet Lactone, and 0.2 g. of Malachite Green Lactone were used as the color formers.
• a pressure-sensitive copying sheet comprising an adsorbent solid acid and a microencapsulated color former capable of forming a distinct color when reacted with said adsorbent solid acid coated on the same or difierent surface of support or supports, said microcapsules containing an organic solvent having dissolved therein a phthalide color former comprising at least one phthalide compound represented by the general formula wherein R represents a member selected from the group consisting of a hydrogen atom, a methyl group, an ethyl group, an acetyl group and a benzyl group; R represents a member selected from the group consisting of a methyl group and an ethyl group; R represents a member selected from the group consisting of a hydrogen atom,
• R represents a member selected from the group consisting of a methyl group and a phenyl group
• X represents a member selected from the group consisting of a methyl group, a methoxy group and an ethoxy group
• Y represents a member selected from the group consisting of a hydrogen atom, a chlorine atom, a bromine atom and a dimethylamino group
• n is an integer from 1 to 4.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Color Printing (AREA)
• Indole Compounds (AREA)
• Heat Sensitive Colour Forming Recording (AREA)

Applications Claiming Priority (1)

Publications (1)

Family

ID=14774184

Family Applications (1)

Country Status (6)

Cited By (13)

Families Citing this family (5)

• 1970
  • 1970-12-28 JP JP45119950A patent/JPS4916726B1/ja active Pending
• 1971
  • 1971-12-08 IE IE1553/71A patent/IE36853B1/xx unknown
  • 1971-12-15 GB GB5836071A patent/GB1347330A/en not_active Expired
  • 1971-12-21 DE DE2163658A patent/DE2163658C3/de not_active Expired
  • 1971-12-23 ES ES398650A patent/ES398650A1/es not_active Expired
  • 1971-12-23 US US00211757A patent/US3829322A/en not_active Expired - Lifetime

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