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Publication numberUS3873340 A
Publication typeGrant
Publication dateMar 25, 1975
Filing dateJul 27, 1972
Priority dateJul 27, 1972
Publication numberUS 3873340 A, US 3873340A, US-A-3873340, US3873340 A, US3873340A
InventorsKimura Shiro, Miyazawa Yoshihide, Motohashi Katsuichi, Ozutsumi Minoru
Original AssigneeHodogaya Chemical Co Ltd
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Pressure-sensitive copying paper containing phenoxazine compounds
US 3873340 A
Abstract
A pressure-sensitive copying paper comprising an adsorbent solid acid and a microencapsulated color former capable of forming a distinct color when reacted with the adsorbent acid coated on the same or a different surface of a support or supports, the microencapsulated color former being at least one phenoxazine compound represented by the formula WHEREIN R1, R2, R3, R4 and Y are as defined hereinafter, is disclosed.
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United States Patent [1 1 Miyazawa et al.

[4 1 Mar. 25, 1975 PRESSURE-SENSITIVE COPYING PAPER CONTAINING PHENOXAZINE COMPOUNDS [75] Inventors: Yoshihide Miyazawa; Minoru Ozutsumi; Katsuichi Motohashi, all of Tokyo; Shiro Kimura, Kanagawa, all of Japan [73] Assignee: Hodogaya Chemical Co., Ltd.,

Tokyo, Japan [22] Filed: July 27, 1972 [21] Appl. No.: 275,583

[52] US. Cl 117/368, 117/36.2, 260/243 A,

[51] llnt. C1 B4lm 5/16 [58] Field of Search 117/362, 36.8; 260/243 A,

[56] References Cited UNITED STATES PATENTS 2,783,227 2/1957 Adams et a1 260/243 A 2,783,228 2/1957 Adams et al 260/243 A 2,915,415 12/1959 Francis et 211v 260/243 A 3,427,180 2/1969 Phillips 117/362 3,536,517 10/1970 Heuvel et al 117/368 Primary ExaminerWilliam D. Martin Assistant Examiner-Bernard D. Pianalto Attorney, Agent, or Firm-Sughrue, Rothwell, Mion, Zinn & Macpeak [57] ABSTRACT A pressure-sensitive copying paper comprising an ad sorbent solid acid and a microencapsulated color former capable of forming a distinct color when reacted with the adsorbent acid coated on the same or a different surface of a support or supports, the microencapsulated color former being at least one phenoxazine compound represented by the formula wherein R R R R and Y are as defined hereinafter, is disclosed.

2 Claims, N0 Drawings PRESSURE-SENSITIVE COPYING PAPER CONTAINING PI-IENOXAZINE COMPOUNDS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a pressure-sensitive copying paper and, more particularly, to a pressuresensitive copying paper having a microcapsule layer containing a novel phenoxazine compound as a color former.

2. Description of the Prior Art 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 referred to as color former") in an organic solvent, and a receiving sheet having thereon a layer of an electron accepting solid. A suitable binder is generally used for coating the solid.

When both sheets are put together in such a manner that an electron donating layer is brought into contact with an electron accepting layer and localized pressure is applied to the combination of sheets by handwriting or typcwriting, the capsules are ruptured and the colorless color former contained in the capsules is adsorbed by the electron accepting solid, which is usually a solid acid, to form a color.

Pressure-sensitive copying paper systems comprising the aforesaid transfer sheet (hereinafter referred to as upper sheet") and a receiving sheet (hereinafter referred to as lower sheet) and an intermediate sheet (hereinafter referred to as middle sheet) are also known. In these systems the middle sheet is usually coated, on opposite surfaces, with a layer of microcapsules containing a color former solution and with a layer of a solid acid and a binder, respectively.

Another type of pressure-sensitive copying system is a recording sheet which can be prepared by applying the above described microcapsules and the adsorbent solid acid on the same surface of a support.

The solid acid used in the conventional type of pressure-sensitive copying papers includes active clay substances such as acid clay, atapalgite, zeolite, bentonite and the like, solid organic acids such as succinic acid, tannic acid, benzoic acid and the like, and acidic organic polymers such as phenol-formaldehyde polycondensates, phenol-acetylene copolymers, styrene-maleic anhydride copolymers containing residual acidic radicals, salicylic acid-formaldehyde polycondensates and the like. The organic solvent for dissolving the color former which is conventionally used includes, for example, ethylene glycol, chlorobenzenes and chlorobiphenyls.

Benzoyl leuco methylene blue is well known as a color former forming a blue color. Benzoyl leuco methylene blue slowly forms a blue color on a lower sheet when an upper sheet having the benzoyl leuco methylene blue thereon is superposed on a lower sheet coated with an active clay substance such as acid clay and localized pressure is applied to the assembly by, e.g., handwriting. However, this compound does not form a clear blue color when a lower sheet coated with an acidic organic polymer such as a phenol-formaldehyde polycondensate is used. It has, therefore, strongly been desired to develop pressure-sensitive copying papers which are capable fo forming a blue color with an excellent fastness to light even on a lower sheet coated with the above described acidic organic polymer, because such pressure-sensitive copying papers are expected to be useful in a wide variety of utilities.

An object of the present invention is, therefore, to provide pressure-sensitive copying papers containing as a color former a phenoxazine compound which rapidly forms a stable blue color having excellent light fastness and water resistance when it is brought into contact with a solid acid.

Another object of the present invention is to provide pressure-sensitive copying papers which can be colored various colors by using a phenoxazine compound in combination with other known color formers.

SUMMARY OF THE INVENTION According to the present invention, there is provided a pressure-sensitive copying paper containing as a color former a phenoxazine compound represented by the formula wherein R and R each represents a lower alkyl group; R represents a lower alkyl or a phenyl group; R, represents a hydrogen atom or a methyl group; and Y is selected from the group consisting of alkyl, alkenyl, styryl, benzyl, phenoxymethylene, phenyl, naphthyl, fury], thienyl, pyridyl and quinolyl groups in which the styryl, benzyl, phenoxymethylene, phenyl and naphthyl groups may be substituted in the nucleus thereof by one of a lower alkyl, a lower alkoxy, a di-lower-alkylamino, a hydroxy, a chloro or a nitro group and the quinolyl group may be substituted in 2-position by either of a lower alkyl or a phenyl group.

DETAILED DESCRIPTION OF THE INVENTION As the result of detailed investigations on color formers capable of forming a blue color on a lower sheet coated with an acidic organic polymer as a solid acid, it was found that, a blue color having an excellent light fastness is gradually formed on a lower sheet when 10- calized pressure is applied by, for example, handwriting to an upper sheet coated with the phenoxazine compound represented by the above formula (I) as a color former superposed on a lower paper coated with an acidic organic polymer, active clay substance or a mixture thereof as a solid acid. It was also found that any desirable color having an excellent light fastness can be formed on a lower sheet when localized pressure is applied by, for example, handwriting to an upper sheet coated with the phenoxazine compound of the above formula (I) in combination with a known color former as a color former superposed on a lower sheet coated with an acidic organic polymer, active clay substance or a mixture thereof as a solid acid.

Representative examples of the phenoxazine compounds of the formula (I) which are particularly useful in the pressure-sensitive copying paper of the present -Continued Color Substituents Chemical Name Former R R R R Y No l8 C H (3 H CH CH 3 Diethylamino-Y-dimethylamino- 8-methyl-l0- l-naphthoyl phenoxazine N 19 0 1-1 .C H CH CH 5-Diechylamino-7-dimethyl OH amino-S-methyl-JLO-(B- hydroxy-2-naphthoyl phenoxazine No.20 C H C H n-C H H Q 00 5-D.iethylamino7di-n- 2 5 2 5 4 9 H3 butylamino-lO-(p-methoxylbenzoyl -phenoxazine No.21 CH 0 1-1 H G OCH 3-(N-Mechyl-N-phenylamino)- 7-diethylamino-lO-(p- The compounds represented by the above formula (I) can be prepared by reacting 1 mole ofa leuco compound represented by the formula (II) wherein R R R and R are as defined above with respect to the formula (I), with l.0 to 5.0 moles of an acid halide represented by the formula (lll).

(ill) wherein X is a halogen atom and Y is as defined above with respect to the formula (I), in the presence of 1.0 to 10.0 moles of an acid acceptor such as sodium hydroxide, sodium carbonate, pyridine or triethylamine in a volatile organic inert solvent such as chloroform, benzene, toluene or chlorobenzenes or a mixture of such a volatile organic inert solvent and water, optionally while passing gaseous nitrogen through the reaction mixture, at a reaction temperature of from 30 to 130C for a period of from 1 to 5 hours. After completion of the reaction, the organic solvent layer is separated, and is treated with a 3 to l0% by weight aqueous hydrogen peroxide solution, washed with water and distilled under reduced pressure to remove any residual organic solvent to obtain the desired color former having the formula (I). If necessary, the color former thus obtained can further be purified, for example, by recrystallization.

The preparation of the individual color formers as listed in the previous table are illustrated by the following production examples in which all parts given are by weight unless otherwise indicated.

PRODUCTION EXAMPLE 1 Preparation of Color Former No. l

A mixture of 2.8 parts of 3,7-bis(diethylamino)- phenoxazine, 2.4 parts of acetyl chloride and 3.4 parts methoxybenzoyl phenoxazine of pyridine was heated at a reaction temperature of from 50 to'60C for 2 hours in 100 parts of chloroform. Thereafter the mixture was treated with a 3% aqueous hydrogen peroxide solution and thoroughly washed with water. The chloroform layer was then separated and treated with an activated carbon, distilled under reduced pressure to remove the residual chloroform and recrystallized from ethyl alcohol to obtain 2.5 parts of a light brown-colored compound having a melting point of l46l47C. A solution of the resulting compound in benzene slowly turned blue when brought into contact with an acid clay or a phenolformaldehyde polycondensate coated on a paper.

The same color former was also obtained by repeating the above procedure using acetyl bromide in place of acetyl chloride.

PRODUCTION EXAMPLE 2 Preparation of Color Former No. 6

To a mixture of 60 parts of toluene and 50 parts of water were added 3.2 parts of 3,7-bis(diethylaminophenoxazine and 4.8 parts of benzoyl chloride, followed by the addition of 14.5 parts of a 17% aqueous sodium hydroxide solution. The mixture was then heated at a reaction temperature of from 50 to 55C for 3 hours and thereafter worked-up in the same manner as described in Production Example 1 to obtain 3.7 parts of a light yellow-colored color former having a melting point of l23-l25C. A solution of the resulting color former in benzene slowly turned blue when brought into contact with an acid clay or a phenolformaldehyde condensate coated on a paper.

PRODUCTION EXAMPLE 3 Preparation of Color Former No. 2|

To a mixture of 100 parts of toluene and parts of water were added 3.6 parts of 3-(N-phen \'l-N- methyl-amino)-7-diethylamino-phenoxazine and 6.8 parts of p-niethoxybenzoyl chloride. followed by the addition of 14.5 parts of a I79? aqueous sodium hydroxide solution. The mixture was then heated at a reaction temperature of from 55 to 60C for 2 hours and thereafter worked-up in the same manner as described in Production Example 1 to obtain 4.0 parts of a light yellow-colored compound having a melting point of 14l-143C. A solution of the resulting compound in benzene slowly turned blue upon contact with an acid clay or a phenolformaldehyde condensate coated on a paper.

PRODUCTION EXAMPLE 4 Preparation of Color Former Nos. 2 to 5, 7 to 13 and 17 to 20 Each of the Color Formers Nos. 2 to 5, 7 to 13 and 17 to 20 was prepared in a similar manner as described in Production Example 2 but using appropriate starting compounds of the formulae (I1) and (Ill). The color formers thus obtained were slightly colored crystals having melting points and an appearance as shown in the following table.

Color Melting Point Appearance of Crystals Former No.2 110 112 Light brown powder No.3 I34 135 Light yellow powder No.4 134 136 Light brown powder No.5 125.5-127 Pale white powder No.7 122 124 Light yellowish brown powder No.8 124.5-126 Light yellow powder No.9 162 163 Pale white powder No.10 85 90 Light green powder No.1 1 142 143 Light brown powder No.l2 l 19 120 Light yellowish green powder No.13 163 166 Light yellow powder No. I 7 121 123 Light yellow powder No.18 103 105 Light yellowish green powder No.19 103 107 Light green powder No.20 92 93 Light yellow powder PRODUC TlON EXAMPLE Preparation of Color Former Nos. 14 to 16 To a mixture of 150 parts of toluene and parts of triethylamine were added under a nitrogen stream 3.2 parts of 3,7-bis(diethylamino)-phenoxazine and the corresponding acid halide, i.e., 5.3 parts of nicotinoyl chloride for Color Former No. 14, 5.3 parts of isonicotinoyl chloride for Color Former No. 15, or 9.8 parts of 2-phenylcinchonoyl chloride for Color Former No. 16. The reaction mixtures in each instance was heated at a reaction temperature of from 50 to 55C for 2 hours under a nitrogen stream and thereafter workedup in the same manner as described in Production Example l to obtain the desired color formers. i.e., 3.8 parts of Color Former No. 14, 3.0 parts of Color Former No. or 4.2 parts of Color Former No. 16, as slightly colored crystals in each instance. The melting points and appearance of the color formers thus obtained are shown in table below.

In preparing pressure-sensitive copying papers using the phenoxazine compounds represented by the formula (l) as color formers, the well-known process disclosed in US. Pat. Nos. 2,800,457 and 2.800.458, Le. a process which utilizes the phenomenon of complex coacervation can advantageously be employed. In this process, the color former is generally used in the amount of from 0.5 to 5.0% by weight relative to the amount of an organic solvent such as ethylene glycol, chlorobenzene or chlorobiphenyl as previously described.

The preparation of pressure-sensitive copying papers using some of the color formers represented by the formula (l) is illustrated in the following examples, in which all parts given are by weight unless otherwise indicated.

EXAMPLE 1 Preparation of Pressure-sensitive Copying Paper Two parts of Color Former No. 21 was dissolved in parts oftrichlorobiphenyl and to the solution were added 20 parts of gum arabic and parts of water while stirring at 50C to form an emulsion. To the emulsion were added. with stirring 20 parts of an acid treated gelatin and 160 parts of water followed by the addition of acetic acid to adjust the pH to 5. 500 parts of water was then added to the emulsion to effect the coacervation thereby forming a dense liquid film of gelatin-gum arabic around the surface of each droplet of trichlorobiphenyl having the color former dissolved therein and, after adjustment of the pH of the mixture to 4.4, 3.8 parts of 37% formalin was added thereto to harden the liquid film. The emulsion was then Cooled to 10C and, after adjustment ofthe pH to 9 by addition of an aqueous sodium hydroxide solution. allowed to stand to complete the encapsulation process. The liquid containing the microcapsules was applied using. for example, a roll coating or air-knife coating procedure to a paper and dried to obtain a colorless coated paper, i.e., an upper sheet. When the upper sheet thus obtained was superposed on a lower sheet coated with, as a solid acid, an acidic organic polymer. active clay substance or a mixture thereof in such a manner that the layer of microcapsules was brought into contact with a layer of the above solid acid and localized pressure was applied to the assembly of sheets by e.g., handwriting, a blue color was gradually formed in the pressed areas of the lower sheet. This blue color changed to a deep shade within several hours. No substantial discoloration of the completely developed blue color was observed when the lower sheet was exposed directly to sun light for a long period of time.

EXAMPLE 2 Preparation of Pressure-sensitive Copying Papers 2.0 parts of each of Color Former Nos. 1 to 20 were separately processed in the same manner as described in Example 1 to form separate liquids containing microcapsules. The liquid was then applied to a paper and dried to obtain a colorless upper sheet. When the upper sheet was superposed on a lower sheet coated with. as a solid acid. an acidic organic polymer. active clay substance or a mixture thereof and localized pressure was applied to the assembly of sheets by. c.g.. handwriting.

a blue color was formed immediately in the pressed areas of the lower sheet. No substantial discoloration of the blue color was observed when the lower sheet was exposed directly to sun light for a long period of time.

EXAMPLE 3 Preparation of Pressure-sensitive Copying Papers taining microcapsules which was then applied to a paper and dried in the same manner as described in Example l to obtain a colorless upper sheet. When the upper sheet was superposed on a lower sheet coated with an acidic organic polymer, active clay substance or mixture thereof as a solid acid and localized pressure was applied to the assembly of sheets by, e.g., handwriting, a blue color was formed immediately in the pressed areas of the lower sheet. No substantial discoloration of the blue color was observed when the lower sheet was exposed directly to sun light for a long period of time. While the invention has been described in detail and in terms of specific embodiments thereo, it will be apparent to those skilled in the art that various modifications and variations can be made therein without departing from the spirit and the scope of the invention.

What is claimed is:

l. A pressure-sensitive copying paper comprising on a support a layer of an encapsulated color former and on the same or a different support a layer of an electron accepting solid, said color former being a phenoxazine compound represented by the formula R 5 6 R N- O 7 N R R (I) 2 2 lo I 3 wherein R, and R, each represents a lower alkyl group; R is a member selected from the group consisting of a lower alkyl group and a phenyl group; R, is a member selected from the group consisting of a hydrogen atom and a methyl group; and Y is a member selected from the group consisting of an alkyl group, an alkenyl group, a styryl group, a benzyl group, a phenoxymethylene group, a phenyl group, a naphthyl group, a furyl group, a thienyl group, a pyridyl group and a quinolyl group, wherein the styryl, benzyl, phenoxymethylene, phenyl, and naphthyl groups may be substituted in the nucleus thereof by a substituent selected from the group consisting of a lower alkyl group, a lower alkoxy group, a di-lower-alkylamino group, a hydroxy group, a chlorine atom and :1 nitro group and wherein the quinolyl group may be substituted in the 2-position thereof by a substituent selected from the group consisting of a lower alkyl group and a phenyl group.

2. The pressure-sensitive copying paper according to claim 1, wherein said color former is a compound selected from the group consisting of 3,7- bis(diethylamino)-lO-acetylphenoxazine, 3,7- bis(diethylamino)-l0-crotonoylphenoxazine, 3,7- bis(diethylamino)-10-cinnamoylphenoxazine, 3,7-

bis(diethylamino0-lO-(p-nitrophenylacetyl)- phenoxazine, 3,7-bis(diethylamino)-lO-(pchlorophenoxyacetyl)-phenoxazine, 3,7 -bis(diethylamino)-IO-benzoylphenoxazine, 3,7-bis(diethylamino)- 10-(p-methylbenzoyl)-phenoxazine, 3,7- bis(diethylamino)-l0(p-methoxybenzoyl) phenoxazine, 3,7-bis(diethylamino)-l0-(pdimethylaminobenzoyl)-phenoxazine, 3,7- bis(diethylamino)-lO-(o-hydroxybenzoyl)- phenoxazine, 3,7-bis(diethylamino)-IO-(p-nitrobenzoyl)-phenoxazine, 3,7bis(diethylamino l 0-( 2- furoyl)-phenoxazine, 3,7-bis(diethylamino)-lO-(2- thienoyl)-phenoxazine, 3,7-bis( diethylaminol 0- nicotinoylphenoxazine, 3,7-bis( diethylamino)- l 0- isonicotinoylphenoxazine, 3,7-bis(diethylamino)-l0- (2phenylcinchonoyl)phenoxazine, 3-diethylamino-7- dimethylamino-S-methyl-IO-(p-methylbenzoyl)- phenoxazine, 3-diethylamino-7-dimethylamino-8- methyl-l0-( l-naphthoyl)-phenoxazine, 3-

diethylamino-7-dimethylamino-8-methyll (H 3- hydroxy-Z-naphthoyl)-phenoxazine, 3-diethylamino-7- di-n-butylnmino-lO-(p-methoxybenzoyli-phenoxazine, 3-(N-methyl-N-phenylamino)-7-diethylamino-l0-(p methoxybenzoyl)-phenoxazine and :1 mixture thereof.

. UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECHN PATENT NO. 3,873,340

DATED ;-March 25, 1975 INVENTORtS) Yoshihide Miyazavva et at H is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

IN THE HEA DING:

Insert Foreign Application Priority Data August 2, 1971 Japanese............,,.............. 57507/71 Signed and sealed this 20th day of May 1975o S EAL) Attest:

Ca MARSHALL DANN RUTH C. MASON Commissioner of Patents Attesting Officer and Trademarks

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2783227 *Jun 27, 1955Feb 26, 1957Ncr CoNaphthoyl leuco methylene blue
US2783228 *Jun 27, 1955Feb 26, 1957Ncr CoNitro derivatives of benzoyl leuco methylene blue
US2915415 *Jun 5, 1958Dec 1, 1959Caribonum LtdLeucauramine derivate of benzoyl leuco methylene blue and transfer sheet coated therewith
US3427180 *Mar 31, 1965Feb 11, 1969Ncr CoPressure-sensitive record system and compositions
US3536517 *Dec 3, 1968Oct 27, 1970Gevaert Photo Prod NvPressure recording process
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4237281 *Feb 23, 1979Dec 2, 1980Ciba-Geigy AktiengesellschaftFor photographic films
US4284696 *May 15, 1978Aug 18, 1981Hodogaya Chemical Co., Ltd.Light transmission particle for forming color image
US4549192 *Jul 31, 1984Oct 22, 1985The Hilton-Davis Chemical Co.Using n-(n-acylamino)-8-(amino)imidazophenoxazine
US4551740 *Jul 31, 1984Nov 5, 1985The Hilton-Davis Chemical Co.Electrochromic and marking systems
US4561001 *Jul 31, 1984Dec 24, 1985The Hilton-Davis Chemical Co.Electrochromic marking systems
US4570171 *Jul 31, 1984Feb 11, 1986The Hilton-Davis Chemical Co.Electrochromic marking systems
US4647525 *Oct 1, 1984Mar 3, 1987Minnesota Mining And Manufacturing CompanyStabilized leuco phenazine dyes and their use in an imaging system
US4775754 *Oct 7, 1987Oct 4, 1988Minnesota Mining And Manufacturing CompanyReacting dicyclohexylcarbodiimide adduct with an oxazine, thiazine or phenazine compound
US4782010 *Dec 29, 1986Nov 1, 1988Minnesota Mining And Manufacturing CompanyOrganic silver salt
US4879383 *Jun 29, 1987Nov 7, 1989Wako Pure Chemical Industries, Ltd.Urea derivatives
US4889932 *Feb 8, 1988Dec 26, 1989Minnesota Mining And Manufacturing CompanyThermography; coatings
US5344928 *Apr 14, 1992Sep 6, 1994Takeda Chemical Industries, Ltd.Phenothiazine compounds for cancer treatment or immunoassay using chemiluminescence
US5532171 *May 23, 1994Jul 2, 1996Takeda Chemical Industries, Ltd.Phenothiazine dyes for photodynamic therapy of cancer or immunoassay
EP0181085A1 *Oct 1, 1985May 14, 1986Minnesota Mining And Manufacturing CompanyStabilized leuco phenazine dyes and their use in an imaging system
Classifications
U.S. Classification503/218, 544/37, 544/103
International ClassificationB41M5/136, C09B19/00, B41M5/132
Cooperative ClassificationB41M5/136, C09B19/00
European ClassificationC09B19/00, B41M5/136