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Publication numberUS3920510 A
Publication typeGrant
Publication dateNov 18, 1975
Filing dateJul 31, 1973
Priority dateAug 1, 1972
Also published asUSRE31412
Publication numberUS 3920510 A, US 3920510A, US-A-3920510, US3920510 A, US3920510A
InventorsYoshihiro Hatano, Kenji Yamamoto
Original AssigneeYamamoto Kagaku Gosei Kk
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Pressure-and-heat-sensitive copying paper
US 3920510 A
Abstract
A heat or pressure sensitive copying paper is provided containing a fluoran compound as a color former, said color being developed in said heat or pressure sensitive copying paper through the application of heat or pressure, said fluoran compound being of the formula WHEREIN R1 is halogen; R2 is hydrogen or methyl; R3 is hydrogen, methyl or ethyl; each of R4 is independently halogen or methyl; R5 is methyl or ethyl; and n is 0 or an integer from 1 to 4.
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United States Patent [191 Hatano et al.

[ 51 Nov. 18, 1975 PRESSURE-AND-HEAT-SENSITIVE COPYING PAPER [75] Inventors: Yoshihiro Hatano, Osaka; Kenji Yamamoto, Yao, both of Japan [73] Assignee: Yamamoto Kagaku Gosei Kabushiki Kaisha, Osaka, Japan [22] Filed: July 31, 1973 [21] Appl. No.1 384,304

[30] Foreign Application Priority Data Aug. 1, 1972 Japan 47-77081 [52] US. Cl. 162/162; 260/335; 282/275 [51] Int. Cl. B410 l/06; B4lm 5/18 [58 Field of Search 117/362; 260/335 1 7 References Cited UNITED STATES PATENTS 6/1972 Kimura et al. 117/36.2 8/1972 Lin 260/335 Lin 117/362 Hoover et al. 117/362 FOREIGN PATENTS OR APPLICATIONS 2,049,503 4/1971 Germany Primary Examiner-Thomas J. Herbert, Jr. Attorney, Agent, or FirmArmstrong, Nikaido & Wegner [57] ABSTRACT A heat or pressure sensitive copying paper is provided containing a fluoran compound as a color former, said color being developed in said heat or pressure sensitive copying paper through the application of heat or pressure, said fluoran compound being of the formula (III) wherein R is halogen; R is hydrogen or methyl; R is hydrogen, methyl or ethyl; each of R is independently halogen or methyl; R is methyl or ethyl; and n is O or an integer from 1 to 4.

19 Claims, No Drawings PRESSURE-AND-HEAT-SENSITIVE COPYING PAPER The present invention relates to copying paper which is heat or pressure sensitive which contains acolor former.

According to a second aspect of the invention, a new series of fluoran compounds are provided which serve as a color former for this paper.

The fluoran compounds of the invention are particu larly useful for developing color in the copying paper having a green or black shade. The fluoran compounds have the general formula wherein R is halogen; R is hydrogen or methyl; R is hydrogen, methyl or ethyl; each of R is independently halogen or methyl; R or ethyl; and n is 0 or an integer from 1 to 4.

Such fluroan compounds as ([11) may be applied to the pressure-sensitive copying'paper in a manner, for example, described in the Japanese Pat. No. 4,614/1971. Also a dye for the pressure-sensitive copying paper is generally applicable to the heat-sensitive copying paper in such a manner as is described in the Japanese Pat. No. 14,039/1970. The product ([1]) can also be applied to the heat-sensitive copying paper in a similar manner. However, when the dye is used for the heat-sensitive copying paper, it is not used in microcapsules of gelatin etc., as in the case of the pressure-sensitive copying paper. Instead, it is used in a powdery state after being pulverized with a color coupler, so that particularly great importance is attached to the stability of the dye itself. For example, 2-anilino-6-diethylaminofluoran (compound IV, developing into a green color) and 2-anilino-3-methyl-6-diethylaminofluoran (compound V, developing into a black color), disclosed in Belgian Pat. No. 744,705, are known as the dyes for pressure-sensitive copying paper that singly develop into a green or black color:

But they have not enough stability to make themselves suitable for heat-sensitive copying paper. That is, when these dyes are pulverized in an aqueous solution of PVA and, then, mixed with bisphenol Aect., in accordance with the method of the Patent No. 14,039/1970, to prepare a coating material for the heat-senstive copying paper, the coating material itself develops into dye by improving light and water resistance of the color which is developed and by suppressing the sublimation.

These fluroan compounds not only are very useful as the dye for heat-sensitive copying paper but also have a high practical value as the dye for pressure-sensitive copying paper.

5 0 Now the present invention is further illustrated by the following specific example:

EXAMPLE 1 Preparation of 2-chloroanilino-6-diethylaminofluoran 1:a -ct (v1) c H on 1 r 2 .J c0 l (VII) (VIII) 25 g of aceto-p-phenetidide, 36.6 g of p-chlorobromobenzene, g of potassium carbonate, 0.7 g of copper powder and a small quantity of iodine were heated under reflux for 48 hours, and then, after addition of 12 g of potassium hydroxide and 60 ml of ethyl alcohol, further heated under reflux for hours. The product was discharged into water, and the precipitate was filtered off and distilled in vacuo. Then 28.7 g (83 per cent of theoretical yield) of 4-chloro-4'-cthoxydiphenylamine (VII) was obtained, and it was found to be white crystals (b.p. 185 to 190C/4 ,Jg, mp. 56 to From the following analysis result, it was confirmed that the product was C H CINO.

Then 10 g of the compound (VII), 13.4 g of 4-diethylamino-2-hydroXy-2' carboxybenzophenone (VIII) and 70 g of concentrated sulfuric acid were stirred at ordinary temperature for 48 hours. The product was discharged into 1 'I of water, and the precipitate was filtered off, washed with an aqueous solution of caustic soda, and recrystallized with toluene. Then 11.8 g (55.5 per cent of theoretical yield) of 2-pchloroani1ino-6-diethylaminofluoran (VI) was obtained. The product was a slightly colored powder (m.p. 210 to 213C) and developed a greencolor in the presenceof a member selected from a group consisting of clay, resin, bisphenol A and the like.

From the following analysis result, it was confirmed that the product was C3OHZ5CINZO3.

Theoretical 72.50 5.04 5.64 Found 73.10 5.11 5.38

EXAMPLE-2 Preparation of 2-m-chloroani1ino 6-diethylaminofluoran (IX) 64 g of m-chloroaniline, 55 g of hydroquinone and 1 g of sulfanilic acid were allowed to react with each other at 200C for 20 hours, and the product was dissolved in anaqueous solution of caustic soda and the filtered. The filtrate was made acidic with acetic acid,

and the precipitate was distilled in vacuo. Then 35 g (31.8 per cent of theoretical yield) of 3-chloro-4- hydroxydiphenylamine (X) was obtained, and it was found to be yellow crystals (b.p. 245 to 247C/11 mmHg, m.p. 96 to 98C).

From the following analysis result, it was confirmed that the product was C H CINO.

C H N Theoretical 65.60 4.56 6.38 Found 65.20 4.70 6.38

Then 14.1 g of the compound (X), l 8.5 g ofthe compound (VIII) and 90 g of concentrated sulfuric acid were stirred at ordinary temperature for 48 hours. The product was discharged into 1 l of water, and the precipitate was filtered off, washed with an aqueous solution of caustic soda, and recrystallized with toluene. Then 13 g (40.8 percent of theoretical yield) of 2-mchloroanilino-6-diethylaminofluoran (1X) was obtained. The product was a pale-purple powder (m.p. 186 to 187C.) and developed a green color in the presence of clay .or resin and a black color in the presence of=bisphenol.A.

From the following analysis result, it was confirmed that the product was C H ClN O Preparation of 2-o-chloroanilino-6 diethylaminofluoran (XI) g of potassium hydroxide and 60 ml of ethylalcohol, further heated under reflux for 20 hours. The product was discharged into water, extracted with 100 ml of'toluene, and distilled in vacuo. Then 29.2 g (-82.5 percent of theoretical yield) of 2-chloro-4'-methoxydiphenylamine (Xll) was obtained, and it was found to be a yel low viscous liquid (b.p. 205 to 2l0Cl7mmHg).

From the following analysis result, it was confirmed that the product was C H ClN O.

c H N Theoretical 66.90 5.14 5.91 5.21 6.01

Found 67 .20

Then g of the compound (x11), 13.4 'g of the compound (Vlll) and 50 g of concentrated sulfuric acid were stirred at ordinary temperature for 48 hours. The product was discharged into l I of water, and theprecipitatewas filtered off, washed with an aqueous solution of caustic soda, and recrystallized with toluene. Then 12.6 g (59.2 per cent of theoretical yield) of 2-0- chloroanilino-6-diethylarninofluoran (Xl) was ob-' tained. The product was a pale-pink powder (m.p. 178- to l80C) and developed a black color in the presence of clay and bisphenol A and-a green color in the pres-- ence of resin.

From the following analysis result, it was confirmed that the product was c u cm o C H N Theoretical 72.50 5.04 5.64 Found 7 1 73.00 5.05 5.48

EXAMPLE 4 Preparation of 2-(3',5'-dichloroanilino)-6-diethylaminofluoran (Xlll) H z s l l NH I (XIII) c9. ergo-Gating c (XIV) 6 cent of theoretical yield) of 3,5-dichloro-4-methoxydiphenylamine (XIV) was obtained, and it was found to be yellow crystals (b.p. 226 to 230C/4 mml-lg, m.p. 106 to 107C).

From the following-analysis result, it was confirmed that the product was C H CI NO.

C H N Theoretical 58.21 4.l0 5.22 ound 57.20 3.95 5.12

Then 15 g of the compound (XIV), 17.6 g of the compound (Vlll) and g of concentrated sulfuric acid were condensed by stirring at ordinary temperature for 48 hours. The product was discharged into l l of water, and the precipitate was filtered off, washed with an aqueous solution of caustic soda, and recrystallized with toluene. Thenl 8 g (60.5 percent of theoretical yield) of 2-(3',5-dichloroanilino)-6-diethylaminofluoran (Xlll) was obtained. The product developed a green color in the presence of resin and a black color in the presence of clay and bisphenol A.

i From the following analysis result, it was confirmed that the product was C H Cl N O C H N Theoretical 67.80 4.52 5.28 Found 68.20 4.59 5.10

EXAMPLE 5 Preparation of 2-(3,4 dichloroanilino)-6-diethylaminofluoran (XV) c 14 o 4 ct 'z s 1 (XVI) 33 g of p-acetanisidide, 68 g of 3,4-dichlorobromc benzene, 16 g of potassiumcarbonate, 1.5 g of coppe powder and a small quantity of iodine were heate under reflux for 48 hours, and then, after addition of l g of potassium hydroxide and 100 ml of ethyl alcoho further heated under reflux for 20 hours. The pi'oduc was discharged into water, and the precipitate was fi tered off and distilled in vacuo. Then 39 g (73 perce1 of theoretical yield) of 3,4-dichloro-4'-methoxyd phenylamine (XVl) was obtained, and it was found be pale-yellow crystals (b.p. 228 to 232C/4 mmH m.p. 101 to 102C).

From the following analysis result, it was confirmed that the product was C H cl No.

Theoretical 58.21

Then 30 g of the compound (XVI), 35 g of the compound (VIII) and 175 g of concentrated sulfuric acid were stirred at ordinary temperature for 48 hours to off, washed with an aqueous solution of caustic soda, and recrystallized with toluene. Then 30.8 g (51.8 percent of theoretical yield) of 2-(3,4- dichloroanilino)-6-diethylaminofluoran (XV) was obtained. The product was slightly colored powder (m.p. 189 to 190C), and developed a black color in the presence of clay, a green color with resin, and a blackish green color with bisphenol A. I

From the following analysis result, it was confirmed that the product was C ,,H CI N O (XVIII) 40 g of 3-rnethyl-p-acetanisidide (Beilsteimsupplement No. 1, vol. 13, p. 223), 51.5 g of p-chlorobromobenzene, 17.5 g of potassium carbonate, 1 g of copper powder and a small quantity of iodine were allowed to. react with each other at 200C for 40 hours, and then, after addition of g of potassium hydroxide and 100 ml of ethyl alcohol, further heated under reflux for 24 hours. The product was discharged into water, extracted with 200 ml of benzene, and distilled in vacuo. Then 48.2 g (87.3 percent of theoretical yield) of 2- methyl-4-methoxy-4-chlorodiphenylamine (XVIII) 8 was obtained, and it was foundto be a yellow viscous liquid (b.p. 185 to 187C/3 mmHg From the. following analysis result, it was confi that the product was C H CINO.

rmed

I Then 24.75 g ofthe compound (XVIII) 31.3 g of the compound (VIII) and 150 gv of concentrated sulfuric acid were stirred at ordinary temperature for 40 hours. The product was discharged into 700 ml of water, and the precipitate was filtered off, washed with an aqueous solution of caustic soda, and recrystalliz ed with 600ml of. toluene. Then 4 .3 g (80.8 percent" r theoretical yield) of 2-p-chloroanilino-3-methyl 6-diethylaminofluoran (XVII) was obtained. The product was a pale yellow powder (m.p. 212 to 213C), and developed a black c'olor'in the presence of clay, resin and bisphenol A respectively. From the following analysis result, it was confirmed that the product was'c H ClNO Theoretical 72.87 5.29 5.48 Found 73.93 5.35 5.31

EXAMPLE 7 Preparation of 2-m-chloroanilino-3-methyl-6-diethylaminofluoran 54.5 g of 3-methyl-p-acetanisidide, g of m-chlorobromobenzene, 2 5 g of potassium carbonate, 1 g of copper powder and a small quantity of iodine were allowed toreact with each other at 220C. for 24 hours, and then, after addition of 27 g of potassium hydroxide and, ml of ethanol, further heated under refluxifor was discharged intowate'r, and the precipitate was filtered off and distilled in'vacuo. Then 61' g (81 percent of theoretical yield of 2-methc H N Theoretical 67.88 5.66 5.66 Found 67.20 5.38 5.41

Then 24.75 g of the compound (XX), 31.3 g of the compound (VIII) and 150 g of concentrated sulfuric acid were stirred at ordinary temperature for 48 hours. Theproduct was discharged into 1 l of water. And the precipitate was filtered off, washed with anaqueous solution of caustic soda, and recrystallized with 300 ml of toluene and'4 g of activated charcoal. Then 27.5 g (53.8 percent of theoretical yield) of 2-mchloroanilino-3-methyl-6-diethylaminofluoran (XIX) was obtained. The product was a white powder (m.p. 211 to 212C), and developed a black color in the presence of'clay, resin and bisphenol A, respectively. From the following analysis result, it was confirmed that the product was C H ClN O- Preparation of 2-o-chloroanilino-3-methyl-6-diethylaminofluoran (XXII) 42.5 g of 3-methyl-pacetanisidide, 50 g of o-chlorobromobenzene, 18 g of potassium carbonate, 1 g of copper powder and a small quantity of iodine were allowed to react with each other at 220C for 24 hours, and then, after addition of 30 g of potassium hydroxide and 100 ml of ethyl alcohol, further heated under reflux for 20 hours. The product was discharged into water, and the precipitate was filtered off and distilled in vacuo. Then 46.9 g percent of theoretical yield) of 2-methyl-4-methoxy-2-chlorodiphenylamine (XXII) was obtained, and it was found to be yellow crystals (m.p. to 91C, b.p. to C/3 mmHg).

From the following analysis result, it was confirmed that the product was C H CINO.

C H N Theoretical 67.88 5.66 5.66 Found 67.05 5.56 5.68

C H N Theoretical 72.87 5.29 5.48 Found 72.91 5.23 5.25

EXAMPLE 9 Preparation of 2-p-bromoanilino-3-methyl-o-diethylaminofluoran (XXIII) c11 cu oyam-@431:

(XXIV) 18.95 g of 3-methyl-p-acetanisidide, 25 g 'of pdibromobenzene, 9 g of potassium carbonate, 0.5 g of copper powder and a small quantity of iodine were allowed to react with each other at 220C for 20 hours, and then, after addition of 20 g of potassium hydroxide and 100 m1 of ethyl alcohol, further heated under reflux for 22 hours. The product was discharged into water, extracted with I ml of toluene, and distilled in vacuo. Then I 1.5 g (37.2 percent of theoretical yield) of 2-methyl-4-methoxy-4'-bromodiphen'ylamine (XXIV) was obtained, and it was found to be a yellow viscous liquid (b.p. 195 to 200C/4 mmHg).

From the following analysis result, it was confirmed that the product was C I-I BrNO.

flux for 20 hours. The product was discharged into water, and the precipitate was filtered off and distilled in vacuo. The 48.7 g (83.4 percent of theoretical yield) of 2,3-dimethyl-4-methoxy-4-chlorodiphenylamine 5 (XXVI) was obtained, and it was found to be pale-yellow crystals (b.p. 200 to 205C/4 mmI-Ig, m.p. 86 to 87C).

From the following analysis result, it was confirmed that the product was C H CINO.

C H N Theoretical 59.57 4.79 4.79 Found 59.91 4.88 4.75 c H N Theoretical 68.83 6 l2 5.35 Found 68.l6 6.04 5.22 Then 5 g of the compound (XXIV), 5.36 g of the that the product was C H BrN O ,Then 26.15 g of the compound (XXVI), 31.3 g of the compound (VIII) and 150 g of concentrated sulfuric acid were stirred at ordinary temperature for 40 hours, and the product was discharged into I I of water. The precipitate was filteredoff, washed with;an aqueous solution of caustic soda, and recrystallized with 600 ml of toluene. The 40.1 g (65 percent of theoretical'yield) of 2-(3-methyl-4'-chloroanilino)-3-methyl-6-diethylaminofluoran (XXV) was obtained. The product was a slightly colored powder (m.p. l48 to 150C) and developed a black color in the presence of clay, resin and bisphenol A, respectively.

From the following analysis resultf 'it was confirmed that the product was C H CIN O C H C H N Theoretical 67.03 4.86 5.05 Found 67.82 4.64 4.95 C H N Theoretical 75.9l 6.00 4.54 35 Found 75.03 5.54 4.52

EXAMPLE l0 Preparation of r 2-(4'-chloro-3-methylanilino)-3-methyl-6-die- EXAMPLE thylaminofluoran (XXV) 40 Preparation of 2-(3,5-dichloroanilino)-3-methyl-6-diethylaminofluoran (XXVII) c n N 2 5 l NH (XXVII) CH CR. cn o NH (XXVI) 40 g of 3-methyl-p-acetanisidide, 5Q gof3-methyl-4- (XXVII'I) I chlorobromobenzene, l7.5 gofpotassium carbonate,l I i g of copper powder and a small quantity of iodine were 40 g Of 3-methyl-p-acetanis|d1de, 55.5 g of 3,5-

allowed to reactwith each other at 210C for -24 hours, and then, after addition of 20 g of potassium hydroxide and ml of ethyl alcohol, further heated under redichlorobromobenz ene-,' l 7.5 of potassium carbonate, I g of copper powder and a small quantity of iodine were allowed to react with'each other for 24 hours, and

1 3 then, after addition of 20 g of potassium hydroxide and 100 ml of ethyl alcohol, further heated under reflux for 20 hours. The product was discharged into water, and the precipitate was filtered off and distilled in vacuo.

Then 44 g (69.8 percent of theoretical yield) of 2- 5 flux for 22 hours. The product was discharged into wamethyl-4-methoxy-3,5f-dichlorodiphenylamine ter, extracted with 100 ml of toluene, and distilled in (XXVIII) was obtained, and it was found to be palevacuo. Then 19 g (66.9 percent of theoretical yield) of yellow crystals (b.p. 192 to 193C/4 mmHg, m.p. 104 2-methyl-4-methoxy-3,4'-dichlorodiphenylamine to 106C). (XXX) was obtained, and it was found to be yellow From the following analysis result, it was confirmed crystals (b.p. 203 to 210C/3 mmHg, m.p. 80 to that the product was C H CI NO. 90C).

From the following analysis result, it was confirmed that the product was C H CI NO. C H N Theoretical 59.57 4.61 4.96 15 Found 59.86 4.74 4.97 C H N Theoretical 59.57 4.61 4.96 Found 57.63 4.32 4.92 Then 28.2 g of the compound (XXVIII) 31.3 g of the compound (VIII) and 150 g of concentrated sulfuric 7 acid were stirred at ordinary temperature for 24 hours, Then 18 g of the compound (XXX), 20 g of the comand the product was discharged into 1 [of water. The pound (VIII) and I00 g of concentrated sulfuric acid precipitate was filtered off, washed with an aqueous sowere stirred at ordinary temperature for 44 hours, and lution of caustic soda, and recrystallized with 700 ml of the product was discharged into 500 ml of water. The toluene. Then 4l .7 g (76.5 percent of theoretical yield) 25 precipitate was filtered off, washed with an aqueous soof 2-( 3',5'-dichloroanilino)-3-methyl-6-diethylaminolution of caustic soda, and recrystallized with 400 ml of fluoran (XXVII) was obtained. 'The product was a toluene. Then 23.7 g (68 percent of theoretical yield) white powder (m.p. 224 to 225C) and developed a of 2-(3,4'-dichloroanilino)-3-methyl-6-diethylaminopurple color in the presence of.clay and a brown color fluoran (XXIX) was obtained. The product was a in the presence of resin and bisphenol A, respectively. slightly colored powder (m.p. 190 to 191C) and de- From the following analysis result, it was confirmed veloped a purple color in the presence of clay and a that the product was C H Cl N O black color in the presence of resin and bisphenol A, 9

respectively. From the following analysis result, it was confirmed H N that the product was C H Cl N O Theoretical 68.26 4.77 5.l4 Found 67.86 4.68 4.89

C H N Theoretical 68.26 4.77 514 40 Found 66.95 4.34 4.83 EXAMPLE l2 Preparation of 2-( 3 ',4 -dichloroanilino)-3-methyl-6-diethylaminofluoran xxrx) EXAMPLE i 5 Preparation of 2-(2',5-dichloroanilino)-6-diethylaminofluoran c n Q /0 Cl (XXXI) 'QMQ Q 2 5 m-r c2 C H o 2 5 NIIQ C 9 C9, (xxrx) l cn c2. (xxxI) CH OGNEFQ-CR.

c H O-Q-NHQ C9. (XXX) 18 g of 3-methyl-p-acetanisidide, 25 g of 3,4- dichlorobromobenzene, 8 g of potassium carbonate,

14 0.5 g of copper powder and a small quantity of iodine were allowed to react with each other at 200C for 24 hours, and then, after addition of 10 g of potassium hydroxide and 50 ml of ethanol, further heated under re- (XXXII) 30 g of p-acetophenetidide, 45.5 g of 2,5-dichlorobromobenzene, 13 g of potassium carbonate, 1 g of copper powder and a small quantity of iodine were allowed to react with each other at 210C for 24 hours, and then, after addition of 15 g of potassium hydroxide and 75 ml of ethanol, further heated under reflux for hours. The product was discharged into water, extracted with 150 ml of toluene, and distilled in vacuo. Then 33.1 g (70 percent of theoretical yield) of 2,5- dichloro-4'-ethoxydiphenylamine (XXXII) was obtained, and it was found to be a yellow viscous liquid (b.p. 190 to 195C/4 mmI-Ig).

From the following analysis result, it was confirmed that the product was C, H CI NO.

16 10g of the compound (VII, see EXAMPLE 1) and 6.5 g of dimethylsulfuric acid were. allowed to react with each other at 90C for 20 hours, and then, after addition of 60 g of a 10 percent aqueous solution of .caustic soda, further heated under stirring for 1 hour.

The product was extracted with 50 ml of toluene and distilled in vacuo. Then 8.8 g (83.2 percent of theoretical yield) of 4-ethoxy-4-chloro-N-methyl-diphenylamine (XXXIV) was obtained, and it was found to be pale-yellow crystals (b.p. 185 to 188C/4 mmHg, m.p. 56 to 57"c I From the following analysis result, it was confirmed that the product was c. H c1No.

C H N C H N Theoretical 59.57 4.61 4.96 Theoretical 68.83 6.12 5.35 Found 59.73 4.64 4.98 Found 68.64 i 6.10 5.27

yield) of 2-(2',5-dichloroanilino)-6-diethylaminofluoran (XXXI) was obtained. The product was a white powder (m.p. 184 to 185C) and developed a black color in the presence of clay and bisphenol A, respectively, and a green color in the presence of resin.

From the following analysis result, it was confirmed that the product was C H Cl N O Then 7 g of the compound (XXXIV), 8.9 gofthe compound (VIII) and 60 g ofv concentrated sulfuric acid were stirred at ordinary temperature for 48 hours, and the product was discharged into 500 ml of water. The precipitate was filtered off, was hed with an aqueous solution of caustic soda, and recrystallized with 120 ml of toluene. Then 10.5 g (71 per cent of theoretical yield) of 2-(4l-chloro-N-methylanilino)-6-diethylaminofluoran (XXXIII) was obtained. The product was a white powder (m.p. 189 to 190C) and developed a green color in the presence of clay, resin and bisphenol A, respectively.

From the following analysis result, it was confirmed that the product was C H CIN O C H N C H N Theoretical 67.80 4.52 5.28 Theoretical 72.87 5.29 5.48 Found 67.65 4.50 5.30 Found 72.45 5.16 5.36

EXAMPLE 14 EXAMPLE 15 Preparation of Preparation of 2-(4'-chloro-N-methylanilino)-6-diethylaminofluoran 2-(4'-chloro-N-ethylanilino)-6-diethylaminofluoran (XXXllI) (XXXV) 2 s 0 0 c H c n /N 1 l m c Ii /N' l 5 2 5 N-U-CZ 2 5 l N o o C O C '-'-"O C11.

(XXXIII) (XXXV) $11 (1 11 c n ofim4 c n o--n \-c2 (XXXIV) (XXXVI) 10 g of the compound (VII, see EXAMPLE 1) and 10 g of dicthylsulfuric acid were allowed to react with each other at 90C for 17 hours, and then, after addition of 50 g of a 10 percent aqueous solution of caustic soda, further heated under stirring for 1 hour. The product was extracted with 50 ml of toluene and distilled in vacuo. Then 7.3 g (65.5 percent of theoretical yield) of 4-ethoxy-4'-chloro-N-ehtyldiphenylamine (XXXVI) was obtained, and it was found to be white crystals (b.p. 187 to 190C/6 mmHg, m.p. 61 to 62C).

From the following analysis result, it was confirmed that the product was C H ClNO.

C H N Theoretical 69.69 6.53 5.08 Found 69.71 6.48 5.02

Then 5 g of the compound (XXXVI), 5.7 g of the compound (VIII) and 40 g of concentrated sulfuric acid were stirred at ordinary temperature for 44 hours, and the product was discharged into 500-ml of water.

The precipitate was filtered off, washed with an aque- C H N Theoretical 73.21 5.53 5.34 Found 72.98 5.52 5.26

EXAMPLE 16 I Preparation of 2-(4'-chloro-3'-methylanilino)-3-methyl-6-dimethylaminofluoran (XXXVll) (XXXVI I 11.45 g of the compound (XXVI, see EXAMPLE 12.5 g of 4-dimethylamino-2-hydroxy-2-carboxybenzophenone and 70 g of concentrated sulfuric acid were stirred at ordinary temperature for 40 hours, and the product was discharged into 1 l of water. The pre- C H N Theoretical 72.50 5.04 5.64 Found 72.70 5.09 5.47

EXAMPLE 17 Preparation of pressure sensitive copying paper 5 g of 2-p-chloroanilino-6-diethylaminofluoran (VI, Example 1 is heated with g of mono-isopropyl biphenyl up to 100C and dissolved into the latter, and then emulsified together with a solution of 25 g of gum arabic in 400 ml of water. Next, a solution of 25 g of gelatin in 400 ml of water is added to complete the emulsification, and acetic acid is added to adjust so as to obtain pH 4. At this time, liquid films of gelatin/gum arabic are formed around oil drops containing fluoran compound. 500 ml of water is added to the emulsion, and then it is cooled to below 10C. 5 ml of 37 percent formalin solution is added to cure the films. A solution of 10 caustic soda is added to adjust so as to obtain pH 9, and the temperature is slowly restored to room temperature. The suspension thus obtained is applied to the under surface of upper leaf, and it is dried. Meanwhile, solid acid such as active clay, phenol compound, etc. is applied to the upper surface of lower leaf.

When copying is carried out by means of the upper leaf and lower leaf prepared by the above-mentioned method, the lower leaf which has active clay or phenol compound on its upper surface rapidly develops green color.

EXAMPLE 18 Preparation of heat-sensitive copying paper 35 G of 2-p-chloroanilino-3-methyl-6-diethylamino fluoran (XVII, Example 6), g of 10 weight percent polyvinyl alcoholaqueous solution, and 65 g of water are ground and mixed for an hour. (A liquid).

Meanwhile, 35 g of bisphenol A, 150 g of 10 weight percent polyvinyl alcohol aqueous solution, and 65 g of water are ground and mixed for an hour. (B liquid) Next, 3 weight parts of A liquid and 67 weight parts of B liquied are mixed and disparsed, and then applied to paper.

When the heat-sensitive copying paper thus prepared is added heat partially by means of a thermal pen or an exothermic head, it rapidly develops black color.

I claim:

l. A heat or pressure sensitive copying paper containing a fluoran compound as a color former, said color being developed in said heat or pressure sensitive copying paper through the application of heat or pressure, said fluoran compound being of the formula wherein R is halogen; R is hydrogen or methyl; R is hydrogen, methyl or ethyl; each of R is independently halogen or methyl; R is methyl or ethyl; and n is O or an integer from 1 to 4.

2. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-p-chloroanilino-6-diethylaminofluoran.

3. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-m-chloroanilino-6-diethylaminot'luoran.

4. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-o-chloroanilino-6-diethylaminofluoran.

5. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-( 3',5'-dichloroanilino)-6- diethylaminofluoran.

6. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-(3',4'-dichloroanilino)-6- diethylaminofluoran.

7. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-p-chloroanilino-3-methyl-6- diethylaminofluoran.

8. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-m-chloroanilino-3-methyl- 6-diethylaminofluoran.

9. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-o-chloroanilino-3-methyl-6- diethylaminofluoran.

-claim 1 wherein said fluoran is 2-(4'-chloro-N- methylanilino)-6-diethylaminofluoran.

16. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-(4'-chloro-N- ethylanilino)-6-diethylaminofluoran.

17. A heat or pressure sensitive copying paper of claim 1 wherein said fluoran is 2-(4'-chloro-3-'- methylanilino)-3-methyl-6-dimethylaminofluoran.

18. A heat sensitive copying paper of claim 1.

19. A pressure sensitive copying paper of claim 1.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3669712 *Jun 26, 1970Jun 13, 1972Fuji Photo Film Co LtdPressure-sensitive copying papers
US3681390 *Nov 16, 1970Aug 1, 1972Ncr CoDialkylamino fluoran chromogenic compounds
US3746562 *Sep 28, 1971Jul 17, 1973NcrMark forming record materials
US3764369 *Apr 21, 1971Oct 9, 1973NcrPressure sensitive recording unit
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US4156682 *Oct 21, 1976May 29, 1979Sumitomo Chemical Company, LimitedFluoran compounds and recording sheet containing them
US4287264 *Mar 7, 1980Sep 1, 1981Labelon CorporationHeat sensitive coating
US4364999 *Aug 24, 1981Dec 21, 1982Hodogaya Chemical Co., Ltd.Heat sensitive record sheet
US4510513 *Jul 13, 1983Apr 9, 1985Hodogaya Chemical Co., Ltd.Heat sensitive record sheet
US4515971 *Jul 6, 1981May 7, 1985Hilton-Davis Chemical Co.5'/6'-Carboxyfluorans and derivatives thereof
US4524373 *Feb 17, 1983Jun 18, 1985Kanzaki Paper Manufacturing Co., Ltd.Fluoran derivatives as new compounds, process for preparing the same and recording system utilizing the same as colorless chromogenic material
US4927802 *Dec 9, 1988May 22, 1990Ppg Industries, Inc.Pressure-sensitive multi-part record unit
US5166350 *Sep 30, 1991Nov 24, 1992Ciba-Geigy CorporationProcess for the manufacture of fluoran compounds
US5284816 *Nov 19, 1992Feb 8, 1994Eastman Kodak CompanyTwo-sided thermal printing system
US6037094 *Oct 23, 1998Mar 14, 2000Cycolor, Inc.Photosensitive material employing microcapsules and superabsorbent polymer
US6127084 *Oct 23, 1998Oct 3, 2000Cycolor, Inc.Photosensitive material employing microcapsules containing a hygroscopic polymer in the internal phase
US6638678Nov 20, 2001Oct 28, 2003Hsbc Bank UsaMethod for improving sensitometric response of photosensitive imaging media employing microcapsules
US6932602Apr 22, 2003Aug 23, 2005Appleton Papers Inc.Dental articulation kit and method
US6964836Mar 15, 2002Nov 15, 2005Eastman Kodak CompanyPhotosensitive microcapsules containing a synthetic viscosity modifier in the continuous phase
US7108190Feb 28, 2003Sep 19, 2006Appleton Papers Inc.Token array and method employing authentication tokens bearing scent formulation information
US8114904Apr 3, 2009Feb 14, 2012Versitech Limited & Morningside Ventures LimitedLuminescence quenchers and fluorogenic probes for detection of reactive species
US9409219Aug 9, 2012Aug 9, 2016Valspar Sourcing, Inc.Compositions for containers and other articles and methods of using same
US9475328Mar 15, 2013Oct 25, 2016Valspar Sourcing, Inc.Developer for thermally responsive record materials
US20040169071 *Feb 28, 2003Sep 2, 2004Appleton Papers Inc.Token array and method employing authentication tokens bearing scent formulation information
US20040214134 *Apr 22, 2003Oct 28, 2004Appleton Papers Inc.Dental articulation kit and method
US20040251309 *Jun 10, 2003Dec 16, 2004Appleton Papers Inc.Token bearing magnetc image information in registration with visible image information
US20060063125 *Aug 23, 2005Mar 23, 2006Hamilton Timothy FMethod and device for enhanced dental articulation
US20080248950 *Oct 3, 2007Oct 9, 2008Ibrahim KatampeInk and Developer System
US20090253118 *Apr 3, 2009Oct 8, 2009Versitech LimitedLuminescence quenchers and fluorogenic probes for detection of reactive species
USRE33815 *Jun 27, 1988Feb 4, 1992Hodogaya Chemical Co., Ltd.Heat sensitive record sheet
EP0048026A1 *Sep 16, 1981Mar 24, 1982Hodogaya Chemical Co., Ltd.Heat sensitive record sheet
EP0098151A2 *Jun 28, 1983Jan 11, 1984Mita Industrial Co. Ltd.Heat-sensitive black recording element
EP0098151A3 *Jun 28, 1983Mar 21, 1984Mita Industrial Co. Ltd.Heat-sensitive black recording element
EP0098728A2 *Jun 28, 1983Jan 18, 1984Mita Industrial Co. Ltd.Heat-sensitive black recording material
EP0098728A3 *Jun 28, 1983Mar 21, 1984Mita Industrial Co. Ltd.Heat-sensitive black recording material
EP0688759A1Jun 22, 1995Dec 27, 1995Fuji Photo Film Co., Ltd.Alpha-resorcylic acid ester derivatives and recording materials incorporating them
EP2848123A1Oct 9, 2009Mar 18, 2015Appvion, Inc.An agriculture actives delivery composition comprising persulfate ion-crosslinked polyvinyl alcohol microcapsules and method of use thereof
WO2009121247A1 *Apr 7, 2009Oct 8, 2009Versitech LimitedLuminescence quenchers and fluorogenic probes for detection of reactive species
WO2010090213A1Feb 3, 2010Aug 12, 2010Fujifilm CorporationThermal distribution display and method for confirming thermal distribution
Classifications
U.S. Classification503/221, 549/226
International ClassificationC07D493/10, B41M5/327, B41M5/145, C09B11/28
Cooperative ClassificationC07D493/10, B41M5/3275, B41M5/1455
European ClassificationB41M5/145B, B41M5/327B, C07D493/10
Legal Events
DateCodeEventDescription
Nov 22, 1983RFReissue application filed
Effective date: 19820603