US3864145A - Pressure sensitive copying paper - Google Patents
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- US3864145A US3864145A US310585A US31058572A US3864145A US 3864145 A US3864145 A US 3864145A US 310585 A US310585 A US 310585A US 31058572 A US31058572 A US 31058572A US 3864145 A US3864145 A US 3864145A
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- United States
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- pressure sensitive
- sensitive copying
- copying paper
- color
- paper
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- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- -1 fluoran compound Chemical class 0.000 claims description 17
- 239000011973 solid acid Substances 0.000 claims description 16
- 239000002775 capsule Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 8
- 239000003849 aromatic solvent Substances 0.000 abstract description 4
- 125000000217 alkyl group Chemical group 0.000 abstract description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 239000013078 crystal Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical compound ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 5
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- XXAGRMCFQRKKEE-UHFFFAOYSA-N 2-(ethylamino)-4-methylphenol Chemical compound CCNC1=CC(C)=CC=C1O XXAGRMCFQRKKEE-UHFFFAOYSA-N 0.000 description 4
- 108010010803 Gelatin Proteins 0.000 description 4
- 229920000084 Gum arabic Polymers 0.000 description 4
- GRSMWKLPSNHDHA-UHFFFAOYSA-N Naphthalic anhydride Chemical compound C1=CC(C(=O)OC2=O)=C3C2=CC=CC3=C1 GRSMWKLPSNHDHA-UHFFFAOYSA-N 0.000 description 4
- 241000978776 Senegalia senegal Species 0.000 description 4
- 235000010489 acacia gum Nutrition 0.000 description 4
- 239000000205 acacia gum Substances 0.000 description 4
- 239000004927 clay Substances 0.000 description 4
- 229920000159 gelatin Polymers 0.000 description 4
- 239000008273 gelatin Substances 0.000 description 4
- 235000019322 gelatine Nutrition 0.000 description 4
- 235000011852 gelatine desserts Nutrition 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- ZKURGBYDCVNWKH-UHFFFAOYSA-N [3,7-bis(dimethylamino)phenothiazin-10-yl]-phenylmethanone Chemical compound C12=CC=C(N(C)C)C=C2SC2=CC(N(C)C)=CC=C2N1C(=O)C1=CC=CC=C1 ZKURGBYDCVNWKH-UHFFFAOYSA-N 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 150000002989 phenols Chemical class 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229960000892 attapulgite Drugs 0.000 description 2
- 239000000440 bentonite Substances 0.000 description 2
- 229910000278 bentonite Inorganic materials 0.000 description 2
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 2
- 235000010290 biphenyl Nutrition 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 150000002596 lactones Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052625 palygorskite Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- LIZLYZVAYZQVPG-UHFFFAOYSA-N (3-bromo-2-fluorophenyl)methanol Chemical compound OCC1=CC=CC(Br)=C1F LIZLYZVAYZQVPG-UHFFFAOYSA-N 0.000 description 1
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 125000000738 acetamido group Chemical group [H]C([H])([H])C(=O)N([H])[*] 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 150000004996 alkyl benzenes Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- FWQHNLCNFPYBCA-UHFFFAOYSA-N fluoran Chemical class C12=CC=CC=C2OC2=CC=CC=C2C11OC(=O)C2=CC=CC=C21 FWQHNLCNFPYBCA-UHFFFAOYSA-N 0.000 description 1
- UMGLBLXWFVODRF-UHFFFAOYSA-N formaldehyde;4-phenylphenol Chemical compound O=C.C1=CC(O)=CC=C1C1=CC=CC=C1 UMGLBLXWFVODRF-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000002430 hydrocarbons Chemical group 0.000 description 1
- 229940107698 malachite green Drugs 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 125000001624 naphthyl group Chemical group 0.000 description 1
- CDKDZKXSXLNROY-UHFFFAOYSA-N octylbenzene Chemical compound CCCCCCCCC1=CC=CC=C1 CDKDZKXSXLNROY-UHFFFAOYSA-N 0.000 description 1
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 150000004897 thiazines Chemical class 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- 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
- C09B11/10—Amino derivatives of triarylmethanes
- C09B11/24—Phthaleins containing amino groups ; Phthalanes; Fluoranes; Phthalides; Rhodamine dyes; Phthaleins having heterocyclic aryl rings; Lactone or lactame forms of triarylmethane 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
- B41M5/136—Organic colour formers, e.g. leuco dyes
- B41M5/145—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring
- B41M5/1455—Organic colour formers, e.g. leuco dyes with a lactone or lactam ring characterised by fluoran compounds
Definitions
- the color former is soluble in aro- UNITED STATES PATENTS matic solvents and also has excellent light fastnessr 3,442,908 5/1969 Orita et a1 260/335 8 Claims, N0 Drawings PRESSURE SENSITIVE COPYING PAPER BACKGROUND OF THE INVENTION Basically, pressure sensitive copying paper consists of two sheets of paper, the lower surface of the upper leaf having applied thereto minute capsules containing a color reactive achromatic substance (hereinafter called a color former) dissolved in a low volatile solvent and the upper surface of the lower leaf being coated with a solid acid, such as acid clay, zeolite, bentonite, attapulgite & phenolic compounds, etc.
- a color former color reactive achromatic substance
- the color former such as lactones, i.e., crystal violet lactone and malachite green lactone; thiazine compounds, i.e., benzoyl leucomethylene blue; and other leucoauramine and spiropyran compounds, and others. They have made it possible to manufacture various kinds of products which develop such colors ranging from yellow and red to blue, green and black.
- lactones i.e., crystal violet lactone and malachite green lactone
- thiazine compounds i.e., benzoyl leucomethylene blue
- other leucoauramine and spiropyran compounds and others.
- the light resistance after development of color particularly when inorganic substances such as acid clay, Silton (manufactured and soled by Mizusawa Chemical Company Ltd), etc. are used as the solid acid, has been unsatisfactory, so that it has been hoped for to fine out some solution for this defect.
- an excellent pressure sensitive copying paper can be obtained by using a new and novel color former which distinguish himself in the speed of color development, and the shade of the color, the simplicity of the manufacturing method and the light resistance of the color developed.
- the color former used in the present invention can be represented by the following general formula (I).
- 3-methyl-6-ethylamino-7-methylnaphthalfluoran (Ill) -NII CzHs 3 crn@ Ka a) l (111) is light brown crystal obtained by condensing 8- (4-methyl-2-hydroxybenzoyl)-a-naphthoic acid (which is obtained by condensing naphthalic anhydride and methacresol through Friedel-Crafts reaction) and 2-ethylaminoparacresol in sulfuric acid and having a melting point of 1 19 to 120C. 1t develops an orange color, reacting with a solid acid, and has a very good light resistance after developing into the color.
- (III) (1V) is light reddish brown crystal obtained by condensing 8-(5-methyl-2'-hydroxy-benzoyl)-anaphthoic acid (which is obtained by condensing naphthalic anhydride and paracresol through Friedel-Crafts reaction) and 2-ethylaminoparacresol in sulfuric acid and having a melting point of 187 to 192C. lt develops a yellowish orange color reacting with a solid acid, and has an excellent light resistance after developing into the color.
- 2-chloro-3-methyl-6-ethylamino-7-methylnaphthal- (V) is light reddish brown crystal obtained by condensing 8-(4-methyl-5'-chloro-2-hydroxybenzoyl)-anaphthoic acid (which is obtained by condensing naph- 'thalic anhydride and 2-chloromethacresol through Friedel-Crafts reaction) and 2 -ethylaminoparacresol in sulfuric acid and having a melting point of 160- 1 65C. It develops a yellowish orange color reacting with a solid acid, and has a remarkably excellent light resistance after developing into the color.
- V1 3-chloro-6-ethylamino-7-methylnaphthalfluoran (V1) 0 Cl Wavnmn (V1) is light reddish brown crystal obtained by condensing 8-(4-chloro-2-hydroxy-benzoyl)-a-naphthoic acid (which is obtained by condensing naphthalic anhydride and methachlorophenol through Friedel-Crafts reaction) and Z-ethylaminoparacresol in sulfuric acid and having a melting point of 167 to 170C. 1t develops a yellowish orange color reacting with a solid acid, and has an excellent light resistance after developing into the color.
- V11 is light ocherous crystal obtained by condensing 8-(2'-hydroxynaphthoyl)-a-naphthoic acid (which is obtained by condensing naphthalic anhydride and B-naphthol through Friedel-Crafts reaction) and 2- ethylaminoparacresol in sulfuric acid and having a melting point of 210 to 214C. 1t develops a black or blackish green color, reacting with a solid acid, and has an excellent light resistance after developing into the color.
- V111 3-methyl-6-diethylaminonaphthalfluoran
- V111 is light brown crystal obtained by condensing 8- (4-methyl-2-hydroxybenzoyl)-a-naphthoic acid (See the description about (111) and methadiethylaminophenol in sulfuric acid and having a melting point of 170 to 174C. 1t develops a reddish purple color, reacting with a solid acid, and has an excellent light resistance after developing into the color.
- EXAMPLE 2 1.2 g of 2-methyl-6-ethylamino-7-methylnaphthalfluoran (IV) was dissolved in 120 g of diphenyl chloride, then the solution thus prepared was treated in the same way as in Example 1 to obtain an aqueous dispersion of minute capsules. This was sprayed and dried into a powder of minute capsules, which was mixed with and dispersed in a 4 percent xylene solution of pphenylphenol formaldehyde condensate. And this dispersed solution was applied onto a sheet of paper and dried. When a regional pressure was exerted on this sheet of paper, it immediately developed a yellowish orange image, which showed an excellent light resistance.
- aromatic solvent used as a solvent in the foregoing examples, the same pressure sensitive copying paper can be obtained without problem with the use of other aromatic solvent.
- aromatic solvents of low volatility include lower alkyl diphenyls, such as methyl-, ethyland propyl diphenyl, and higher alkyl benzenes, such as dodecyl-, decyland octyl benzene, having a boiling point of above C. If the boiling point of the solvent is at least 150C, it has sufficient low volatility according to the invention.
- the solid acid functions as an electron acceptive adsorbent.
- zeolite bentonite, attapulgite and Silton (manufactured and saled by Mizusawa Chemical Company) can be used with excellent results.
- R R and R are members selected from the group consisting of hydrogen, methyl and halogen; R and R are both hydrogen or one of R and R is hydrogen, and the other is methyl or ethyl; and R is a member selected from the group consisting of hydrogen, methyl, amino and acetylamino; also R and R when joined together represent a hydrocarbon residue which forms a benzene ring.
- Pressure sensitive copying paper according to claim 1 comprising an upper leaf having said fluoran compound applied thereto, said compound being dissolved in a solvent of low volatility and the resulting solution being packed in minute capsules, and lower leaf having applied thereto a solid acid.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Color Printing (AREA)
Abstract
An excellent pressure sensitive copying paper is provided by applying a color former certain encapsuled 6-di lower alkyl amino-naphthalfluoran compounds to either a single sheet or to the upper leaf of a pressure sensitive paper. The color former is soluble in aromatic solvents and also has excellent light fastness.
Description
United States Patent Seki et a1. 5] Feb. 4, 1975 [54] PRESSURE SENSITIVE COPYING PAPER 3,506,471 4/1970 Kimura et a1. 117/362 3,514.311 5/1970 K t t'l 117/362 [75] Inventors: Hlmmlts Sek'; Ken! Yamamml 3,649,649 3/1972 260/335 x both ofOsaka-Japan 3.691.203 9/1972 Koya et a1 117/368 [73] Assignee: Yarnamoto Kaguku Gosei Kabushiki FQREIGN PATENTS OR APPUCATIONS Osaka Japan 1.018,?93 2/1966 Great Britain 2611/336 1 1 pp N913101585 Chemical Abstracts. Vol. 24. 1930 page 3.7130.
' Related US. Application Data P E Th J H b t J 1 rzmary xamzner omas er er r. [62] D1v1s10n of Ser. No. 208,415, Dec. 15, 1971. Attorney g or Firm Armstrong Nikaido & [30] Foreign Application Priority Data Wagner Dec. 15,1970 Japan 45-112053 ABSTRACT [52] U.S. c1 ll7/36.2, 117/368, 260/335 An excellent Pressure Sensitive py P p is P [51] Int. Cl. B4lc l/06 Vided pp a color former Certain encapsuled [58] Field of Search 117/362, 36.8; 260/335 lower alkyl amino-naphthalfluoran compounds to either a single sheet or to the upper leaf of a pressure [56] R f en Ci d sensitive paper. The color former is soluble in aro- UNITED STATES PATENTS matic solvents and also has excellent light fastnessr 3,442,908 5/1969 Orita et a1 260/335 8 Claims, N0 Drawings PRESSURE SENSITIVE COPYING PAPER BACKGROUND OF THE INVENTION Basically, pressure sensitive copying paper consists of two sheets of paper, the lower surface of the upper leaf having applied thereto minute capsules containing a color reactive achromatic substance (hereinafter called a color former) dissolved in a low volatile solvent and the upper surface of the lower leaf being coated with a solid acid, such as acid clay, zeolite, bentonite, attapulgite & phenolic compounds, etc. When the lower surface of the upper leaf and the upper surface of the lower leaf are put together and pressure is applied to the upper surface of the upper leaf by handwriting or typing, the capsules under pressure are broken and the color former contained therein is adsorbed by the solid acid on the upper surface of the lower leaf to develop a color, thus providing a copy.
There is also a type of pressure sensitive copying paper having a mechanism to develop a color when a regional pressure is exerted upon a sheet of paper holding capsules, which contain a color former, and a solid acid on or within it. However, such type is quite similar to the first-mentioned pressure sensitive copying paper (consisting of two sheets of paper, an upper and lower leaf) with respect to the mechanism of developing a color, and thus the same color former can be used for both types. And any of the above-mentioned facts belongs to the prior-known arts.
Conventionally, a number of compounds have been known to be useful as the color former, such as lactones, i.e., crystal violet lactone and malachite green lactone; thiazine compounds, i.e., benzoyl leucomethylene blue; and other leucoauramine and spiropyran compounds, and others. They have made it possible to manufacture various kinds of products which develop such colors ranging from yellow and red to blue, green and black. However, the light resistance after development of color, particularly when inorganic substances such as acid clay, Silton (manufactured and soled by Mizusawa Chemical Company Ltd), etc. are used as the solid acid, has been unsatisfactory, so that it has been hoped for to fine out some solution for this defect. It is only benzoyl leucomethylene blue that shows a satisfactory light resistance, but it develops a color at a very low speed. Therefore it can not be used for practical purposes, unless it is mixed with some other color former which develops a color at a higher speed. Even this mixed use offers much inconvenience from a practical point of view, since benzoyl leucomethylene blue, which develops a blue color, imposes a restriction on the variety.
SUMMARY In accordance with the invention, an excellent pressure sensitive copying paper can be obtained by using a new and novel color former which distinguish himself in the speed of color development, and the shade of the color, the simplicity of the manufacturing method and the light resistance of the color developed.
The color former used in the present invention can be represented by the following general formula (I).
That is to say, we have found that the fluoran compounds which have a naphthalene ring in the structure of the lactone ring can become a color former with an excellent light resistance and that they can be readily synthesized by the process shown by the following reaction formula.
COOII l DETAILED DESCRIPTION The following are typical examples of the novel color former.
3-methyl-6-ethylamino-7-methylnaphthalfluoran (Ill) -NII CzHs 3 crn@ Ka a) l (111) is light brown crystal obtained by condensing 8- (4-methyl-2-hydroxybenzoyl)-a-naphthoic acid (which is obtained by condensing naphthalic anhydride and methacresol through Friedel-Crafts reaction) and 2-ethylaminoparacresol in sulfuric acid and having a melting point of 1 19 to 120C. 1t develops an orange color, reacting with a solid acid, and has a very good light resistance after developing into the color.
(III) (1V) is light reddish brown crystal obtained by condensing 8-(5-methyl-2'-hydroxy-benzoyl)-anaphthoic acid (which is obtained by condensing naphthalic anhydride and paracresol through Friedel-Crafts reaction) and 2-ethylaminoparacresol in sulfuric acid and having a melting point of 187 to 192C. lt develops a yellowish orange color reacting with a solid acid, and has an excellent light resistance after developing into the color.
2-chloro-3-methyl-6-ethylamino-7-methylnaphthal- (V) is light reddish brown crystal obtained by condensing 8-(4-methyl-5'-chloro-2-hydroxybenzoyl)-anaphthoic acid (which is obtained by condensing naph- 'thalic anhydride and 2-chloromethacresol through Friedel-Crafts reaction) and 2 -ethylaminoparacresol in sulfuric acid and having a melting point of 160- 1 65C. It develops a yellowish orange color reacting with a solid acid, and has a remarkably excellent light resistance after developing into the color.
3-chloro-6-ethylamino-7-methylnaphthalfluoran (V1) 0 Cl Wavnmn (V1) is light reddish brown crystal obtained by condensing 8-(4-chloro-2-hydroxy-benzoyl)-a-naphthoic acid (which is obtained by condensing naphthalic anhydride and methachlorophenol through Friedel-Crafts reaction) and Z-ethylaminoparacresol in sulfuric acid and having a melting point of 167 to 170C. 1t develops a yellowish orange color reacting with a solid acid, and has an excellent light resistance after developing into the color.
l,2-benzo-6-ethylamino-7-methylnaphthalfluoran (V11) is light ocherous crystal obtained by condensing 8-(2'-hydroxynaphthoyl)-a-naphthoic acid (which is obtained by condensing naphthalic anhydride and B-naphthol through Friedel-Crafts reaction) and 2- ethylaminoparacresol in sulfuric acid and having a melting point of 210 to 214C. 1t develops a black or blackish green color, reacting with a solid acid, and has an excellent light resistance after developing into the color.
3-methyl-6-diethylaminonaphthalfluoran (V111) (V111) is light brown crystal obtained by condensing 8- (4-methyl-2-hydroxybenzoyl)-a-naphthoic acid (See the description about (111) and methadiethylaminophenol in sulfuric acid and having a melting point of 170 to 174C. 1t develops a reddish purple color, reacting with a solid acid, and has an excellent light resistance after developing into the color.
Now the present invention if further illustrated by the following examples.
EXAMPLE 1.
6 0 g of gelatin and 60 g of gum arabic were dissolved in 50 ml of water of 40C. On the other hand, 1.2 g of 3-methyl--ethylamino-7-methylnaphthalfluoran (Ill) was dissolved in 120 g of diphenyl chloride, and then this solution was added to the abovementioned aqueous solution of gelatin and gum arabic and perfectly dispersed into an emulsion by a homomixer. Water of 50C was added until its volume became 2,000 ml in total, followed by 90 ml of percent acetic acid. While stirring, water of 50C was further added until the total weight became 4 kg, and the stirring was continued for a period ofan hour. While still stirring, the solution was cooled down to below 10C with ice water, and 10 percent caustic soda was added until a pH of 9 was reached and gradually returned to room temperature. The product was applied onto the lower surface of the upper leaf and dried. On the other hand, a solid acid such as acid clay or phenolic compounds, was applied onto the upper surface of the lower leaf.
When copying was carried out with the upper and lower leaves thus prepared, an orange image developed, which showed an excellent light resistance.
EXAMPLE 2 1.2 g of 2-methyl-6-ethylamino-7-methylnaphthalfluoran (IV) was dissolved in 120 g of diphenyl chloride, then the solution thus prepared was treated in the same way as in Example 1 to obtain an aqueous dispersion of minute capsules. This was sprayed and dried into a powder of minute capsules, which was mixed with and dispersed in a 4 percent xylene solution of pphenylphenol formaldehyde condensate. And this dispersed solution was applied onto a sheet of paper and dried. When a regional pressure was exerted on this sheet of paper, it immediately developed a yellowish orange image, which showed an excellent light resistance.
EXAMPLE 3.
1.2 g of 2-chloro-3-methyl-6-ethylamino-7-methylnaphthalfluoran (V) was dissolved in 120 g of diphenyl chloride. By treating this solution in the same way as in Example 1, an aqueous dispersion of minute capsules was obtained. This was mixed with 8 g of fine power of p-phenylphenol formaldehyde condensate to disperse the latter therein, and further 40 g of pulp was added thereto. Then the dispersion was diluted with water until the final solid content became 0.5 percent. Then the product was run onto a Fourdrinier screen to be made into a sheet of paper. when this sheet of paper was subjected to a regional pressure, it immediately developed a reddish orange image, which showed an excellent light resistance.
EXAMPLE 4.
60 g of gelatin and 60 g/gum arabic were dissolved in /of 50 ml of water of 40C. On the other hand, 1.0 g of 3-chloro-7-acetylaminonaphthalfluoran (V111) was dissolved in 120 g of diphenyl chloride, and then this solution was added to the above-mentioned aqueous solution of gelatin and gum arabic and perfectly dispersed into an emulsion by a homo-mixer. Water of 50C was added until its volume became 2,000 ml in total, followed by 90 ml of 10 percent acetic acid. While stirring, water of 50C was further added until the total weight became 4 kg, and the stirring was continued for a period of an hour. While still stirring, the solution was reached and gradually returned to room temperature. The product was applied onto the lower surface of the upper leaf and dried. On the other hand. a solid acid such as acid clay or phenolic compounds. was applied onto the upper surface of the lower leaf.
When copying was carried out with the upper and lower leaves thus prepared, an bluish green image developed, which showed an excellent light resistance.
formaldehyde condensate. And this dispersed solution was applied onto a sheet of paper and dried. When a cooled down to below 10C with ice water, and 10 per-" cent caustic soda was added until a pH of 9 was regional pressure was exerted on this sheet of paper, it
developed a bluish green image, which showed an excellent light resistance.
EXAMPLE 6.
1.0 g of 3-chloro-7-acetylaminonaphthalfluoran (Vlll) was dissolved in I20 g of diphenyl chloride. By treating this solution in the same way as in Example 4. an aqueous dispersion of minute capsules was obtained. This was mixed with 8 g of fine powder of pphenylphenol formaldehyde condensate to disperse the latter therein, and further 40 g of pulp was added thereto. Then the dispersion was diluted with water until the final solid content became 0.5 percent. Then the product was run onto a Fourdrinier screen to be made into a sheet of paper. When this sheet of paper was subjected to a regional pressure, it developed a bluish green image, which showed an excellent light resistance.
Although an aromatic solvent was used as a solvent in the foregoing examples, the same pressure sensitive copying paper can be obtained without problem with the use of other aromatic solvent. Other aromatic solvents of low volatility include lower alkyl diphenyls, such as methyl-, ethyland propyl diphenyl, and higher alkyl benzenes, such as dodecyl-, decyland octyl benzene, having a boiling point of above C. If the boiling point of the solvent is at least 150C, it has sufficient low volatility according to the invention.
The solid acid functions as an electron acceptive adsorbent. In lieu of those used in the previous examples zeolite, bentonite, attapulgite and Silton (manufactured and saled by Mizusawa Chemical Company) can be used with excellent results.
What is claimed is:
1. In a pressure sensitive copying paper, a paper sheet having applied thereto at least one fluoran compound of the formula:
wherein R R and R are members selected from the group consisting of hydrogen, methyl and halogen; R and R are both hydrogen or one of R and R is hydrogen, and the other is methyl or ethyl; and R is a member selected from the group consisting of hydrogen, methyl, amino and acetylamino; also R and R when joined together represent a hydrocarbon residue which forms a benzene ring.
2. Pressure sensitive copying paper according to claim 1 comprising an upper leaf having said fluoran compound applied thereto, said compound being dissolved in a solvent of low volatility and the resulting solution being packed in minute capsules, and lower leaf having applied thereto a solid acid.
3. Pressure sensitive copying paper according to claim 1 in which a single sheet of paper has applied thereto said fluoran compound, said compound being dissolved in a solvent of low volatility and the resulting
Claims (7)
- 2. Pressure sensitive copying paper according to claim 1 comprising an upper leaf having said fluoran compound applied thereto, said compound being dissolved in a solvent of low volatility and the resulting solution being packed in minute capsules, and lower leaf having applied thereto a solid acid.
- 3. Pressure sensitive copying paper according to claim 1 in which a single sheet of paper has applied thereto sAid fluoran compound, said compound being dissolved in a solvent of low volatility and the resulting solution being packed in minute capsules, and a solid acid.
- 4. Pressure sensitive copying paper according to claim 1 wherein the fluoran compound is 3-methyl-6-ethylamino-7-methylnaphthalfluoran.
- 5. Pressure sensitive copying paper according to claim 1 wherein the fluoran compound is 2-methyl-6-ethylamino-7-methylnaphthalfluoran.
- 6. Pressure sensitive copying paper according to claim 1 wherein the fluoran compound is 2-chloro-3-methyl-6-ethylamino-7-methylnaphthalfluoran.
- 7. Pressure sensitive copying paper according to claim 1 wherein the fluoran compound is 3-chloro-6-ethylamino-7-methylnaphthalfluoran.
- 8. Pressure sensitive copying paper according to claim 1 wherein the fluoran compound is 1,2-benzo-6-ethylamino-7-methylnaphthalfluoran.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB5772671A GB1336955A (en) | 1970-12-15 | 1971-12-13 | Fluoran compounds and their use in pressure sensitive copying paper |
| US05/208,415 US3997561A (en) | 1970-12-15 | 1971-12-15 | Pressure sensitive copying paper |
| US310585A US3864145A (en) | 1970-12-15 | 1972-11-29 | Pressure sensitive copying paper |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP45112053A JPS493047B1 (en) | 1970-12-15 | 1970-12-15 | |
| US05/208,415 US3997561A (en) | 1970-12-15 | 1971-12-15 | Pressure sensitive copying paper |
| US310585A US3864145A (en) | 1970-12-15 | 1972-11-29 | Pressure sensitive copying paper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3864145A true US3864145A (en) | 1975-02-04 |
Family
ID=27312165
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/208,415 Expired - Lifetime US3997561A (en) | 1970-12-15 | 1971-12-15 | Pressure sensitive copying paper |
| US310585A Expired - Lifetime US3864145A (en) | 1970-12-15 | 1972-11-29 | Pressure sensitive copying paper |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US05/208,415 Expired - Lifetime US3997561A (en) | 1970-12-15 | 1971-12-15 | Pressure sensitive copying paper |
Country Status (2)
| Country | Link |
|---|---|
| US (2) | US3997561A (en) |
| GB (1) | GB1336955A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3985936A (en) * | 1974-01-29 | 1976-10-12 | Ciba-Geigy Corporation | Pressure-sensitive and/or heat sensitive copying or recording material |
| US4024157A (en) * | 1973-10-05 | 1977-05-17 | Sumitomo Chemical Company Limited | Fluoran compounds and recording sheet containing them |
| US4122089A (en) * | 1976-02-23 | 1978-10-24 | Sankio Chemical Co., Ltd. | Aminothiofluoran compounds, process for the production thereof, and recording elements containing the same |
| US4156682A (en) * | 1973-10-05 | 1979-05-29 | Sumitomo Chemical Company, Limited | Fluoran compounds and recording sheet containing them |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0262810B1 (en) * | 1986-09-03 | 1992-12-09 | Fuji Photo Film Co., Ltd. | Sheet recording material containing dye-forming components |
| AU605792B2 (en) * | 1987-07-01 | 1991-01-24 | Fuji Photo Film Co., Ltd. | Recording material |
| US6020481A (en) * | 1996-04-01 | 2000-02-01 | The Perkin-Elmer Corporation | Asymmetric benzoxanthene dyes |
| GB9818836D0 (en) | 1998-08-29 | 1998-10-21 | Ciba Sc Holding Ag | Process for the manufacture of mixed fluran systems |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3442908A (en) * | 1965-12-09 | 1969-05-06 | Nisso Kako Co Ltd | 6-dialkylaminofluorans |
| US3506471A (en) * | 1966-11-14 | 1970-04-14 | Fuji Photo Film Co Ltd | Pressure-sensitive fluorane derivative containing copying paper |
| US3514311A (en) * | 1967-10-31 | 1970-05-26 | Fuji Photo Film Co Ltd | Pressure sensitive 3-substituted amino - 6 chlorofluoran containing copying paper |
| US3649649A (en) * | 1967-07-10 | 1972-03-14 | Nisso Kako Co Ltd | Fluoran derivatives and preparation thereof |
| US3691203A (en) * | 1970-04-06 | 1972-09-12 | Sumitomo Chemical Co | Fluoran derivatives for pressure sensitive copying paper |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2031023A (en) * | 1933-06-30 | 1936-02-18 | Ici Ltd | Rhodamine coloring matters and process for preparing the same |
| GB1018793A (en) * | 1961-08-31 | 1966-02-02 | Burroughs Corp | Coating and marking method utilizing biphenols and substituted phenols and colored products thereof |
-
1971
- 1971-12-13 GB GB5772671A patent/GB1336955A/en not_active Expired
- 1971-12-15 US US05/208,415 patent/US3997561A/en not_active Expired - Lifetime
-
1972
- 1972-11-29 US US310585A patent/US3864145A/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3442908A (en) * | 1965-12-09 | 1969-05-06 | Nisso Kako Co Ltd | 6-dialkylaminofluorans |
| US3506471A (en) * | 1966-11-14 | 1970-04-14 | Fuji Photo Film Co Ltd | Pressure-sensitive fluorane derivative containing copying paper |
| US3649649A (en) * | 1967-07-10 | 1972-03-14 | Nisso Kako Co Ltd | Fluoran derivatives and preparation thereof |
| US3514311A (en) * | 1967-10-31 | 1970-05-26 | Fuji Photo Film Co Ltd | Pressure sensitive 3-substituted amino - 6 chlorofluoran containing copying paper |
| US3691203A (en) * | 1970-04-06 | 1972-09-12 | Sumitomo Chemical Co | Fluoran derivatives for pressure sensitive copying paper |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4024157A (en) * | 1973-10-05 | 1977-05-17 | Sumitomo Chemical Company Limited | Fluoran compounds and recording sheet containing them |
| US4156682A (en) * | 1973-10-05 | 1979-05-29 | Sumitomo Chemical Company, Limited | Fluoran compounds and recording sheet containing them |
| US3985936A (en) * | 1974-01-29 | 1976-10-12 | Ciba-Geigy Corporation | Pressure-sensitive and/or heat sensitive copying or recording material |
| US4122089A (en) * | 1976-02-23 | 1978-10-24 | Sankio Chemical Co., Ltd. | Aminothiofluoran compounds, process for the production thereof, and recording elements containing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| US3997561A (en) | 1976-12-14 |
| GB1336955A (en) | 1973-11-14 |
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