US3725416A - 7-piperidinofluoran - Google Patents

7-piperidinofluoran Download PDF

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Publication number
US3725416A
US3725416A US00093897A US3725416DA US3725416A US 3725416 A US3725416 A US 3725416A US 00093897 A US00093897 A US 00093897A US 3725416D A US3725416D A US 3725416DA US 3725416 A US3725416 A US 3725416A
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US
United States
Prior art keywords
color
piperidinofluoran
black
sheet
compounds
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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US00093897A
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English (en)
Inventor
K Yamamoto
N Sasaki
M Terayama
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Yamamoto Chemicals Inc
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Yamamoto Chemicals Inc
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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

Definitions

  • ABSTRACT Compounds and a pressure-sensitive copying sheet containing said compounds as a color-forming agent art provided said compounds have the following general formula:
  • each of R and R is independently alkyl of up to 4 carbon atoms; and each of X and Y is independently hydrogen, halogen of alkylrof up to 4 carbon atoms.
  • This invention relates to a pressure-sensitive copying sheet and more particularly to a pressure-sensitive copying sheet using a novel fluoran compound as a color forming agent.
  • a pressure-sensitive copying sheet which comprises an upper sheet and a lower sheet.
  • the back of the upper sheet is coated with a thin layer of micro-capsules which can be ruptured by a local pressure imparted, for example, by handwriting with pen, pencile, ball-point pen or the like or by typewriting and which contain an electron donating, adsorbable and color-developable colorless organic compound (hereinafter referred to as color forming agent") dissolved in a non-volatile solvent or oil.
  • color forming agent an electron donating, adsorbable and color-developable colorless organic compound
  • the upper sheet is placed upon the lower sheet in such a manner that the back face of the upper sheet would contact the surface of the lower sheet.
  • a local pressure is applied on the exposed surface of the upper sheet by handwriting or typewriting, the micro-capsules are ruptured and the color-forming colorless agent is transferred from the upper sheet to the surface layer on the lower sheet and is adsorbed by the electron acceptive adsorbent to develope color.
  • CVL has an advantage that it is high in the color-forming reaction velocity but has a drawback that the resistance to light and water or moisture is poor.
  • BLMB has a drawback that its color-forming reaction velocity is low but has an advantage that it, once color-developed, has a high resistance to light and water or moisture. Therefore, when these two agents are used together the respective drawbacks are mutually compensated.
  • CVL BLMB mixed system has another drawback that it can develope only a bluish color and not black.
  • black color is desirable because a black image is more distinctively. legible and because a black image can be reproduced or copyed in a more sharp, dense and legible image, than from a bluish image, by the presently available copying machines of various types such as Xerox, thermography, etc. utilizing ultraviolet rays or short wave visible rays.
  • the first one is to use a mixture of various color-forming agents to develope a color as close to black as possible.
  • Most typical proposal in this respect is to add a red color-forming agent (such as Rhodamine-lactam) to the above mentioned CVL BLMB system to develope violet color which is more close to black than blue of the CVL BLMB system.
  • a red color-forming agent such as Rhodamine-lactam
  • Another measure which has been proposed is to incorporate an ultraviolet absorber into the color forming agent so that the developed image may be reproduced by copying machines.
  • these methods have not been fully satisfactory.
  • Another object of this invention is to provide a pressure-sensitive copying sheet by using the above mentioned novel compound.
  • this invention provides color-developable substantially colorless organic compounds having the following general formula:
  • each of R, and R is a lower alkyl radicals having 1 4 carbon atoms and each of X and Y a member selected from the group consisting of hydrogen, halogen atoms (e.g.' chlorine, bromine, etc.) and lower alkyl radicals of l 4 carbon atoms.
  • halogen atoms e.g.' chlorine, bromine, etc.
  • the piperidino radical-containing fluoran compounds represented by the above indicated general formula (l) are novel compounds which are substantially colorless but, upon adsorption on a phenolic resin (electron acceptive adsorbent) can develope black color.
  • a phenolic resin electron acceptive adsorbent
  • the said compounds may develope a color ranging from dark red to reddish violet. Therefore in latter cases (the use of an inorganic electron accepting solid adsorbent), black color can be developed by using the compound of the formula (I) together with a small amount of other color developing agent such as 3- diethylamino-7-benzylamino fluoran, etc. disclosed in US. Pat. No. 3,501,331 (Canadian Pat. No. 814,948).
  • the piperidino groupcontaining fluoran compounds of this invention are compatible with conventional color-forming agent, soluble in various solvents or oils and the color developed therefrom is high in resistance or fastness to light. Therefore, the colorforming agents (piperidino group-containing fluoran compounds) of this invention are excellent for use in making pressure-sensitive copying sheet.
  • the piperidino-containing fluoran compounds of the general formula (I) may be prepared, for example, as follows. Thus, p-anisidine or its nucleus substitute is reacted with 1,5-dibromopentane to obtain pperidinoanisol or its derivative of the formula:
  • 3- diethylamino-7piperidinofluoran of the formula A is as follows.
  • 27 g. of p-anisidine and 17.5 g. of 1,5- dibromopentane in 50 ml. of methanol were refluxed for 17 hours.
  • 50 g. of 20 percent aqueous solution of sodium hydroxide was added to the reaction mixture, and the formed oily layer was separated and purified by vacuum distillation to recover the fraction of l 14l 18 C./4 mml-lg., which is colorless p-piperidinoanisol. Yield 9.5 g. (65.6 percent oftheory).
  • EXAMPLE 1 In 500 ml. of water there were dissolved at 40C. 600 g. of gelatin and 60 g. of gum arabic. On the other hand, g. of 3diethylamino-7-piperidinofluoran were dissolved in 150 g. of diphenylchloride. The latter solution was added to the former solution and the mixture was emulsified by a homogenizer. Then water at 50C. was added thereto until the whole becomes 2000 ml. Then 90 ml.
  • the coating composition thus prepared was applied on the lower surface of the upper sheet by roll-coating and dried.
  • an aqueous gelatine solution containing powder of phenolic resin (p-phenylphenol-formaldehyde condensation product) dispersed therein was applied on the upper face of a lower sheet and was dried.
  • the coated upper sheet was placed on the coated lower sheet in such a way that the respective coated layers contact intimately with each other.
  • black color was rapidly developed on the written area on the upper face of the lower sheet. This color did not fade even upon exposure to the sun light for a long time.
  • EXAMPLE 2 The same procedure as in Example 1 was repeated except that 3-diethylamino-5methyl-7- piperidinofluoran was used instead of 3-diethylamino- 4-piperidinofluoran. Upon writing, black color was developed when phenolic resin used as the absorbent, while dark reddish violet was developed when silton was used as the adsorbent.
  • EXAMPLE 3 The procedure same as in Example 1 was repeated except that, instead of 5 g. of 3-diethylamino-7- piperidinofluoran, there were used a mixture of 4.5 g. of 3diethylamino-7-piperidinofluoran and 0.5 g. of 3- diethylamino-7-benzylaminofluoran (US. Pat. No. 3,501,33l and silton was used as the adsorbent. Upon writing there was developed black color.
  • EXAMPLE 4 The same procedure as in Example 1 was repeated except that 3-diethylamino-5chloro-7- piperidinofluoran (C), 3-dimethylamino-7- piperidinofluoran (D) or 3-dimethylamino-5me'thyl-7- 50C. until the whole becomes 4 kg.
  • the stirring was piperidinofluoran (E) was used in place of 3- di'ethylamino-7-piperidinofluoran. Upon writing the following colored copies were obtained.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Color Printing (AREA)
US00093897A 1969-12-05 1970-11-30 7-piperidinofluoran Expired - Lifetime US3725416A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP44098034A JPS4816202B1 (is") 1969-12-05 1969-12-05

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US3725416A true US3725416A (en) 1973-04-03

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3837889A (en) * 1972-02-21 1974-09-24 Wiggins Teape Ltd Colour formers
US3930672A (en) * 1973-03-23 1976-01-06 Hodogaya Chemical Co., Ltd. Pressure-sensitive copying paper containing lactone compounds derived from pyridine-carboxylic acid
US3959571A (en) * 1973-05-22 1976-05-25 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives and the preparation and use thereof
US4046776A (en) * 1974-04-09 1977-09-06 Ciba-Geigy Corporation Heterocyclic substituted lactone compounds

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102078016B1 (ko) 2018-04-10 2020-04-07 삼성전기주식회사 적층형 커패시터

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442908A (en) * 1965-12-09 1969-05-06 Nisso Kako Co Ltd 6-dialkylaminofluorans

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442908A (en) * 1965-12-09 1969-05-06 Nisso Kako Co Ltd 6-dialkylaminofluorans

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Ramette et al., J. Am. Chem. Soc. 78, 4872 8 (1956). *
Viktorova et al., Chem. Abstracts 64:7546d. *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3837889A (en) * 1972-02-21 1974-09-24 Wiggins Teape Ltd Colour formers
US3930672A (en) * 1973-03-23 1976-01-06 Hodogaya Chemical Co., Ltd. Pressure-sensitive copying paper containing lactone compounds derived from pyridine-carboxylic acid
US3959571A (en) * 1973-05-22 1976-05-25 Shin Nisso Kako Co., Ltd. Chromogenic fluoran derivatives and the preparation and use thereof
US4046776A (en) * 1974-04-09 1977-09-06 Ciba-Geigy Corporation Heterocyclic substituted lactone compounds

Also Published As

Publication number Publication date
JPS4816202B1 (is") 1973-05-21

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