US3769062A - Pressure-sensitive recording paper - Google Patents

Pressure-sensitive recording paper Download PDF

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Publication number
US3769062A
US3769062A US00160775A US3769062DA US3769062A US 3769062 A US3769062 A US 3769062A US 00160775 A US00160775 A US 00160775A US 3769062D A US3769062D A US 3769062DA US 3769062 A US3769062 A US 3769062A
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United States
Prior art keywords
pressure
recording paper
ether
sensitive recording
color
Prior art date
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
Application number
US00160775A
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English (en)
Inventor
S Ishige
T Hayashi
H Matsukawa
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Fujifilm Holdings Corp
Original Assignee
Fuji Photo Film Co Ltd
Priority date (The priority date 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 date listed.)
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Publication date
Application filed by Fuji Photo Film Co Ltd filed Critical Fuji Photo Film Co Ltd
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Publication of US3769062A publication Critical patent/US3769062A/en
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    • 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

Definitions

  • This invention relates to a pressure-sensitive record- 5 2.
  • Description of the Prior Art Pressure-sensitive recording paper as it has been known, for example, by US Pat. Nos. 2,712,507, 2,730,465, and 2,730,457, is based on the utilization of microcapsules containing a solution of a substantially colorless organic compound (hereinafter, referred to color former) and an electron-accepting adsorbent substance (hereinafter referred to color developer).
  • color former substantially colorless organic compound
  • color developer electron-accepting adsorbent substance
  • an upper sheet means a support having coated thereon, a layer of microcapsules containing a color former
  • an intermediate sheet means a support having coated on one surface, a layer of microcapsules containing a color former and having coated on the opposite surface, a layer of color developer
  • an undersheet means a support having coated thereon, a color developer.
  • a single-fold sheet means a support having coated thereon, a layer of microcapsules and a color developer, simultaneously.
  • the color formers are malachite green t n which s ,.3-b (eim MlamimnhsnrD- phthalide, benzoyl leuco methylene blue, crystal violet lactone, which is 3,3bis(p-dimethylaminophenyl)-6 dimethylamino phthalide, Rhodamine B lactam, 3- dialkylaminoJ dialkylamino-fluorans, and 3 -methyl-
  • the color developen which is capable for forming a color dye when contacted with the color former, may be an active clay substance, such as acid clay, active clay, attapulgite, zeolite or bentonite, and organic acidic substances, such as succinic acid, tannic acid, gallic acid, pentachlorophenol and phenol resins.
  • the light resistance of the color dye formed by reaction of the color former and color developer depends upon the structure of the color former and also upon the color developer.
  • the color developers now in wide use are clays, such as acidic clay.
  • the light resistance of the color dye formed on an under sheet using this developer, although differing in the type of the color former, is generally poor except benzoyl leucomethylene blue.
  • the color former most often employed is a mixture of crystal violet lactone and benzoyl leuco methylene blue. Since crystal violet lactone has a very poor resistance to light, the color dye formed on the color developer sheet fades when allowed to stand indoors or exposed to sunlight. Consequently, only the light blue color formed from methylene blue remains, which obviously reduces the commercial value of the recording paper.
  • m nq:7rdi thyl miwfluq an isusefii It develops a green cdlor on acid clay, but changes to red brown on standing indoors or on exposure to sun. light. Accordingly, the black or green color formed by.
  • 3benzylamino-7-diethylaminofluoran assumes a reddish color on standing indoors or exposure to sunlight, resulting in a reduction in the commercial value of the pressure-sensitive recording paper.
  • the foregoing object is achieved by incorporating at least one ether derivative of an aromatic hydroxyl compound in the coating layer of the pressure-sensitive recording paper.
  • Examples of the ether derivative of the aromatic hydroxyl compound applicable to this invention include p-chloroanisole, p-methylanisole, p-acetoxyanisole, pacetaminoanisole, o-chloroanisole, m-chloroanisole, N
  • the acceptable amount of the ether derivative of the aromatic hydroxyl compound applicable to this invention ranges from 10 to 200% by weight based on the weight of the color former used, or 0.2 to 10% based on the weight of the color developer used.
  • Microcapsules containing the color former may be produced, for example, by the process disclosed in U.S. Pat. No. 2,700,458, but the process of microcapsulation is not limited to such, since the present invention is directed to incorporation of the ether derivative.
  • Example I former oil in which 3% of hydroquinone dimethyl ether had been dissolved. This mixed solution was emulsified and dispersed.
  • the color former oil consisted of a solution of four parts of diphenyl chloride and one part of kerosene in which 2% of crystal violet lactone was dissolved.
  • the addition of the sodium hydroxide was performed with meticulous care so as not to coagulate the system. With continued stirring, the liquid was heated to 50 C. After cooling to C., the microcapsule liquid thus obtained was coated onto a paper having a unit weight of 40 g/rn in an amount of 6 g/m as solid content, and dried to make an upper sheet of pressure sensitive recording paper.
  • Example 2 To 40 parts of a color former oil consisting of a solution of 2% crystal violet lactone in an oil conposed of four parts of diphenyl chloride and one part of kerosene was dissolved 3%, based on the color former oil, of N-(B-cyanoethyl) p-anisidine. The solution was microencapsulated in the same manner as in Example 1. The resulting microcapsule liquid was coated onto a paper having a unit weight of 40 g/m in an amount of 6 g/m as solid content, and dried to form an upper sheet of pressure-sensitive recording paper.
  • a color former oil consisting of a solution of 2% crystal violet lactone in an oil conposed of four parts of diphenyl chloride and one part of kerosene was dissolved 3%, based on the color former oil, of N-(B-cyanoethyl) p-anisidine.
  • the solution was microencapsulated in the same manner as in Example 1.
  • the resulting microcapsule liquid was coated
  • Example ⁇ I To 40 parts of a color former oil obtained by dissolving 2% crystal violet lactone in an oil consisting of four parts of diphenyl chloride and one part of kerosene was dissolved 3% by weight, based on the oil, of pmethylanisole. The solution was microencapsulated in the same way as in Example l. The res uIting microcapsule liquid was coated o rito a paper having a unit weight of 40 g/m in an amount of 6 g/m as solid content, and dried to form an upper sheet of pressure-sensitive recording paper.
  • C0MPARATIYE EXAMPLE 1 40 parts of a color former oil obtained by dissolving 2% crystal violet Iactone in an oil consisting of four parts of diphenyl chloride and one part of kerosene was microencapsulated in the same manner as in Example I. The resulting microcapsule liquid yv a s coated onto a paper having a unit weight of 40 g/m in an amount of 6 g/m as solid content, and dried-to form an upper sheet of pressure-sensitive recording paper.
  • Comparative test 1 Each fthssnrs ee Q E mP s d 3 n if Comparative Example 1 was superposed on the under sheet, and a pressure of 600 Kg/cm was applied to produce a color. After allowing the specimen to stand for 1 hour in dark, the spectral absorption curve (fresh) in a wave-length region of 700 to 380 mp. was measured with respect to the developed color. The results are shown in FIG. 1,(1)'to (4)..
  • the measurement of the spectral absorption curve was performed using a Beckman spectrophotometer, Type DB.
  • the light resistance values were obtained as follows:
  • Example 5 In 40 parts of a'color former oil obtained by dissolvl ififii l i j IQPIFPPKPEEZSLQQEKQEPEE! IE3) oil consisting of four parts of diphenyl chloride and one part of kerosene was dissolved 3%, based on the oil, of N-(B-cyano-ethyl)-p-anisidine. The solution wa s microencapsulatedin the same wayas in Example 1. The resulting microcapsule liquid was coated on a paper having a unit weight of 40 g/m in an amount of 6 g/m as solid content, and dried to form an upper sheet of pressure-sensitive recording paper.
  • Example 6 COMPARATIVE EXAMPLE 2 40 parts of a color former oil obtained by dissolving 2% 3-methyl-2,2'-spirobi(benzo[fjchromenefin an oilconsisting of four parts of diphenyl chloride and one part of kerosene was microencapsulated in the same way as in Example l. The resulting microcapsule solution was coated on a paper having a unit weight of 40 g/m in an amount of 6 g/m as solid content, and dried to form an upper sheet of pressure-sensitive recording paper. Comparative test 2 Each of the upper sheets obtained in Examples 4, 5 and 6 and Comparative Example 2 was superposed on the test under sheet, and a pressure of 600 Kg/cm was applied to develop a color.
  • Example 7 To 40 parts of a color former oil obtained by dissolv oil consisting of four parts of diphenyl chloride and one part of kerosene was dissolved 3%, based on the oil, of hydroquinone dimethyl ether. The solution was microencapsulated in the same way as set forth in Example 1. The resulting microcapsule liquid was coated on a paper having unit weight of 4Og/m in an amount of 6 g/m as solid content, and dried to form an upper sheet of pressure-sensitive recording paper.
  • the resulting microcapsule liquid was coated on a paper having a unit weight of 40 g/m in an amount of 6 g/m as solid content, and dried to form an upper sheet of pressuresensitive recording paper.
  • Example 4 perpo sed on each of the under sheets obtained in Example l and Comparative Example 4. and a pressure of 600 Kg/cm was applied aaawmpa color. Afifhllowing the paper to stand for 1 hour in dark, the spectral absorption curve (fresh) in a wavelength region of 700 to 380 mp. was measured. The spectral absorption curve of the developedcolor after sunlight exposure for 1 hour and 3 hours, respectively,-was also measured. The results are shown in FIG. 4, (1).
  • the result of Comparative Example 4 was the same as that of Com-j parative Example 1. The light resistance values were calculated in the same way as in Comparative Test 1.
  • the spectral absorption curve fresh in a wavelength region of 700 to 380 mp. was measured.
  • ether derivative is a member selected from the group consisting of p-chloroanisoleppmethylanisole, p-acetoxyanisole, p-acetaminoanisole, o-chloroanisole, m-chloroanisole, Nfi-cyanoethyl p -anisidene, p r netltoxyacetophenone, pmethoxybenzophenone, 2,2-biZEifieih6fifi1'fiy1 1556 pane, catechol dimethyl ether, resorcinol dimethyl ether, hydroquinone dimethyl ether, catechol diethyl ether, resorcinol dipropyl ether, hydroquinone dibutyl ether, p-methoxybenzoic acid ethyl ester, p-ethoxybenzenesdlfonamide, l -phenoxy-2-cyanoethane, 1-phenoxy-2
  • said color former is a member selected from the group consisting of malachite green, benzoyl leuco methylene blue, crystal violet lactone, Rhodamine B .lactam, 3-dialkylamino Tdialkylamino-fluorans, and
  • said color developer is a member selected resins.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
US00160775A 1970-07-08 1971-07-08 Pressure-sensitive recording paper Expired - Lifetime US3769062A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP45059698A JPS4833212B1 (enrdf_load_stackoverflow) 1970-07-08 1970-07-08

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US3769062A true US3769062A (en) 1973-10-30

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Country Status (8)

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US (1) US3769062A (enrdf_load_stackoverflow)
JP (1) JPS4833212B1 (enrdf_load_stackoverflow)
BE (1) BE769713A (enrdf_load_stackoverflow)
CA (1) CA952381A (enrdf_load_stackoverflow)
ES (1) ES392889A1 (enrdf_load_stackoverflow)
FR (1) FR2100432A5 (enrdf_load_stackoverflow)
GB (1) GB1354969A (enrdf_load_stackoverflow)
IE (1) IE36673B1 (enrdf_load_stackoverflow)

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3871900A (en) * 1972-07-28 1975-03-18 Fuji Photo Film Co Ltd Recording sheet
US3900217A (en) * 1970-06-13 1975-08-19 Fuji Photo Film Co Ltd Pressure-sensitive copying paper
US3915731A (en) * 1972-01-28 1975-10-28 Mizusawa Industrial Chem Aqueous composition containing color former for pressure-sensitive production
US3968299A (en) * 1975-02-21 1976-07-06 Angleman John D Two-way, selective directional, image-transfer sheet
US3979141A (en) * 1974-11-21 1976-09-07 Moore Business Forms, Inc. Pressure-sensitive recording system comprising 3'-amino-6' or 7'-(pyrazol-1-yl)fluoran compounds as color precursors
US4066568A (en) * 1975-08-07 1978-01-03 Nippon Pulp Industry Company Limited Method of producing microcapsules
US5135437A (en) * 1989-11-13 1992-08-04 Schubert Keith E Form for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same
US5137494A (en) * 1989-11-13 1992-08-11 Schubert Keith E Two-sided forms and methods of laying out, printing and filling out same
US5154668A (en) * 1989-04-06 1992-10-13 Schubert Keith E Single paper sheet forming a two-sided copy of information entered on both sides thereof
US5197922A (en) * 1989-04-06 1993-03-30 Schubert Keith E Method and apparatus for producing two-sided carbonless copies of both sides of an original document
US5224897A (en) * 1989-04-06 1993-07-06 Linden Gerald E Self-replicating duplex forms
US5248279A (en) * 1989-04-06 1993-09-28 Linden Gerald E Two-sided, self-replicating forms
US5395288A (en) * 1989-04-06 1995-03-07 Linden; Gerald E. Two-way-write type, single sheet, self-replicating forms
US6280322B1 (en) 1989-11-13 2001-08-28 Gerald E. Linden Single sheet of paper for duplicating information entered on both surfaces thereof

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2005030888A1 (en) 2003-09-29 2005-04-07 Fuji Photo Film Co., Ltd. Ink for inkjet printing, ink set for inkjet printing, inkjet recording material and producing method for inkjet recording material, and inkjet recording method.
EP2130876A1 (en) 2004-02-24 2009-12-09 FUJIFILM Corporation Inorganic fine particle dispersion and manufacturing method thereof as well as image-recording material
JP4250121B2 (ja) 2004-07-02 2009-04-08 富士フイルム株式会社 インクジェット記録用媒体
JP2009034942A (ja) 2007-08-03 2009-02-19 Fujifilm Corp インクジェット記録用媒体
JP2009107319A (ja) 2007-11-01 2009-05-21 Fujifilm Corp インクジェット記録材料
JP2010030197A (ja) 2008-07-30 2010-02-12 Fujifilm Corp インクジェット記録方法
JP2010030196A (ja) 2008-07-30 2010-02-12 Fujifilm Corp インクジェット記録方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3455721A (en) * 1964-12-21 1969-07-15 Ncr Co Color sensitized record material comprising phenolic resin and acid type mineral
US3509174A (en) * 1967-01-30 1970-04-28 Ncr Co 3-(indol-3-yl)-phthalides
US3592677A (en) * 1967-02-07 1971-07-13 Fuji Photo Film Co Ltd Pressure sensitive recording materials

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3455721A (en) * 1964-12-21 1969-07-15 Ncr Co Color sensitized record material comprising phenolic resin and acid type mineral
US3509174A (en) * 1967-01-30 1970-04-28 Ncr Co 3-(indol-3-yl)-phthalides
US3592677A (en) * 1967-02-07 1971-07-13 Fuji Photo Film Co Ltd Pressure sensitive recording materials

Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3900217A (en) * 1970-06-13 1975-08-19 Fuji Photo Film Co Ltd Pressure-sensitive copying paper
US3915731A (en) * 1972-01-28 1975-10-28 Mizusawa Industrial Chem Aqueous composition containing color former for pressure-sensitive production
US3871900A (en) * 1972-07-28 1975-03-18 Fuji Photo Film Co Ltd Recording sheet
US3979141A (en) * 1974-11-21 1976-09-07 Moore Business Forms, Inc. Pressure-sensitive recording system comprising 3'-amino-6' or 7'-(pyrazol-1-yl)fluoran compounds as color precursors
US3968299A (en) * 1975-02-21 1976-07-06 Angleman John D Two-way, selective directional, image-transfer sheet
US4066568A (en) * 1975-08-07 1978-01-03 Nippon Pulp Industry Company Limited Method of producing microcapsules
US5197922A (en) * 1989-04-06 1993-03-30 Schubert Keith E Method and apparatus for producing two-sided carbonless copies of both sides of an original document
US5154668A (en) * 1989-04-06 1992-10-13 Schubert Keith E Single paper sheet forming a two-sided copy of information entered on both sides thereof
US5224897A (en) * 1989-04-06 1993-07-06 Linden Gerald E Self-replicating duplex forms
US5248279A (en) * 1989-04-06 1993-09-28 Linden Gerald E Two-sided, self-replicating forms
US5395288A (en) * 1989-04-06 1995-03-07 Linden; Gerald E. Two-way-write type, single sheet, self-replicating forms
US5137494A (en) * 1989-11-13 1992-08-11 Schubert Keith E Two-sided forms and methods of laying out, printing and filling out same
US5135437A (en) * 1989-11-13 1992-08-04 Schubert Keith E Form for making two-sided carbonless copies of information entered on both sides of an original sheet and methods of making and using same
US6280322B1 (en) 1989-11-13 2001-08-28 Gerald E. Linden Single sheet of paper for duplicating information entered on both surfaces thereof

Also Published As

Publication number Publication date
DE2134114B2 (de) 1973-06-07
DE2134114A1 (de) 1972-02-17
IE36673L (en) 1972-01-08
BE769713A (fr) 1971-11-16
CA952381A (en) 1974-08-06
ES392889A1 (es) 1974-07-16
GB1354969A (en) 1974-06-05
IE36673B1 (en) 1977-02-02
FR2100432A5 (enrdf_load_stackoverflow) 1972-03-17
JPS4833212B1 (enrdf_load_stackoverflow) 1973-10-12

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