US3867169A - Non-carbon copying upper paper - Google Patents

Non-carbon copying upper paper Download PDF

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Publication number
US3867169A
US3867169A US280163A US28016372A US3867169A US 3867169 A US3867169 A US 3867169A US 280163 A US280163 A US 280163A US 28016372 A US28016372 A US 28016372A US 3867169 A US3867169 A US 3867169A
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United States
Prior art keywords
paper
microspheres
process according
microcapsules
coating
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Expired - Lifetime
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US280163A
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English (en)
Inventor
Hideo Shimizu
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.)
APPLETON PAPERS INCA CORP OF DE
Appvion Operations Inc
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Mitsubishi Paper Mills Ltd
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Assigned to APPLETON PAPERS INC.A CORP. OF DE. reassignment APPLETON PAPERS INC.A CORP. OF DE. ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: MITSUBISHI PAPER MILLS, LTD.
Assigned to APPLETON PAPERS INC. reassignment APPLETON PAPERS INC. MERGER (SEE DOCUMENT FOR DETAILS). FILED 12/1781, EFFECTIVE DATE: 01/02/82 STATE OF INCORP. DE Assignors: GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS), TUVACHE, INC.
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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
    • B41M5/1243—Inert particulate additives, e.g. protective stilt materials

Definitions

  • a non-carbon copying paper comprising upper paper, lower paper and/or at least one intermediates paper
  • smoothness of coating surface of the upper or intermediate paper can be improved and smudge formation on the paper and changes in compositions of coating material during application can be prevented by incorporating microspheres, e.g., vinyliclene chloride-acrylic acid ester copolymer microspheres in the coating layer of microcapsules on the upper or intermediate paper.
  • FIG. 1 A first figure.
  • the present invention relates to an improved noncarbon copying paper.
  • a non-carbon copying paper generally comprises an upper paper the back face of which is coated with microcapsules in which an oil in which an electron donating organic color former, e.g., a triphenylmethane dye such as crystal violet lactone, a leuco dye such as benzoil leucomethylene blue is dissolved is contained by coacervation method disclosed in US. Pat. No. 2,800,457, a lower paper the top face of which is coated with a solid acid such as attapulgite, montmorillonite, bentonite, Japanese acid clay, kaolin or an oil soluble phenol resin and at least one intermediate papers, the top face of which is coated with a solid acid and the back face of which is coated with microcapsules.
  • an electron donating organic color former e.g., a triphenylmethane dye such as crystal violet lactone, a leuco dye such as benzoil leucomethylene blue is dissolved
  • a solid acid such as attapulgite, montmorillon
  • the coated face of the upper paper and that of the lower paper are allowed to contact with each other of the intermediate paper or papers are put therebetween and writing pressure is applied to the top face of the upper paper to form a coloredimage corresponding to said pressure applied image on the lower paper or the intermediate paper,
  • the kind of starch can be suitably selected and moreover since the particle size is relatively uniform, the smoothness of the coated face of the upper paper can be considerably improved. Furthermore, the aqueous coating material prepared by mixing the starch particles and the microcapsules is considerably improved in stability and the degree of increase of viscosity is low. However, with progress of the coating of the coating material, the compositions of the coating material change because the specific gravity (about 1.6) and average particle size (about 30p) of the starch particles are considerably greater than the specific gravity (about 1.0) and the particle size (3-20 1.) of the microcapsules. That is, accumulation of precipitate of the starch particles in the coating material or increase of proportion of the starch particles in the coating material are caused and the characteristics of the upper paper (amount of coating material, smoothness, color formation, smudge, etc.) change.
  • FIG. 1 shows a rough cross section of micro-capsule
  • FIG. 2 shows a rough cross section of micro-sphere expanded after heating
  • FIG. 3 shows a rough cross section of an upper paper of immediately after coating of an aqueous coating material containing microcapsules, microspheres, etc. to a support (before drying and
  • FIG. 4 shows a rough cross section of an upper paper in usable state as non-carbon copying paper after drymg.
  • microsphere used herein means, as shown in FIG. I, a fine sphere comprising wall 1 of vinylidene chloride-acrylic acid ester copolymer and foaming hydrocarbon 2 contained therein, which has a specific gravity of about 1.3 and an average particle size of about 5,u and which is converted into particles of about 30 .t (l0 a, preferably 20 50 in average particle size by expansion of wall 1 caused by foaming of the hydrocarbon at a temperature of 120C as shown in FIG. 2 (In this respect, see microsphere XD 7059.] of Dow Chemical Company).
  • a suitable amount of said microspheres can be well mixed with microcapsules and substantially no precipitation occurs because the particle size of the microspheres is extremely smaller than that of cellulose fibers and starch particles and is nearly comparable to that of the microcapsules and moreover, the microspheres have a low specific gravity. Furthermore, addition of only a small amount of the microspheres can accomplish the purpose.
  • the mixing ratio of the microcapsules to the microspheres is 1 20 prefera bly 100:2 l0
  • microsphere 1 When such aqueous mixed liquid is applied to a paper, microsphere 1 is in the state of fine sphere immediately after coating as shown in FIG. 3. At the heat drying step, the microsphere is expanded and as shown in FIG. 4, microsphere 1 becomes larger than microcapsule 2. Moreover, even after expansion, the microsphere maintains spherical shape and hence it has an excellent smoothness.
  • the size of the microsphere can be optionally adjusted by controlling the drying conditions of the coat ing material such as heating temperature, heating time, etc. Therefore, use of the micros'pherescan provide characteristics of upper paper in accordance with the incorporated in the microcapsules layer on the back face of the intermediate paper to obtain the same effects.
  • microspheres used in the present invention are not limited to vinylidene chloride-acrylic acid ester copolymer 5 microspheres of Dow Chemical Company, but any microspheres which can foam and expand by heating can 'be used.
  • microspheres can be The present invention will be illustrated in the following Examples.
  • EXAMPLE '1 An oil obtained by dissolving 2 parts of Crystal Violet Lactone and 1 part of Benzoil Leuco Methylene Blue in 100 parts of tripropylnaphthalene was encapsulated by the coacervation method disclosed in US. Pat. No. 2,800,457. The average particle size of thus obtained microcapsules was 10p and solid matter was 18.0
  • Microcapsules 100 parts Microsphere XD7059.1 (net amount) 2 parts MS-3800 (20 7: aqueous solution of Japan Food oxidized starch) 50 parts (Adhesive) The above components were mixed and stirred in a tank with stirrer.
  • aqueous coating material solid matter 4O Said upper paper was superposed'on a lower paper and degree of smudge formed was examined to find that the smudge formation was very little.
  • the application of the coating material was continued for further several hours to find that the compositions of the coating material were substantially the same as those at the beginning of the application.
  • EXAMPLE 2 Using the microcapsules of Example 1, a coating ma- 50 terial comprising the following components was prepared.
  • the microspheres were expanded to an average particle size of 30p. (20 The smoothness of the coating surface of thus obtained upper paper was excellent.
  • Said upper paper was superposed on a lower paper and smudge formation was observed to find that the smudge was caused with extreme difficulty. The application was continued for further several hours to find that the compositions of the coating material were substantially the same as those at beginning.
  • Example 1 Using the microcapsules of Example I, a coating material comprising the following components was prepared.
  • Microcapsules 100 parts K.C. Flock (pulp fine powders manufactured by Kokusaku Pulp K.K., net amount) 20 parts MS-3800 (20 aqueous solution) i 80 parts
  • K.C. Flock Pulp fine powders manufactured by Kokusaku Pulp K.K.
  • MS-3800 (20 aqueous solution) i 80 parts
  • coating material was coated in a net amount of 9 g/m on one face of a base paper of 40 g/m with an air knife coater and was dried with a hot air drier of an internal temperature of 120C to obtain an upper paper.
  • the smoothness of the coating surface of the upper paper was very low.
  • Said upper paper was superposed on a lower paper and degree of smudge formation was observed to find that somewhat smudge was formed.
  • the compositions of the coating material were examined to find that the proportion of the K.C. Flock increased and viscosity was increased.
  • Reference Example 2 Reference Example 1 was repeated except that 20 parts ofwheat flour (particle size 2535;t) was substituted for the KC. Flock to produce an upper paper. The smoothness of the coating surface of said upper paper was excellent. The upper paper was superposed on a lower paper and degree of smudge formation was examined to find thatthe smudge occurred with difficulty.
  • Example 2 Smudge caused by upper paper Little Little Great Little (remarkable) Change in compositions of coating Almost none Almost none Extremely Great material great (remarkable) (remarkable)
  • Viscosity after coating of 3 I 58 cp 56 cp 350 cp 9() cp hours Increase of viscosity of +3 cp +l cp +250 cp +25 cp coating material** Bekk smoothness. The viscosity was measured with Brookfield viscometer,
  • a method of producing non-carbon paper comprising coating a paper substrate with a mixture containing therein microcapsules containing an encapsulated dye-oil and microspheres containing a foaming hydrocarbon, said microspheres having a particle size of about microns, and heating said coated paper thus expanding said microspheres to a particle size of 10-70 microns.
  • microspheres are vinylidene chlorideacryli c acid ester copolymer microspheres.
  • microcapsules have a size of 3-20 microns and the ratio of microcapsules to microspheres -is 100.0-20.
  • microspheres are of a vinylidene chloride-acrylic acid ester copolymer.
  • noncarbon paper comprises an-upper paper and a lower paper and a coating is applied to the back face of the upper paper.

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  • Paper (AREA)
  • Color Printing (AREA)
  • Manufacturing Of Micro-Capsules (AREA)
US280163A 1971-08-30 1972-08-14 Non-carbon copying upper paper Expired - Lifetime US3867169A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP6641271A JPS545325B2 (fr) 1971-08-30 1971-08-30

Publications (1)

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US3867169A true US3867169A (en) 1975-02-18

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US280163A Expired - Lifetime US3867169A (en) 1971-08-30 1972-08-14 Non-carbon copying upper paper

Country Status (8)

Country Link
US (1) US3867169A (fr)
JP (1) JPS545325B2 (fr)
BE (1) BE788109A (fr)
CA (1) CA985100A (fr)
DE (2) DE7231286U (fr)
ES (1) ES406138A1 (fr)
FR (1) FR2151990A5 (fr)
GB (1) GB1401675A (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955026A (en) * 1973-10-02 1976-05-04 Fuji Photo Film Co., Ltd. Pressure-sensitive recording sheet
US3955025A (en) * 1973-10-02 1976-05-04 Fuji Photo Film Co., Ltd. Pressure-sensitive copying sheet
US8679296B2 (en) 2012-07-31 2014-03-25 Kimberly-Clark Worldwide, Inc. High bulk tissue comprising expandable microspheres
AU2015202713B2 (en) * 2015-01-08 2017-06-01 Taiwan Hopax Chems Mfg. Co., Ltd. Carbonless copy note pad

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5844504B2 (ja) * 1975-03-04 1983-10-04 株式会社東芝 ハンソウシヤ
JPS553969A (en) * 1978-06-26 1980-01-12 Mitsubishi Paper Mills Ltd Single layer self-color developing pressure-sensitive recording paper
JPS56192A (en) * 1979-06-18 1981-01-06 Mitsubishi Paper Mills Ltd Preparation of press-sensitive copying paper
JPS59135185A (ja) * 1983-01-21 1984-08-03 Mitsubishi Paper Mills Ltd 感圧複写紙用保護材
JPS59138487A (ja) * 1983-01-28 1984-08-08 Mitsubishi Paper Mills Ltd 感圧複写紙用保護材
JPS60154544U (ja) * 1984-03-24 1985-10-15 松下電工株式会社 天井裏収納箱
JPS60154545U (ja) * 1984-03-24 1985-10-15 松下電工株式会社 収納箱の取付装置
JPS619479U (ja) * 1984-06-25 1986-01-20 松下電工株式会社 収納装置
DE3512565A1 (de) * 1985-04-06 1986-10-16 Basf Ag, 6700 Ludwigshafen Mikrokapseln und deren verwendung
US6866906B2 (en) 2000-01-26 2005-03-15 International Paper Company Cut resistant paper and paper articles and method for making same
RU2330911C2 (ru) 2002-09-13 2008-08-10 Интернэшнл Пейпер Компани Бумага с улучшенной жесткостью и пухлостью и способ для ее изготовления
EP2295633A1 (fr) 2005-03-11 2011-03-16 International Paper Company Compositions contenant des microsphères extensibles et composé ionique, ainsi que procédés de fabrication et d'utilisation associés
CN104032622A (zh) 2008-08-28 2014-09-10 国际纸业公司 可膨胀的微球及其制造和使用方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711375A (en) * 1951-08-24 1955-06-21 Ncr Co Pressure sensitive manifold sheet
US2730457A (en) * 1953-06-30 1956-01-10 Ncr Co Pressure responsive record materials
US3179600A (en) * 1960-03-10 1965-04-20 Ncr Co Minute color-forming capsules and record material provided with such
US3265524A (en) * 1963-02-08 1966-08-09 Ignacio P Echeagaray Recording blank
US3554932A (en) * 1967-03-28 1971-01-12 Shell Oil Co Production of foamed thermoplastic
US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US3625736A (en) * 1967-10-27 1971-12-07 Fuji Photo Film Co Ltd Pressure-sensitive copying unit containing granular resinous material and method of making
US3726755A (en) * 1966-09-29 1973-04-10 Owens Corning Fiberglass Corp High-strength foam material

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2711375A (en) * 1951-08-24 1955-06-21 Ncr Co Pressure sensitive manifold sheet
US2730457A (en) * 1953-06-30 1956-01-10 Ncr Co Pressure responsive record materials
US3179600A (en) * 1960-03-10 1965-04-20 Ncr Co Minute color-forming capsules and record material provided with such
US3265524A (en) * 1963-02-08 1966-08-09 Ignacio P Echeagaray Recording blank
US3726755A (en) * 1966-09-29 1973-04-10 Owens Corning Fiberglass Corp High-strength foam material
US3554932A (en) * 1967-03-28 1971-01-12 Shell Oil Co Production of foamed thermoplastic
US3615972A (en) * 1967-04-28 1971-10-26 Dow Chemical Co Expansible thermoplastic polymer particles containing volatile fluid foaming agent and method of foaming the same
US3625736A (en) * 1967-10-27 1971-12-07 Fuji Photo Film Co Ltd Pressure-sensitive copying unit containing granular resinous material and method of making

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3955026A (en) * 1973-10-02 1976-05-04 Fuji Photo Film Co., Ltd. Pressure-sensitive recording sheet
US3955025A (en) * 1973-10-02 1976-05-04 Fuji Photo Film Co., Ltd. Pressure-sensitive copying sheet
US8679296B2 (en) 2012-07-31 2014-03-25 Kimberly-Clark Worldwide, Inc. High bulk tissue comprising expandable microspheres
AU2015202713B2 (en) * 2015-01-08 2017-06-01 Taiwan Hopax Chems Mfg. Co., Ltd. Carbonless copy note pad

Also Published As

Publication number Publication date
GB1401675A (en) 1975-07-16
DE7231286U (de) 1975-11-13
DE2241586B2 (fr) 1974-08-22
DE2241586C3 (de) 1975-04-10
CA985100A (en) 1976-03-09
DE2241586A1 (de) 1973-03-15
FR2151990A5 (fr) 1973-04-20
BE788109A (fr) 1972-12-18
ES406138A1 (es) 1975-08-01
JPS4832013A (fr) 1973-04-27
JPS545325B2 (fr) 1979-03-15

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AS Assignment

Owner name: APPLETON PAPERS INC.

Free format text: MERGER;ASSIGNORS:TUVACHE, INC.;GERMAINE MONTEIL COSMETIQUES CORPORATION (CHANGED TO APPLETON PAPERS);REEL/FRAME:004108/0262

Effective date: 19811215