EP0141856B1 - Papier pour copies sensible a la pression - Google Patents

Papier pour copies sensible a la pression Download PDF

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Publication number
EP0141856B1
EP0141856B1 EP84901410A EP84901410A EP0141856B1 EP 0141856 B1 EP0141856 B1 EP 0141856B1 EP 84901410 A EP84901410 A EP 84901410A EP 84901410 A EP84901410 A EP 84901410A EP 0141856 B1 EP0141856 B1 EP 0141856B1
Authority
EP
European Patent Office
Prior art keywords
pressure
copying paper
sensitive copying
parts
fatty acid
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
Application number
EP84901410A
Other languages
German (de)
English (en)
Other versions
EP0141856A1 (fr
EP0141856A4 (fr
Inventor
Takao Kosaka
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.)
Mitsubishi Paper Mills Ltd
Original Assignee
Mitsubishi Paper Mills 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.)
Filing date
Publication date
Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Publication of EP0141856A1 publication Critical patent/EP0141856A1/fr
Publication of EP0141856A4 publication Critical patent/EP0141856A4/fr
Application granted granted Critical
Publication of EP0141856B1 publication Critical patent/EP0141856B1/fr
Expired legal-status Critical Current

Links

Classifications

    • 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

  • This invention relates to a pressure-sensitive copying paper, particularly, a pressure-sensitive copying paper free from smudge.
  • Pressure-sensitive copying papers consist basically of (a) an upper sheet obtained by coating one side of a substrate such as a paper with microcapsules containing an oil type solution containing an electron-donating, colorless dye as a color former and drying the coated substrate, (b) a lower sheet obtained by coating one side of a substrate with a coating fluid containing an electron-accepting, solid acid (a color developer) and an adhesive and drying the coated substrate, and optionally (c) an intermediate sheet obtained by coating one side of a substrate with said microcapsules and the other side of the substrate with said electron-accepting, solid acid and said adhesive and drying the coated substrate (such pressure sensitive copying papers being referred to as separating type pressure sensitive paper).
  • separating type pressure sensitive paper There are also self-contained type pressure-sensitive copying papers wherein a substrate is coated at same one side with color former-containing microcapsules and a color developer.
  • starch grains show a fairly good effect in smudge prevention.
  • starches have a specific gravity of 1.6 which is considerably larger than that (about 1) of microcapsules and moreover there are used starches having particle diameters ordinarily of 20 to 30 p
  • starch grains cause precipitation, whereby the coating fluid causes compositional change during a continuous, long term coating operation and there occurs quality deterioration of sheets due to color development, smudging, etc. of microcapsules-coated sheet surfaces.
  • the particle diameters and hardnesses of starch grains reduce the color developability between a color former and a color developer at a low writing pressure, whereby color development becomes insufficient in copying of a large number of sheets.
  • cellulose fine powders are obtained by grinding a wood pulp mechanically or chemically, and their particle sizes are broad with a medium size being about 30 p in width and about 100 p in length and their specific gravities are about 1.
  • a coating fluid as a stilt, (see e.g. FR-A-1.066.210, which is the prior art from which the present invention has been developed)
  • its specific gravity is about same as the specific gravity of microcapsules
  • the present inventors made an extensive study on further improvement of the smudge preventability of a coating containing microcapsules and cellulose fine powder fluid free from precipitation and excellent in color developability at a low writing pressure. As a result, it was found that combined used of (a) a cellulose fine powder as a stilt and (b) a fatty acid amide as a lubricant in a coating fluid shows an outstanding smudge prevention effect without sacrificing the merits of an original coating fluid. Based on this finding, the present invention has been attained.
  • the fatty acid amide gives little effect for improvement of smudge prevention.
  • the fatty acid amide is used in a coating fluid containing microcapsules and starch grains or plastic beads as a stilt, the fatty acid amide gives little effect for improvement of smudge prevention but, when the fatty acid amide is used in a coating fluid containing microcapsules and a cellulose fine powder as a stilt, the fatty acid amide does show an outstanding effect.
  • the fatty acid amide as a lubricant when used in a coating fluid containing microcapsules and a cellulose fine powder as a stilt, the fatty acid amide is located close to the surface of a coated layer due to the affinity of the amide with the coated layer when the coating fluid is coated at a high speed by a coater or the like and dried rapidly or due to the migration of the amide and thereby the fatty acid amide can function well as a lubricant.
  • fatty acid amide used as a lubricant in the present invention there can be mentioned fatty acid amides such as stearamide, ethylenebisstearamide and the like. In combination with these fatty acid amides there may be used other lubricants such as aliphatic hydrocarbons (a paraffin, a polyethylene and the like), higher fatty acids derived from tallow, coconut oil and the like, higher aliphatic alcohols, metal soaps (calcium stearate, zinc stearate and the like), and higher fatty acid esters.
  • aliphatic hydrocarbons a paraffin, a polyethylene and the like
  • higher fatty acids derived from tallow coconut oil and the like
  • metal soaps calcium stearate, zinc stearate and the like
  • the amounts of the cellulose fine powder (stilt) and the fatty acid amide (lubricant) used in the present invention 5 to 70 parts by weight (hereinunder referred to simply as parts) of the cellulose fine powder is preferable relative to 100 parts of microcapsules.
  • the fatty acid amide is used in an amount of 0.9 part or less, the effect is low.
  • it is used in an amount of 16 parts or more color developability is badly affected. Therefore, 1 to 15 parts of the fatty acid amide is preferable. 15 to 60 parts of the cellulose fine powder and 2 to 10 parts of the fatty acid amide are more preferable.
  • the microcapsules can be produced, for example, by the following methods.
  • microcapsules production is not restricted to these methods.
  • the colorless dye which is a color former there can be used known leuco dyes for pressure-sensitive recording, such as, for example, a triphenylmethane compound, a diphenylmethane compound, a xanthene compound, a thiazine compound and a spiropyran compound.
  • color formers are dissolved or dispersed in an appropriate oily solvent, emulsified into minute droplets in water or in a hydrophilic solvent and then microencapsulated by one of the above mentioned encapsulation methods.
  • oily solvent there are used non-volatile solvents such as alkyl naphthalenes, diarylethanes, alkylbiphenyls, hydrogenated terphenyls and esters.
  • the electron-accepting substance which is a color developer and forms a color by contacting with the above mentioned color former
  • inorganic color developers e.g. acid clay, active clay, attapulgite, zeolite
  • phenols phenol-aldehyde polymers
  • phenolacetylene polymers phenolacetylene polymers
  • maleic acid-modified rosin aromatic carboxylic acids (e.g. salicylic acid or its derivatives) and their metal salts, etc.
  • a coating fluid is coated on a substrate at a high speed by the use of a coater having a coater head such as an air knife, a blade roll, a bar or the like.
  • the present invention will be described more specifically by means of Examples.
  • the pressure-sensitive copying paper of the present invention is not restricted to a separating type mentioned in Examples but does also include a self-contained type.
  • aqueous solution containing 10% of an ethylene-maleic anhydride copolymer, 10 parts of urea, 1 part of resorcin and 200 parts of water were mixed and made into a solution.
  • the solution was adjusted to a pH of 3.5 by the use of a 20% aqueous sodium hydroxide solution.
  • a dye solution obtained by dissolving 10 parts of Crystal Violet Lactone in 90 parts of diisopropylnaphthalene was dispersed in the above aqueous solution to prepare an oil-in-water type emulsion having oil droplets of 3 to 5 p in diameter. Thereto was added 25 parts of a 37% aqueous formaldehyde solution. The system was kept at 55°C with stirring.
  • a coating fluid having a total solid content of 20% was prepared by mixing the following materials.
  • This fluid was coated on a plain paper of 40 g/m 2 by the use of an air knife coater at a speed of 100 m/min so that the coated amount became 5 g/m 2 , and the coated paper was dried to obtain a color former sheet.
  • a color developer sheet there was used a pressure-sensitive copying paper (Mitsubishi NCR paper CF) wherein a substrate was coated at one side with a solid acid as an electron-accepting substance (oil-soluble phenol resin of novolac type). These sheets were superimposed so that their coated sides faced with each other. Then, color development characteristics and smudge-preventing characteristics were examined. The results are shown in Table 1.
  • Crystal Violet Lactone 2 Parts was dissolved in 100 parts of Hisol SAS-295 (diarylethane type solvent, manufactured by Nippon Petrochemicals Co., Ltd.). This solution was subjected to dispersion and emulsification. Encapsulation was conducted by a coacervation method using gelatin-gum arabic. The microcapsule dispersion had a microcapsule content of 20% and the microcapsules had an average particle diameter of 10 ⁇ .
  • a coating fluid having a total solid content of 20% was prepared by mixing the following materials.
  • Example 1 The same procedure as in Example 1 was conducted except that ethylenebisstearamide used in Example 1 was not added. The results are shown in Table 1.
  • Example 1 The same procedure as in Example 1 was conducted except that KC Flock used in Example 1 was replaced by wheat starch. The results are shown in Table 1.
  • color development (T.I.) is given as a concentration of a color developed by a typewriter and smudging (F.S.) is an index indicating the staining of a coating layer due to friction. They are given by the following formula.
  • a larger number indicates lower color development or less staining.
  • 0, A and X are results by visual evaluation.

Landscapes

  • Color Printing (AREA)

Abstract

Papier pour copies sensible à la pression comprenant un support enduit d'une couche contenant des micro-capsules à l'intérieur desquelles se trouve un agent de formation de couleurs, ou un agent colorant incolore, pouvant réagir avec un révélateur de couleur pour former une couleur, la couche contenant en outre une poudre fine de cellulose et un amide d'acide gras. La poudre de cellulose et l'amide permettent d'empêcher avec une efficacité remarquable les salissures du papier pour copies.

Claims (9)

1. Papier pour copie sensible à la pression comprenant un substrat ayant sur un côté une couche de revêtement contenant des microcapsules contenant un colorant incolore comme générateur de couleur qui développe une couleur par réaction avec un révélateur couleur et une poudre de cellulose fine, caractérisé en ce que la couche de revêtement contient en outre un amide d'acide gras.
2. Papier pour copie sensible à la pression suivant la revendication 1, dans lequel l'amide d'acide gras est l'éthylène-bisstéaramide.
3. Papier pour copie sensible à la pression suivant la revendication 1, dans lequel la quantité de la poudre fine de cellulose est de 5 à 70 parties en poids (désignées simplement ci-après par parties) pour 100 parties des microcapsules.
4. Papier pour copie sensible à la pression suivant la revendication 3, dans lequel la quantité de la poudre de cellulose fine est de 15 à 60 parties.
5. Papier pour copie sensible à la pression suivant la revendication 1, dans lequel la quantité de l'amide d'acide gras est de 1 à 15 parties pour 100 parties des microcapsules.
6. Papier pour copie sensible à la pression suivant la revendication 5, dans lequel la quantité de l'amide d'acide gras est de 2 à 10 parties.
7. Papier pour copie sensible à la pression suivant la revendication 1, qui est un papier pour copie sensible à la pression du type à séparation comprenant une feuille supérieure et une feuille inférieure.
8. Papier pour copie sensible à la pression suivant la revendication 7, qui a au moins une feuille intermédiaire entre la feuille supérieure et la feuille inférieure.
9. Papier pour copie sensible à la pression suivant la revendication 1, qui est un papier pour copie sensible à la pression du type autonome dans lequel (a) des microcapsules contenant un colorant incolore comme générateur de couleur et (b) un révélateur couleur sont appliqués du même côté d'un substrat.
EP84901410A 1983-04-04 1984-04-03 Papier pour copies sensible a la pression Expired EP0141856B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP58059059A JPS59184695A (ja) 1983-04-04 1983-04-04 感圧複写紙
JP59059/83 1983-04-04

Publications (3)

Publication Number Publication Date
EP0141856A1 EP0141856A1 (fr) 1985-05-22
EP0141856A4 EP0141856A4 (fr) 1985-09-26
EP0141856B1 true EP0141856B1 (fr) 1988-07-27

Family

ID=13102391

Family Applications (1)

Application Number Title Priority Date Filing Date
EP84901410A Expired EP0141856B1 (fr) 1983-04-04 1984-04-03 Papier pour copies sensible a la pression

Country Status (5)

Country Link
EP (1) EP0141856B1 (fr)
JP (1) JPS59184695A (fr)
AU (1) AU565566B2 (fr)
DE (1) DE3472930D1 (fr)
WO (1) WO1984003860A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4533567A (en) * 1983-05-24 1985-08-06 Ncr Corporation Carbonless paper coating formulation
AU4235785A (en) * 1984-04-21 1985-11-15 Mitsubishi Paper Mills Ltd. Pressure-sensitive copying paper

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL76787C (fr) * 1951-08-24 1900-01-01
US3186861A (en) * 1960-06-08 1965-06-01 Mead Corp Process for producing pressure sensitive record paper
JPS5268513A (en) * 1975-12-04 1977-06-07 Fuji Photo Film Co Ltd Record sheets
JPS545322A (en) * 1977-06-14 1979-01-16 Mitsubishi Electric Corp Coding and decoding system for time sharing line
JPS5660289A (en) * 1979-10-23 1981-05-25 Mitsubishi Paper Mills Ltd Pressure-sensitive recording paper and manufacture thereof
JPS56121790A (en) * 1980-03-03 1981-09-24 Mitsubishi Paper Mills Ltd Pressure-sensitive copying paper
JPS5964387A (ja) * 1982-10-06 1984-04-12 Mitsubishi Paper Mills Ltd 単一層型自己発色性感圧記録材料

Also Published As

Publication number Publication date
WO1984003860A1 (fr) 1984-10-11
EP0141856A1 (fr) 1985-05-22
EP0141856A4 (fr) 1985-09-26
DE3472930D1 (en) 1988-09-01
AU2810284A (en) 1984-10-25
AU565566B2 (en) 1987-09-17
JPS59184695A (ja) 1984-10-20

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