EP0022875B1 - Materiau d'enregistrement sensible a la pression - Google Patents

Materiau d'enregistrement sensible a la pression Download PDF

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Publication number
EP0022875B1
EP0022875B1 EP80900070A EP80900070A EP0022875B1 EP 0022875 B1 EP0022875 B1 EP 0022875B1 EP 80900070 A EP80900070 A EP 80900070A EP 80900070 A EP80900070 A EP 80900070A EP 0022875 B1 EP0022875 B1 EP 0022875B1
Authority
EP
European Patent Office
Prior art keywords
color
layer
sensitive recording
coated layer
pressure
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
EP80900070A
Other languages
German (de)
English (en)
Other versions
EP0022875A4 (fr
EP0022875A1 (fr
Inventor
Isamu Yoshino
Yasohachi Takahashi
Osamu Fujii
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.)
Naigai Ink Manufacturing Co Ltd
Mishima Paper Manufacturing Co Ltd
Original Assignee
Naigai Ink Manufacturing Co Ltd
Mishima Paper Manufacturing 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.)
Filing date
Publication date
Application filed by Naigai Ink Manufacturing Co Ltd, Mishima Paper Manufacturing Co Ltd filed Critical Naigai Ink Manufacturing Co Ltd
Publication of EP0022875A1 publication Critical patent/EP0022875A1/fr
Publication of EP0022875A4 publication Critical patent/EP0022875A4/fr
Application granted granted Critical
Publication of EP0022875B1 publication Critical patent/EP0022875B1/fr
Expired legal-status Critical Current

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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
    • B41M5/132—Chemical colour-forming components; Additives or binders therefor
    • 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

Definitions

  • This invention relates to a pressure-sensitive recording material which can produce multiple copies by pressures such as printing or writing pressure. More specifically, it relates to a pressure-sensitive recording material having a surface coated layer of a novel structure.
  • Figures 1 to 3 are examples of prior art pressure-sensitive recording materials in which two color-forming components are coated on the surfaces of supports in a face-to-face relationship;
  • Figures 4 and 5 show examples of coated layers in the present invention;
  • Figure 6 shows an example of a spot-type pressure-sensitive recording business form which utilizes the pressure-sensitive recording materials of this invention. All of these drawings are cross-sectional views.
  • 1 represents a support, 2, a microcapsular layer containing a liquid comprising a color-forming agent; 3, a layer of a solid containing a coloring agent; 4 and 5, layers formed by spot-coating only the desired portions with a holt-melt type coating containing a color-forming agent; 5', a layer formed by coating the entire surface with the hot-melt type coating, and 6, a layer having absorbent micropores consisting of micro-capsules, a fine powder and a binder.
  • Pressure-sensitive recording materials having two-color forming components coated on the surfaces of separate supports are of the type shown in Figure 1.
  • one of the color-forming components is encapsulated in microcapsules (2) and coated on the undersurface of an upper support (1), and the other color-forming component is present as a coated layer (3) on the top surface of a lower support (1).
  • the liquid contained in the microcapsules (2) flows out and is transferred to, and absorbed by, the coated layer (3), and simultaneously, the two color-forming components react with each other to form a colored substance and thus to form an image on the receptive surface of the coated layer (3).
  • the transferable coated layer (4) is transferred to the receptive coated layer (3), and conversely, the receptive layer (3) is transferred to the transferable layer (4).
  • the present invention provides a pressure-sensitive recording material comprising a transferable coated layer of a hot- melt type coating containing one color-forming component and a receptive coated layer having absorbent micropores and consisting of micro- capsules which contain another color-forming component, a fine powder and a binder.
  • the invention is defined precisely in claim 1.
  • Figures 4 and 5 illustrate this invention.
  • Figure 4 shows a material in which a transferable coated layer (5) is spot-coated on the undersurface of an upper support (1)
  • Figure 5 shows a material in which a transferable coated layer (5) is coated on the entire undersurface of the upper support (1).
  • (6) represents a layer having absorbent micropores and consisting of the microcapsules, a fine powder and a binder, which is applied to the top surface of the lower support (1).
  • many pressure-sensitive recording sheets are of the type in which micro- capsules containing one color-forming component as a liquid are kept present in the transferable coated layer when the liquid in the capsules is caused to be transferred to the opposite receptive surface to form a color thereon.
  • the present invention is based on the theory that microcapsules are caused to be present in the receptive layer and the liquid therein is flowed out and absorbed in the layer, instead of causing microcapsules containing a color-forming component to be present in the transferable coated layer and transferring them to the receptive coated layer.
  • the first feature of the present invention is that microcapsules containing one color-forming component are included in the receptive coated layer.
  • the hot-melt type coating is called a hot-melt ink or hot-melt wax, and has the advantage that this coating is easy to spot-coat and needs only to be cooled after coating without the need for drying, and moreover, the coating head is simple and the rate of coating can be increased.
  • the hot- melt coating is used in the construction shown in Figure 3 inconveniences are caused.
  • the transferable coated layer composed of such a hot-melt coating containing a color-forming component is combined with the structure in which the microcapsulses are included in the receptive coated layer, i.e. the first feature described above, the advantages of the two cooperate with each other to give good results.
  • first and second features alone are still inconvenient, however. If the microcapsules are ruptured immediately before the hot-melt type coating of the transferable coated layer is transferred upon the application of printing pressure to the surfaces of the microcapsules in the receptive coated layer, the liquid comes out and is transferred to the transferable coated layer to form a color. Or because the hot-melt type coating cannot be transferred, an image is not formed well. Hence, the results are undesirable.
  • the receptive coated layer is formed as a layer of the structure having absorbent micropores and composed of microcapsules, a fine powder and a binder in the ratios given in claim 1, and the liquid which comes out upon the application of pressure is instantaneously and completely absorbed in the receptive coated layer.
  • the hot-melt type coating is completely transferred, and back-transferring of the liquid does not occur.
  • the layer of the structure having absorbent micropores also has an action of protecting the microcapsules against an external force.
  • the diameter of the capillary should be as small as possible.
  • the diameter of the capillary should be as large as possible.
  • the liquid which has flowed from the micro- capsules it is desirable for the liquid which has flowed from the micro- capsules to be instantaneously and completely absorbed by the aforesaid coated layer. Consequently it is desirable that the diameter of absorbent micropores should be large.
  • the size of the microcapsules is usually about 1 to 10 microns and the amount of the liquid contained in the microcapsules is small, if the diameter of pores existing in the neighborhood is too large, the liquid does not at all move along the pores, that is, it is not absorbed. Accordingly, the diameter of the absorbent micropores should be smaller than about 10 microns. Furthermore, in order to increase the ability of absorbing liquid, the total volume of the pores should be large.
  • the microcapsules are spherical when they are dispersed in a liquid, but when they are coated and dried, they form a nearly continuous phase with not so many interstices left among the microcapsules.
  • the interstices are filled with the powder or a fine fibrous powder in order to leave fine spaces after drying.
  • the above is based on presumption from calculated values.
  • the fine powders in actual use are not spherical or cylindrical but irregularly-shaped. Thus, the particle size distribution exists continuously, and there may be a deviation from the calculated values.
  • the above table shows a part of this situation.
  • the receptive layer and the transferable layer are set opposite to each other and letters are printed, an image appears in the transferable layer upon the migration of the color-forming component in the microcapsules to the color-forming component of the transferable layer. This shows that the liquid contained in the ruptured microcapsuies - cannot be fully absorbed by the receptive layer and the excess of the liquid is transferred to the transferable surface.
  • the amount of the microcapsules in the receptive coated layer is less than 20%, the liquid in the microcapsules is all absorbed by the receptive coated layer to prevent coloration at the transferable coated layer.
  • the total volume of the absorbent micropores which gives such an effect has to do not only with the amount of a fine powder to be blended, but also directly with the amount of the binder added.
  • the total pore volume decreases when the binder is added in a large amount, and increases when it is added in a small amount.
  • the support when absorbent, it absorbs the binder incorporated in the coating, and changes the amount of the binder remaining in the dried coated layer. Accordingly, the absorbency of the support also affects the total pore volume.
  • the support in this invention is mainly paper.
  • a non-absorbent material such as plastic films and metal foils may optionally be used.
  • the material for the support there is no particular limit to the material for the support.
  • color-forming components various combinations of compounds which react with each other to form a colored substance can be used. Since in this invention, one component of the combination is used in the form of a hotmelt type coating, substances having strong volatility at about 100°C or substances which are liquid at room temperature are undesirable.
  • inorganic color developing agents such as activated clay, colloidal silica or zeolite and various organic color developing agents.
  • the compounds in these combinations may be used interchangeably in the transferable coated layer and the receptive coated layer.
  • a combination of a ferric salt of a fatty acid with a higher alcohol ester of gallic acid, and a combination of a vanadium compound such as stearyl trimethyl ammonium vanadate and a higher alcohol ester of gallic acid are also used. If desired, these combinations may be used as mixtures.
  • the fine powder denotes various inorganic and organic white pigments, starch particles, wood cellulose powder, etc. It should not be the one which forms a color upon contact with the microcapsules containing a color-forming component. This is because even when the color-forming component is kept inside the microcapsules, it is by no means sure that the color-forming component does not at all adhere to the outside wall of the capsules. For example, for capsules containing crystal violet lactone, etc., fine powders which do not cause color formation, such as calcium carbonate or aluminum hydroxide are desirable.
  • the shape, size and size distribution of the fine powder have to do with the formation of absorbent micropores, and become factors which determine the rate and amount of absorbing the liquid in the capsules.
  • desirable fine powders are those which exhibit a nearly spherical shape and have a particle diameter of 0.5 to 20 microns and a particle size distribution which is concentrated as much as possible on one point.
  • the wood cellulose powder desirably has a size of less than 300 mesh.
  • Natural and synthetic polymers which do not form a color with the color-forming component are used as the binder. Since the amount of the binder added is an important factor in forming absorbent micropores, it should be determined so as to maintain a balance against the amount of the capsules by considering the aforesaid calculated values of the remaining space at the time of filling spherical bodies into a box and the shape, size and size distribution of the fine powder used.
  • the hot-melt type coating should be transferable, it is desirable to form a primer layer before its coating.
  • the primer the above-exemplified polymers used as binders may be used. Those having good effect of sealing are selected.
  • Materials for the hot-melt type coating other than the color-forming component include at least one involatile high melting substance selected from the group consisting of high melting natural waxes, (e.g. carnauba wax, candelilla wax and montan wax), oils, fats, hardened oils, higher fatty acids, polyvalent metal salts of higher fatty acids and petroleum waxes. If desired, minor amounts of involatile solvents may be added. Furthermore, stabilizers such as antioxidants and ultraviolets absorbents may be added as required.
  • a stack of a plurality of the pressure-sensitive recording material of this invention can be used as a pressures-sensitive recording business form.
  • Microcapsules containing colorless dyes were prepared in the following manner.
  • Crystal violet lactone (50 g) and 30 g of benzoyl leuco methylene blue were dissolved in alkylnaphthalene (KMC-113, Kureha Chemical) to form 1000 g of a solution.
  • the solution was dispersed in a solution of 200 g of gelatin in 1500 g of water with stirring at high speed by a homomixer. Then, a solution of 40g of carboxy methyl cellulose in 3000g of water was added. Furthermore, 2000g of water was added. Then, 90g of 10% acetic acid was added to adjust the pH of the mixture to 4.0.
  • the solution was then cooled with ice to 7°C, and 150g of 37% formaldehyde was added, and then 300g of 4% sodium hydroxide was added to adjust the pH of the mixture to 9.0.
  • the mixture was maintained at 50°C for 1 hour, and 200g of wood cellulose powder (KC Flock-300, Sanyo Kokusaku Pulp) was added.
  • the mixture was then stored at room temperature. If desired, some amount of an ultraviolet absorbent may be added to the alkylnaphthalene.
  • the formulation (parts by weight) of a coating for the receptive coated layer was as follows:
  • aqueous dispersion of the above formulation having a solids concentration of 18% was coated by an air knife at a rate of 3.5 g/m 2 on wood free paper having basis weight of 40 g/m 2 and consisting of 70% LBKP and 30% NBKP.
  • An 8% polyvinyl alcohol solution had been coated on the back surface of the paper by a Meyer bar to prevent curling and give barrier property as a primer for the transferable coated layer.
  • a hot-melt type coating for the transferable coated layer consisting of the following formulation was spot-coated at a rate of 3.0 g/m 2 by a hot-melt transfer gravure technique to that surface of the paper which had been given barrier property as above.
  • the formulation (parts by weight) of the hot-melt coating was as follows:
  • the above ingredients were melt-mixed by a kneader at 80°C, and used as the hot-melt type coating.
  • micro- capsules containing an iron compound were prepared. That is, 80g of a ferric salt of mixed coconut oil fatty acid was dissolved in oxyethylene lauryl ether (Actinol, Matsumoto Kosan) to form 1000g of a solution. Using the resulting solution, microcapsules were prepared.
  • a coating for a receptive coated layer was also prepared in accordance with Example 1.
  • Example 2 Ten coated sheets obtained in accordance with Example 1 were superimposed and letters were printed on the assembly. The rate of color formation was somewhat lower than in Example 1, but a black image having good fastness to light was obtained.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Thermal Transfer Or Thermal Recording In General (AREA)

Abstract

Materiau d'enregistrement sensible a la pression qui comprend une couche de revetement de transfert et une couche de revetement de reception, chacune d'entre elles contenant l'un des deux ingredients aptes a former une couleur par reaction mutuelle qui est dispose sur la surface d'un support different tel que du papier (1), la couche de revetement de transfert etant du type couche de peinture fondant a la chaleur (5 ou 5') contenant l'un des ingredients de formation de la couleur et la couche de revetement de reception etant une couche poreuse (6) possedant de fins pores d'absorption constitues par des microcapsules renfermant l'autre ingredient generateur de coloration, une fine poussiere et un liant. Une pluralite de materiaux d'enregistrement sensibles a la pression superposes peuvent etre utilises en tant que notes ou petits messages d'enregistrement sensibles a la pression.

Claims (4)

1. Matière d'enregistrement sensible à la pression dans laquelle deux composantes chromogènes aptes à engendrer une substance colorée en réagissant l'une avec l'autre sont formés sur les surfaces de supports séparés, l'une des composantes sous la forme d'une couche appliquée transférable et l'autre sous la forme d'une couche appliquée réceptive, la couche transférable étant une couche d'un revêtement du type fusible à chaud qui contient une composante chromogène et la couche réceptive étant une couche comportant des micropores absorbants et constituée de 10 à 35 % en poids de microcapsules renfermant l'autre composante chromogène, de 70 à 50 % en poids d'une poudre fine et de 20 à 15 % en poids d'un liant, cette poudre fine et ce liant ne devant pas produire une couleur avec la composante chromogène des microcapsules, et le volume desdits micropores étant supérieur au volume total du liquide contenu dans les micro- capsules.
2. Matière d'enregistrement sensible à la pression selon la revendication 1, dans laquelle la couche du revêtement du type fusible à chaud comprend l'une des composantes chromogènes et au moins une substance non volatile à haut point de fusion prise dans l'ensemble constitué par les cires naturelles à hautes températures de fusion, les huiles, les graisses, les huiles durcies, les acides gras supérieurs, les sels de métaux multivalents et d'acides gras supérieurs, et les cires de pétrole.
3. Matière d'enregistrement sensible à la pression selon l'une des revendications précédentes, dans laquelle la poudre fine est un pigment minéral blanc, un pigment organique blanc, de l'amidon en particules ou de la cellulose de bois en poudre.
4. Matière d'enregistrement sensible à la pression selon l'une quelconque des revendications précédentes, dans laquelle le liant est un polymère naturel ou synthétique.
EP80900070A 1978-12-18 1980-07-01 Materiau d'enregistrement sensible a la pression Expired EP0022875B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP53154872A JPS5835479B2 (ja) 1978-12-18 1978-12-18 感圧性記録材料
JP154872/78 1979-12-18

Publications (3)

Publication Number Publication Date
EP0022875A1 EP0022875A1 (fr) 1981-01-28
EP0022875A4 EP0022875A4 (fr) 1982-04-22
EP0022875B1 true EP0022875B1 (fr) 1985-03-13

Family

ID=15593763

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80900070A Expired EP0022875B1 (fr) 1978-12-18 1980-07-01 Materiau d'enregistrement sensible a la pression

Country Status (5)

Country Link
EP (1) EP0022875B1 (fr)
JP (1) JPS5835479B2 (fr)
DE (2) DE2953431C1 (fr)
GB (1) GB2048331B (fr)
WO (1) WO1980001263A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0651422B2 (ja) * 1985-10-16 1994-07-06 内外カ−ボンインキ株式会社 感圧感熱多重複写紙
DE69117554T2 (de) * 1990-03-27 1996-07-18 The Wiggins Teape Group Ltd., Basingstoke, Hampshire Druckempfindliches Aufzeichnungspapier
CA2051206A1 (fr) * 1990-11-21 1992-05-22 John F. Oliver Papier autocopiant pour impression par jet d'encre
DE4207754A1 (de) * 1992-03-11 1993-09-23 Foldenauer Willi Wischfeste kennzeichnungs-vorrichtung

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4833204B1 (fr) * 1969-04-08 1973-10-12

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3079351A (en) * 1958-11-26 1963-02-26 Moore Business Forms Inc Copying materials and emulsions
FR1589881A (fr) * 1967-10-27 1970-04-06
NO127489B (fr) * 1967-11-02 1973-07-02 Ncr Co
JPS4833204A (fr) * 1971-09-06 1973-05-08
JPS5017886B2 (fr) * 1971-10-18 1975-06-25
US3857718A (en) * 1972-05-24 1974-12-31 Swift & Co Pressure-sensitive transfer coating
AT331825B (de) * 1972-09-21 1976-08-25 Koreska Gmbh W Durchschreibematerial
US4063754A (en) * 1976-05-07 1977-12-20 The Mead Corporation Process for the production of pressure sensitive carbonless record sheets using novel hot melt systems and products thereof
NO771012L (no) * 1976-05-07 1977-11-08 Mead Corp Karbonfritt gjennomslagspapir og fremgangsm}te for fremstilling derav
JPS608960B2 (ja) * 1978-06-28 1985-03-06 内外インキ製造株式会社 感圧複写紙

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4833204B1 (fr) * 1969-04-08 1973-10-12

Also Published As

Publication number Publication date
GB2048331A (en) 1980-12-10
JPS5582692A (en) 1980-06-21
GB2048331B (en) 1983-04-20
DE2953431C1 (de) 1983-03-03
DE2953431A1 (de) 1981-01-08
JPS5835479B2 (ja) 1983-08-02
EP0022875A4 (fr) 1982-04-22
WO1980001263A1 (fr) 1980-06-26
EP0022875A1 (fr) 1981-01-28

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