EP0375847B1 - Couche pour feuilles d'enregistrement sensibles à la pression et feuille d'enregistrement pourvue de cette couche - Google Patents

Couche pour feuilles d'enregistrement sensibles à la pression et feuille d'enregistrement pourvue de cette couche Download PDF

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Publication number
EP0375847B1
EP0375847B1 EP89117982A EP89117982A EP0375847B1 EP 0375847 B1 EP0375847 B1 EP 0375847B1 EP 89117982 A EP89117982 A EP 89117982A EP 89117982 A EP89117982 A EP 89117982A EP 0375847 B1 EP0375847 B1 EP 0375847B1
Authority
EP
European Patent Office
Prior art keywords
microcapsules
solvent
sensitive recording
recording sheet
sheet
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
EP89117982A
Other languages
German (de)
English (en)
Other versions
EP0375847A2 (fr
EP0375847A3 (fr
Inventor
Fumio Oiso Branch Factory Nishiyama
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.)
Nippon Paper Industries Co Ltd
Original Assignee
Nippon Paper Industries Co Ltd
Jujo Paper 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 Nippon Paper Industries Co Ltd, Jujo Paper Co Ltd filed Critical Nippon Paper Industries Co Ltd
Publication of EP0375847A2 publication Critical patent/EP0375847A2/fr
Publication of EP0375847A3 publication Critical patent/EP0375847A3/fr
Application granted granted Critical
Publication of EP0375847B1 publication Critical patent/EP0375847B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime 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
    • B41M5/165—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 characterised by the use of microcapsules; Special solvents for incorporating the ingredients

Definitions

  • the invention relates to a coating composition containing microcapsules for a pressure-sensitive recording sheet.
  • a pressure-sensitive recording sheet is a copy paper which allows a copy to be made without carbon paper.
  • pressure-sensitive recording sheets consist of an upper sheet, a middle sheet and a lower sheet.
  • the surface of the middle sheet (CFB) is coated with a layer comprising a color developing agent consisting of an acidic substance, and the underside of the middle sheet is coated with microcapsules containing a solution of a leuco dye.
  • Pressure-sensitive recording sheets produce a colored impression when typing or typing with a typewriter, or when using mechanical printing, and allow multiple copies to be made at the same time.
  • the pressure sensitive recording sheets have a disadvantage of undesirable color development in the cases where the recording is unnecessary, for example when copying or printing. It is known that this undesirable color development, which is caused by the thermal effects of the environment, as often occur during storage in a room or warehouse, during transport or when printing for the production of booklets, worsens the legibility (causes background contamination), and that Value of goods reduced as pressure-sensitive recording sheets. To prevent this color development (background contamination), it has been proposed to make the wall of the microcapsules thick, to protect the microcapsules by adding water-soluble polymers, latex, etc. to the dye contained in the microcapsules, and the like.
  • microcapsule wall requires a larger amount of wall material, which leads to an increase in the cost of the microcapsules.
  • the addition of water-soluble polymers, latex, etc. is not desirable because it also increases costs, lowers color developability, and adversely affects the performance of a pressure-sensitive sheet.
  • JP-OL 62-267184 and Japanese Patent Publication 53-21328 describe a pressure-sensitive recording sheet to which the following mixture is applied: microcapsules (1) containing a recording solvent dissolving a colorless dye for a pressure-sensitive recording sheet, and microcapsules (2), which are larger than the microcapsules (1) and contain a solvent which does not dissolve the dye.
  • the object of the above JP-OL and Japanese patent publication is to provide a means which prevents contamination of the paper by the recording solvent which has leaked out from broken microcapsules, that is, from the small one accidentally exerted by rubbing Pressure, etc. broken microcapsules (2).
  • the solvent contained in the larger microcapsules (2) is independent of the dye-dissolving recording solvent in the microcapsules (1), and it is a solvent with a high boiling point and a low odor that affects the color development of the leuco dye not prevented.
  • the solvent in the microcapsules (2) be the same as the recording solvent in the microcapsules (1).
  • Japanese Patent Publication 53-21328 describes that the microcapsules (1) contain a solution in which a colorless dye (leuco dye) is dissolved in a solvent with a weak affinity for the color developing agent, and that the microcapsules (2) are a solvent with a contain strong affinity for the color developing agent.
  • the solvent with a strong affinity for the color developing agent is the same as the solvent used in the microcapsules A of the present invention.
  • the object of the above Japanese patent publication is to prevent contamination of the paper by breaking the microcapsules.
  • EP-A-204 460 describes a carbonless copying system with two types of microcapsules.
  • the first type of microcapsule contains a solution or suspension of one of two dye-forming components of the system.
  • the first type of microcapsule thus contains a dye precursor or a reactive clay or a reactive resin in solution or suspension.
  • the second type of microcapsule contains only a solvent that is capable of dissolving or suspending one or both of the dye-forming components.
  • the copier system gives an improved image without the use of an additional dye precursor.
  • the invention has for its first object to provide a pressure sensitive recording sheet in which undesired color development, i.e. soiling caused by thermal effects is avoided without lowering the image density and without causing an increase in costs.
  • the invention is based on the second object of providing a coating material for the above pressure-sensitive recording sheet.
  • This object is achieved in that a coating composition with microcapsules A, which contain a solution of a colorless dye (leuco dye) for a pressure-sensitive recording sheet in a solvent S1, is produced and another coating composition is produced with microcapsules B, which contain a dye-free solvent S2 , which does not dissolve the dye and which has a lower boiling point than the solvent S1, and that the coating composition with the microcapsules A and that with the microcapsules B are applied or printed separately or in a mixture on a substrate for a pressure-sensitive recording sheet.
  • a coating composition with microcapsules A which contain a solution of a colorless dye (leuco dye) for a pressure-sensitive recording sheet in a solvent S1
  • microcapsules B which contain a dye-free solvent S2 , which does not dissolve the dye and which has a lower boiling point than the solvent S1
  • the coating composition for a pressure-sensitive recording sheet can be applied to a substrate with a coating device or with a printing machine.
  • a paper, film or sheet can be used as the substrate.
  • pressure-sensitive recording sheets are not particularly restricted.
  • both a coating composition of a mixture of microcapsules A and B and a protective layer of a resin film can be applied to a sheet coated with a color developing agent, or a coating composition of a mixture of microcapsules A and B and other microcapsules which are a color developing agent can be applied.
  • the solvent S1 for the dye contained in the microcapsules A is a solvent with a high boiling point, low odor and low toxicity, in which the colorless dye can be dissolved.
  • Typical examples of this solvent S1 are, for example, diarylalkanes such as phenylxylylethane, phenylxylylmethane, ethylphenylphenylethane and butylphenylphenylmethane; Alkylnaphthalenes such as mono- and diisopropylnaphthalenes; Alkyl biphenyls such as isopropyl biphenyl and butyl biphenyl; partially hydrogenated terphenyl; and the same.
  • the solvent S2 contained in the microcapsules B is a dye-free solvent that has no colorless dye contains, has a different chemical constitution than the solvent S1 contained in the microcapsules A and has a lower boiling point than the solvent S1.
  • Typical examples of this solvent S2 are, for example, hydrocarbons of the paraffin series and of the naphthen series, alkylbenzenes and the like. If the boiling point is too low, encapsulation is difficult and the capsule wall is fragile. Therefore, the boiling point is preferably higher than 100 ° C, particularly preferably higher than 150 ° C.
  • the upper limit of the boiling point is determined depending on the solvent S1 contained in the microcapsules A; the solvent S2 generally has a boiling point that is at least 10 ° C lower, preferably a boiling point that is at least 30 ° C lower than the solvent S1.
  • Suitable dyes as described in many patent publications on pressure-sensitive recording sheets can be used as the colorless dye contained in the microcapsules A.
  • these dyes are: 3,3-bis (p-dimethylaminophenyl) -6-dimethylaminophthalide (crystal violet lactone), 3,3'-bis (p-dimethylaminophenyl) phthalide, 3- (4-diethylamino-2 -ethoxyphenyl) -3- (1-ethyl-2-methylindol-3-yl) -5-azaphthalide, di- (N-methyl-N-phenylanilino) carbazolylmethane, 3-diethylamino-6-methyl-7-anilinofluorane, 3-diethylamino-6-methyl-7-o-phenyldimethylanilinofluoran, and the like
  • the materials for the capsule wall of the microcapsules A and B according to the invention and the process according to the invention for producing the microcapsules are not particularly limited.
  • Typical chemicals for the capsule wall according to the invention are, for example, gelatin, melamine-formaldehyde precondensate, melamine-urea-formaldehyde precondensate, Condensate from a urea-formaldehyde mixture using an acid catalyst, isocyanatamine resin, isocyanate polyol resin, epoxy resin and the like.
  • Typical examples of the process according to the invention for producing the microcapsules are, for example, coacervation processes, in-situ polymerisation processes, interfacial polymerisation processes and the like.
  • the particle size of the microcapsules has a great influence on the color development and the degree of contamination.
  • the microcapsules A according to the invention have an average particle size of about 3 to 15 ⁇ m, and the microcapsules B according to the invention have an average particle size of 2 to 10 ⁇ m, preferably 3 to 8 ⁇ m.
  • the microcapsules B containing only one solvent per 100 parts by weight of the microcapsules A containing the dye solution. If the amount of microcapsules B used is too small, the effect according to the invention is slight. If an excessive amount of microcapsules B is used, the color development, a function crucial for a pressure-sensitive recording sheet, is deteriorated.
  • the dye-dissolving solvent S1 and the dye-free (dye-free) and the dye-non-solvent S2 are individually encapsulated, and that the capsules obtained are present separately.
  • the cause of the improvement in thermal pollution from this invention is unclear, but the following is believed.
  • the solvent S2 evaporates from the microcapsules B first because it has a lower boiling point than the solvent S1.
  • the solvent S2 leads to no color development on the surface of the layer with the color developing agent because it contains no dye.
  • the color developing agent in turn is surrounded by the solvent S2, which essentially cannot dissolve the dye. Color development is therefore difficult, even if the dye solution in the microcapsules A emerges through the capsule wall. This improves or prevents the contamination from the dye caused by thermal effects. If the two kinds of solvents are mixed and encapsulated evenly, the object of the present invention cannot be achieved and the crystallization of the dye easily occurs, which is a disadvantage.
  • the invention is illustrated by the following examples and comparative examples. Parts and percent are parts by weight and percent by weight.
  • the dispersion of the microcapsules B obtained according to (1) and the dispersion of the microcapsules A obtained according to (2) were mixed in a mixing ratio of 15 to 85 (solids basis), to make a dispersion of microcapsules. 20 parts of starch particles were added to 150 parts of this dispersion. The resulting dispersion was adjusted to a concentration of 12% with water. A coating composition for a pressure-sensitive recording sheet is thus obtained.
  • the coating composition obtained in (3) was applied to a base paper of 40 g / m2 in a coating amount of 3.5 g / m2 (solid content) by means of a Meyer rod (# 14) to produce an upper sheet.
  • the above upper sheet and a lower sheet (NW-40B, manufactured by JUJO PAPER CO., LTD.) are laid on each other so that the coated surfaces of the sheets touch each other.
  • the stacked sheets are thermally treated at 105 ° C for 16 hours under a pressure of 80 g / cm2.
  • the degree of thermal pollution is assessed from the pollution of the lower sheet.
  • the reflectivities of a bottom sheet before and after the thermal treatment are measured by a color difference meter (model TC-1500 MC, manufactured by Tokyo Denshoku Co.).
  • the degree of thermal pollution is the difference between the degrees of reflection before and after the thermal treatment.
  • the image density is determined as follows.
  • the above stacked sheets are colored by a typewriter.
  • the image density of the sheet 1 hour after color development is measured using a color difference meter.
  • An upper sheet was prepared in the same manner as in Example 1, but using a 4.29% solution of crystal violet lactone in the preparation of the microcapsules A and the microcapsules B and A in a mixing ratio of 30 to 70 in the preparation of the coating composition used.
  • a coating composition of 40 parts of a polyvalent metal salt of a carboxylated terpene phenol, 100 parts of calcium carbonate, 10 parts of styrene-butadiene latex (40%) and 10 parts of oxidized Starch was applied by means of a Meyer stick (# 14) in a coating amount of 4.0 g / m2 (solids content) to a capsule-coated surface of the upper sheet obtained according to (4) of Example 1.
  • a single pressure-sensitive recording sheet was obtained.
  • Top sheets are made in the same manner as in Example 1, except that the solvents for microcapsules A and B and the mixing ratio of the microcapsules are varied as described in Table 1. The concentration of crystal violet lactones was adjusted to 3.00% after the mixing.
  • An upper sheet was produced in the same manner as in Example 1 using this coating composition.
  • the sheets obtained according to Comparative Examples 6 to 7 have severe thermal soiling.
  • a pressure-sensitive recording sheet in which a coating composition according to the invention with the microcapsules A and B is applied to a substrate has an improved degree of thermal soiling without lowering the image density, the microcapsules A being a colorless dye for a contain pressure-sensitive recording sheet dissolving solvent S1, and the microcapsules B contain a dye-free, the dye-non-solvent solvent S2.

Landscapes

  • Color Printing (AREA)
  • Heat Sensitive Colour Forming Recording (AREA)

Claims (8)

  1. Masse de revêtement pour une feuille d'enregistrement sensible à la pression, caractérisée par le fait qu'elle contient une combinaison de microcapsules A et B, les microcapsules A contenant une solution, dans un solvant S1, d'un colorant incolore pour une feuille d'enregistrement sensible à la pression, et les microcapsules B contenant un solvant S2, qui ne dissout pas le colorant et présente un point d'ébullition inférieur à celui du solvant S1, et ne contient pas de colorant.
  2. Masse de revêtement selon la revendication 1, caractérisée par le fait que le solvant S2 a un point d'ébullition inférieur d'au moins 10̸°C à celui du solvant S1.
  3. Masse de revêtement selon l'une des revendications 1 ou 2, caractérisée par le fait que le solvant S2 a un point d'ébullition inférieur d'au moins 30̸°C à celui du solvant S1.
  4. Masse de revêtement selon l'une des revendications 1 à 3, caractérisée par le fait que les microcapsules A présentent une granulométrie moyenne d'environ 3 à 15 µm et que les microcapsules B présentent une granulométrie moyenne d'environ 2 à 10̸ µm.
  5. Masse de revêtement selon l'une des revendications 1 à 4, caractérisée par le fait que l'on emploie 1 à 90̸ parties en poids de microcapsules B pour 10̸0̸ parties en poids de microcapsules A.
  6. Masse de revêtement selon l'une des revendications 1 à 5, caractérisée par le fait que l'on emploie 20̸ à 70̸ parties en poids de microcapsules B pour 10̸0̸ parties en poids de microcapsules A.
  7. Feuille d'enregistrement sensible à la pression, caractérisée par le fait qu'elle est revêtue des microcapsules A et B, les microcapsules A contenant une solution, dans un solvant S1, d'un colorant incolore pour une feuille d'enregistrement sensible à la pression et les microcapsules B contenant un solvant S2 qui ne dissout pas le colorant et présente un point d'ébullition inférieur à celui du solvant S1, et ne contient pas de colorant.
  8. Procédé de fabrication de la feuille d'enregistrement sensible à la pression de la revendication 7, caractérisé par le fait que l'on dépose les microcapsules A et B telles que définies dans la revendication 7, en mélange ou séparément l'une de l'autre, sur un substrat pour une feuille d'enregistrement sensible à la pression.
EP89117982A 1988-12-24 1989-09-28 Couche pour feuilles d'enregistrement sensibles à la pression et feuille d'enregistrement pourvue de cette couche Expired - Lifetime EP0375847B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP326935/88 1988-12-24
JP63326935A JP2885812B2 (ja) 1988-12-24 1988-12-24 感圧複写紙用塗料及び感圧複写紙

Publications (3)

Publication Number Publication Date
EP0375847A2 EP0375847A2 (fr) 1990-07-04
EP0375847A3 EP0375847A3 (fr) 1991-05-15
EP0375847B1 true EP0375847B1 (fr) 1994-09-14

Family

ID=18193414

Family Applications (1)

Application Number Title Priority Date Filing Date
EP89117982A Expired - Lifetime EP0375847B1 (fr) 1988-12-24 1989-09-28 Couche pour feuilles d'enregistrement sensibles à la pression et feuille d'enregistrement pourvue de cette couche

Country Status (4)

Country Link
US (1) US5013708A (fr)
EP (1) EP0375847B1 (fr)
JP (1) JP2885812B2 (fr)
DE (1) DE58908362D1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5969004A (en) * 1993-10-15 1999-10-19 The Gillette Company Aqueous inks
US5888283A (en) * 1996-11-05 1999-03-30 The Standard Register Company High solids direct thermal ink composition and method of making and using same

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3617334A (en) * 1968-11-08 1971-11-02 Ncr Co Pressure-sensitive sheet material
CH501771A (de) * 1969-01-15 1971-01-15 Ciba Geigy Ag Druckempfindliches Durchschreibematerial
JPS5321328A (en) * 1976-08-12 1978-02-27 Nissan Motor Co Ltd Control device for number of fuel supply cylinder
DE3030478A1 (de) * 1980-08-12 1982-03-25 Schneider, Walter, Dr., 8160 Miesbach Farbreaktiospapier
JPS59156788A (ja) * 1983-02-26 1984-09-06 Dainippon Printing Co Ltd 感圧複写紙の製造法
US4636818A (en) * 1985-06-05 1987-01-13 Moore Business Forms, Inc. Carbonless system including solvent-only microcapsules
JP2902419B2 (ja) * 1989-10-13 1999-06-07 大豊工業株式会社 すべり軸受

Also Published As

Publication number Publication date
JP2885812B2 (ja) 1999-04-26
EP0375847A2 (fr) 1990-07-04
JPH02171281A (ja) 1990-07-02
EP0375847A3 (fr) 1991-05-15
US5013708A (en) 1991-05-07
DE58908362D1 (de) 1994-10-20

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