EP0442507A1 - Procédé pour le durcissement et la fixation de particules émulsifiées et feuille d'enregistrement sans carbone sensible à la pression l'utilisant - Google Patents

Procédé pour le durcissement et la fixation de particules émulsifiées et feuille d'enregistrement sans carbone sensible à la pression l'utilisant Download PDF

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Publication number
EP0442507A1
EP0442507A1 EP91102117A EP91102117A EP0442507A1 EP 0442507 A1 EP0442507 A1 EP 0442507A1 EP 91102117 A EP91102117 A EP 91102117A EP 91102117 A EP91102117 A EP 91102117A EP 0442507 A1 EP0442507 A1 EP 0442507A1
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EP
European Patent Office
Prior art keywords
photo
sensitive recording
radiation
curing
curable material
Prior art date
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Granted
Application number
EP91102117A
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German (de)
English (en)
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EP0442507B1 (fr
Inventor
Masahiro Sakamoto
Akira Hasegawa
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
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Publication of EP0442507A1 publication Critical patent/EP0442507A1/fr
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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
    • B41M5/1246—Application of the layer, e.g. by printing

Definitions

  • the present invention relates to a process for curing and setting emulsified particles using a new coating solution in which a remarkably superior productivity is achieved. More specifically, the present invention relates to a carbonless pressure-sensitive recording sheet using this process.
  • microcapsule formation is known as an effective means for curing and setting emulsified particles.
  • the content, the so-called core material, of microcapsules includes pharmaceuticals, agricultural chemicals, perfumes, dyestuffs, liquid crystals, temperature-indicating materials, adhesives and the like.
  • the microcapsules are used in a broad field with the view to the curing of a core material, the control of the release of a core material, the control of a reaction, the solidification of a liquid and the like.
  • One of the applications in large scales lies in the field of carbonless pressure-sensitive recording sheets, wherein the process for producing microcapsules requires high control techniques.
  • the obtained synthetic resin film of capsules has a sufficient hardness and compactness, and is superior in heat, humidity and solvent resistance. This film allows a high consistency coating, which causes a wide applicability.
  • the unreacted monomer such as formaldehyde, isocyanates, polyamines, etc. remains in the microcapsule slurry, and therefore much time and labor is required to remove the unreacted monomers, involving the risk of injuring the capsule film properties.
  • an emulsification, a capsule-forming reaction and a capsule treating step are necessary.
  • the coating solution produced from the microcapsules is applied onto a flexible substrate by using various coating means.
  • various coating means air knife coater, bar coater, curtain coater, blade coater and the like are useful if a large amount of coating is to be applied but are not suitable for a partial coating matching to a minor production of various kinds.
  • the partial printing with silkscreen system, gravure system, flexo system, etc. does not provide a sufficient performance in point of the coating characteristics of the microcapsule dispersion formed in a hydrophilic medium, and is not suitable for the minor production of many kinds. As a result, these are not suitable to meet various quality requirements of a minor production in using microcapsule-forming process.
  • the transfer recording papers using no microcapsule-forming process are employed in wide fields, as seen in back-carbon papers.
  • These socalled carbonless pressure-sensitive recording sheets using no microcapsule-forming process are as follows.
  • Japanese Patent Laid-Open Application No. 57-77410 discloses a process for producing a carbonless pressure-sensitive recording material providing, between a flexible substrate and an upper coating layer of a curing layer, an intermediate layer of porous filling substances impregnated in a liquid medium in which a colorless or pale-colored dye precursor is dissolved or dispersed.
  • Japanese Patent Laid-Open Application No. 56-60289 discloses a process for producing a carbonless pressure-sensitive recording paper which is produced by the application of an aqueous dispersed coating solution composed of both a high oil-absorbing powder impregnated with a hydrophobic liquid dissolving a carbonless dye precursor and a higher fatty acid amide or a mixture of other waxes therewith.
  • Japaneses Patent Laid-Open Application No. 60-7931 discloses a process for a microcapsule-forming reaction in a short time by irradiating a reaction vessel with light, in which the time is too long to achieve a practically useful capsule production (production of 100 kg/hr)
  • the present invention which changes remarkably the conception about curing and setting the conventional emulsified particles, provides both a process for curing and setting the emulsified particles efficiently and a pressure-sensitive recording paper obtainable in high productivity by using this process.
  • the present invention has following advantages.
  • the above subjects are achieved by a process for curing and setting emulsified particles contained in an emulsion comprising a photo- or radiation- curable material, which process comprises curing the photo- or radiation- curable material by the irradiation with light or radiation in a coating process.
  • the carbonless pressure-sensitive recording sheet of the present invention is obtained by the application of the above process for curing and setting emulsified particles in an emulsion containing a carbonless dyestuff, a coat-surface treating agent composed of at least a white color pigment or filler, a buffer agent for a pressure-sensitive recording paper and a binder.
  • the carbonless pressure-sensitive recording sheet of the present invention allows a partial printing, which was only insufficiently possible with the conventional carbonless pressure-sensitive recording sheets.
  • Fig. 1 shows a process-diagram indicating the process-time of the Examples and the Comparative Example.
  • a photo- or radiation- curable material is cured by the irradiation with light or radiation in a coating process.
  • the coating process means "before, in, or after” adhesion of the emulsion on a substrate.
  • the photo- or radiation-curable material of the present invention includes any of the well-known photo- or radiation curable materials, and is preferably at least one of monomers and oligomers having following properties.
  • aliphatic methacrylate cyclic aliphatic di(meth)acrylate, aliphatic di(meth)acrylate, aliphatic tri(meth)acrylate, aliphatic tetra(meth)acrylate, aromatic (meth)acrylate, epoxy(meth)acylate, glycerol(meth)acrylate, 2-hydroxyalkyl(meth)acrylate,methoxyalkylene (meth)acrylate, methoxydialkylene(meth)acrylate, methoxy-tri-alkylene (meth)acrylate, methoxytetraalkylene (meth)acrylate, methoxy polyalkylene (meth)acrylate, oligoester (meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol tetra(meth)acrylate, alkylmodified
  • the addition amount of a photo- or radiation- curable material varies with the intended use , but is in the range of 1-20 % by weight, based on the emulsified particles, in the carbonless pressure- sensitive recording sheet.
  • a photo-curing initiator and a sensitizer must be used in addition to the above photo- or radiation curable material.
  • the photo-curing initiator which is the conventional agent for UV curing,includes, for example, acrylated benzophenone, benzil, benzoylalkylether, benzophenone, xanthone thioxanthone, acetophenone, hydroxy phenyl ketone and the like.
  • the addition amount of the photo-curing initiator is in the range of 0.1-20 % by weight, based on the photo- or radiation- curable material.
  • the above photo-or radiation- curable material can be employed, wherein the amount used is in the range of 1-20 % by weight, based on the hydrophobic substance. If necessary, the photo-curing initiator and sensitizer used for the above photo-curing can be applicable again.
  • the emulsified particles are formed by dissolving a colorless dyestuff for carbonless pressure-sensitive recording sheets in a hydrophobic liquid composed of the usual oil for carbonless pressure-sensitive recording sheets, and the emulsion is obtained by emulsifying the above particles in the aqueous solution of a water soluble emulsifier as a hydrophobic core substance.
  • the photo- or radiation-curable material is preferably added to the hydrophobic core substance by dissolution, but it can also be added to the continuous phase of the emulsion or to both.
  • the water-soluble emulsifier which is preferably that for the usual process of pressure-sensitive recording capsules, includes, for example, an acrylic acid polymer, maleic anhydride copolymer, styrene-sulfonic acid copolymer ,polyvinyl alcohol, gelatin,carboxy methylcellulose, casein, starch, gum arabic and the like. If necessary, a small amount of a surface active agent can be used.
  • the size of the emulsified particles varies with the uses,but is most preferably in the range of 0.1-5 ⁇ .
  • a size of less than 0.1 ⁇ provides an inferior color-forming effect, which tends to cause troubles in obtaining multiple copies.
  • a size of more than 5 ⁇ causes troubles in stabilizing the emulsified particles in the coating, so that an uniform coating is difficult to achieve.
  • a particle size of more than 5 ⁇ on a substrate is not preferable, since it causes a smudge in the color-formation by unusual pressure.
  • a coat-surface-treating agent must be added into the continuous phase of the emulsion.
  • the coat-surface-treating agent has the five following functions.
  • coating pigments and paper fillers are effectively used.
  • the above pigments and fillers include, for example, kaolin, calcium carbonate, magnesium carbonate, titanium dioxide, aluminum hydroxide, aluminum oxide, amorphous silica and silicate, satin white, talc, zinc oxide, barium sulfate and plastic pigment. These pigments and fillers can be used alone,but preferably in combination. Practically, the use of at least 10% of titanium dioxide, based on pigment and filler, provides the aimed sheet.
  • the buffer agent which is that for a pressure-sensitive recording sheet, includes, for example, pulp powder, starch particles, glass beads, plastic beads, polyolefine particles, etc. These agents are appropriately added thereto for the purpose of preventing the rupture of the emulsified particles after forming films by the irradiation with light or radiation.
  • binders photo- or radiation-curable binders are effective, in addition to binders for pressure-sensitive recording sheets.
  • the usual binders include, for example, water-soluble natural polymers such as gelatin, albumine, caseins, starch powder, celluloses, gums and the like; and water-soluble synthetic polymers such as polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid copolymers, maleic anhydride copolymers,polyacrylic amide and the like.
  • binders include latexes, such as styrene-butadiene copolymer, acrylonitrile-butadiene copolymer, acrylic ester-base latex, vinyl acetate-base latex, methyl methacrylate butadiene-base latex and carboxylated latex thereof, etc.
  • the photo- or radiation-curable binders include, for example, partial cinnamoyl esters of polyvinyl alcohol, amylose, starch, alginic acid and the like; cinnamylidene acetic ester; cyanocinnamylidene acetic ester; water-soluble acrylic esters; polyalkylene glycol acrylamides; and the like.
  • the above binders can be used alone or in combination.
  • binder there are added, optionally, dispersing agents, surface active agents, antifoamers, antiseptics, fluorescence dyestuffs, cross-linking agents, photo initiators, sensitizers and the like.
  • the obtained emulsified substance can be applied onto a substrate by mass production coaters, for example, air knife coater, roll coater, blade coater, bar coater, curtain coater, etc.
  • the coating can be applied by a printer, such as gravure-, flexo-, screen- or letterpress-printers fitted with a light-irradiation or radiation installation.
  • these curable material is promptly polymerized to form a cure-film, which cures and sets emulsified particles in an emulsion.
  • parts and % mean parts by weight and % by weight, respectively.
  • a hydrophobic solution was prepared by dissolving 10 parts polyurethane acrylate(trade name: Beam Set 575, manufactured by Arakawa Kagaku Kogyo Co.) as a photo-curable material and 1 part of hydroxymethyl propiophenone(trade name:Daro Cure 1173, manufactured by Merck Co.) as a photo-curing initiator.
  • the obtained hydrophobic solution was added to the hydrophilic medium, and was emulsified to an average particle size of 2.1 ⁇ to prepare a stable hydrophilic emulsion.
  • a coat-surface-treating agent was prepared from 10 parts of a 60% aqueous dispersed titanium dioxide solution and 25 parts of a 60% aqueous dispersed aluminum hydroxide solution. 35 parts of wheat starch as a buffer agent were added to the coat-surface-treating agent with agitation. After complete dispersing, 10 parts (as solid) of styrene-butadiene base latex, 167 parts of the beforehand prepared emulsion containing both a color-forming agent and a photo-curable material and 60 parts of water were further added thereto to produce a coating solution.
  • the above coating solution was coated on a fine paper of 40g/m2 by means of a Meyer bar to prepare a coated paper having a coating amount of 3.4 g/m2. Then, the coated paper was irradiated with UV rays in an irradiation distance of 10 cm and in a conveyer speed of 1.5 m/min. by means of a 3 kW high voltage metal halide lamp to cure the film. Thus, a top sheet for carbonless pressure-sensitive recording sheets was obtained.
  • the process and test results are summarized in Fig. 1 and Table 1.
  • the emulsion of Example 2 was prepared in the same manner as the emulsion of Example 1 but without the photo-curing initiator.
  • a coating solution was prepared in the same procedure as in Example 1.
  • the above coating solution was coated on a fine paper of 40 g/m2 by means of a Meyer bar to prepare a coated paper having a coating amount of 3.5 g/m2. Then, a film curing treatment was made using an acceleration voltage of 175 kV, an electron beam amount of 5 M rad and an irradiation speed of 20 m/min. to prepare a top sheet for carbonless pressure-sensitive recording papers.
  • a film curing treatment was made using an acceleration voltage of 175 kV, an electron beam amount of 5 M rad and an irradiation speed of 20 m/min.
  • a coat-surface treating agent was prepared from 10 parts of a 60% beforehand dispersed titanium dioxide solution and 25 parts of a 60% aqueous calcium carbonate dispersion. 35 parts of wheat starch as a buffer agent were added to the coat-surface-treating agent with stirring. After complete dispersing, 10 parts (as solid) of acrylic ester base latex, 167 parts of the above hydrophilic emulsion containing a color-forming agent and a radiation- curable material and 60 parts of water were added thereto to prepare a coating solution.
  • the coating and film-curing processes were made according to the same procedure as in Example 2 to prepare a top sheet for pressure-sensitive recording papers.
  • Example 4 The emulsion of Example 4 was prepared in the same manner as in Example 1 except that the hydrophilic emulsion of Example 1 was emulsified to an average particle size of 0.5 ⁇ .
  • a coat-surface-treating agent was prepared by mixing 20 parts of a 60% aqueous dispersed titanium dioxide solution and 35 parts of a 60% aqueous calcium carbonate dispersion having an average particle size of 1.7 ⁇ with stirring. After complete dispersing, 15 parts of acrylic ester base latex as a binder, 167 parts of the beforehand prepared emulsion containing a color-forming agent and a photo-curable material and 20 parts of water were added thereto to prepare a coating solution.
  • the above coating solution was coated on a fine paper of 40 g/m2 in a coating amount of 1.5g/m2 by means of a flexo printer installed with an UV-irradiation equipment (Irradiation condition: 3 kW metal halide lamp) under a coating speed of 5 m/min.
  • the coating was irradiated with UV rays in an irradiation distance of 7 cm to cure a film.
  • a particle coated top sheet for carbonless pressure-sensitive recording papers was obtained.
  • the process and test results are summarized in Fig. 1 and Table 1.
  • a 3% aqueous ethylene maleic anhydride copolymer solution (trade name:EMA-31, manufactured by Monsanto Chemical Co.) were adjusted to a pH-value of 4 with a 20% aqueous sodium hydroxide solution to prepare a hydrophilic medium.
  • 100 parts of alkylnaphthalene (trade name: KMC oil, manufactured by Kureha Chemical Co.) and 37 parts of crystal violet lactone were dissolved in the hydrophilic medium, and then emulsified to an average particle size of 4.5 ⁇ .
  • a melamine-formaldehyde prepolymer which was produced from 30 parts of formalin and 10 parts of melamine at 60°C, was added to the above emulsion.
  • the temperature of the system was held at 60-70°C for 3 hours.
  • the system was adjusted to a pH-value of 7.5 by adding a 28% aqueous ammonia solution thereto to prepare a microcapsule dispersion. The time required for preparing this solution was 5 hours.
  • the coating solution was coated on a base paper of 40 g/m2 in a coating amount of 3.5 g/m2 by means of a Meyer bar, and dried in an oven at 105°C for 60 sec. to prepare a top sheet for pressure-sensitive recording papers.
  • the process and test results are summarized in Fig. 1 and Table 1.
  • the setting of the emulsified particles which had been achieved only by an encapsulation process, was performed very simply in the present invention.
  • the present invention provides carbonless pressure-sensitive recording papers which, as compared to conventional pressure-sensitive recording paper have equal copying suitablity and can be prepared in a simpler process and in a shorter time.
  • the partial coating of the carbonless pressure-sensitive recording sheet is possible owing to the improvement of printability.
  • the present invention provides the following effects:

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EP19910102117 1990-02-15 1991-02-14 Procédé pour le durcissement et la fixation de particules émulsifiées et feuille d'enregistrement sans carbone sensible à la pression l'utilisant Expired - Lifetime EP0442507B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP3470790 1990-02-15
JP34707/90 1990-02-15

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EP0442507A1 true EP0442507A1 (fr) 1991-08-21
EP0442507B1 EP0442507B1 (fr) 1995-05-17

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EP (1) EP0442507B1 (fr)
AU (1) AU630273B2 (fr)
DE (1) DE69109701T2 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770499A1 (fr) * 1995-10-26 1997-05-02 Columbia Ribbon Manufacturing Company Limited Méthode pour former une couche sur un support et un objet formé par ce procédé

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1127377B (de) * 1960-04-14 1962-04-12 Pelikan Werke Wagner Guenther Verfahren zur Herstellung eines UEbertragungsblattes fuer Aufzeichnungs- und Vervielfaeltigungszwecke mit Farbreaktions-Komponenten
GB1161934A (en) * 1966-07-13 1969-08-20 Mead Corp Pressure Sensitive Paper and Method of Producing Same
US3535140A (en) * 1965-12-20 1970-10-20 Appleton Coated Paper Co Method for manufacture of dual coated manifold sheet with pressure rupturable materials
FR2350206A1 (fr) * 1976-05-07 1977-12-02 Mead Corp Formulaire sans carbone a copies multiples et son procede de fabrication

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62103186A (ja) * 1985-10-31 1987-05-13 Teikoku Ink Seizo Kk 感圧複写紙及びその製造方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1127377B (de) * 1960-04-14 1962-04-12 Pelikan Werke Wagner Guenther Verfahren zur Herstellung eines UEbertragungsblattes fuer Aufzeichnungs- und Vervielfaeltigungszwecke mit Farbreaktions-Komponenten
US3535140A (en) * 1965-12-20 1970-10-20 Appleton Coated Paper Co Method for manufacture of dual coated manifold sheet with pressure rupturable materials
GB1161934A (en) * 1966-07-13 1969-08-20 Mead Corp Pressure Sensitive Paper and Method of Producing Same
FR2350206A1 (fr) * 1976-05-07 1977-12-02 Mead Corp Formulaire sans carbone a copies multiples et son procede de fabrication

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 11, no. 321 (M-633)(2768) 20 October 1987, & JP-A-62 103186 (TEIKOKU INK SEIZO K.K.) 13 May 1987, *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0770499A1 (fr) * 1995-10-26 1997-05-02 Columbia Ribbon Manufacturing Company Limited Méthode pour former une couche sur un support et un objet formé par ce procédé

Also Published As

Publication number Publication date
DE69109701D1 (de) 1995-06-22
AU630273B2 (en) 1992-10-22
DE69109701T2 (de) 1996-02-22
AU7026791A (en) 1991-08-22
EP0442507B1 (fr) 1995-05-17

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