EP0144438B1 - Verfahren zur herstellung von druckempfindlichem blattmaterial - Google Patents

Verfahren zur herstellung von druckempfindlichem blattmaterial Download PDF

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Publication number
EP0144438B1
EP0144438B1 EP84902055A EP84902055A EP0144438B1 EP 0144438 B1 EP0144438 B1 EP 0144438B1 EP 84902055 A EP84902055 A EP 84902055A EP 84902055 A EP84902055 A EP 84902055A EP 0144438 B1 EP0144438 B1 EP 0144438B1
Authority
EP
European Patent Office
Prior art keywords
soybean powder
pressure
coating
defatted soybean
pressure sensitive
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
EP84902055A
Other languages
English (en)
French (fr)
Other versions
EP0144438A4 (de
EP0144438A1 (de
Inventor
Hideaki Mitsubishi Seishi Takasago-Ryo Senoh
Takao 2108 Mikage Kosaka
Nobuhiro Mitsubishi Seishi Sakaemachi Kagota
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 EP0144438A1 publication Critical patent/EP0144438A1/de
Publication of EP0144438A4 publication Critical patent/EP0144438A4/de
Application granted granted Critical
Publication of EP0144438B1 publication Critical patent/EP0144438B1/de
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
    • B41M5/1243—Inert particulate additives, e.g. protective stilt materials

Definitions

  • This invention relates to a novel method of making pressure sensitive sheet materials. More particularly, it relates to an improvement in the method for making pressure sensitive sheet materials, such as carbonless pressure sensitive recording paper and pressure sensitive adhesive sheet, comprising a support in sheet form and, provided thereon, a coating of pressure-rupturable microcapsules.
  • a typical example is a carbonless pressure sensitive recording paper utilizing the color reaction which takes place in a solvent medium between a colorless dye and a color developer such as activated clay, acid clay, phenol resins, aromatic carboxylic acids or metallic salts thereof.
  • Examples of carbonless pressure sensitive recording sheets include a combination type comprising, on one hand, a sheet carrying a coating formed by emulsifying a solution of a colorless dye dissolved in a solvent, encasing the emulsified finely divided liquid particles in protective pellicles of natural or synthetic polymers (i.e. microencapsulation), and coating the resulting microcapsule suspension on a support, and, on the other hand, a sheet comprising a support and, provided thereon, a coating of color developers; and a single-layer type comprising a support and, provided thereon, a coating containing both the said microencapsulated colorless dye and the color developer or microencapsulated color developer.
  • a combination-type carbonless pressure sensitive recording paper comprising a sheet carrying a coating of microencapsulated solution of a color developer and a sheet carrying a coating of a colorless dye.
  • pressure sensitive sheet materials than the carbonless recording paper include a pressure sensitive adhesive sheet carrying a coating of adhesive-containing microcapsules or a coating of solvent- containing microcapsules and an adhesive, and an encapsulated perfume sheet carrying a coating of microencapsulated perfume.
  • the carbonless pressure sensitive recording sheet materials which are commercially manufactured on the largest scale of all other pressure sensitive sheet materials, are now in use in various commodity areas such as computer output recording sheets, business slips, and business manifolding forms, and are required to have performance characteristics which comply with the requirements of particular uses. For this reason, in preparing the microcapsule dispersion, various auxiliary agents are added to meet various requirements.
  • Examples of proposed stilt materials for use in carbonless pressure sensitive recording paper include fine powders of starch derivatives (Japanese Patent Publication No. 1,178/72), starch grains having an average diameter as large as at least about 1.2 times the microcapsule diameter (Japanese Patent Publication No. 33,204/73), corncob (waste part of an ear of corn after removal of corn grains) [Japanese Patent Application No. 16,708/73], microspheres expandable by heating [Japanese Patent Application No. 32,013/73], starch grains of large diameter derived from beans other than soybean [Japanese Patent Application No. 34,013/76], acid-modified polyolefin particles [Japanese Patent Application No.
  • Stilt materials generally used forthe purpose of preventing the recording sheet from the smudging due to unintentional rupture of the microcapsules are finely powdered cellulose, finely powdered raw starch, talc, kaolin, bentonite, pyrophyllite, and inorganic pigments such as zinc oxide, titanium oxide, and alumina.
  • an object of this invention is to provide a method of making pressure sensitive sheet materials which are lessened in susceptibility to the unintentional rupture of microcapsules and the attendant smudging, to an extent sufficient for practical use, while the color developing function being retained or improved.
  • Another object of this invention is to provide a method of making pressure sensitive sheet materials, according to which it is possible to retard the viscosity increase in the coating composition during manufacture or application and to minimize the fluctuation in component distribution of the coating composition in order to keep the coating surface from deterioration in quality or to keep the distribution of stilt materials uniform throughout the coating composition.
  • the invention comprises a method for production of a pressure sensitive sheet material by coating pressure-rupturable microcapsules and a soybean powder on a sheet support, and is characterized in that said defatted soybean powder on a sheet support, and is characterized in that said defatted soybean powder has a protein content of from 45 to 55% per weight and a water-soluble nitrogen content of from 5 to 15% per weight ofthetotal nitrogen content and has been produced by treating and modifying a solvent-extracted soybean powder with an alcohol.
  • the coating composition is kept from viscosity increase during its manufacture and retains desirable fluidity so as to improve spreadability of the composition; moreover, owing to sufficient water-retentivity.
  • the fluctuation in component distribution is kept low throughout the coating composition so that after application of the composition, there is obtained a coat of uniform surface quality.
  • the alcohol-treated defatted quality at normal level the alcohol-treated defatted soybean powder exhibits distinguished stilt effect so that the unintentional rupture of microcapsules and the attendant smudging under light pressing can be minimized.
  • the defatted soybean in powder form contains proteins, fats, fibrous matters, ash; polysaccharides such as galactan and pentosan; saccharides such as sucrose, stachyose, and raffinose; and vitamins.
  • the defatted soybean In manufacturing the defatted soybean, it is general practice to remove, in the first step, fatty matters fromthe raw soybean by expression or solvent extraction. Since the removal of fatty matters by expression is insufficient, it has recently become a common practice to use the solvent extraction which reduces the residual fatty matter content of the defatted soybean down to 1 % or below. In the extraction, benzene and n-hexane are generally used as the defatting solvent.
  • the treated soybean is stripped of the solvent by treating with steam at elevated temperatures or by treating under reduced pressure or with a solvent vapor at low temperatures.
  • the defatted soybean powder used in this invention is obtained from the solvent-extracted soybean by treating with alcohols such as methanol, ethanol, and propyl alcohol. If the defatted soybean produced by expression is used as stilt material, owing to the residual oil which amounts to about 8%, there will occur in the coating layer a phenomenon of cissing which hinders uniform distribution of the stilt material.
  • the defatted soybean powder used in this invention is that obtained from the solvent-extracted soybean by treating and modifying with an alcohol to adjust the protein content to 45 to 55%, the water-soluble nitrogen content being 5 to 15% of the total nitrogen content.
  • Such a defatted soybean powder is an effective stilt material and, in addition, has an advantage of improving the water retentivity of the capsule- containing coating composition on account of the presence of water-soluble constituents. If the water-soluble nitrogen content exceeds 15% of the total nitrogen, gelation will take place in the coating composition, whereas if the content is below 5%, the water retention becomes insufficient.
  • the principal object of treating and modifying the defatted soybean with an alcohol is deodorizing and decoloring.
  • the resulting defatted soybean powder is a powder material which is nonsticky, easy to handle, and pale amber yellow in color. As a consequence, the coating layer containing such a stilt material is excellent in surface brightness.
  • a powder material prepared by dissolving raw soybean or defatted soybean in an alkali solution and reprecipitating with an acid is generally a high-purity (e.g. 85%) protein substance and substantially devoid of water-solubility, the water-soluble nitrogen content being 1% of the total nitrogen or less.
  • FR-A-2 404 533 which is the nearest prior art document
  • soybean powder is unsuitable for actual use, because if it is added to a capsule- containing coating composition, the composition becomes less uniform in component distribution, as compared with the composition prepared according to this invention.
  • the defatted soybean powder used in this invention is amorphous in particle shape and has an average particle size of from 10 to 60 um, especially preferred size being 20 to 30 !-1m which are larger than the capsule size, though not limitative. If necessary, the defatted soybean powder can be used in combination with other known stilt materials such as, for example, finely powdered cellulose or wheat starch to obtain also a desirable result.
  • Typical examples of the processes for producing microcapsules used in this invention are physical, coacervation, interfacial polymerization, and in situ polymerization processes.
  • colorless dyes enclosed in the capsules include phthalides such as 3,3-bis(4-dimethylaminophenyl)-6-dimethylaminophthalide and 3,3-bis(1,2-dimethylindol-3-yl)-5-dimethylaminophthalide; fluoranes such as 3-diethylamino-6-methyl-7-anilinofluorane, 3-(N-methyicyciohexytamino)-6-methyi-7-aniiinofiuorane, 3-diethylamino-6-methyl-7-chlorofluorane, 3-diethylamino-6-methyl-7-chlorofluorane, and 3-diethylamino-7-dibenzylaminofluorane; thiazine compounds such as benzoylleuco methylene blue; lactams such as N-(p-nitrophenyl)-rhodamine B
  • the pellicle materials for microcapsules there may be mentioned, nonlimitatively, unmodified or partially modified natural polymers such as gelatin, cellulose derivatives, and starch derivatives; and synthetic resins such as urea-formaldehyde resin, melamine-formaldehyde resin, reaction products of isocyanate compounds and hexamethylenediamine, and reaction products of adipic acid dichloride and hexamethylenediamine.
  • synthetic resins such as urea-formaldehyde resin, melamine-formaldehyde resin, reaction products of isocyanate compounds and hexamethylenediamine, and reaction products of adipic acid dichloride and hexamethylenediamine.
  • capsule wall properties such as heat resistance, solvent resistance, water resistance, chemical resistance, and impact resjstance
  • microcapsules covered with synthetic resins are preferred.
  • solvents of high boiling points which can be at least one selected from natural oils such as petroleum- or mineral-base oils, and animal- or vegetable-base oils or from synthetic oils. Especially preferred are those which dissolve the colorless dyes.
  • natural oils such as petroleum- or mineral-base oils, and animal- or vegetable-base oils or from synthetic oils.
  • solvents of high boiling points which can be at least one selected from natural oils such as petroleum- or mineral-base oils, and animal- or vegetable-base oils or from synthetic oils.
  • those which dissolve the colorless dyes are particularly preferred.
  • alkylated biphenyls, alkylated terphenyls, alkylated naphthalenes, triarylmethanes, diarylalkanes, phthalic esters, phosphoric esters, sulfonic esters, diaryl ethers, and higher alkylbenzenes but the invention is not limited thereto.
  • the pressure sensitive sheet material manufactured according to this invention comprises at least a support, microcapsules, and a defatted soybean powder obtained from the solvent-extracted soybean by treating and modifying with an alcohol.
  • the present sheet material may contain binders including water-soluble natural binders such as starch and carboxymethylcellulose; and water-soluble synthetic binders such as polyvinyl alcohol, polyvinylpyrrolidone, and polyacrylic acid; and latices such as styrene-butadiene latex, styrene-butadiene- acrylic acid latex, butadiene rubber latex, and neoprene rubber latex.
  • lubricant or extender inorganic pigments such as talc, titanium dioxide, zinc oxide, calcium carbonate, and activated clay; and organic lubricants such as ethylene-bisstearamide.
  • the coating composition of this invention can be applied by any of the known techniques such as, for example, air knife coating, blade coating, bill blade coating, roll bar coating, three-applicator-roll coating, and curtain coating.
  • the blade coating is effectively used in applying a high-solid content coating composition.
  • the coating composition of this invention can be efficiently applied also by the blade coating technique, because even at high solids concentration, it is hardly subject to fluctuation in distribution of components and has excellent fluidity.
  • the defatted soybean powder and the microcapsules should be present on the same side of the support. Therefore, it can be added to the coating composition which is to form the microcapsule layer, or to the coating composition which is to form an under- and/or over-layer to the microcapsule layer.
  • S-Sanmeat As examples of commercial solvent extracted soybean powder products, mention may be made of "S-Sanmeat” (Ajinomoto Co.) extra grade (7.0% of water, 54.0% of protein, and 0.2% of oil) and first grade (7.5% of water, 49.0% of protein, and 0.2% of oil).
  • the above solution of an electron donating leuco dye in the high-boiling solvent was emulsified in 100 parts of a 5-% aqueous solution of a styrene-maleic acid copolymer.
  • An aqueous solution of melamine-formaldehyde prepolymer was prepared by heating a mixture (adjusted to pH 9.5 with sodium hydroxide) of 10 parts of melamine, 25 parts of 37-% formalin, and 20 parts of water.
  • the prepolymer solution was added to the above emulsion and allowed to react with stirring at 75°C for 90 minutes.
  • the reaction mixture was cooled to room temperature and adjusted to pH 9.5 with sodium hydroxide to obtain a microcapsule dispersion.
  • An upper sheet was obtained in the same manner as in Example, except that 35 parts of wheat starch was used in place of the defatted soybean powder treated with an alcohol.
  • An upper sheet was obtained in the same manner as in Example, except that 35 parts of finely powdered cellulose was used in place of the defatted soybean powder treated with an alcohol.
  • An upper sheet was obtained in the same manner as in Example, except that the defatted soybean powder treated with an alcohol was omitted and each 13 parts of polyvinyl alcohol and a styrene-butadiene latex were used as binder for 100 parts of the capsules, the coverage with respect to capsules being the same as in Example.
  • An upper sheet was obtained in the same manner as in Example, except that 35 parts of solvent-defatted soybean (50% in protein content) not treated with an alcohol was used in place of the defatted soybean powder treated with an alcohol.
  • An upper sheet was obtained in the same manner as in Example, except that 35 parts of a high-purity soybean protein powder having a water-insoluble protein content of about 85% or above was used in place of the defatted soybean powder treated with an alcohol.
  • a pressure sensitive recording sheet (Mitsubishi NCR paper CF) carrying a coating of an electron accepting solid acid (oil-soluble novolak-type phenol resin) was used as color developer sheet (under sheet).
  • the upper sheet was placed on the under sheet so as to bring both coated sides in contact with each other and tested for coloring characteristics and smudge characteristics.
  • the test results were as shown in the table.
  • the test results for smudge characteristics were as shown in the table.
  • the coloring intensity is the intensity of color measured after one hour of pressure application at 90 kg/cm by means of a calender.
  • the smudge is expressed in terms of reflectance measured 24 hours after rubbing under a load of 450 g/cm 3. All numerical values were corrected for the background condition. Marks, o and X, were the results of visual inspection performed at the same time.
  • a recording paper system comprising a powder material obtained by treating and modifying the solvent-defatted soybean with an alcohol showed especially well-balanced practical characteristics, being excellent in coloring characteristics, less subject to smudging, low in viscosity of the coating composition, and less subject to the fluctuation of component distribution in the coating composition.
  • the method of this invention is suitable for the production of carbonless pressure sensitive recording paper, pressure sensitive adhesive sheet, perfume-containing capsule sheet, and the like. Above all, it is especially suited for the production of pressure sensitive recording paper, because it keeps the recording paper from smudging due to uninternational rupture of the microcapsules.

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  • Color Printing (AREA)
  • Manufacturing Of Micro-Capsules (AREA)

Claims (4)

1. Verfahren zur Herstellung eines druckempfindlichen Blattmaterials, bei dem man durch Druck zerbrechbare Mikrokapseln und Sojapulver auf einen Blattträger beschichtet, dadurch gekennzeichnet, dass das entfettete Sojabohnenpulver einen Proteingehalt von 45 bis 55 Gew.% und einen Gehalt an wasserlöslichem Stickstoff von 5 bis 15 Gew.%, bezogen auf dem Gesamtstickstoffgehalt, aufweist und hergestellt wurde, indem man ein lösungsmittelextrahiertes Sojabohnenpulver mit einem Alkohol behandelte und modifizierte.
2. Verfahren zur Herstellung eines druckempfindlichen Blattmaterials gemäss Anspruch 1, dadurch gekennzeichnet, dass das entfettete Sojabohnenpulver eine durchschnittliche Teilchengrösse von 10 bis 60 11m hat.
3. Verfahren zur Herstellung eines druckempfindlichen Blattmaterials gemäss Anspruch 1, dadurch gekennzeichnet, dass die Überzugszusammensetzung, mit welcher die Überzugsschicht, welche das entfettete Sojabohnenpulver enthält, hergestellt wird, erhalten wurde, indem man das entfettete Sojabohnenpulver zu einer Mikrokapseln enthaltenden Überzugszusammensetzung gibt.
4. Verfahren zur Herstellung eines druckempfindlichen Blattmaterials gemäss Anspruch 1, dadurch gekennzeichnet, dass die Überzugszusammensetzung, welche die das entfettete Sojabohnenpulver enthaltende Überzugsschicht ergibt, keine Kapseln enthält und über und/oder unter die Mikrokapselschicht aufgebracht wird.
EP84902055A 1983-05-21 1984-05-18 Verfahren zur herstellung von druckempfindlichem blattmaterial Expired EP0144438B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP89644/83 1983-05-21
JP58089644A JPS59214685A (ja) 1983-05-21 1983-05-21 感圧シ−ト材料製造方法

Publications (3)

Publication Number Publication Date
EP0144438A1 EP0144438A1 (de) 1985-06-19
EP0144438A4 EP0144438A4 (de) 1985-10-10
EP0144438B1 true EP0144438B1 (de) 1988-08-10

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EP84902055A Expired EP0144438B1 (de) 1983-05-21 1984-05-18 Verfahren zur herstellung von druckempfindlichem blattmaterial

Country Status (4)

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EP (1) EP0144438B1 (de)
JP (1) JPS59214685A (de)
AU (1) AU2960984A (de)
WO (1) WO1984004728A1 (de)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0491487B1 (de) * 1990-12-15 1993-07-21 The Wiggins Teape Group Limited Druckempfindliches Aufzeichnungspapier
WO2005082156A1 (ja) * 2004-02-26 2005-09-09 Fuji Oil Company, Limited 大豆たん白含有溶液乃至ゲル

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5134013A (de) * 1974-06-10 1976-03-23 Staley Mfg Co A E

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2743800C3 (de) * 1977-09-29 1980-04-03 Feldmuehle Ag, 4000 Duesseldorf Druckempfindliches Aufzeichnungsmaterial und Streichmasse zu semer Herstellung
JPH05134013A (ja) * 1991-11-15 1993-05-28 Sharp Corp 半導体検査装置

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5134013A (de) * 1974-06-10 1976-03-23 Staley Mfg Co A E

Also Published As

Publication number Publication date
AU2960984A (en) 1984-12-18
EP0144438A4 (de) 1985-10-10
WO1984004728A1 (en) 1984-12-06
EP0144438A1 (de) 1985-06-19
JPS59214685A (ja) 1984-12-04

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