EP0017386B1 - Selbstaufzeichnendes druckempfindliches Aufnahmepapier - Google Patents

Selbstaufzeichnendes druckempfindliches Aufnahmepapier Download PDF

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Publication number
EP0017386B1
EP0017386B1 EP19800300838 EP80300838A EP0017386B1 EP 0017386 B1 EP0017386 B1 EP 0017386B1 EP 19800300838 EP19800300838 EP 19800300838 EP 80300838 A EP80300838 A EP 80300838A EP 0017386 B1 EP0017386 B1 EP 0017386B1
Authority
EP
European Patent Office
Prior art keywords
colour
self
recording paper
pressure sensitive
sensitive recording
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
EP19800300838
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English (en)
French (fr)
Other versions
EP0017386A1 (de
Inventor
Mitsutu Fuchigami
Isao Nagayasu
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
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Application filed by Mitsubishi Paper Mills Ltd filed Critical Mitsubishi Paper Mills Ltd
Publication of EP0017386A1 publication Critical patent/EP0017386A1/de
Application granted granted Critical
Publication of EP0017386B1 publication Critical patent/EP0017386B1/de
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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 self-contained pressure sensitive recording paper.
  • a known pressure sensitive recording paper system generally comprises a combination of a top sheet coated with microcapsules enwrapping a colourless due as colour former and an undersheet coated on one side with a colour developer which is an acidic substance such as, for example, activated acid clay, a phenolic resin, or a salicyclic acid derivative or its metal salt.
  • a colour developer which is an acidic substance such as, for example, activated acid clay, a phenolic resin, or a salicyclic acid derivative or its metal salt.
  • Another known pressure sensitive recording paper is "self-contained” and comprises a supporting sheet and, coated on one side, two consecutive coatings of a colour former-containing microcapsule layer and a colour developer layer.
  • This recording paper can be printed with letters by means of a typewriter without using an inked ribbon, or can provide a copy by writing or printing on a superposed ordinary paper sheet.
  • JP-A-6,207/72 has disclosed an improved coater for applying two coating layers in manufacturing such a self-contained pressure sensitive recording paper.
  • a self-contained pressure sensitive recording paper of the single coating type having one of the reactants encapsulated is most preferable in view of not only production cost but also product quality, particularly the initial speed of image colour formation.
  • commercialization of such a type of recording paper has been hindered by lack of proper microencapsulation techniques. For instance, if microcapsules having the wall phase of gelatin as major component produced by complex coacervation are used, coloration of the recording paper will occur all over the coated side. In the coacervation technique described in Research Disclosure No.
  • a gelatin membrane wall is strengthened by cross-linking with a melamine-formaldehyde precondensate, which may be used as the sole hardening agent but is more preferably used as a secondary hardening agent together with glutaraldehyde or formaldehyde as primary hardening agent.
  • a melamine-formaldehyde precondensate which may be used as the sole hardening agent but is more preferably used as a secondary hardening agent together with glutaraldehyde or formaldehyde as primary hardening agent.
  • microcapsules having a wall phase of urea-formaldehyde resin As described in 9,079/76.
  • a technique in which the membrane wall is formed by cross-linking a water soluble polymer with a urea-formaldehyde precondensate, the wall being strengthened by additionally cross-linking with a melamine formaldehyde precondensate.
  • EP-A-001 1367 published on 28th May, 1980, and having a priority of 10/10/1978, discloses compositions for a self contained pressure sensitive recording paper, said compositions containing solid particles of a colour developer which are microencapsulated, preferably by in situ polymerization of melamine formaldehyde, microcapsules of a chromogenic material and about 25% by weight of the total weight of the capsules of colour developer and chromogenic material, of uncooked wheat starch.
  • DE-A-2.820.462 discloses a self-contained pressure sensitive recording paper of the single coating layer type comprising a supporting paper sheet and coated thereon a single layer of a mixture including (a) a colour former, (b) a colour developer, which colour developer is in a liquid medium encapsulated by a wall membrane of a urea-formaldehyde resin, the encapsulation being effected by in-situ polymerization using an ethylene-maleic-anhydride copolymer as emulsifier, the colour developer being a phenolic resin or salicyclic acid or a derivative thereof or a metal salt of salicyclic acid or of said derivative and (c) starch particles, the starch particles being present in an amount of at least 150% by weight of the total dry weight of the microcapsules.
  • a self-contained pressure sensitive recording paper of the single layer type applied with a single coating composition containing the colour former and the colour developer has been disclosed in JP-A-16,096/72.
  • this type of recording paper provides an improvement in reducing spontaneous background staining (self-staining)
  • this recording paper has the disadvantage of marked yellowing and insufficient density of the developed image colour, this being because a hydrophilic film-forming polymeric substance impregnated with a phenol-aldehyde resin is used as the capsule wall material.
  • JP-A-6,413/75 has proposed the addition of amines to alleviate the self-staining problem. Although effective to some degree, the addition of an amine in an amount required for the complete prevention of self-staining brings about an interference with the colour-forming reaction and also a tendency to produce yellowing of the sheet surface.
  • JP-B-1 0,780/72 A method is described in JP-B-1 0,780/72, in which the coating composition is incorporated into the paper web during web formation.
  • the colour forming reaction takes place within the paper sheet, resulting in insufficient density of the image colour.
  • the disclosed method is not suitable for encapsulating oil-soluble acidic colour developers such as phenolic resins, salicylic acid derivatives or metal salts thereof, this being because active hydrogen atoms of these colour developers react with the isocyanate compounds used in forming the capsule membrane.
  • oil-soluble acidic colour developers such as phenolic resins, salicylic acid derivatives or metal salts thereof
  • This invention provides a self-contained pressure sensitive recording paper of the single coating layer type which is resistant to spontaneous background staining and has an excellent colour forming ability.
  • a self-contained pressure sensitive recording paper in accordance with the invention is of the single coating layer type and comprises a supporting paper sheet and coated thereon a single layer of a mixture including a colour former, a colour developer and starch particles.
  • the colour developer is a phenolic resin or a salicyclic acid or a derivative thereof or a metal salt of salicyclic acid or of the derivative.
  • At least the colour developer is encapsulated by a wall membrane of a melamine-formaldehyde resin, the encapsulation being effected by in-situ polymerization using a styrene-maleic anhydride copolymer as emulsifier.
  • the starch particles are present in the mixture in an amount of at least 150% by weight of the total dry weight of the microcapsules.
  • This "dry” weight includes the weight of any liquid in the core but not that of moisture on the capsule wall.
  • At least the colour developer (and preferably the colour former also) is in a liquid medium and we find that, by encapsulating at least the colour developer (and preferably the colour former also) with the melamine-formaldehyde wall membrane material, self-staining can be prevented and colour forming quality improved.
  • a coating layer of a recording paper embodying the invention may be formed by the application of a mixture of the following five components onto a substrate sheet: (1) a colourless dye as the colour former, (2) a phenolic resin, salicylic acid or a salicyclic acid derivative or a metal salt of the said acid or derivative as the colour developer, (3) starch particles, (4) a pigment, and (5) a binder.
  • the colour former (1) or the colour developer (2) In encapsulating the colour former (1) or the colour developer (2), it is used generally in the form of dispersion or solution in an oily substance, except for the case of a phenolic resin (colour developer) if it is liquid at ambient temperatures.
  • the colour former used may be a known electron donating leuco dye such as typically crystal violet lactone or a fluorane derivative.
  • the colour developer used is typically a substituted phenol-formaldehyde resin described in JP-B-20,144/67 or a polyvalent metal salt of a salicylic acid derivative described in JP-B-25,174/76.
  • Examples of desirable colour developers include p-phenylphenol-formaldehyde resin, 3,5-di-tert-butylsalicylic acid or zinc salt thereof, and 3,5-di(dimethylbenzyl) salicylic acid or zinc salt thereof.
  • the high-boiling oily substance for use in combination with a colour former or colour developer may, for example, be "SAS” (a commercially available diarylethane type oil produced by Nippon Petrochemical Co.) or "KMC” ( a commercially available dialkylnaphthalene type oil produced by Kureha Chemical Industry Co.), both of which have been used in conventional carbonless copy paper sheets. If necessary, these oils can be admixed with known oils of the ester type or aliphatic type.
  • capsule membrane are important particularly when a self-contained pressure sensitive recording paper is to be prepared with a single coating composition. As mentioned above, it is necessary to encapsulate at least one of the colour former and colour developer with a wall material comprising substantially a melamine-formaldehyde resin. A satisfactory self-contained pressure sensitive recording paper is not obtained if encapsulation is performed by conventionally used or proposed coacervation of gelatin or interfacial polymerization of a polyamide, presumably because of unsatisfactory properties of the capsule wall.
  • the capsules are able to retain their contents firmly throughout the coating operation.
  • the encapsulation is performed by an in-situ polymerization process such as that disclosed, for example, in P-A-49,984/79, but, as mentioned above, using a styrene-maleic anhydride as the emulsifier. Capsules excellent in uniformity of the particle size and heat resistance of the capsule wall may then be obtained.
  • a large amount of starch particles is employed in the coating layer (as mentioned above the amount is at least 1 50% by weight of the total dry weight of the microcapsules), improved properties as compared with those of conventional recording papers can be achieved.
  • a suitable size of starch particles in a coating of a recording paper embodying the invention is in the range of from about 10 to about 30 ⁇ .
  • the pigments use is made of those well known in the art such as clays, kaolin, calcined clays, calcium carbonate, titanium oxide, zinc oxide, and plastic pigments.
  • the pigment may be used to improve the brightness of paper, printability and colour forming performance.
  • the amount to be used is preferably in the range of from about 10 to about 100 parts for 100 parts of capsules, depending on the type of pigment used.
  • binders used in recording paper embodying this invention are the same as those generally used in usual copying paper, such as hydroxyethylcellulose, modified starches, carboxymethylcellulose, acrylic latices, SBR latices, and polyvinyl alcohol.
  • microcapsules with the wall phase of a melamine-formaldehyde resin are most suitable for entrapping the colour developer for use in the above-said self-contained pressure sensitive recording paper of the single coating type having each of the colour-forming reactants encapsulated, in preparing a self-contained pressure sensitive recording paper of the single coating type having both of the reactants encapsulated. We find that this may be achieved without encountering the difficulties of known pressure sensitive recording papers previously discussed.
  • a recording paper embodying the invention it is possible to use, as usual, other known additives, for example, ultraviolet absorbers, antioxidants, dispersants, water-proofing agents, lubricants and defoamers.
  • the coating composition may be applied by known methods such as air-knife coating, roll coating or blade coating.
  • Hisol SAS a commercially available diarylethane oil produced by Nippon Petrochemical Co.
  • p-phenylphenol PR 26142 produced by Sumitomo Durez Co.; m.p. 86°C
  • a melamine-formaldehyde early-stage condensate was prepared by heating at 80°C a mixture of 20 parts of melamine and 45 parts of 37-% formalin, said mixture having been adjusted to pH 8.5 with sodium hydroxide.
  • the early-stage condensate was added to the above emulsion and the resulting mixture was allowed to react by heating at 70°C for one hour to obtain microencapsulated colour developer having an average particle size of 5.2 fL .
  • Microencapsulation of a colour developer was carried out in a manner similar to that in Example 1 using an internal phase oil comprising 20 parts of zinc 3,5-di-tert-butylsalicylate, 40 parts of KMC-113 (an oil produced by Kureha Chemical Industry Co.) and 40 parts of a high-boiling aliphatic hydrocarbon oil (No. 3 ink solvent).
  • the resulting microcapsules had an average particle size of 3.5,u.
  • Microencapsulation of a colour former was carried out in a manner similar to that in Example 1 using an internal phase oil comprising 5 parts of crystal violet lactone (CVL) and 95 parts of KMC-113 to obtain microencapsulated colour former having an average particle size of 4 ⁇ .
  • an internal phase oil comprising 5 parts of crystal violet lactone (CVL) and 95 parts of KMC-113 to obtain microencapsulated colour former having an average particle size of 4 ⁇ .
  • a uniform fluid composition was prepared by thorough mixing of the following components:
  • the above composition was applied by means of a metering bar onto a paper sheet to prepare a self-contained pressure sensitive sheet of single coating layer type having one of the colour-forming reactants microencapsulated.
  • the application rate was 6 g/m 2 .
  • the above 20-% CVL dispersion was an aqueous dispersion of finely ground CVL cystals, said CVL being in solid state and not encapsulated.
  • a coating composition of the following formulation was prepared.
  • the above coating composition was applied by means of an air-knife coater onto a sheet of fine paper at an application rate of 7.5 g/m 2 in terms of solids to prepare a self-contained recording sheet of the single coating layer type having colour-forming reactants each encapsulated.
  • This white self-contained pressure sensitive recording sheet showed no self-staining tendency. Upon impression by means of a typewriter, there was instantly formed a sharp image, bright deep blue in colour.

Landscapes

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

Claims (2)

1. Selbstaufzeichnendes druckempfindliches Aufnahmepapier vom Einzelbeschichtungstyp, enthaltend ein Trägerpapierblatt und darauf eine einzelne Schicht aus einer Mischung, einschließend (a) einen Farbbildner, (b) einen Farbentwickler, wobei der Farbentwickler sich in einem flüssigen Medium befindet, welches durch eine Wandmembran aus einem Aminoplastharz eingekapselt ist, wobei die Einkapselung durch in situ-Polymerisation unter Verwendung eines Maleinsäureanhydrid-enthaltenden Copolymers als Emulgator durchgeführt wurde, der Farbentwickler ein Phenolharz oder Salicylsäure oder ein Derivat davon oder ein Metallsalz der Salicylsäure oder ein Derivat davon ist und (c) Stärkepartikel, wobei die Stärkepartikel in einer Menge von wenigstens 150 Gew.-% des Gesamttrockengewichtes der Mikrokapseln vorliegen, dadurch gekennzeichnet, daß die Wandmembran aus einem Melamin-Formaldehyd-Harz besteht und daß das als Emulgator verwendete Copolymer ein Styrol-Maleinsäureanhydrid-Copolymer ist.
2. Selbstaufzeichnendes druckempfindliches Aufnahmepapier gemäß Anspruch 1, worin sowohl der Farbbildner als auch der Farbentwickler in einem Melamin-Formaldehyd-Harz unter Verwendung eines Styrol-Maleinsäureanhydrid-Copolymers als Emulgator eingekapselt sind.
EP19800300838 1979-03-28 1980-03-19 Selbstaufzeichnendes druckempfindliches Aufnahmepapier Expired EP0017386B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP54036688A JPS5833116B2 (ja) 1979-03-28 1979-03-28 自己発色型感圧記録紙
JP36688/79 1979-03-28

Publications (2)

Publication Number Publication Date
EP0017386A1 EP0017386A1 (de) 1980-10-15
EP0017386B1 true EP0017386B1 (de) 1984-12-12

Family

ID=12476759

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19800300838 Expired EP0017386B1 (de) 1979-03-28 1980-03-19 Selbstaufzeichnendes druckempfindliches Aufnahmepapier

Country Status (3)

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EP (1) EP0017386B1 (de)
JP (1) JPS5833116B2 (de)
DE (1) DE3069782D1 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6861145B2 (en) * 2000-10-09 2005-03-01 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschubg E.V. Solid matter micro-encapsulated by an aminoplast and method for producing the same

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8706667D0 (en) * 1987-03-20 1987-04-23 Wiggins Teape Group Ltd Self-adhesive label assembly
JPH02197327A (ja) * 1989-01-24 1990-08-03 Nippon Steel Corp Ｕｏ鋼管の０プレス方法および装置
JPH1161023A (ja) * 1997-08-14 1999-03-05 Ricoh Co Ltd 孔版印刷用感圧発色型インキおよび孔版印刷方法
WO2013183080A1 (en) * 2012-06-04 2013-12-12 Empire Technology Development Llc Coating materials, manufacturing methods thereof, and coated structures
CN109880684A (zh) * 2019-01-28 2019-06-14 洛阳烨方新材料科技有限公司 一种水性月桂酸分散液及其制备方法

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1507739A (en) * 1975-11-26 1978-04-19 Wiggins Teape Ltd Capsules
US4100103A (en) * 1976-12-30 1978-07-11 Ncr Corporation Capsule manufacture
JPS6026039B2 (ja) * 1977-09-05 1985-06-21 三菱製紙株式会社 自己発色型感圧記録紙
GB2015611B (en) * 1978-03-06 1982-12-22 Mitsubishi Paper Mills Ltd Micro-capsule-incorporated fibrous sheet
US4201404A (en) * 1978-05-17 1980-05-06 Minnesota Mining And Manufacturing Company Pressure-sensitive marking materials

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6861145B2 (en) * 2000-10-09 2005-03-01 Fraunhofer-Gesellschaft Zur Forderung Der Angewandten Forschubg E.V. Solid matter micro-encapsulated by an aminoplast and method for producing the same

Also Published As

Publication number Publication date
JPS5833116B2 (ja) 1983-07-18
EP0017386A1 (de) 1980-10-15
JPS55128492A (en) 1980-10-04
DE3069782D1 (en) 1985-01-24

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