EP0657300A1 - Couche acceptrice pour feuilles d'enregistrement sensible à la pression - Google Patents

Couche acceptrice pour feuilles d'enregistrement sensible à la pression Download PDF

Info

Publication number
EP0657300A1
EP0657300A1 EP94118477A EP94118477A EP0657300A1 EP 0657300 A1 EP0657300 A1 EP 0657300A1 EP 94118477 A EP94118477 A EP 94118477A EP 94118477 A EP94118477 A EP 94118477A EP 0657300 A1 EP0657300 A1 EP 0657300A1
Authority
EP
European Patent Office
Prior art keywords
caco3
recording
weight
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.)
Granted
Application number
EP94118477A
Other languages
German (de)
English (en)
Other versions
EP0657300B1 (fr
Inventor
Rolf Dr. Dipl.-Chem. Bosenick
Manfred Dr. Dipl.-Chem. Spangenberg
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.)
Zanders Feinpapiere AG
Original Assignee
Zanders Feinpapiere AG
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 Zanders Feinpapiere AG filed Critical Zanders Feinpapiere AG
Publication of EP0657300A1 publication Critical patent/EP0657300A1/fr
Application granted granted Critical
Publication of EP0657300B1 publication Critical patent/EP0657300B1/fr
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Images

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
    • B41M5/155—Colour-developing components, e.g. acidic compounds; Additives or binders therefor; Layers containing such colour-developing components, additives or binders
    • 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

  • the invention relates to the use of a special CaCO3 in the acceptor layers of self-copying pressure-sensitive recording materials.
  • Pressure sensitive recording materials have been known for many years.
  • a color former contained in a solvent and used as a reactant, is transferred from the back of the sheet (CB sheet) printed on the front side to a layer arranged below (CF sheet) with a receiving or accepting layer and by reaction with a so-called acceptor a colored record.
  • CB sheet the back of the sheet
  • CF sheet a layer arranged below
  • acceptor a colored record the so-called single-leaf type
  • both reactants are arranged separately from one another in a layer and are brought into contact with one another by the applied contact.
  • Phenolic resins, their derivatives, salicylic acid derivatives and their polymers are used as organic acceptors in the acceptor layers.
  • a color developer preparation for the production of receiving sheets of pressure-sensitive recording materials is known, which contains a p-alkylphenol resin, optionally CaCO3 and calcium oxide, calcium hydroxide and / or magnesium oxide and conventional binders.
  • hydrorybenzoic acid and hydroxynaphtholic acid derivatives and their metal salts are used as organic acceptors in combination with binders and pigments, including CaCO3 in acceptor layers of pressure-sensitive recording materials.
  • a color development sheet for pressure-sensitive recording materials is known with a color development layer which contains an organic acceptor CaCO3 and polyvinyl alcohol-acrylamide copolymer.
  • the CaCO3 has an average particle size of less than 0.6 ⁇ m and is present in the layer with a proportion of at least 30% by weight of the dry constituents.
  • the combination of PVA-acrylamide copolymer and CaCO3 improves the recording capacity and the printability of the sheet.
  • EP-A-60 386 describes the combination of CaCO3, styrene butadiene latex and organic acceptor in color development sheets for pressure-sensitive recording materials.
  • the precipitated CaCO3 has an average particle size of less than 0.6 ⁇ m and is used in a 5-20-fold excess, based on the organic acceptor.
  • the finely divided CaCO3 with a large specific surface area absorbs the carrier liquid with the color former particularly well, but causes a high binder requirement, so that a modified styrene-butadiene copolymer latex with a particle size of less than 0.08 ⁇ m must be used as the binder component in order to ensure sufficient strength of the recording layer to achieve without significantly reducing printability.
  • the proportion of the organic acceptor in the receiving layers is usually 5-20% by weight, based on the weight of the coating.
  • the remaining components are binders and pigments or fillers.
  • the intensity of the color formation depends largely on the uniform distribution of the organic acceptor in the layer. This distribution is supported by the use of pigments, which also influence the adsorption capacity of the layer against the carrier liquid for the color former.
  • the paper must also ensure problem-free printability in offset printing, ie it must have no line picking, filing or printing ink build-up etc.
  • the possible causes for this effect are the covering of the active centers of the acceptor by binders and the sealing of the CF layer against the carrier liquid of the color former, i.e. the low porosity of the layer.
  • the object of the invention is to further improve the write-through performance of pressure-sensitive recording materials with an organic acceptor in the CF layer compared to the known recording materials.
  • a receiving sheet for pressure-sensitive recording systems with a recording layer arranged on the top of the paper sheet, which contains organic acceptor, binder, pigments / fillers and CaCO3, characterized by the use of CaCO3 with an average particle size of 0.8 to 1 , 2 ⁇ m and a BET surface area of 8-12 m2 / g.
  • the oil number of CaCO3 is usually determined and specified according to DIN 53 199. It is 40-60 g / 100 g pigment and is relatively high based on the comparatively low BET value of 8-12 m2 / g. Even higher adsorption values are achieved if the color former solvent is used instead of the linseed oil commonly used for the DIN method.
  • One, for example with diisopropylnaphthalene (KMC 113, Rütgerswerke, Duisburg) determined 'oil number' for the special CaCO3 to be used according to the invention is 80-95 g / 100 g pigment.
  • FIG. 1 shows the decrease in the oil number determining the adsorption capacity with increasing shear duration.
  • the CaCO3 to be used according to the invention was dispersed in water with a commercially available dispersant (polyacrylate) (150 g CaCO3 in 120 g water in a 1000 ml beaker and 3500 rpm) and exposed to the shear stress for up to 90 minutes. Then the CaCO3 was separated from the dispersing liquid, dried and the oil number was determined using KMC oil. It shows that the adsorption capacity of the CaCO3 decreases significantly when it is exposed to intense shear stress for longer.
  • a commercially available dispersant polyacrylate
  • CaCO3 samples were incorporated after shear stress into a coating composition for a recording layer and a recording sheet was prepared.
  • a recording sheet was prepared using a commercially available CB sheet (54 g / m 2), a recording was made on the recording sheet with an AEG Olympia Standard 200i typewriter.
  • the intensity of the recording is determined as the difference between the brightness of the recording and the background or sheet without recording.
  • the brightness is measured with an ELREPHO device type 2000 at 550 nm (filter Y).
  • the brightness differences determined in percent are converted into dimensionless values by forming the ratio: Difference in brightness Ratio value 24.3 ⁇ 1 26.3 ⁇ 1.5 28.3 ⁇ 2 30.3 ⁇ 2.5 32.3 ⁇ 3
  • Figure 2 shows that the intensity of the recording decreases with increasing shear stress of the CaCO3.
  • the oil number of CaCO3 is in addition to the mean particle size and the specific surface area according to BET a feature with which a suitable CaCO3 can be distinguished from less suitable CaCO3. It is particularly advantageous to deviate from the DIN specification when determining the oil number and to use the diisopropylnaphthalene known as color former solvent instead of linseed oil and to determine a modified oil number.
  • the known compounds can be used as organic acceptors in the recording layers, for example phenolic compounds such as phenolic resin, zinc-modified phenolic resins, organic aromatic acids and their metal salts, salicylic acid derivatives, naphtholic acid derivatives, which are used individually or in combination with one another.
  • the proportion of organic acceptor in the recording layer can be from 3-10% by weight, preferably 5-8% by weight, based on the weight of the dry layer.
  • binders for pigmented paper coatings can be used as binders for the recording layer.
  • These include water-soluble binders such as polyvinyl alcohol and its derivatives, starch and starch derivatives, maleic anhydride copolymers, cellulose ethers such as methyl cellulose, ethyl cellulose, hydroxypropyl cellulose, CMC, but also aqueous dispersions of synthetic polymers, so-called latices such as acrylic polymers and copolymers, styrene copolymers, polyvinyl acetate and copolymers.
  • the proportion of binder in the recording layer can be 5-15% by weight, based on the weight of the dry layer.
  • pigments and fillers customary for such recording layers can also be used, for example clay, titanium dioxide, ZnO, aluminum oxide, aluminum hydroxide, other calcium carbonates or silicon dioxide.
  • the proportion of special CaCO3 to be used according to the invention should be 20% by weight to 50% by weight, based on the weight of the dry layer.
  • the proportion of additional further pigments can be 30% by weight to 60% by weight, based on the weight of the dry layer.
  • the ratio of organic acceptor to special CaCO3 in the recording layer can be 1: 4 to 1:10.
  • the ratio of special CaCO3 to other pigments and fillers used in the recording layer can be 1: 3 to 1: 1.
  • the recording layer can additionally contain customary auxiliaries for producing and applying the coating composition, such as dispersing aids, defoamers, rheology control agents, but also antioxidants, UV stabilizers and the like in customary amounts.
  • customary auxiliaries for producing and applying the coating composition, such as dispersing aids, defoamers, rheology control agents, but also antioxidants, UV stabilizers and the like in customary amounts.
  • the constituents of the recording layer are applied in the form of an aqueous coating composition in which the constituents are dissolved or dispersed to a conventional base paper with a basis weight of 30 g / m2 to 100 g / m2 using a conventional coating device and dried.
  • the coating weight of the dried layer is 2-10 g / m2, preferably 3-6 g / m2.
  • the aqueous coating composition was formulated with a dry matter content of approximately 40% by weight and applied to a base paper with a coat weight of approximately 5 g / m 2 (dried) and dried.
  • a recording was made using a commercial CB sheet (54 g / m2) with a typewriter type AEG Olympia 200i.
  • the intensity of the recording was determined as a difference in brightness and converted into dimensionless values by forming the ratio.
  • This conversion makes sense because it enables a direct comparison with the printability of the surface, which can be described with picking values according to the Tappi method T 459 om-88, after the picking value obtained has been expressed here as a ratio.
  • the procedure is shown in the following conversion table: Picking value according to M 459 Ratio value 14 ⁇ 2.0 13 ⁇ 1.6 12th ⁇ 1.2 11 ⁇ 0.8 10th ⁇ 0.4

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Color Printing (AREA)
  • Paper (AREA)
EP94118477A 1993-12-10 1994-11-24 Couche acceptrice pour feuilles d'enregistrement sensible à la pression Expired - Lifetime EP0657300B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE4342140A DE4342140C2 (de) 1993-12-10 1993-12-10 Aufzeichnendes Blatt für druckempfindliche Aufzeichnungssysteme
DE4342140 1993-12-10

Publications (2)

Publication Number Publication Date
EP0657300A1 true EP0657300A1 (fr) 1995-06-14
EP0657300B1 EP0657300B1 (fr) 1996-07-24

Family

ID=6504657

Family Applications (1)

Application Number Title Priority Date Filing Date
EP94118477A Expired - Lifetime EP0657300B1 (fr) 1993-12-10 1994-11-24 Couche acceptrice pour feuilles d'enregistrement sensible à la pression

Country Status (3)

Country Link
EP (1) EP0657300B1 (fr)
DE (2) DE4342140C2 (fr)
ES (1) ES2091079T3 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102014108341A1 (de) 2014-06-13 2015-12-17 Papierfabrik August Koehler Se CF-Papier
EP2546066B2 (fr) † 2011-07-14 2018-06-27 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573085A (en) * 1968-07-03 1971-03-30 Engelhard Min & Chem Abrasive-containing capsular coating composition for pressure-sensitive record paper
GB2022166A (en) * 1978-03-14 1979-12-12 Fuji Photo Film Co Ltd Pressure-sensitive recording material
GB2028888A (en) * 1978-08-23 1980-03-12 Mitsubishi Paper Mills Ltd Colour-developing sheet for pressure-sensitive copying paper

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6013839B2 (ja) * 1980-11-12 1985-04-09 十條製紙株式会社 感圧複写用顕色シ−ト
EP0072380A1 (fr) * 1981-08-14 1983-02-23 Mitsubishi Paper Mills, Ltd. Feuille de développement pour système d'enregistrement sans carbone

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3573085A (en) * 1968-07-03 1971-03-30 Engelhard Min & Chem Abrasive-containing capsular coating composition for pressure-sensitive record paper
GB2022166A (en) * 1978-03-14 1979-12-12 Fuji Photo Film Co Ltd Pressure-sensitive recording material
GB2028888A (en) * 1978-08-23 1980-03-12 Mitsubishi Paper Mills Ltd Colour-developing sheet for pressure-sensitive copying paper

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2546066B2 (fr) † 2011-07-14 2018-06-27 Mitsubishi HiTec Paper Europe GmbH Matériel d'enregistrement sensible à la pression et procédé pour sa fabrication
DE102014108341A1 (de) 2014-06-13 2015-12-17 Papierfabrik August Koehler Se CF-Papier

Also Published As

Publication number Publication date
DE4342140A1 (de) 1995-06-14
EP0657300B1 (fr) 1996-07-24
DE59400453D1 (de) 1996-08-29
ES2091079T3 (es) 1996-10-16
DE4342140C2 (de) 1997-03-06

Similar Documents

Publication Publication Date Title
DE60314608T2 (de) Zusammensetzung zur oberflächenbehandlung von papier
DE69011991T2 (de) Registriermittel und Verfahren zum Registrieren damit.
DE69310107T2 (de) Aufzeichnungsblatt für Tintenstrahlschreiber und Verfahren zu seiner Herstellung
EP0192252B1 (fr) Procédé d'amélioration du "holdout" des couleurs d'impression, laques et masses de revêtement sur des produits en feuille constitués de fibres et de désencrage des fibres ainsi que masse pour la mise en oeuvre du procédé et produits en feuille obtenus
DE69700580T2 (de) Tintenstrahlaufzeichnungsblatt mit einer hochglänzenden Schicht
DE4330428A1 (de) Tintenstrahlaufzeichnungsblatt
CH623876A5 (fr)
EP1126081B1 (fr) Support pour couches d'enregistrement
DE3506710A1 (de) Copolymerlatex
DE69712421T2 (de) Mattgestrichenes papier und verfahren zu siener herstellung
DE68914130T3 (de) Zeitungspapier.
DE60015459T2 (de) Verfahren um den Reibungsbeiwert von Tintenstrahl-Empfangsmaterialien zu modifizieren
DE60012254T2 (de) Tintenstrahlaufzeichnungsmedium
EP3323624B1 (fr) Matériau de transfert adhésif microporeux
EP3098085A1 (fr) Matériau de transfert pour l'impression par sublimation
CH622715A5 (fr)
DE2822961A1 (de) Druckempfindliches kopiermaterial
DE2602444A1 (de) Waessrige streichmassen fuer papier und karton fuer den tiefdruck
EP0919396B1 (fr) Pigment pour développeur de couleur pour papiers d'enregistrement sans carbone, son procédé de fabrication, le papier d'enregistrement sans carbone et la composition de revetement contenant le pigment
DE2854318C2 (fr)
DE3750356T2 (de) Durchsichtiger kunststoffilm zur verwendung beim drucken.
EP0657300B1 (fr) Couche acceptrice pour feuilles d'enregistrement sensible à la pression
DE2449616C3 (de) Verfahren zur Herstellung von gestrichenen Papieren
EP0909242B1 (fr) Feuille de reproduction thermosensible
DE2743800B2 (de) Druckempfindliches Aufzeichnungsmaterial und Streichmasse zu seiner Herstellung

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19950327

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): BE DE ES FR GB IT LU NL

17Q First examination report despatched

Effective date: 19950718

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAH Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOS IGRA

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): BE DE ES FR GB IT LU NL

ITF It: translation for a ep patent filed
REF Corresponds to:

Ref document number: 59400453

Country of ref document: DE

Date of ref document: 19960829

ET Fr: translation filed
REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2091079

Country of ref document: ES

Kind code of ref document: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2091079

Country of ref document: ES

Kind code of ref document: T3

GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)

Effective date: 19961029

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 20000919

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20001006

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20001114

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 20001116

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20001129

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20001130

Year of fee payment: 7

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20001204

Year of fee payment: 7

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011124

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011125

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20011130

REG Reference to a national code

Ref country code: GB

Ref legal event code: IF02

BERE Be: lapsed

Owner name: ZANDERS FEINPAPIERE A.G.

Effective date: 20011130

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020601

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020702

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20011124

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20020730

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee

Effective date: 20020601

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 20021213

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES;WARNING: LAPSES OF ITALIAN PATENTS WITH EFFECTIVE DATE BEFORE 2007 MAY HAVE OCCURRED AT ANY TIME BEFORE 2007. THE CORRECT EFFECTIVE DATE MAY BE DIFFERENT FROM THE ONE RECORDED.

Effective date: 20051124