EP0803373A1 - Utilisation d'un polymère à base de composés vinylhétérocycliques basiques pour la revêtement de matériels imprimables - Google Patents

Utilisation d'un polymère à base de composés vinylhétérocycliques basiques pour la revêtement de matériels imprimables Download PDF

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Publication number
EP0803373A1
EP0803373A1 EP19970106530 EP97106530A EP0803373A1 EP 0803373 A1 EP0803373 A1 EP 0803373A1 EP 19970106530 EP19970106530 EP 19970106530 EP 97106530 A EP97106530 A EP 97106530A EP 0803373 A1 EP0803373 A1 EP 0803373A1
Authority
EP
European Patent Office
Prior art keywords
polymer
coating
use according
vinylimidazole
weight
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.)
Ceased
Application number
EP19970106530
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German (de)
English (en)
Inventor
Bernhard Dr. Fussnegger
Manfred Dr. Baumeister
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.)
BASF SE
Original Assignee
BASF SE
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Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP0803373A1 publication Critical patent/EP0803373A1/fr
Ceased 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
    • B41M5/50—Recording sheets characterised by the coating used to improve ink, dye or pigment receptivity, e.g. for ink-jet or thermal dye transfer recording
    • B41M5/52—Macromolecular coatings
    • B41M5/5254—Macromolecular coatings characterised by the use of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds, e.g. vinyl polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31855—Of addition polymer from unsaturated monomers
    • Y10T428/3188—Next to cellulosic
    • Y10T428/31895—Paper or wood

Definitions

  • the invention relates to the use of a polymer based on a basic vinyl heterocycle with a pK a of at least 3.8 for coating printable materials, in particular for coating paper and plastic film intended for inkjet printing.
  • Ink-jet inks are solutions of anionic dyes in water or aqueous organic mixtures. When producing a printed product, these inks are sprayed onto a printable surface in a dot-like manner. In order to prevent the size and shape of the applied ink dots from changing due to melting and the edges becoming blurred, the inks must be fixed immediately during application. This is done by fixing the anionic dyes to polymers with which the printable materials have previously been coated. The ink is bound to the polymers either via an ionic mechanism (cationic polymers) or via ⁇ - ⁇ interactions (neutral polymers).
  • soluble cationic polymers predominantly of the quaternary ammonium compound type, have been used as dye-fixing components. These are formulated with absorbent pigments and applied to them.
  • JP 06143800 describes a silica gel in combination with a quaternary polyethyleneimine, a two-layer structure of the components being provided.
  • JP 06092007 it is proposed to use a calcium carbonate as filler directly in papermaking, which is treated with a formulation which contains a copolymer of trimethylammonium methacrylate and vinyl alcohol.
  • EP 487 349 describes silica gel particles which have been treated with a cationic polyamine (Cypro 514®).
  • JP 01009776 proposes the cationic copolymer of diallyldimethylammonium chloride and acrylamide for this purpose.
  • JP 63307979 proposes coating paper for ink-jet printing with a hydrophilic, soluble copolymer of vinylimidazole, vinylpyrrolidone and vinylbenzylsulfonic acid (60:30:10).
  • JP 63307979 the porous system is produced by crosslinking gelatin with 1,4-butanediol diglycidyl ether.
  • the main disadvantage is the reactivity of this component. After the addition of water and the beginning of the crosslinking reaction, the formulation can only be processed in the coating systems for a short time.
  • the invention was therefore based on the object to provide polymers for coating printable materials which meet the above. Do not have disadvantages.
  • EP-A-4 38 713 such polymers are used to remove heavy metals from wine and wine-like beverages. Reference is expressly made to this document with regard to the production of the polymers.
  • Basic vinyl heterocycles (a) are to be understood here as meaning saturated and aromatically unsaturated heterocycles with a vinyl group and at least one basic tertiary ring nitrogen atom with a pK a of at least 3.8.
  • the ring can also contain alkyl groups with 1 to 4 carbon atoms, phenyl or benzyl groups or a fused second one Wear ring.
  • N-vinylimidazole and derivatives thereof such as 2-methyl-1-vinylimidazole, 4-methyl-1-vinylimidazole, 5-methyl-1-vinylimidazole, 2-ethyl-1-vinylimidazole, 2-propyl -1-vinylimidazole, 2-isopropyl-1-vinylimidazole, 2-phenyl-1-vinylimidazole, 1-vinyl-4,5-benzimidazole.
  • the following can also be used, for example: 2-vinylpyridine, 4-vinylpyridine and 2-methyl-5-vinylpyridine. Mixtures of basic vinyl heterocycles with one another can of course also be used.
  • Preferred monomers (a) are N-vinylimidazole and 2-methyl-N-vinylimidazole.
  • the monomers (a) are used in an amount of 50-99.5, preferably 60-96% by weight, based on the total polymer.
  • Suitable crosslinkers (c) are those which contain two or more radically copolymerizable vinyl groups in the molecule.
  • Alkylenebisacrylamides such as methylenebisacrylamide and N, N'-bisacryloylethylenediamine, in addition N, N'-divinylethylene urea, N, N'-divinylpropylene urea, ethylidene-bis-3- (N-vinylpyrrolidone) and N, N'-divinyldiimidazolyl- (2 , 2 ') - and 1,1'-bis (3,3'-vinylbenzimidazolid-2-one) -1,4-butane.
  • crosslinking agents are, for example, alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate, aromatic divinyl compounds such as divinylbenzene and divinyltoluene, and allyl acrylate, divinyldioxane, pentaerythritol triallyl ether and mixtures thereof.
  • alkylene glycol di (meth) acrylates such as ethylene glycol di (meth) acrylate and tetramethylene glycol di (meth) acrylate
  • aromatic divinyl compounds such as divinylbenzene and divinyltoluene
  • allyl acrylate divinyldioxane
  • pentaerythritol triallyl ether pentaerythritol triallyl ether and mixtures thereof.
  • the crosslinkers (c) are used in an amount of 0.5-10, preferably 1-4% by weight, based on all the monomers of the polymer.
  • the comonomers (b) are polymerized in amounts of up to 49.5%, preferably up to 30% by weight, particularly preferably up to 20% by weight, based on the total monomer mixture.
  • suitable comonomers (b) are styrene, acrylic esters, vinyl esters, acrylamides and N-vinyl-dihydropyridines.
  • Preferred comonomers (b) are N-vinyl lactams such as 3-methyl-N-vinyl pyrrolidone, in particular N-vinyl caprolactam and N-vinyl pyrrolidone (VP).
  • Polymers which are particularly suitable for the use according to the invention are those made from N-vinylimidazole (VI), N-vinylpyrrolidone (VP) and N, N'-divinylethyleneurea (DVEH), in particular from 80-90% by weight VI, 5-15 % By weight of VP and 2-5% by weight of DVEH.
  • VI N-vinylimidazole
  • VP N-vinylpyrrolidone
  • DVEH N, N'-divinylethyleneurea
  • the monomer mixture consisting of basic vinyl heterocycle, the crosslinking agent and optionally N-vinyllactam or another comonomer, is rendered inert by introducing nitrogen and then heated to 100 to 200, preferably 150 to 180 ° C. It is advantageous if a weak stream of nitrogen is further introduced into the mixture. It is particularly advantageous if the batch is brought to the boil by applying a vacuum. Depending on the type of monomers used and the temperature selected, the mixture then polymerizes within 1 to 20 hours.
  • a preferred method of preparation is precipitation polymerization in water.
  • the concentration of the monomers in the reaction mixture is expediently chosen so that the mixture remains readily stirrable over the entire duration of the reaction. If the water is too little, the polymer grains become sticky, so that stirring becomes more difficult than without water.
  • the appropriate monomer concentration based on the aqueous mixture, is about 5 to 30, preferably 8 to 15,% by weight. They can be increased to 50% by weight if powerful stirrers are available. It may also be appropriate to start the polymerization with a relatively concentrated solution and then to dilute it with water in the course of the reaction.
  • the polymerization is expediently carried out at pH values above 6 in order to avoid possible saponification of the comonomers and / or crosslinking agents.
  • the pH can be adjusted by adding small amounts of bases such as sodium hydroxide or ammonia or the usual buffer salts such as soda, sodium bicarbonate or sodium phosphate.
  • the exclusion of oxygen can be achieved by keeping the polymerization batch at the boil and / or, as mentioned, using an inert gas such as nitrogen.
  • the polymerization temperature can be 30 to 150 ° C here. Is preferably carried out at 40 to 100 ° C.
  • a reducing agent such as sodium sulfite, sodium pyrosulfite, sodium dithionite, ascorbic acid and the like in order to completely remove dissolved oxygen before or at the start of the polymerization to add.
  • the water-soluble comonomer preferably NVP or an N-vinyllactam
  • the crosslinking agent water and, if appropriate, a buffer and a reducing agent are heated in a gentle stream of nitrogen until the first polymer particles show up. Then a mixture of the vinyl heterocycle and the remaining crosslinking agent and optionally water, which had been rendered inert by blowing in nitrogen, is added as a diluent within 0.2 to 6 hours.
  • the start of the polymerization can often be started by adding from 0.01 to 5% by weight, based on the monomer mixture, of a crosslinked, less swellable polymer based on basic vinyl heterocycles with a pK a value of at least 3.8 or vinyl lactams, in particular N-vinylimidazole and N-vinylpyrrolidone, are accelerated.
  • the polymer obtained from the aqueous suspension can be isolated by filtration or centrifugation, followed by washing with water and drying in conventional dryers such as a circulating air or vacuum drying cabinet, paddle dryer or current dryer.
  • the polymer is generally used in amounts of 0.5-90, preferably 2-20,% by weight, based on the total dry weight of the coating formulation.
  • the particle size distribution of the polymer particles is usually in the range from 0.01-100 ⁇ m, preferably in the range from 0.3-20 ⁇ m.
  • Another component of the coating formulation is a binder.
  • a binder for example, polyvinyl alcohols or polyvinylpyrrolidones with K values between 60 and 90 are well suited as binders.
  • Fillers known from paper production such as barium sulfate, calcium carbonate, kaolin, talc, titanium dioxide or silicates, can be added as further constituents of the coating formulation.
  • the ingredients are in a liquid medium, preferably in water. suspended, the solids content usually being between 30 and 80% and a viscosity (Brookfield) between 100 and 3000 mPas being achieved.
  • the solids content usually being between 30 and 80% and a viscosity (Brookfield) between 100 and 3000 mPas being achieved.
  • This suspension is used directly to coat the materials to be printed.
  • Papers and cardboards as well as plastic films are particularly suitable as materials for the use according to the invention.
  • the printable materials generally do not need to be pretreated before the coating composition containing the polymer is applied.
  • a mixture of 4 parts of N-vinylpyrrolidone, 0.1 part of N, N'-divinylethylene urea (DVEH), 50 parts of water and 0.5 part of sodium hydroxide solution (5% strength) was placed in a stirred vessel and heated to 60 ° C. in a stream of nitrogen . After addition of 0.01 part of sodium dithionite, the mixture was stirred at 70 ° C. for 60 min.
  • a solution of 37 parts of N-vinylimidazole and 1.2 parts of DVEH in 50 parts of water was metered into the suspension thus obtained within 3 hours.
  • the mixture was then polymerized at 70 ° C for 2 hours.
  • the preparation was carried out by washing on a suction filter, washing with water and drying in a circulating air cabinet 60 ° C. A white fine-grained product was obtained in a yield of 95%.
  • a solution of a mixture of 15 parts of N-vinyl-1,4-dihydropyridine and 15 parts of N-vinylpyrrolidone was in a stirrer equipped with a reflux condenser in 200 parts of water with the addition of 0.6 part of N, N'-divinylethylene urea, first in a Temperature of 60 ° C with nitrogen gassing and then mixed with 1 part of sodium dithionite. After one hour, a solution of 70 parts of N-vinylimidazole and 1.4 parts of N, N'-divinylethylene urea in 200 parts of water was added to the primary suspension thus obtained. The mixture was heated to 80 ° C. with stirring and polymerized for 8 hours. After the precipitation polymer obtained had been separated off on a suction filter, it was carefully washed with water and dried in a vacuum drying cabinet at 50.degree. The yield of white fine-grained and odorless powder was 94.7%.
  • 10 parts of the comminuted polymer according to Example 2 were incorporated with 75 parts of calcium carbonate (95%) with a particle diameter of less than 2 ⁇ m and 10 parts of poly (trimethylammonium methyl methacrylate) and 5 parts of Kurraray R1130® polyvinyl alcohol in 100 parts of water and homogenized.
  • the dispersion obtained in this way was leveled out on the paper using a doctor blade, a doctor blade, a film press, an air brush or a coating press.
  • the application quantity was between 2 and 15 g per m 2 of paper.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Paints Or Removers (AREA)
  • Application Of Or Painting With Fluid Materials (AREA)
  • Paper (AREA)
  • Ink Jet Recording Methods And Recording Media Thereof (AREA)
EP19970106530 1996-04-25 1997-04-21 Utilisation d'un polymère à base de composés vinylhétérocycliques basiques pour la revêtement de matériels imprimables Ceased EP0803373A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19616529 1996-04-25
DE1996116529 DE19616529A1 (de) 1996-04-25 1996-04-25 Verwendung eines Polymerisats auf Basis von basischen Vinylheterozyklen zur Beschichtung von bedruckbaren Materialien

Publications (1)

Publication Number Publication Date
EP0803373A1 true EP0803373A1 (fr) 1997-10-29

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EP19970106530 Ceased EP0803373A1 (fr) 1996-04-25 1997-04-21 Utilisation d'un polymère à base de composés vinylhétérocycliques basiques pour la revêtement de matériels imprimables

Country Status (5)

Country Link
US (1) US5939469A (fr)
EP (1) EP0803373A1 (fr)
JP (1) JPH1081063A (fr)
CA (1) CA2203175A1 (fr)
DE (1) DE19616529A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001096122A1 (fr) * 2000-06-09 2001-12-20 3M Innovative Properties Company Amelioration apportee a des supports poreux recepteurs de jets d'encre

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1309927B1 (it) 1999-11-22 2002-02-05 Ferrania Spa Foglio recettore per stampa a getto di inchiostro comprendente uncopolimero
AU2001222589A1 (en) 2000-06-09 2001-12-24 3M Innovative Properties Company Materials and methods for creating waterproof, durable aqueous inkjet receptive media
US6555213B1 (en) 2000-06-09 2003-04-29 3M Innovative Properties Company Polypropylene card construction
US6506478B1 (en) 2000-06-09 2003-01-14 3M Innovative Properties Company Inkjet printable media
US6503608B2 (en) 2001-01-26 2003-01-07 Eastman Kodak Company Ink jet printing method
DE10138631A1 (de) * 2001-08-13 2003-02-27 Basf Ag Verfahren zur Herstellung von beschichtetem Papier mit hoher Weiße
US20040024083A1 (en) * 2002-07-30 2004-02-05 Lee Melissa D. Fluid set for ink-jet printers
EP1666547B1 (fr) * 2003-09-11 2010-06-09 DIC Corporation Dispersion aqueuse de pigments destinee a une encre pour jet d'encre et composition d'encre pour jet d'encre
JP5258237B2 (ja) * 2006-09-14 2013-08-07 富士フイルム株式会社 インク組成物、インクジェット記録方法、平版印刷版の製造方法、及び平版印刷版

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075034A (en) * 1980-04-22 1981-11-11 Polaroid Corp Copolymeric mordants and photographic products and processes utilising them
US4451582A (en) * 1982-03-13 1984-05-29 Basf Aktiengesellschaft Preparation of insoluble, only slightly swellable polymers of basic vinyl-heterocyclic compounds
GB2156367A (en) * 1984-03-23 1985-10-09 Ciba Geigy Ag Radiation-sensitive polymers which form a metal complex, process for the polymerisation of acetylene, and coated material
JPS63307979A (ja) * 1987-06-10 1988-12-15 Fuji Photo Film Co Ltd インクジエツト記録用シ−ト
EP0698500A1 (fr) * 1994-08-22 1996-02-28 Fuji Photo Film Co., Ltd. Feuille réceptrice d'images et méthode pour former des images
EP0767072A1 (fr) * 1995-10-06 1997-04-09 Seiko Epson Corporation Matériau d'enregistrement avec une couche absorbante pour l'encre

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2629712B2 (ja) * 1987-07-03 1997-07-16 日東紡績株式会社 インクジェット記録用紙
CA2051206A1 (fr) * 1990-11-21 1992-05-22 John F. Oliver Papier autocopiant pour impression par jet d'encre
JPH0692007A (ja) * 1992-09-09 1994-04-05 Mitsubishi Paper Mills Ltd 記録用紙
JP3123268B2 (ja) * 1992-11-09 2001-01-09 王子製紙株式会社 インクジェット記録用シート

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2075034A (en) * 1980-04-22 1981-11-11 Polaroid Corp Copolymeric mordants and photographic products and processes utilising them
US4451582A (en) * 1982-03-13 1984-05-29 Basf Aktiengesellschaft Preparation of insoluble, only slightly swellable polymers of basic vinyl-heterocyclic compounds
GB2156367A (en) * 1984-03-23 1985-10-09 Ciba Geigy Ag Radiation-sensitive polymers which form a metal complex, process for the polymerisation of acetylene, and coated material
JPS63307979A (ja) * 1987-06-10 1988-12-15 Fuji Photo Film Co Ltd インクジエツト記録用シ−ト
EP0698500A1 (fr) * 1994-08-22 1996-02-28 Fuji Photo Film Co., Ltd. Feuille réceptrice d'images et méthode pour former des images
EP0767072A1 (fr) * 1995-10-06 1997-04-09 Seiko Epson Corporation Matériau d'enregistrement avec une couche absorbante pour l'encre

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 013, no. 143 (M - 811) 7 April 1989 (1989-04-07) *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2001096122A1 (fr) * 2000-06-09 2001-12-20 3M Innovative Properties Company Amelioration apportee a des supports poreux recepteurs de jets d'encre
KR100769754B1 (ko) * 2000-06-09 2007-10-23 쓰리엠 이노베이티브 프로퍼티즈 캄파니 개선된 다공성 잉크젯 수용 매체

Also Published As

Publication number Publication date
DE19616529A1 (de) 1997-11-06
JPH1081063A (ja) 1998-03-31
US5939469A (en) 1999-08-17
CA2203175A1 (fr) 1997-10-25

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