EP0014904B1 - Papierstreichmassen - Google Patents

Papierstreichmassen Download PDF

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Publication number
EP0014904B1
EP0014904B1 EP80100620A EP80100620A EP0014904B1 EP 0014904 B1 EP0014904 B1 EP 0014904B1 EP 80100620 A EP80100620 A EP 80100620A EP 80100620 A EP80100620 A EP 80100620A EP 0014904 B1 EP0014904 B1 EP 0014904B1
Authority
EP
European Patent Office
Prior art keywords
weight
copolymer
parts
acid
paper
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
EP80100620A
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German (de)
English (en)
French (fr)
Other versions
EP0014904A1 (de
Inventor
Kurt Dr. Wendel
Guenter Dr. Hirsch
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
Priority to AT80100620T priority Critical patent/ATE361T1/de
Publication of EP0014904A1 publication Critical patent/EP0014904A1/de
Application granted granted Critical
Publication of EP0014904B1 publication Critical patent/EP0014904B1/de
Expired legal-status Critical Current

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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters

Definitions

  • the invention relates to paper coating slips containing 5 to 25 parts by weight of a copolymer A with a glass transition temperature of -40 to + 50 ° C. in the form of aqueous dispersions and 0.5 to 10 parts by weight of at least one to 100 parts by weight of a finely divided pigment Contain copolymers B from a high molecular weight copolymer containing carboxyl groups.
  • paper coating slips are used for the production of coated printing papers, which consist essentially of a pigment dispersed in water, for. B. kaolin, calcium carbonate or titanium dioxide, and a binder.
  • B. kaolin a pigment dispersed in water
  • binders While previously only high-molecular natural products such as starch or casein were used as binders, attempts are increasingly being made to replace all or part of the natural products with synthetic, high-molecular polymers in the form of aqueous dispersions. Binders based on natural products have the disadvantages that they are not always of the same quality, are sensitive to the attack by microorganisms, have to be broken down by complex processes and produce brittle lines. Binders based on synthetic high polymers do not have all of the disadvantages mentioned for natural binders, but they still need improvement.
  • the invention has for its object to provide a paper coating slip which has a high water retention, and whose binder brings about the effect of any optical brighteners present.
  • binder combinations mentioned give the paper coating slips according to the invention a high water retention, so that they can be easily processed on conventional coating systems.
  • copolymers B activate the optical brighteners.
  • Suitable copolymers A of the binder mixture are all commercially available synthetic binders which are present as an aqueous dispersion.
  • the polymers have a glass transition temperature of -40 to + 50 ° C.
  • Typical monomers involved in the construction of these polymers are, for example, esters of acrylic acid and methacrylic acid, acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, C 3 - to C 5 -ethylenically unsaturated mono- and dicarboxylic acids, half-esters of ethylenically unsaturated C 3 - bis C 5 -dicarboxylic acids, vinyl chloride, vinylidene chloride, mono- or polyethylenically unsaturated hydrocarbons, such as ethylene, propylene, butylene, 4-methylpentene-1, styrene, butadiene, isoprene and chloroprene, vinyl esters, vinyl sulfonic acid, and esters
  • Suitable copolymers A are known, for example, from DE-AS 1 100450.
  • such copolymers can also contain styrene and / or butadiene and / or acrylonitrile and ethylenically unsaturated acids.
  • other polymerizable hydrophilic compounds can also be copolymerized into the copolymers.
  • hydroxyl group-containing monomers such as hydroxypropyl acrylate and methacrylate.
  • the acrylic esters used in the polymerization can be derived, for example, from monohydric alcohols having 1 to 12 carbon atoms.
  • the acrylic ester content in these copolymers can vary within wide limits, e.g. B.
  • ethylenically unsaturated acids in these copolymers is generally up to 10% by weight.
  • Particularly suitable ethylenically unsaturated acids are acrylic acid, methacrylic acid, vinylsulfonic acid, acrylamidopropanesulfonic acid and itaconic acid.
  • the polymethacrylates have a structure similar to that of the polyacrylates, but contain a methacrylic acid ester instead of an acrylic acid ester. However, it is also possible to copolymerize acrylic acid esters and methacrylic acid esters together with other ethylenically unsaturated compounds and to use them as component A of the binder combination. Ethylene or propylene, for example, are also suitable as comonomers.
  • copolymer A also suitable as copolymer A are copolymers of butadiene and styrene. These copolymers contain 20 to 60% by weight of butadiene and 40 to 80% by weight of styrene and / or acrylonitrile. They can contain further comonomers, for example esters of ethylenically unsaturated carboxylic acids having 3 to 5 carbon atoms and optionally up to 10% by weight of other ethylenically unsaturated copolymerizable compounds, such as acrylic acid, methacrylic acid, maleic acid, crotonic acid and fumaric acid. Polymers of this type, and also polyacrylates, are known for example from DE-PS 1 546 316.
  • Suitable styrene-butadiene copolymers which contain an ethylenically unsaturated carboxylic acid or a half ester of an ethylenically unsaturated dicarboxylic acid in copolymerized form and are used as copolymer A are known from DE-AS 1 221 748.
  • copolymer A in the paper coating slip according to the invention polymers which are derived from vinyl esters, for. B. of the type of vinyl acetate or vinyl propionate and polymerizable hydrocarbons, e.g. B. derive ethylene or propylene, for example, copolymers of vinyl esters with acrylic esters and / or methacrylic esters and / or acrylonitrile and other polymerizable hydrophilic compounds, for. B. contain copolymerized ethylenically unsaturated compounds, such as acrylamide, N-methylolacrylamide, N-methylolmethacrylamide, vinyl chloride or vinylidene chloride.
  • Suitable vinyl ester copolymers are known for example from DE-PS 1 264 945. Homopolymers of vinyl esters can also be used.
  • comonomers of group b acrylic acid and / or methacrylic acid in particular are used. These comonomers are preferably present in the copolymers B in an amount of 15 to 40% by weight.
  • maleic acid semiesters which are also to be used as comonomer of group b), those which are derived from monohydric alcohols having 1 to 4 carbon atoms are particularly suitable.
  • Comonomers of group c) which are 5 to 50, preferably 20 to 40% by weight of the structure of copolymers B are acrylonitrile, methacrylonitrile, esters of acrylic acid or methacrylic acid with monohydric C 1 -C 4 -alcohols and vinyl esters of saturated C 2 - to C 4 -carboxylic acids.
  • carboxylic acid esters especially suitable are methyl acrylate, ethyl acrylate, methyl methacrylate, vinyl acetate and vinyl propionate.
  • Preferably used as comonomer of group c) is acrylonitrile, methyl acrylate and / or ethyl acrylate.
  • the polymerization of the monomers is started using the usual polymerization initiators.
  • peroxides such as peroxydisulfates, hydrogen peroxide, hydroperoxides and azo compounds, and also redox catalysts can be used.
  • the usual polymerization regulators can be used, e.g. B. mercaptans, such as t-dodecyimercaptan, thioglycolic acid etc. or hydroxylammonium salts.
  • emulsifiers are used to emulsify the comonomers which are insoluble or only very sparingly soluble in water.
  • the copolymerization can For example, be carried out batchwise in a stirred tank by first introducing part of the monomer mixture and then adding the rest in accordance with the polymerization process. However, the reaction can also be carried out continuously in a cascade.
  • the paper coating slips according to the invention contain 5 to 25 parts by weight, based in each case on 100 parts by weight of pigment, of polymer A and 0.5 to 10 parts by weight of the solid copolymer B.
  • These polymer combinations are excellent binders for paper coating slips. They are preferably used for the production of such paper coating slips which contain 0.1 to 2% by weight of an optical brightener.
  • Optical brighteners are described, for example, in summary by H. Gold in Venkataraman, The Chemistry of Synthetic Dyes, Academic Press, New York and London 1971, Volume 5, Chapter 8, pages 536 to 679. Optical brighteners are commercially available, so that this can be found superfluous explanations are unnecessary. For more detailed characterization of this class of substances, however, reference is made to DE-OS 2 628 878 and DE-AS 1 795 047. This describes optical brighteners based on stilbene derivatives, which are preferably used.
  • copolymers A and B are mixed with fillers or pigments in a manner known per se. Suitable substances of this type are above all clay minerals, calcium carbonates, calcium aluminum pigments or titanium dioxide. If necessary, other auxiliaries can also be added to the paper coating slips, for example alkalis, such as sodium hydroxide, potassium hydroxide or ammonia or else white pigments based on water-insoluble urea-formaldehyde condensation products or other known paper auxiliaries, such as urea, melamine, melamine-formaldehyde resins or urea Formaldehyde resins.
  • alkalis such as sodium hydroxide, potassium hydroxide or ammonia
  • white pigments based on water-insoluble urea-formaldehyde condensation products or other known paper auxiliaries, such as urea, melamine, melamine-formaldehyde resins or urea Formaldehyde resins.
  • a dispersant e.g. B. low molecular weight polymers of acrylic acid, especially the ammonium or sodium salts of polyacrylic acid with a K value of 10 to 35.
  • the order in which the individual components of the paper coating slip are mixed is not critical. However, it proves advantageous to add the copolymer B at the end of the coating color preparation.
  • the copolymers B can be regarded as cobinders because they themselves have a pigment binding capacity.
  • the copolymers B also act in partially neutralized or fully neutralized form as a thickener, i.e. H. they increase the viscosity of the aqueous paper coating slip. They also increase the water retention of the coating color, lower it, not the effect of the optical brightener, but on the contrary, activate it. It is already possible to achieve the effects described with relatively small amounts of polymer B used, for example 0.5 to 10% by weight of the solid product, preferably 0.5 to 3% by weight of water-soluble copolymer B, are sufficient on the pigment weight in order to achieve the above-mentioned quality improvements of coating color and paper.
  • the invention is illustrated by the following examples.
  • the parts given in the examples are parts by weight, the percentages relate to the weight of the substances, unless stated otherwise.
  • the K values of the copolymers B are between approximately 60 and 140, preferably between 80 and 120.
  • a 2-1 flask is used as the polymerization apparatus, which is equipped with a stirrer, reflux condenser, thermometer and 2 feed vessels.
  • the polymerization is carried out in the absence of oxygen in a nitrogen atmosphere.
  • the feed vessel I contains a mixture which was prepared as follows: To 548 g of water, 7 g of a 28% strength solution of a reaction product were added, which by sulfation of 3 mol of ethylene oxide with 1 mol of a C 12 / C 14 -saturated aliphatic alcohol and neutralization of the reaction product was obtained.
  • the inlet 11 consists of 100 g of water and 4 g of sodium peroxydisulfate. 10% of feed II and 274 g of water are placed in the polymerization apparatus and heated to a temperature of 90 ° C. with stirring. As soon as the temperature of the initial charge is 90 ° C., the feeds I and II are allowed to flow in with thorough mixing within 2 hours and the polymerization is carried out at 90 ° C. Then another 4 g of sodium peroxydisulfate dissolved in 100 g of water are added to the polymerization batch within 50 minutes. After polymerization for 1 hour, the reaction mixture is cooled and then filtered. An approximately 28% aqueous solution of the copolymer B1 is obtained.
  • Example 2 The polymerization apparatus described in Example 1 is used, 335 g of water are placed in it and the mixture is heated to a temperature of 85 ° C.
  • feed I a mixture of 670 g of water and 18 g of a 28% solution of the sodium salt of the sulfuric acid half-ester of 3-fold is used ethoxylated C 12 / G 14 alcohol mixtures, 75 g acrylic acid, which are neutralized with 42 g 50% sodium hydroxide solution, 200 g methyl acrylate, 225 g hydroxypropyl acrylate (mixture of 1-hydroxy-2-propyl and 2-hydroxy-1-propyl acrylate in Weight ratio about 33: 67) and 0.75 g of dodecyl mercaptan used.
  • An aqueous solution of 5 g of sodium peroxydisulfate in 200 g of water is used as feed II. Inlets I and II are added to the template heated to 85 ° C. within 2.5 hours and polymerized at the temperature mentioned.
  • a paper coating slip which is suitable for the production of paper and for offset printing
  • 80 parts of spreading clay and 20 parts of calcium carbonate pigment are dispersed in a 66% strength aqueous slurry using 0.2 parts with the aid of a powerful dispersing unit Sodium hydroxide solution and 0.3 part of a commercially available dispersant based on low molecular weight polyacrylic acid.
  • 12 parts (based on the solids content) of an aqueous dispersion of a copolymer A composed of 50% n-butyl acrylate and 50% styrene are added to the pigment slurry.
  • a coating color for the production of coated cardboard is obtained as described in Example 1 by using the pigment slurry described there with 15 parts of a commercial butadiene-styrene copolymer (48% butadiene and 48% styrene) containing 4% carboxyl groups, based on Solids content of the dispersion, mixed as copolymer A and water was added until the solids content of the mixture was 43%. Then, based on the solids content, 0.7 part of the copolymer B2 and 1 part of a commercial optical brightener based on stilbene derivatives (Blancophor PSG) are added. Then adjust the pH to 8.5 and homogenize the mixture for 15 minutes.
  • a coating color is obtained which can be processed perfectly on an air brush coating system or a roller coating system. The properties of the coating color and the cardboard coated with it are given in the table.
  • a coating color for the production of art paper 80 parts of coating clay and 20 parts of satin white are dispersed with 1.2 parts of a commercially available dispersant based on low molecular weight polyacrylic acid and 0.2 part of sodium hydroxide solution, so that an approximately 54% aqueous slurry is obtained. 16 parts of a copolymer A composed of 50% n-butyl acrylate and 50% vinyl acetate are mixed into this pigment slurry. Then 2.5 parts, based on the solids content, of copolymer B2 and 1 part of a commercial optical brightener based on stilbene derivatives (Blancophor PSG) are added with vigorous stirring, and the solids content of the coating color is adjusted to 50% by adding water. The pH of the paper coating slip is adjusted to 11.3 and the paper coating slip is then mixed for a further 15 minutes. It can then be processed perfectly on a doctor coating system. The results are summarized in the table.
  • the table also shows properties of coating colors and coated papers which were obtained in accordance with the comparative examples.
  • a synthetic or natural cobinder instead of the copolymer B, was used, which corresponds to the prior art.
  • the paper coating slips were otherwise prepared as described in Examples 1 to 3.
  • Copolymer A according to Example 1 and instead of the copolymer B1 casein.
  • Copolymer A according to Example 2 and a commercial starch instead of the copolymer B2.
  • Copolymer A according to Example 3 and instead of the copolymer B2, a copolymer of 12% vinyl acetate, 30% methyl acrylate and 12% acrylic acid.
  • Water retention was expressed in seconds. It is the time in which the aqueous phase of the coating color stained with an acidic red dye is penetrated so far through a blue-band filter that it reduces its reflectance, measured with a reflectance photometer (filter 4), to 40% of the original value.
  • the degree of whiteness was stated as reflectance, measured with UV-rich xenon light without a filter.
  • the increase in whiteness relates to the corresponding value obtained with a UV filter.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Glass Compositions (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)
  • Tires In General (AREA)
  • Lubricants (AREA)
  • Polishing Bodies And Polishing Tools (AREA)
EP80100620A 1979-02-15 1980-02-07 Papierstreichmassen Expired EP0014904B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT80100620T ATE361T1 (de) 1979-02-15 1980-02-07 Papierstreichmassen.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE2905765 1979-02-15
DE19792905765 DE2905765A1 (de) 1979-02-15 1979-02-15 Papierstreichmassen

Publications (2)

Publication Number Publication Date
EP0014904A1 EP0014904A1 (de) 1980-09-03
EP0014904B1 true EP0014904B1 (de) 1981-11-04

Family

ID=6062985

Family Applications (1)

Application Number Title Priority Date Filing Date
EP80100620A Expired EP0014904B1 (de) 1979-02-15 1980-02-07 Papierstreichmassen

Country Status (9)

Country Link
US (1) US4384069A (es)
EP (1) EP0014904B1 (es)
JP (1) JPS55112396A (es)
AT (1) ATE361T1 (es)
CA (1) CA1143883A (es)
DE (2) DE2905765A1 (es)
ES (1) ES488597A1 (es)
FI (1) FI64209C (es)
NO (1) NO156872C (es)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024301B1 (de) * 1979-08-16 1984-03-14 Werkzeugmaschinenfabrik Oerlikon-Bührle AG Verfahren zur Herstellung von Kegel- und achsversetzten Zahnradpaaren

Families Citing this family (22)

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Publication number Priority date Publication date Assignee Title
DE3202061A1 (de) * 1982-01-23 1983-08-04 Röhm GmbH, 6100 Darmstadt Papierstreichmasse
EP0109463B2 (en) * 1982-11-23 1989-10-18 The Dow Chemical Company Polymeric compositions useful as binders in coating colors and coating colors prepared therefrom
GB8330404D0 (en) * 1983-11-15 1983-12-21 Dow Chemical Europ Activation of fluorescent whitening agents
JPS6189267A (ja) * 1984-10-08 1986-05-07 Nippon Carbide Ind Co Ltd アクリル系樹脂エマルジヨン被覆用組成物
DE3720860A1 (de) * 1987-06-24 1989-01-05 Basf Ag Lagerstabile waessrige polymerdispersionen
US5221557A (en) * 1991-12-19 1993-06-22 W. R. Grace & Co.-Conn. V-groovable gravure printable paper
US5413834A (en) * 1992-03-31 1995-05-09 Specialty Paperboard/Endura, Inc. Miter-foldable saturated paper-based overlay system and method for fabricating the same
US6258412B1 (en) 1993-06-09 2001-07-10 Charles Ewing Method of making an artistic medium
DE19732032A1 (de) * 1997-07-25 1999-01-28 Bayer Ag Weißgetönte Polymerisate sowie ihre Verwendung in Streichmassen für die Beschichtung von Substraten
US6030443A (en) * 1999-04-29 2000-02-29 Hercules Incorporated Paper coating composition with improved optical brightener carriers
DE19960863A1 (de) * 1999-12-17 2001-06-28 Basf Ag Mit Polyvinylalkohol stabilisierte Polymerisate zur Verstärkung der optimalen Aufhellung von Beschichtungsmassen
US7732525B2 (en) * 2004-05-20 2010-06-08 Ciba Specialty Chemicals Water Treatments Limited Polymers for paper and paperboard coatings
CN101228238A (zh) * 2005-07-04 2008-07-23 苏德-化学股份公司 具有高固体含量的层状硅酸盐浆状物
US8277908B2 (en) * 2006-05-11 2012-10-02 Xerox Corporation Substrate fluorescence mask for embedding information in printed documents
US8980504B2 (en) * 2006-05-11 2015-03-17 Xerox Corporation Substrate fluorescence mask utilizing a multiple color overlay for embedding information in printed documents
US8283004B2 (en) * 2006-05-11 2012-10-09 Xerox Corporation Substrate fluorescence pattern mask for embedding information in printed documents
US8821996B2 (en) * 2007-05-29 2014-09-02 Xerox Corporation Substrate fluorescent non-overlapping dot patterns for embedding information in printed documents
US8455087B2 (en) * 2007-06-05 2013-06-04 Xerox Corporation Infrared encoding of security elements using standard xerographic materials with distraction patterns
US8460781B2 (en) * 2007-06-05 2013-06-11 Xerox Corporation Infrared encoding of security elements using standard xerographic materials
US8009329B2 (en) * 2007-11-09 2011-08-30 Xerox Corporation Fluorescence-based correlation mark for enhanced security in printed documents
FI122694B (fi) 2008-12-18 2012-05-31 Kemira Oyj Menetelmä vesipitoisen pigmenttilietteen reologisten ominaisuuksien parantamiseksi ja dispergointiaine
FI124806B (fi) * 2008-12-18 2015-01-30 Kemira Oyj Päällystyspastakoostumus ja sillä päällystetty paperi tai kartonki

Family Cites Families (7)

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Publication number Priority date Publication date Assignee Title
FR1510289A (fr) * 1966-01-19 1968-01-19 Dow Chemical Co Perfectionnement aux compositions de liaison pour pigments, destinées notamment à l'enduction du papier
GB1441109A (en) * 1973-01-23 1976-06-30 Ici Ltd Coating compositions
AU474688B2 (en) * 1973-08-15 1975-02-20 Sumitomo Naugatuck Co. Ltd. Copolymer latex and paper coating composition thereof
JPS554151B2 (es) * 1974-02-26 1980-01-29
US4102843A (en) * 1977-01-07 1978-07-25 Rohm And Haas Company Dispersing paint pigments
NO149177C (no) * 1977-01-28 1984-02-29 Basf Ag Papirbestrykningsmasser
US4258104A (en) * 1979-04-27 1981-03-24 The Dow Chemical Company Aqueous polymeric dispersions, paper coating compositions and coated paper articles made therewith

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0024301B1 (de) * 1979-08-16 1984-03-14 Werkzeugmaschinenfabrik Oerlikon-Bührle AG Verfahren zur Herstellung von Kegel- und achsversetzten Zahnradpaaren

Also Published As

Publication number Publication date
EP0014904A1 (de) 1980-09-03
FI800325A (fi) 1980-08-16
FI64209C (fi) 1983-10-10
JPS6235520B2 (es) 1987-08-03
FI64209B (fi) 1983-06-30
DE3060063D1 (en) 1982-01-14
NO156872C (no) 1987-12-09
JPS55112396A (en) 1980-08-29
CA1143883A (en) 1983-03-29
NO156872B (no) 1987-08-31
NO800413L (no) 1980-08-18
US4384069A (en) 1983-05-17
ATE361T1 (de) 1981-11-15
ES488597A1 (es) 1980-10-01
DE2905765A1 (de) 1980-09-04

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