EP0019170B1 - Mixture of binders for paper coating compositions - Google Patents
Mixture of binders for paper coating compositions Download PDFInfo
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- EP0019170B1 EP0019170B1 EP80102414A EP80102414A EP0019170B1 EP 0019170 B1 EP0019170 B1 EP 0019170B1 EP 80102414 A EP80102414 A EP 80102414A EP 80102414 A EP80102414 A EP 80102414A EP 0019170 B1 EP0019170 B1 EP 0019170B1
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- acrylic acid
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- 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
Definitions
- the pigment lines produced in this way have an insufficient printability in gravure printing, which manifests itself in the fact that the gravure printing ink, especially in the semitones, is not transferred to the stitch sufficiently uniformly, and so-called “missing dots” occur in the print.
- DE-C-1 258 721 discloses binder mixtures for neutral or alkaline paper coating slips based on aqueous dispersions.
- emulsion copolymers A which contain 40 to 70 parts by weight of styrene, 30 to 60 parts by weight of an ester of acrylic or methacrylic acid with alcohols which contain 2 to 12 carbon atoms in the chain, and optionally up to 10 parts of other ethylenically unsaturated consist of copolymerizable compounds and an emulsion copolymer B of 15 to 55 percent by weight acrylic and / or methacrylic acid, optionally up to 10 percent by weight acrylic and / or methacrylamide and 85 to 45 percent by weight other monomers which form water-insoluble homopolymers, of which at least 20 percent by weight, based on these are hydrophobic monomers, esters of acrylic acid or methacrylic acid with alcohols containing 1 to 4 carbon atoms.
- the binder mixture contains 5 to 40 parts by weight of at least one copolymer B and 95 to 60 parts by weight of at least one copolymer A.
- the paper coating colors which are produced using these binder mixtures meet the processing requirements, but no longer meet the increased demands on the printability of them coated papers in rotogravure.
- the object of the invention is to provide a binder which, in comparison to known binders, can be used in a smaller amount for the preparation of paper coating slips and which results in coated papers which, particularly in magazine gravure printing, result in a better print loss.
- the copolymer A of the binder mixture contains, as an essential component, acrylic acid esters with monohydric alcohols which have 2 to 8 carbon atoms. Specifically, these are, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-, iso- and / or tert-butyl acrylate and 2-ethylhexyl acrylate. Those acrylic acid esters which are derived from isobutanol and n-butanol are preferably used to construct copolymers A.
- copolymer A up to 50% by weight of the esters of acrylic acid and monohydric C 2 -C 8 -alcohols can be replaced by methyl acrylate and / or by esters of methacrylic acid and monohydric C 2 -C 8 -alcohols.
- the acrylic acid esters make up 80 to 96, preferably 80 to 90 percent by weight of the emulsion copolymers A.
- the copolymers A contain, as a further constituent, a monomer from the group styrene, methyl methacrylate or acrylonitrile. These monomers make up 0 to 19.5, preferably 3 to 15 percent by weight of the copolymers A.
- Another essential component of the copolymers A are water-soluble homopolymers forming monomers. It is e.g. B. to ethylenically unsaturated C 3 - to C s carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid or crotonic acid, the corresponding acid amides of the ethylenically unsaturated carboxylic acids, for. B. acrylamide and methacrylamide, half esters and half amides of maleic acid and strongly acidic monomeric compounds such as vinylsulfonic acid, styrene-p-sulfone acid, acrylamidopropanesulfonic acid, and sodium vinyl sulfonate.
- carboxylic acids such as acrylic acid, methacrylic acid, maleic acid or crotonic acid
- the corresponding acid amides of the ethylenically unsaturated carboxylic acids for. B. acrylamide and methacrylamide, half esters and half amides of male
- the copolymer A preferably contains 1.0 to 5% of the water-soluble homopolymers forming monomers, of which acrylic acid, acrylamide and methacrylamide or mixtures thereof are preferably used.
- the glass transition temperature of copolymer A can be between -20 and + 10 ° C. (For the definition of the glass transition temperature see P. J. Flory, Principles of Polymer Chemistry, Georgia University Press, Ithaka, New York, 1953, page 56.)
- the emulsion copolymers B are known from DE-C-1 258 728. These copolymers contain 15 to 55 percent by weight of acrylic acid or methacrylic acid, 0 to 10 percent by weight, in particular 2 to 6 percent by weight, acrylamide or methacrylamide and 85 to 45 percent by weight of hydrophobic, water-insoluble homopolymers forming monomers, of which at least 20 percent by weight of esters of acrylic acid or methacrylic acid with aliphatic C. i - to C 4 alcohols. As hydrophobic, water-insoluble homopolymers forming monomers such. B.
- acrylic and methacrylic acid esters of higher aliphatic, cycloaliphatic or aromatic hydroxyl compounds into consideration preferably vinyl acetate, vinyl propionate, acrylic acid methyl ester, acrylic acid ethyl ester and acrylonitrile.
- the copolymers B preferably contain acrylic acid and / or methacrylic acid and exclusively or predominantly acrylic acid and methacrylic acid esters of monohydric alcohols having 1 to 4 carbon atoms.
- terpolymers are preferably used which also contain copolymerized acrylonitrile, vinyl acetate or acrylamide or methacrylamide.
- the copolymers A and B can be prepared by polymerizing the monomers in an aqueous emulsion by processes known per se using the customary anionic or nonionic emulsifiers in the presence of polymerization initiators.
- Suitable emulsifiers are, for example, n-dodecylsulfonic acid potassium or sodium, isooctylbenzenesulfonic acid sodium or potassium salts of the sulfuric acid half-esters of long-chain alcohols with an even carbon number or the corresponding ethoxylated (e.g. with 2 to 25 moles of ethylene oxide) products and with 5 to 25 moles of ethylene oxide p-isooctylphenol and sodium lauryl sulfate.
- the emulsifiers are generally used in amounts of 0.5 to 5 percent by weight, based on the monomers to be polymerized.
- radical-forming compounds such as peroxides, persulfates or azo compounds can be used as polymerization initiators.
- potassium persulfate, cumene hydroperoxide or hydrogen peroxide are suitable.
- activated initiator systems e.g. B. with a system of potassium persulfate and ascorbic acid, oximethanesulfonic acid sodium or triethanolamine.
- the temperatures during the polymerization are in the usual range, e.g. B. between 70 and 95 ° C, they can be lower if redox catalysts are used. It is also possible to polymerize at higher temperatures and under pressure.
- chain transfer agents e.g. B. dodecyl mercaptan and halogenated hydrocarbons such as chloroform, carbon tetrachloride and tetrachlorethylene.
- the binder mixture according to the invention contains 95 to 70 parts by weight of the emulsion copolymer A and 5 to 30 parts by weight of the copolymer B. Outside this range, binder mixtures are obtained whose properties are not so advantageous.
- the paper coating slips contain 3 to 7, preferably 4.5 to 5.5 parts by weight of the binder mixture according to the invention per 100 parts by weight of a finely divided pigment. They can also contain conventional additives, e.g. B. 0.05 to 3 percent by weight of a dispersant based on low molecular weight polymers of acrylic acid (K value of the polymer between 10 and 25) optical brighteners and conventional auxiliaries, such as stearates, shading dyes, foam inhibitors, etc.
- conventional additives e.g. B. 0.05 to 3 percent by weight of a dispersant based on low molecular weight polymers of acrylic acid (K value of the polymer between 10 and 25) optical brighteners and conventional auxiliaries, such as stearates, shading dyes, foam inhibitors, etc.
- aqueous dispersions of copolymers A and B are mixed before the coating color is prepared or during the preparation of the coating color.
- the order in which the individual components are added when preparing the coating color is also irrelevant to the properties of the coating slip or the paper coated with it.
- the mixture of the two copolymers A and B is notable for an exceptionally high storage stability which exceeds that of the known binder mixtures.
- the solids content of the dispersions of copolymers A and B can be varied within a wide range.
- Dispersions with a very high solids content e.g. B. 45 to 50 weight percent.
- the highly concentrated aqueous polymer dispersions are also easy to handle, for example they can be pumped.
- a base such as ammonia, sodium carbonate, an amine or sodium hydroxide solution
- the viscosity increases.
- the finished paper coating slips can be applied to base papers by all known methods. Due to the high shear stability, the paper coating slips can be processed on high-speed roller or doctor coating systems. They are mainly used for the production of such papers that are printed in magazine gravure. This paper gives better print loss than paper made from known paper coating slips. The better quality of the printing loss in gravure printing is determined on the basis of missing dots.
- the binder mixture according to the invention for the production of paper coating slips, based on pigment, less binder is required than is the case with the known binder mixtures. Despite the reduced binder content in the paper coating slips obtained using the binder mixture according to the invention, there is no dusting of the pigment coating on the papers coated with these paper coating slips.
- the parts mentioned in the following examples are parts by weight.
- Feed 1 consists of 460 parts of water, 32 parts of a 28% solution of the sodium salt of a sulfated reaction product from a C 12 / G 14 alcohol which has been reacted with 3 mol of ethylene oxide, 738 parts (82%) of isobutyl acrylate, 126 parts (14 %) Methyl methacrylate, 18 parts (2%) acrylic acid and 18 parts (2%) methacrylamide.
- Feed 2 consists of 200 parts of water and 4.5 parts of potassium peroxydisulfate.
- This copolymer is prepared analogously to copolymer A 1, except that it is composed of 85% isobutyl acrylate, 12% acrylonitrile, 1.5% acrylic acid and 1.5% methacrylamide.
- a copolymer B 1 is prepared which is composed of 75% ethyl acrylate, 5% acrylamide and 20% acrylic acid.
- 100 parts of a commercially available spreading clay are stirred into an aqueous solution of 0.3 part of sodium polyacrylate with a K value of 12 using a high-speed stirrer.
- 9.6 parts of a mixture consisting of 80 parts of a 50% aqueous dispersion of copolymer A 2 and 20 parts of a 45% aqueous dispersion of copolymer B 1 are added as binders, and the coating color is brought to a pH by adding sodium hydroxide solution set from 8.5. With a solids content of 58%, the coating slip has a viscosity of 1400 mPas (measured with a Brookfield viscometer at 100 rpm).
- the paper coating slip thus produced is applied with the aid of a doctor coating system at a speed of 800 m / min to paper which is composed of 55% wood pulp, 45% bleached sulfate pulp, has an ash content of 6% and a weight per unit area of 38 g / m 2 .
- the paper is coated on both sides.
- the coating is 10 g / m 2 and side.
- the paper which is satinised in the super calender at a speed of 300 m / min and 2000 N / cm line printing, has good gloss and smoothness and excellent printability.
- a print that is applied with the help of a Haindl laboratory gravure printing device has, in semitones, less than 10 missing dots on an area of 30 cm 2 . The missing dots were determined by visually counting the missing areas.
- a paper coating slip is produced in accordance with the procedure given in Example 1, but 10.2 parts of a binder mixture of 75 parts of the 50% strength aqueous dispersion of the copolymer are used, based on 100 parts of a commercially available coating clay sates A 1 and 25 parts of the 45% aqueous dispersion of the copolymer B 1.
- the viscosity of the coating color at a solids content of 56% is 1300 mPas (Brookfield viscometer 100 rpm).
- a paper coating slip is prepared as described in Example 1, but 10.2 parts of a mixture of 80 parts of a 50% aqueous dispersion of a copolymer of 55% isobutyl acrylate, 42% styrene, 1 are used as the binder, based on 100 parts of coating clay , 5% acrylic acid and 1.5% methacrylamide and 20 parts of the 45% dispersion of copolymer B 1.
- the coating color has a viscosity of 1200 mPas (Brpokfield viscometer 100 rpm) at a solids content of 56%.
- the paper coated and satined with this paper coating slip in accordance with the specification given in Example 1 has more than 20 missing dots on an area of 30 cm 2 in halftone gravure printing.
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Abstract
Description
Es ist seit längerem bekannt, wäßrige Dispersionen von Acrylester-Copolymerisaten als synthetische Bindemittel für sich allein oder gemeinsam mit natürlichen Bindemitteln, wie Stärke, Casein oder Sojaprotein, zu verwenden. Sie weisen aber auf schnellaufenden Streichmaschinen oft eine unzureichende Scherstabilität und eine unbefriedigende Verträglichkeit mit bestimmten Pigmenten, wie Satinweiß, auf. Aus der US-A-3 081 198 ist bekannt, als synthetische Bindemittel für Papierstreichmassen Mischungen von Acrylester- und Vinylester-Copolymerisaten mit Acrylsäure-Acrylester-Copolymerisaten zu verwenden. Die damit hergestellten Pigmentstriche weisen eine ungenügende Bedruckbarkeit im Tiefdruck auf, die sich darin äußert, daß die Tiefdruckfarbe vor allem in den Halbtönen nicht ausreichend gleichmäßig auf den Stich übertragen wird und damit Fehlstellen, sogenannte »missing dots«, im Druck auftreten.It has long been known to use aqueous dispersions of acrylic ester copolymers as synthetic binders on their own or together with natural binders, such as starch, casein or soy protein. However, they often have inadequate shear stability and unsatisfactory compatibility with certain pigments, such as satin white, on high-speed coating machines. From US-A-3,081,198 it is known to use mixtures of acrylic ester and vinyl ester copolymers with acrylic acid-acrylic ester copolymers as synthetic binders for paper coating slips. The pigment lines produced in this way have an insufficient printability in gravure printing, which manifests itself in the fact that the gravure printing ink, especially in the semitones, is not transferred to the stitch sufficiently uniformly, and so-called “missing dots” occur in the print.
Aus der DE-C-1 258 721 sind Bindemittelmischungen für neutrale oder alkalische Papierstreichmassen auf der Basis von wäßrigen Dispersionen bekannt. Es handelt sich dabei um Emulsionscopolymerisate A, die 40 bis 70 Gewichtsteile Styrol, 30 bis 60 Gewichtsteile eines Esters der Acryl- oder Methacrylsäure mit Alkoholen, die 2 bis 12 Kohlenstoffatome in der Kette enthalten, und gegebenenfalls bis zu 10 Teilen anderen äthylenisch-ungesättigten-copolymerisierbaren Verbindungen bestehen und einem Emulsionscopolymerisat B aus 15 bis 55 Gewichtsprozent Acryl- und bzw. oder Methacrylsäure, gegebenenfalls bis zu 10 Gewichtsprozent Acryl- und/oder Methacrylamid und 85 bis 45 Gewichtsprozent anderen, wasserunlösliche Homopolymerisate bildenden Monomeren, wovon mindestens 20 Gewichtsprozent, bezogen auf diese hydrophoben Monomeren, Ester der Acrylsäure oder Methacrylsäure mit Alkoholen sind, die 1 bis 4 Kohlenstoffatome enthalten. Die Bindemittelmischung enthält 5 bis 40 Gewichtsteile mindestens eines Copolymerisates B und 95 bis 60 Gewichtsteile mindestens eines Copolymerisates A. Die Papierstreichfarben, die unter Verwendung dieser Bindemittelmischungen hergestellt werden, erfüllen zwar die verarbeitungstechnischen Anforderungen, genügen aber nicht mehr den gestiegenen Ansprüchen an die Bedruckbarkeit der damit gestrichenen Papiere im Magazintiefdruck.DE-C-1 258 721 discloses binder mixtures for neutral or alkaline paper coating slips based on aqueous dispersions. These are emulsion copolymers A which contain 40 to 70 parts by weight of styrene, 30 to 60 parts by weight of an ester of acrylic or methacrylic acid with alcohols which contain 2 to 12 carbon atoms in the chain, and optionally up to 10 parts of other ethylenically unsaturated consist of copolymerizable compounds and an emulsion copolymer B of 15 to 55 percent by weight acrylic and / or methacrylic acid, optionally up to 10 percent by weight acrylic and / or methacrylamide and 85 to 45 percent by weight other monomers which form water-insoluble homopolymers, of which at least 20 percent by weight, based on these are hydrophobic monomers, esters of acrylic acid or methacrylic acid with alcohols containing 1 to 4 carbon atoms. The binder mixture contains 5 to 40 parts by weight of at least one copolymer B and 95 to 60 parts by weight of at least one copolymer A. The paper coating colors which are produced using these binder mixtures meet the processing requirements, but no longer meet the increased demands on the printability of them coated papers in rotogravure.
Aufgabe der Erfindung ist es, ein Bindemittel zur Verfügung zu stellen, das, verglichen mit bekannten Bindemitteln, in geringerer Menge zur Bereitung von Papierstreichmassen eingesetzt werden kann und gestrichene Papiere ergibt, die vor allem im Magazintiefdruck einen besseren Druckausfall ergeben.The object of the invention is to provide a binder which, in comparison to known binders, can be used in a smaller amount for the preparation of paper coating slips and which results in coated papers which, particularly in magazine gravure printing, result in a better print loss.
Die Aufgabe wird erfindungsgemäß gelöst mit einem Bindemitteigemisch für Papierstreichmassen auf der Basis von wäßrigen Dispersionen aus 95 bis 70 Gewichtsteilen eines Emulsionscopolymerisates A, das Acrylsäureester und äthylenisch ungesättigte Carbonsäuren einpolymerisiert enthält, und 5 bis 30 Gewichtsteilen eines Copolymerisates B aus 15 bis 55 Gewichtsprozent Acryl- und bzw. oder Methacrylsäure, gegebenenfalls bis zu 10 Gewichtsprozent Acryl-und bzw. od'1r Methacrylamid und 85 bis 45 Gewichtsprozent anderen, wasserunlösliche Homopolymerisate bildenden Monomeren, wovon mindestens 20 Gewichtsprozent, bezogen auf diese hydrophoben Monomeren, Ester der Acrylsäure oder Methacrylsäure mit Alkoholen, die 1 bis 4 Kohlenstoffatome enthalten, sind, wenn das Copolymerisat A
- (a) 80 bis 96 Gewichtsprozent Ester der Acrylsäure mit einwertigen C2- bis C8-Alkoholen,
- (b) bis zu 19,5 Gewichtsprozent Styrol, Acrylnitril und/oder Methacrylsäuremethylester, und
- (c) 0,5 bis 10 Gewichtsprozent andere wasserlösliche Homopolymerisate bildende Monomere
- (a) 80 to 96 percent by weight esters of acrylic acid with monohydric C 2 to C 8 alcohols,
- (b) up to 19.5 percent by weight styrene, acrylonitrile and / or methyl methacrylate, and
- (c) 0.5 to 10 percent by weight of other water-soluble homopolymers forming monomers
Das Copolymerisat A der Bindemittelmischung enthält als wesentlichen Bestandteil Acrylsäureester mit einwertigen Alkoholen, die 2 bis 8 Kohlenstoffatome aufweisen. Es handelt sich hierbei im einzelnen beispielsweise um Acrylsäureäthylester, Acrylsäure-n-propylester, Acrylsäureisopropylester, Acrylsäure-n-, iso-und/oder tert.-Butylester und Acrylsäure-2- äthylhexylester. Vorzugsweise verwendet man zum Aufbau der Copolymerisate A diejenigen Acrylsäureester, die sich von Isobutanol und n-Butanol ableiten. Im Copolymerisat A können bis zu 50 Gew.-% der Ester aus Acrylsäure und einwertigen C2- bis C8-Alkoholen durch Acrylsäuremethylester und/oder durch Ester aus Methacrylsäure und einwertigen C2- bis C8-Alkoholen ersetzt werden. Die Acrylsäureester sind zu 80 bis 96, vorzugsweise 80 bis 90 Gewichtsprozent am Aufbau der Emulsionscopolymerisate A beteiligt.The copolymer A of the binder mixture contains, as an essential component, acrylic acid esters with monohydric alcohols which have 2 to 8 carbon atoms. Specifically, these are, for example, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-, iso- and / or tert-butyl acrylate and 2-ethylhexyl acrylate. Those acrylic acid esters which are derived from isobutanol and n-butanol are preferably used to construct copolymers A. In copolymer A, up to 50% by weight of the esters of acrylic acid and monohydric C 2 -C 8 -alcohols can be replaced by methyl acrylate and / or by esters of methacrylic acid and monohydric C 2 -C 8 -alcohols. The acrylic acid esters make up 80 to 96, preferably 80 to 90 percent by weight of the emulsion copolymers A.
Die Copolymerisate A enthalten als weiteren Bestandteil ein Monomeres der Gruppe Styrol, Methacrylsäuremethylester oder Acrylnitril. Diese Monomeren sind zu 0 bis 19,5, vorzugsweise 3 bis 15 Gewichtsprozent am Aufbau der Copolymerisate A beteiligt.The copolymers A contain, as a further constituent, a monomer from the group styrene, methyl methacrylate or acrylonitrile. These monomers make up 0 to 19.5, preferably 3 to 15 percent by weight of the copolymers A.
Ein weiterer, wesentlicher Bestandteil der Copolymerisate A sind wasserlösliche Homopolymerisate bildende Monomere. Es handelt sich hierbei z. B. um äthylenisch ungesättigte C3- bis Cs-Carbonsäuren, wie Acrylsäure, Methacrylsäure, Maleinsäure oder Crotonsäure, die entsprechenden Säureamide der äthylenisch ungesättigten Carbonsäuren, z. B. Acrylamid und Methacrylamid, Halbester und Halbamide der Maleinsäure sowie um stark saure monomere Verbindungen, wie Vinylsulfonsäure, Styrol-p-sulfonsäure, Acrylamidopropansulfonsäure, und Natriumvinylsulfonat. Diese Gruppe von Monomeren ist zu 0,5 bis 10 Gewichtsprozent am Aufbau der Copolymerisate beteiligt. Vorzugsweise enthält das Copolymerisat A 1,0 bis 5% der wasserlösliche Homopolymerisate bildenden Monomeren, von denen vorzugsweise Acrylsäure, Acrylamid und Methacrylamid oder deren Mischungen eingesetzt werden. ,Another essential component of the copolymers A are water-soluble homopolymers forming monomers. It is e.g. B. to ethylenically unsaturated C 3 - to C s carboxylic acids, such as acrylic acid, methacrylic acid, maleic acid or crotonic acid, the corresponding acid amides of the ethylenically unsaturated carboxylic acids, for. B. acrylamide and methacrylamide, half esters and half amides of maleic acid and strongly acidic monomeric compounds such as vinylsulfonic acid, styrene-p-sulfone acid, acrylamidopropanesulfonic acid, and sodium vinyl sulfonate. This group of monomers makes up 0.5 to 10 percent by weight of the copolymers. The copolymer A preferably contains 1.0 to 5% of the water-soluble homopolymers forming monomers, of which acrylic acid, acrylamide and methacrylamide or mixtures thereof are preferably used. ,
Die Glastemperatur des Copolymerisates A kann zwischen -20 und +10°C liegen. (Zur Definition der Glastemperatur vgl. P. J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaka, New York, 1953, Seite 56.)The glass transition temperature of copolymer A can be between -20 and + 10 ° C. (For the definition of the glass transition temperature see P. J. Flory, Principles of Polymer Chemistry, Cornell University Press, Ithaka, New York, 1953, page 56.)
Die Emulsionscopolymerisate B sind aus der DE-C-1 258 728 bekannt. Diese Copolymerisate enthalten 15 bis 55 Gewichtsprozent Acrylsäure oder Methacrylsäure, 0 bis 10 Gewichtsprozent, insbesondere 2 bis 6 Gewichtsprozent, Acrylamid oder Methacrylamid und 85 bis 45 Gewichtsprozent hydrophobe, wasserunlösliche Homopolymerisate bildende Monomere, von denen mindestens 20 Gewichtsprozent Ester der Acrylsäure oder Methacrylsäure mit aliphatischen Ci- bis C4-Alkoholen sind. Als Hydrophobe, wasserunlösliche Homopolymerisate bildende Monomere kommen z. B. Acrylsäure- und Methacrylsäureester höherer aliphatischer, cycloaliphatischer oder aromatischer Hydroxylverbindungen in Betracht, vorzugsweise Vinylacetat, Vinylpropionat, Acrylsäuremethylester, Acrylsäureäthylester und Acrylnitril. Die Copolymerisate B enthalten vorzugsweise Acrylsäure und/oder Methacrylsäure und ausschließlich oder überwiegend Acrylsäure- und Methacrylsäureester von einwertigen Alkoholen mit 1 bis 4 Kohlenstoffatomen. Außerdem kommen vorzugsweise Terpolymerisate in Betracht, die noch Acrylnitril, Vinylacetat oder Acrylamid oder Methacrylamid einpolymerisiert enthalten.The emulsion copolymers B are known from DE-C-1 258 728. These copolymers contain 15 to 55 percent by weight of acrylic acid or methacrylic acid, 0 to 10 percent by weight, in particular 2 to 6 percent by weight, acrylamide or methacrylamide and 85 to 45 percent by weight of hydrophobic, water-insoluble homopolymers forming monomers, of which at least 20 percent by weight of esters of acrylic acid or methacrylic acid with aliphatic C. i - to C 4 alcohols. As hydrophobic, water-insoluble homopolymers forming monomers such. B. acrylic and methacrylic acid esters of higher aliphatic, cycloaliphatic or aromatic hydroxyl compounds into consideration, preferably vinyl acetate, vinyl propionate, acrylic acid methyl ester, acrylic acid ethyl ester and acrylonitrile. The copolymers B preferably contain acrylic acid and / or methacrylic acid and exclusively or predominantly acrylic acid and methacrylic acid esters of monohydric alcohols having 1 to 4 carbon atoms. In addition, terpolymers are preferably used which also contain copolymerized acrylonitrile, vinyl acetate or acrylamide or methacrylamide.
Die Copolymerisate A und B können durch Polymerisation der Monomeren in wäßriger Emulsion nach an sich bekannten Verfahren unter Verwendung der üblichen anionischen bzw. nichtionischen Emulgiermittel in Gegenwart von Polymerisationsinitiatoren hergestellt werden. Geeignete Emulgiermittel sind beispielsweise n-dodecylsulfonsaures Kalium bzw. Natrium, isooctylbenzolsulfonsaures Natrium oder Kaliumsalze der Schwefelsäurehalbester von langkettigen Alkoholen mit gerader Kohlenstoffzahl oder der entsprechenden äthoxylierten (z. B. mit 2 bis 25 Mol Äthylenoxid) Produkte, sowie mit 5 bis 25 Mol Äthylenoxid umgesetztes p-Isooctylphenol und Natriumlaurylsulfat. Die Emulgatoren werden in der Regel in Mengen von 0,5 bis 5 Gewichtsprozent, bezogen auf die zu polymerisierenden Monomeren, eingesetzt.The copolymers A and B can be prepared by polymerizing the monomers in an aqueous emulsion by processes known per se using the customary anionic or nonionic emulsifiers in the presence of polymerization initiators. Suitable emulsifiers are, for example, n-dodecylsulfonic acid potassium or sodium, isooctylbenzenesulfonic acid sodium or potassium salts of the sulfuric acid half-esters of long-chain alcohols with an even carbon number or the corresponding ethoxylated (e.g. with 2 to 25 moles of ethylene oxide) products and with 5 to 25 moles of ethylene oxide p-isooctylphenol and sodium lauryl sulfate. The emulsifiers are generally used in amounts of 0.5 to 5 percent by weight, based on the monomers to be polymerized.
Als Polymerisationsinitiatoren können übliche radikalbildende Verbindungen, wie Peroxide, Persulfate oder Azoverbindungen verwendet werden. Beispielsweise eignen sich Kaliumpersulfat, Cumolhydroperoxid oder Wasserstoffperoxid. Es ist auch möglich, die Polymerisation mit Hilfe von Redox-Katalysatoren oder mit aktivierten Initiatorsystemen zu initiieren, z. B. mit einem System aus Kaliumpersulfat und Ascorbinsäure, oximethansulfonsaurem Natrium oder Triäthanolamin. Die Temperaturen bei der Polymerisation liegen in dem üblichen Bereich, z. B. zwischen 70 und 95°C, sie können niedriger liegen, sofern man Redox-Katalysatoren einsetzt. Ebenso ist es möglich, auch bei höheren Temperaturen und unter Druck zu polymerisieren. Um das Molekulargewicht der Polymerisate zu regeln, kann man bei der Polymerisation die gebräuchlichen Kettenüberträger verwenden, z. B. Dodecylmercaptan und halogenierte Kohlenwasserstoffe, wie Chloroform, Tetrachlorkohlenstoff und Tetrachloräthylen..Conventional radical-forming compounds such as peroxides, persulfates or azo compounds can be used as polymerization initiators. For example, potassium persulfate, cumene hydroperoxide or hydrogen peroxide are suitable. It is also possible to initiate the polymerization using redox catalysts or with activated initiator systems, e.g. B. with a system of potassium persulfate and ascorbic acid, oximethanesulfonic acid sodium or triethanolamine. The temperatures during the polymerization are in the usual range, e.g. B. between 70 and 95 ° C, they can be lower if redox catalysts are used. It is also possible to polymerize at higher temperatures and under pressure. To control the molecular weight of the polymers, one can use the usual chain transfer agents in the polymerization, e.g. B. dodecyl mercaptan and halogenated hydrocarbons such as chloroform, carbon tetrachloride and tetrachlorethylene.
Das Bindemittelgemisch gemäß der Erfindung enthält 95 bis 70 Gewichtsteile des Emulsionscopolymerisates A und 5 bis 30 Gewichtsteile des Copolymerisates B. Außerhalb dieses Bereiches werden Bindemittelmischungen erhalten, deren Eigenschaften nicht so vorteilhaft sind.The binder mixture according to the invention contains 95 to 70 parts by weight of the emulsion copolymer A and 5 to 30 parts by weight of the copolymer B. Outside this range, binder mixtures are obtained whose properties are not so advantageous.
Die Papierstreichmassen enthalten auf 100 Gewichtsteile eines feinteiligen Pigments 3 bis 7, vorzugsweise 4,5 bis 5,5 Gewichtsteile der erfindungsgemäßen Bindemittelmischung. Sie können außerdem übliche Zusatzstoffe enthalten, z. B. 0,05 bis 3 Gewichtsprozent eines Dispergiermittels auf Basis von niedrigmolekularen Polymerisaten der Acrylsäure (K-Wert des Polymerisates zwischen 10 und 25) optische Aufheller sowie übliche Hilfsstoffe, wie Stearate, Nuancierfarbstoffe, Schaumverhüter usw.The paper coating slips contain 3 to 7, preferably 4.5 to 5.5 parts by weight of the binder mixture according to the invention per 100 parts by weight of a finely divided pigment. They can also contain conventional additives, e.g. B. 0.05 to 3 percent by weight of a dispersant based on low molecular weight polymers of acrylic acid (K value of the polymer between 10 and 25) optical brighteners and conventional auxiliaries, such as stearates, shading dyes, foam inhibitors, etc.
Um die gewünschten technischen Effekte zu erreichen, ist es gleichgültig, ob man die wäßrigen Dispersionen der Copolymerisate A und B vor der Bereitung der Streichfarbe oder während der Herstellung der Streichfarbe mischt. Auch die Reihenfolge der Zugabe der einzelnen Komponenten bei der Streichfarbenbereitung ist ohne Bedeutung für die Eigenschaften der Streichmasse oder des damit gestrichenen Papiers. Zur Vereinfachung der Streichfarbenbereitung ist es jedoch von Vorteil, wenn man die wäßrigen Dispersionen der Copolymerisate A und B vor der Herstellung der Streichfarbe in dem in Betracht kommenden Mengenverhältnis mischt. Die Mischung der beiden Copolymerisate A und B zeichnet sich durch eine außergewöhnlich hohe Lagerstabilität aus, die diejenige der bekannten Bindemittelmischungen übertrifft. Der Feststoffgehalt der Dispersionen der Copolymerisate A und B kann in einem weiten Bereich variiert werden. Vorzugsweise verwendet man Dispersionen mit einem sehr hohen Feststoffgehalt, z. B. 45 bis 50 Gewichtsprozent. Auch die hochkonzentrierten wäßrigen Polymerisatdispersionen sind leicht handhabbar, sie können beispielsweise gepumpt werden. Beim Neutralisieren der Copolymerisate B bzw. der Mischung der Copolymerisate A und B durch Zusatz einer Base, wie Ammoniak, Natriumcarbonat, eines Amins oder von Natronlauge, nimmt die Viskosität zu. Je nach Feststoffgehalt der Dispersion kann man bei der Neutralisation der Copolymerisate eineIn order to achieve the desired technical effects, it does not matter whether the aqueous dispersions of copolymers A and B are mixed before the coating color is prepared or during the preparation of the coating color. The order in which the individual components are added when preparing the coating color is also irrelevant to the properties of the coating slip or the paper coated with it. To simplify the preparation of coating colors, it is advantageous, however, if the aqueous dispersions of copolymers A and B are mixed in the appropriate ratio before the coating color is prepared. The mixture of the two copolymers A and B is notable for an exceptionally high storage stability which exceeds that of the known binder mixtures. The solids content of the dispersions of copolymers A and B can be varied within a wide range. Dispersions with a very high solids content, e.g. B. 45 to 50 weight percent. The highly concentrated aqueous polymer dispersions are also easy to handle, for example they can be pumped. When the copolymers B or the mixture of the copolymers A and B are neutralized by adding a base, such as ammonia, sodium carbonate, an amine or sodium hydroxide solution, the viscosity increases. Depending on the solids content of the dispersion, one can be used in the neutralization of the copolymers
Die fertigen Papierstreichmassen können nach allen bekannten Verfahren auf Rohpapiere aufgebracht werden. Die Papierstreichmassen können auf Grund der hohen Scherstabilität auf schnellaufenden Walzen- oder Schaberstreichanlagen verarbeitet werden. Sie werden vor allem für die Herstellung solcher Papiere eingesetzt, die im Magazintiefdruck bedruckt werden. Auf diesen Papieren erhält man einen besseren Druckausfall als auf solchen Papieren, zu deren Herstellung bekannte Papierstreichmassen verwendet wurden. Die bessere Qualität des Druckausfalls beim Tiefdruck wird anhand von Fehlstellen (missing dots) bestimmt. Bei Verwendung der erfindungsgemäßen Bindemittelmischung zur Herstellung von Papierstreichmassen benötigt man, bezogen auf Pigment, weniger Bindemittel als dies bei den bekannten Bindemittelmischungen der Fall ist. Trotz des erniedrigten Bindemittelgehaltes in den Papierstreichmassen, die unter Verwendung der erfindungsgemäßen Bindemittelmischung erhalten werden, tritt bei den mit diesen Papierstreichmassen gestrichenen Papieren kein Stauben des Pigmentstrichs ein.The finished paper coating slips can be applied to base papers by all known methods. Due to the high shear stability, the paper coating slips can be processed on high-speed roller or doctor coating systems. They are mainly used for the production of such papers that are printed in magazine gravure. This paper gives better print loss than paper made from known paper coating slips. The better quality of the printing loss in gravure printing is determined on the basis of missing dots. When using the binder mixture according to the invention for the production of paper coating slips, based on pigment, less binder is required than is the case with the known binder mixtures. Despite the reduced binder content in the paper coating slips obtained using the binder mixture according to the invention, there is no dusting of the pigment coating on the papers coated with these paper coating slips.
Die in den folgenden Beispielen genannten Teile sind Gewichtsteile. Die K-Werte wurden bestimmt nach H. Fikentscher, Cellulose-Chemie, 13, 58-64 und 71 bis 74 (1932) in 0,5%igem Dimethylformamidlösungen bei 20°C; dabei bedeutet K=k · 103.The parts mentioned in the following examples are parts by weight. The K values were determined according to H. Fikentscher, Cellulose-Chemie, 13, 58-64 and 71 to 74 (1932) in 0.5% dimethylformamide solutions at 20 ° C; where K = k · 103.
Man bereitet zunächst zwei verschiedene Zuläufe. Zulauf 1 besteht aus 460 Teilen Wasser, 32 Teilen einer 28%igen Lösung des Natriumsalzes eines sulfatierten Umsetzungsproduktes aus einem C12/G14-Alkohol, der mit 3 Mol Äthylenoxid umgesetzt ist, 738 Teilen (82%) Isobutylacrylat, 126 Teilen (14%) Methylmethacrylat, 18 Teilen (2%) Acrylsäure und 18 Teilen (2%) Methacrylamid. Zulauf 2 besteht aus 200 Teilen Wasser und 4,5 Teilen Kaliumperoxidisulfat.First, two different inlets are prepared. Feed 1 consists of 460 parts of water, 32 parts of a 28% solution of the sodium salt of a sulfated reaction product from a C 12 / G 14 alcohol which has been reacted with 3 mol of ethylene oxide, 738 parts (82%) of isobutyl acrylate, 126 parts (14 %) Methyl methacrylate, 18 parts (2%) acrylic acid and 18 parts (2%) methacrylamide. Feed 2 consists of 200 parts of water and 4.5 parts of potassium peroxydisulfate.
In einem Rührgefäß, das mit Rührer, Rückflußkühler, Thermometer und 2 Zulaufgefäßen ausgestattet ist und beheizt werden kann, werden 230 Teile Wasser, 56 Teile des Zulaufs 1 und 40 Teile des Zulaufs 2 vorgelegt und auf eine Temperatur von 85°C erhitzt. Nach 15minütigem Anpolymerisieren läßt man den Zulauf 1 innerhalb von 2 Stunden, den Zulauf 2 innerhalb von 21/2 Stunden bei einer Temperatur von 85°C in das Rührgefäß fließen. Nachdem der Zulauf 2 vollständig in das Rührgefäß dosiert wurde, hält man die Temperatur des Reaktionsgemisches noch 2 Stunden lang bei 85° C, kühlt es auf 20° C, stellt den pH-Wert durch Zugabe von Ammoniak auf 5 ein und filtriert. Bei der Polymerisation entstand kein Koagulat. Man erhielt auf diese Weise eine 50%ige wäßrige Dispersion.230 parts of water, 56 parts of feed 1 and 40 parts of feed 2 are placed in a stirred vessel which is equipped with a stirrer, reflux condenser, thermometer and 2 feed vessels and can be heated and heated to a temperature of 85.degree. After 15 minutes of initial polymerization is allowed to feed 1 over 2 hours, the Feed 2 flow within 2 1/2 hours at a temperature of 85 ° C in the mixing vessel. After feed 2 has been completely metered into the stirred vessel, the temperature of the reaction mixture is kept at 85 ° C. for a further 2 hours, it is cooled to 20 ° C., the pH is adjusted to 5 by adding ammonia and the mixture is filtered. No coagulum formed during the polymerization. A 50% aqueous dispersion was obtained in this way.
Dieses Copolymerisat wird analog dem Copolymerisat A 1 hergestellt, jedoch mit der Ausnahme, daß es aus 85% Isobutylacrylat, 12% Acrylnitril, 1,5% Acrylsäure und 1,5% Methacrylamid aufgebaut ist.This copolymer is prepared analogously to copolymer A 1, except that it is composed of 85% isobutyl acrylate, 12% acrylonitrile, 1.5% acrylic acid and 1.5% methacrylamide.
Nach der im Beispiel 1 der DE-C-1 258 721 beschriebenen Vorschrift wird ein Copolymerisat B 1 hergestellt, das aus 75% Äthylacrylat, 5% Acrylamid und 20% Acrylsäure aufgebaut ist.According to the procedure described in Example 1 of DE-C-1 258 721, a copolymer B 1 is prepared which is composed of 75% ethyl acrylate, 5% acrylamide and 20% acrylic acid.
In eine wäßrige Lösung von 0,3 Teilen Natriumpolyacrylat eines K-Wertes von 12 werden mit Hilfe eines Schnellrührers 100 Teile eines handelsüblichen Streichclays eingerührt. Als Bindemittel werden 9,6 Teile einer Mischung, bestehend aus 80 Teilen einer 50%igen wäßrigen Dispersion des Copolymerisates A 2 und 20 Teilen einer 45%igen wäßrigen Dispersion des Copolymerisates B 1 zugegeben und die Streichfarbe durch Zufügen von Natronlauge auf einen pH-Wert von 8,5 eingestellt. Bei einem Feststoffgehalt von 58% hat die Streichmasse eine Viskosität von 1400 mPas (gemessen mit einem Brookfield-Viskosimeter bei 100 UpM).100 parts of a commercially available spreading clay are stirred into an aqueous solution of 0.3 part of sodium polyacrylate with a K value of 12 using a high-speed stirrer. 9.6 parts of a mixture consisting of 80 parts of a 50% aqueous dispersion of copolymer A 2 and 20 parts of a 45% aqueous dispersion of copolymer B 1 are added as binders, and the coating color is brought to a pH by adding sodium hydroxide solution set from 8.5. With a solids content of 58%, the coating slip has a viscosity of 1400 mPas (measured with a Brookfield viscometer at 100 rpm).
Die so hergestellte Papierstreichmasse wird mit Hilfe einer Schaberstreichanlage bei einer Geschwindigkeit von 800 m/min auf ein Papier aufgetragen, das aus 55% Holzschliff, 45% gebleichtem Sulfatzellstoff zusammengesetzt ist, einen Aschegehalt von 6% und ein Flächengewicht von 38 g/m2 hat. Das Papier wird beidseitig gestrichen. Der Strichauftrag beträgt 10 g/m2 und Seite. Das im Superkalander bei einer Geschwindigkeit von 300 m/min und 2000 N/cm Liniendruck satinierte Papier weist guten Glanz und gute Glätte und eine hervorragende Bedruckbarkeit auf. Ein Druck, der mit Hilfe eines Haindl-Labortiefdruckgerätes aufgetragen wird, hat im Halbton auf einer Fläche von 30 cm2 weniger als 10 missing dots (Fehlstellen im Druck). Die missing dots wurden bestimmt, indem man die Fehlstellen visuell auszählte.The paper coating slip thus produced is applied with the aid of a doctor coating system at a speed of 800 m / min to paper which is composed of 55% wood pulp, 45% bleached sulfate pulp, has an ash content of 6% and a weight per unit area of 38 g / m 2 . The paper is coated on both sides. The coating is 10 g / m 2 and side. The paper, which is satinised in the super calender at a speed of 300 m / min and 2000 N / cm line printing, has good gloss and smoothness and excellent printability. A print that is applied with the help of a Haindl laboratory gravure printing device has, in semitones, less than 10 missing dots on an area of 30 cm 2 . The missing dots were determined by visually counting the missing areas.
Nach der im Beispiel 1 angegebenen Vorschrift wird eine Papierstreichmasse hergestellt, jedoch verwendet man, bezogen auf 100 Teile eines handelsüblichen Streichclays, 10,2 Teile einer Bindemittelmischung aus 75 Teilen der 50%igen wäßrigen Dispersion des Copolymerisates A 1 und 25 Teilen der 45%igen wäßrigen Dispersion des Copolymerisats B 1. Die Viskosität der Streichfarbe beträgt bei einem Feststoffgehalt von 56% 1300 mPas (Brookfield-Viskosimeter 100 UpM). Bei der Prüfung des Druckausfalls gemäß Beispiel 1 werden im Halbton weniger als 10 missing dots ermittelt.A paper coating slip is produced in accordance with the procedure given in Example 1, but 10.2 parts of a binder mixture of 75 parts of the 50% strength aqueous dispersion of the copolymer are used, based on 100 parts of a commercially available coating clay sates A 1 and 25 parts of the 45% aqueous dispersion of the copolymer B 1. The viscosity of the coating color at a solids content of 56% is 1300 mPas (Brookfield viscometer 100 rpm). When testing the pressure drop according to Example 1, fewer than 10 missing dots are determined in the semitone.
Die Herstellung einer Papierstreichmasse erfolgt wie im Beispiel 1 angegeben, jedoch verwendet man als Bindemittel, bezogen auf 100 Teile Streichclay, 10,2 Teile eines Gemisches aus 80 Teilen einer 50%igen wäßrigen Dispersion eines Copolymerisates aus 55% Isobutylacrylat, 42% Styrol, 1,5% Acrylsäure und 1,5% Methacrylamid und 20 Teilen der 45%igen Dispersion des Copolymerisats B 1. Die Streichfarbe hat bei einem Feststoffgehalt von 56% eine Viskosität von 1200 mPas (Brpokfield-Viskosimeter 100 UpM). Das mit dieser Papierstreichmasse gemäß der im Beispiel 1 angegebenen Vorschrift gestrichene und satinierte Papier hat beim Tiefdruck im Halbton mehr als 20 missing dots auf einer Fläche von 30 cm2.A paper coating slip is prepared as described in Example 1, but 10.2 parts of a mixture of 80 parts of a 50% aqueous dispersion of a copolymer of 55% isobutyl acrylate, 42% styrene, 1 are used as the binder, based on 100 parts of coating clay , 5% acrylic acid and 1.5% methacrylamide and 20 parts of the 45% dispersion of copolymer B 1. The coating color has a viscosity of 1200 mPas (Brpokfield viscometer 100 rpm) at a solids content of 56%. The paper coated and satined with this paper coating slip in accordance with the specification given in Example 1 has more than 20 missing dots on an area of 30 cm 2 in halftone gravure printing.
Claims (2)
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
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AT80102414T ATE2447T1 (en) | 1979-05-17 | 1980-05-05 | BINDING AGENT FOR PAPER COATINGS. |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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DE2919937 | 1979-05-17 | ||
DE19792919937 DE2919937A1 (en) | 1979-05-17 | 1979-05-17 | Binder mix for paper coating slips |
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Publication Number | Publication Date |
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EP0019170A1 EP0019170A1 (en) | 1980-11-26 |
EP0019170B1 true EP0019170B1 (en) | 1983-02-09 |
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ID=6070970
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EP80102414A Expired EP0019170B1 (en) | 1979-05-17 | 1980-05-05 | Mixture of binders for paper coating compositions |
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EP (1) | EP0019170B1 (en) |
AT (1) | ATE2447T1 (en) |
DE (2) | DE2919937A1 (en) |
FI (1) | FI71570C (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US7217443B2 (en) | 2000-03-06 | 2007-05-15 | Rohm And Haas Company | Binder composition |
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Publication number | Priority date | Publication date | Assignee | Title |
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DE19727503A1 (en) * | 1997-06-27 | 1999-01-07 | Basf Ag | Paper coating slips based on binders with N-vinylformamide derivatives |
WO2008095878A2 (en) * | 2007-02-08 | 2008-08-14 | Basf Se | Water-soluble binders for paper coating slips |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
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NL131848C (en) * | 1963-11-20 | 1900-01-01 | ||
NO149177C (en) * | 1977-01-28 | 1984-02-29 | Basf Ag | paper coating |
-
1979
- 1979-05-17 DE DE19792919937 patent/DE2919937A1/en not_active Withdrawn
-
1980
- 1980-05-05 DE DE8080102414T patent/DE3061869D1/en not_active Expired
- 1980-05-05 EP EP80102414A patent/EP0019170B1/en not_active Expired
- 1980-05-05 AT AT80102414T patent/ATE2447T1/en not_active IP Right Cessation
- 1980-05-14 FI FI801564A patent/FI71570C/en not_active IP Right Cessation
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
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US7217443B2 (en) | 2000-03-06 | 2007-05-15 | Rohm And Haas Company | Binder composition |
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ATE2447T1 (en) | 1983-03-15 |
DE3061869D1 (en) | 1983-03-17 |
FI801564A (en) | 1980-11-18 |
FI71570C (en) | 1987-01-19 |
FI71570B (en) | 1986-10-10 |
DE2919937A1 (en) | 1980-11-27 |
EP0019170A1 (en) | 1980-11-26 |
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