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
• • 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]
  • Y10T428/31725—Of polyamide
  • Y10T428/31768—Natural source-type polyamide [e.g., casein, gelatin, etc.]
  • Y10T428/31772—Next to cellulosic
  • Y10T428/31775—Paper
• • 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
• • 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
• • 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
  • Y10T428/31906—Ester, halide or nitrile of addition polymer

Definitions

• 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% by weight of acrylic and / or meth acrylic acid, optionally up to 10% by weight of acrylic and / or methacrylamide and 85 to 45% by weight of other monomers which form water-insoluble homopolymers, of which at least 20% by weight, based on these hydrophobic monomers, are 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 min- minutely d of a copolymer B and 95 to 60 parts by weight of at least one copolymer A.
• the paper coating colors prepared using these binder mixtures that meet, although the technical processing requirements, sufficient but not more the increased demands on the printability of the coated papers in magazine gravure.
• a coating slip for the production of art paper which is based on 100 parts by weight of a pigment, 8 to 25 parts by weight of a water-insoluble copolymer from at least one alkyl acrylate and 2.5 to 7 parts by weight.
• % of at least one amide for example contains the methacrylic acid or acrylic acid or a salt of a water-insoluble copolymer from at least one alkyl acrylate and 2.5 to 7% by weight of an ethylenically unsaturated carboxylic acid such as itaconic acid, aconitic acid, maleic acid, fumaric acid or the dimeric or trimeric methacrylic acid as the sole binder.
• copolymers which contain 4 to 5% by weight or more of copolymerized acrylic acid or methacrylic acid increase the viscosity of alkaline paper coating slips to an undesirable extent, so that their use in paper coating slips as the sole binder is out of the question.
• the object of the invention is to provide a binder for paper coating slips, which as density-L ' Ges binder can be used and at the same time gives the paper coating slip a sufficiently high viscosity and water retention, so that the usual additives for increasing the viscosity and water retention of paper coating slips can be dispensed with.
• the emulsion copolymers are prepared by known processes.
• An essential constituent of these copolymers are C 4 to C 8 alkyl acrylates, such as n-butyl acrylate, isobutyl acrylate, pentyl acrylate, n-hexyl acrylate and 2-ethylhexyl acrylate, and mixtures of C 4 to C 8 alkyl acrylates with optionally minor amounts of C 4 - Up to C 8 -dialkyl esters of maleic acid, for example di-n-butyl ester of maleic acid, di-isobutyl ester of maleic acid and maleic acid di-2-ethylhexyl ester.
• the maleic esters mentioned are considered for the partial replacement of the coming acrylic acid esters are used and are optionally up to 20 wt .-% in the monomer mixture a).
• the acrylic acid and maleic esters of monohydric primary or secondary C 4 conduct - to C s -alcohols from.
• the monomers of group a) are contained in the copolymer either alone or as a mixture.
• the monomers of group a) make up 30 to 80, preferably 35 to 50% by weight of the emulsion copolymer.
• the emulsion copolymers contain the monomers of group b), specifically acrylic acid or methacrylic acid and also mixtures of acrylic acid and methacrylic acid. These two ethylenically unsaturated carboxylic acids make up 8 to 30, preferably 12 to 20% by weight of the copolymer.
• the emulsion copolymers for modification can optionally contain copolymerized vinyl propionate, vinyl acetate, methyl acrylate and / or ethyl acrylate and / or ⁇ -branched C 10 -monocarboxylic acid vinyl esters as monomers of group c). These monomers are present in the copolymer up to a maximum of 50% by weight.
• the monomers of group d) are only used selectively when it is a question of modifying the properties of the emulsion copolymer to some extent. This is done by using a further group of monomers, for example mostly water-soluble monomers, such as acrylamide, methacrylamide, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and / or acrylonitrile.
• a further group of monomers for example mostly water-soluble monomers, such as acrylamide, methacrylamide, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid and / or acrylonitrile.
• This too Group of monomers can be used either alone or as a mixture in the emulsion polymerization. These monomers can be present in the copolymer in an amount of up to 5% by weight.
• the properties of the emulsion copolymers can also be modified by carrying out the emulsion polymerization in the presence of up to 3% by weight, based on the monomer mixture, of crosslinking monomers (monomers of group e).
• monomers are, for example, methylene-bis (meth) acrylamides, di- and poly- (meth) acrylates of di- or polyvalent C 2 -C 6 -alcohols, divinyldioxane, diallyl phthalate, di- or triallyl ether of di- or polyvalent alcohols , in particular of pentaerythritol, di- (meth) acrylates of polyethylene or propylene glycols.
• aqueous emulsions of the monomers are first prepared.
• the monomers are preferably mixed and emulsified in water with the aid of emulsifiers.
• Suitable emulsifiers are, for example, the alkali and ammonium salts of n-dodecylsulfonic acid, dodecylbenzenesulfonic acid or the corresponding salts of the sulfuric acid half-esters of long-chain alcohols with an even carbon number or higher fatty alcohols reacted with 2 to 25 mol of ethylene oxide, and the corresponding sulfuric acid alcohols with sulfuric acid to the corresponding sulfuric alcohols be implemented.
• ethylene oxide reacted alkylphenols for example para-iso-octylphenol or their sulfuric acid semiesters in the form of the Na or K salts.
• the corresponding salts of sulfosuccinic acid are also suitable as emulsifiers.
• the emulsifiers are usually in amounts of 0.5 to 5 wt .-%, based on the monomers to be polymerized, used.
• the dispersions can be prepared using the so-called monomer feed process, which does not pre-emulsify.
• radical-forming compounds such as peroxides, persulfates, hydroperoxides or azo compounds can be used as polymerization initiators.
• potassium persulfate, cumene hydroperoxide or hydrogen peroxide are suitable.
• activated initiator systems e.g. with a system of potassium persulfate and ascorbic acid or oximethanesulfonic acid sodium or triethanolamine.
• the temperatures during the polymerization are in the usual range, e.g. between 70 and 95 ° C, but they can also be lower if redox catalysts are used. It is also possible to polymerize at higher temperatures and under pressure.
• chain transfer agents can be used in the polymerization, e.g. Dodecyl mercaptan and halogenated hydrocarbons such as chloroform, carbon tetrachloride and tetrachlorethylene.
• Ierstreichmassen p for Pa the usual used for fine-particle pigments into consideration are, for example, the various clay varieties, chalk, satin white and titanium dioxide.
• the paper coating slips used for the production of deep printing papers are used, contain for 100 parts by weight of a finely divided pigment 4 to 7, preferably 4.2 to 5.5 parts by weight of one of the emulsion copolymers described above or a mixture of the emulsion copolymers in question.
• the pH of the finished paper coating slip is generally between 6.5 and 10, preferably between 8 and 9.5.
• 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 and foam preventers , Bases, etc.
• the pH of the finished paper coating slip is generally between 6.5 and 10, preferably between 8 and 9.5.
• about 10 to 20 parts by weight of the emulsion copolymers described above are used per 100 parts by weight of a finely divided pigment.
• the alkali-thickenable emulsion copolymers are also suitable as the sole binder in paper coating slips which are used for the production of papers which are printed in letterpress and flexographic printing.
• the emulsion copolymers to be used according to the invention are used as the sole binder which can be thickened with alkali (for example sodium hydroxide solution, potassium hydroxide solution, ammonia and amines) in paper coating slips and do not require any further additives, such as thickeners or natural and other synthetic binders.
• alkali for example sodium hydroxide solution, potassium hydroxide solution, ammonia and amines
• which - even if the copolymer is used as a binder in paper coating slips - can be printed excellently in gravure printing without the pigment coat being dusted in.
• the papers obtained in this way can be better printed using gravure printing than papers which are made using other binders or binder mixtures have been produced. The better quality of the printing loss in gravure printing is assessed on the basis of missing dots.
• the finished paper coating slips can be applied to base papers by all known methods. Because of the high shear stability of the emulsion copolymers, the paper coating slips can be used on high-speed roller or doctor coating systems. An unsized base paper is preferably coated. In addition, it is also possible to apply pigment coats to papers that have been glued either in bulk or in the surface.
• Emulsion co-polymer I Emulsion co-polymer I
• the feed vessel I contained an aqueous emulsion of 560 parts of n-butyl acrylate, 70 parts of methacrylic acid, 70 parts of acrylic acid and 270 parts of water; the emulsion was prepared by mixing the components mentioned in the presence of 25 parts of a 28% strength aqueous solution of the sodium salt of a sulfated reaction product from a straight-chain C 12 / C 14 alcohol (coconut fatty alcohol) with 2.5 mol of ethylene oxide as emulsifier.
• the second feed vessel was a solution of 1.05 parts of potassium peroxodisulfate in 150 parts of water (feed II).
• Emulsion co-polymer II Emulsion co-polymer II
• a copolymer of 35% n-butyl acrylate, 15% acrylic acid, 35% ethylhexyl acrylate and 15% vinyl acetate was produced in the polymerization apparatus described above.
• a feed I was first prepared, consisting of an emulsion of 245 parts of n-butyl acrylate, 245 parts of 2-ethylhexyl acrylate, 105 parts of vinyl acetate, 105 parts of acrylic acid, 235 parts of water and 140 parts of a 20% solution of the sodium salt of the sulfated reaction product from isooctylphenol with 25 moles of ethylene oxide.
• a solution of 3.5 parts of potassium peroxodisulfate in 150 parts of water was used as feed II.
• Emulsion copolymer III Emulsion copolymer III
• a further emulsion copolymer is prepared in the apparatus specified above, in which an emulsion is used as feed I, which is obtained by emulsifying 364 parts of n-butyl acrylate, 175 parts of vinyl propionate, 70 parts of vinyl acetate and 91 parts of acrylic acid with 140 parts of a 20% strength solution emulsified the sodium salt of a sulfated reaction product from isooctylphenol with 25 moles of ethylene oxide in 267 parts of water.
• a solution of 3.5 parts of potassium peroxodisulfate in 150 parts of water was used as feed II.
• feed III was used, which consisted of a solution of 0.7 parts of ascorbic acid and 0.014 parts of iron ammonium sulfate in 100 parts of water.
• the coating color was applied to a wood-containing coating base paper at a speed of 40 m / min using a doctor coating system, the coat weight was 11 g / m 2 and page.
• the paper satined in the laboratory calender had a line strength of 73 cm / sec (according to the IGT method).
• a print which was applied with the help of a Halndl laboratory gravure printing device, had in the halftone on an area of 30 cm 2 less than 10 missing dots Print).
• the missing dots were determined by visually counting the missing points.
• the coating color had a viscosity of 1160 mPas (100 rpm Brookfield) and a water retention capacity of 64 sec.
• the line After drying and calendering, the line had a dry picking strength (according to the IGT method) of 157 cm / sec and a wet picking resistance of 47% (densitometer value of the wet line plucked according to the IGT method as a percentage of the densitometer value of the full tone) and thus showed excellent strength for offset printing.
• the coating color was applied to the wood-containing coating base paper as in Example la. After drying and satinizing, a value of 51 cm / sec was measured according to IGT. Printed in the gravure printing device, fewer than 10 missing dots were shown in a halftone over an area of 30 cm 2 .
• a coating slip prepared in accordance with Example 1b with the emulsion polymer II had a viscosity of 1080 mPas and a water retention capacity of 45 seconds at a solids content of 56% and a pH of 8.6.
• the paper coated as before had a dry picking resistance of after satinizing 126 cm / sec and a wet pick resistance of 27%. The strength values were thus on the level of conventional offset papers.
• Example la was repeated with the exception that instead of the binder described therein, the same amount (atro) of emulsion copolymer III in the form of the 43.7% strength aqueous dispersion was used as the sole alkali-thickenable binder.
• a paper coating slip with a solids content of 56% was obtained, the viscosity of which at a pH of 8.6 was 1800 mPas, and a value of 24 sec was determined for the water retention capacity.
• the coating color was applied to the wood-containing coating base paper as in Example 1 and dried.
• the test for pick resistance according to IGT showed a value of 44 cm / sec for the satined paper. Less than 10 missing dots were counted in the halftone of the paper printed in rotogravure over an area of 30 cm 2 .
• the emulsion polymer III When used in the same manner and in the same amount as described in Example 1b, the emulsion polymer III gave a viscosity of 1400 mPas and a water retentivity at a solids content of the coating color of 50%. ability of 63 sec.
• the dry pick resistance according to IGT was 112 cm / sec, the wet pick resistance 23%. The strength values were thus on the level of conventional offset papers.
• the paper coating slip was prepared as indicated in Example 1a, but 6 parts of non-alcoholic based on 100 parts of pigment of a binder mixture according to Example 2 of DE-PS 12 64 945 were used as binders.
• This binder consisted of a mixture of 70 parts of a 50% dispersion of a copolymer of 55 parts of butyl acrylate, 45 parts of vinyl acetate and 2 parts of acrylic acid and 30 parts of a 30% dispersion of a copolymer of 112.5 parts of ethyl acrylate, 30 parts of acrylic acid and 7.5 parts of acrylamide.
• the coating color had a solids content of 51%, a viscosity of 1060 mPas and a water retention capacity of 43 seconds.
• the paper coated with this paper coating slip in accordance with the instructions given in Example 1 had a pick resistance of 36 cm / sec and 15 to 20 missing dots on an area of 30 cm 3 for gravure printing in halftone
• Example 1b The binder mixture used for comparison from DE-PS 12 64 945 / Example 2 resulted in that in Example 1b coating color described with a binder amount of 11 parts atro, based on 100 parts of pigment, after the wet pick resistance of 12%.
• the strength of the coating was below the level of comparable offset papers, which have a dry pick resistance of over 100 cm / sec and a wet pick resistance of over 20%.

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• Chemical & Material Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Paper (AREA)
• Paints Or Removers (AREA)

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• 1981
  • 1981-02-02 DE DE19813103463 patent/DE3103463A1/de not_active Withdrawn
• 1982
  • 1982-01-11 US US06/338,487 patent/US4397984A/en not_active Expired - Fee Related
  • 1982-01-28 EP EP82100567A patent/EP0057857A1/fr not_active Withdrawn
  • 1982-01-29 CA CA000395208A patent/CA1167990A/fr not_active Expired
  • 1982-02-01 DK DK42782A patent/DK42782A/da not_active Application Discontinuation
  • 1982-02-01 ES ES509231A patent/ES509231A0/es active Granted
  • 1982-02-01 NO NO820288A patent/NO820288L/no unknown
  • 1982-02-01 JP JP57013405A patent/JPS57149594A/ja active Pending
  • 1982-02-02 AU AU80112/82A patent/AU8011282A/en not_active Abandoned

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