EP1001083A1 - Composition polymérique rétentrice d'eau et activatrice d'azurants optiques, sauces de couchage pour papier, et papier couché - Google Patents

Composition polymérique rétentrice d'eau et activatrice d'azurants optiques, sauces de couchage pour papier, et papier couché Download PDF

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Publication number
EP1001083A1
EP1001083A1 EP99420217A EP99420217A EP1001083A1 EP 1001083 A1 EP1001083 A1 EP 1001083A1 EP 99420217 A EP99420217 A EP 99420217A EP 99420217 A EP99420217 A EP 99420217A EP 1001083 A1 EP1001083 A1 EP 1001083A1
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EP
European Patent Office
Prior art keywords
pva
water
paper coating
weight
sauces
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Application number
EP99420217A
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German (de)
English (en)
French (fr)
Inventor
Jean-Bernard Egraz
Georges Ravet
Jean-Marc Suau
Isabelle Capra-Ogier
Henri Grondin
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Coatex SAS
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Coatex SAS
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Publication of EP1001083A1 publication Critical patent/EP1001083A1/fr
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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
    • D21H19/60—Polyalkenylalcohols; Polyalkenylethers; Polyalkenylesters
    • 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
    • D21H3/00—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body
    • D21H3/82—Paper or cardboard prepared by adding substances to the pulp or to the formed web on the paper-making machine and by applying substances to finished paper or cardboard (on the paper-making machine), also when the intention is to impregnate at least a part of the paper body by adding insoluble coloured substances, e.g. powders, fibres, pieces of metal, for obtaining different colours in the paper fancy papers; substances characterised by their physical appearance, e.g. form, rather than by their chemical constitution
    • 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
    • D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
    • D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
    • D21H21/30—Luminescent or fluorescent substances, e.g. for optical bleaching
    • 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]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31591—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

Definitions

  • the present invention relates to the technical sector of coating sheets of paper.
  • a coating composition is deposited on the surface or surfaces of the support which can contain one or more mineral fillers, one or more binders and various additives.
  • the purpose of the coating is to improve certain physical and optical characteristics paper, such as its gloss, whiteness, opacity, capacity printing with ink, its ⁇ smoothness ⁇ and other properties of great importance commercial.
  • a paper coating composition generally consists of a filler which can be one or more pigments, one or more polymeric binders and various additives such as in particular a lubricant such as a calcium stearate, a wax, or a fatty acid ester, and optionally anti-foaming agents, and the like, well known of the skilled person.
  • a filler which can be one or more pigments, one or more polymeric binders and various additives such as in particular a lubricant such as a calcium stearate, a wax, or a fatty acid ester, and optionally anti-foaming agents, and the like, well known of the skilled person.
  • the coating sauce After depositing on the support, the coating sauce has a natural tendency to transfer into the support, all or part of the water and of the water-soluble parts which it contains. It is necessary to control a migration too fast which would harm the characteristics physical and optical layer.
  • Natural agents or synthetics such as carboxymethylcellulose (CMC), starch, alcohols polyvinyl (PVA) or certain latex or highly polymer emulsions carboxylated or polycarboxylates, for example of the polyacrylate type.
  • CMC carboxymethylcellulose
  • PVA alcohols polyvinyl
  • certain latex or highly polymer emulsions carboxylated or polycarboxylates for example of the polyacrylate type.
  • Such products are described for example in patent EP 0 509 878.
  • alkali swellable polymers A particular class of retention agents is called alkali swellable polymers, and is described in the aforementioned EP patent, and as a prior art in US patent 4,780,500 which will be explained below.
  • the main important optical characteristics of paper are, among others, opacity, shine and whiteness, especially for printed media.
  • optical brighteners are generally and not limiting of the type comprising in their molecule the stilbene site substituted by diamines and groups sulfonic. These brighteners convert part of the invisible UV radiation in the radiation from the visible spectrum and generally in the range from blue to purple.
  • a nonlimiting example of a stilbene disulfonic acid derivative used as optical brightener is the product ⁇ TINOPAL TM (SPP Z or ABP Z or SK) ⁇ marketed by the Ciba Company.
  • optical brightener is the product ⁇ BLANKOPHOR TM (P or BPN) ⁇ marketed by the Bayer Company.
  • ⁇ activation ⁇ we mean here the implementation of a co-product that will reveal and mainly to amplify the brightening effect.
  • the papermaker therefore finds himself in the presence of two properties which he is eminently desirable to strengthen, but which are mostly antagonistic.
  • US Patent 4,780,500 describes water retention agents consisting essentially of acrylic acid monomer and secondarily of itaconic acid monomer, molecular weight from 100,000 to 800,000.
  • Patent GB 1 467 127 mentions the possible use of PVA as a binder in coating compositions, in the same way as starch, casein, etc. It mentions the possible presence of optical brighteners (page 2 line 10) but without posing the problem of their activation in relation to water retention.
  • Patent GB 1 271 282 describes a latex mixture, one of which has a high proportion of styrene. This latex mixture gives water retention but nowhere only the presence of PVA is indicated.
  • liquid polymeric aqueous composition is stable, that is to say that it remains homogeneous for several days after storage without stirring at ambient temperature, this stability being an imperative condition of transport, use and marketing of the composition.
  • the invention also makes it possible to control the rheology of the coating sauces, that is to say to choose the viscosities of the medium according to the requirements of the application.
  • the Claimant considers that the selection criteria used for the choice of PWA according to the invention ensure the compatibility and stability with the retention agent.
  • the polymer composition or composition polymer is characterized in that it contains a percentage of PVA greater than 20% by weight and preferably more than 50%.
  • the viscosity of the PVA is determined using Ostwald viscometer, No. 4080 apparatus from Prolabo with the capillary has a length of 100 mm and a reservoir with a capacity of 10 ml.
  • a quantity of PVA weighed at 1 mg is introduced. close, corresponding to 2.105 g for a PVA at 1% humidity, 2.128 g for a PVA at 2% humidity, 2.151 g for a PVA at 3% humidity, or 2.174 g for a PVA at 4% humidity. Then 50 ml of distilled water, measured exactly with a pipette, are added.
  • the solution whose viscosity is to be determined must be free of materials insoluble materials capable of modifying the flow regime of the fluid in the capillary of the viscometer. It may therefore be necessary to filter or centrifuge the solution.
  • the viscosity is measured using the aforementioned viscometer immersed in a thermostatically controlled bath at 20 ° C ⁇ 0.05 ° C.
  • the invention also relates to the stable liquid polymeric aqueous composition.
  • optical brightener activator and water-retaining agent containing at least one PVA (alcohol polyvinyl) and at least one water-soluble polymer at neutral or alkaline pH, characterized in that the water-soluble polymer is a dispersion copolymer having more than 20% by weight (20% to 75%) of monomers containing acid groups and more particularly carboxylic.
  • the copolymer in dispersion can be chosen from copolymers of at least one acid-functional monomers such as acrylic and / or methacrylic acid, itaconic, citraconic, crotonic, fumaric, maleic, isocrotonic, mesaconic, sinapic, undecylenic, angelic and / or their respective anhydrides and / or hemiesters of diacids, acrylamido-methyl-propane-sulfonic acid, phosphates or acid sulfates of ethylene glycol acrylates and methacrylates, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol and polybutylene glycol or other.
  • acid-functional monomers such as acrylic and / or methacrylic acid, itaconic, citraconic, crotonic, fumaric, maleic, isocrotonic, mesaconic, sinapic, undecylenic, angelic and / or their
  • the monomer (s) without an acid group can be chosen without limitation among the derivatives of the aforementioned acids such as in particular the acrylates or methacrylates methyl, ethyl, butyl, 2-ethyl-hexyl, or among acrylonitrile, the methacrylonitrile, acrylamide, methacrylamide, n-methylolacrylamide, and among vinyl and / or styrenic monomers such as for example vinyl acetate, styrene, methylstyrene, diisobutylene, divinylbenzene, methylvinyl ether or also vinylcaprolactam or their mixtures.
  • They can also be chosen from oxyalkylated unsaturated monomers ethylenic terminated by a chain, linear or branched, such as linear groups or branched alkyl, aryl, alkylaryl, arylalkyl having from 1 to 50 carbon atoms and in particular the di-, tri- and tetrastyrylphenol groups, nonylphenols and others.
  • these monomers without acid group can optionally be chosen from monomers having at least two ethylenic unsaturations such as in particular, and without limitation, the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurate, ethers allylics obtained from polyols such as pentaerythritol, sorbitol, sucrose or other.
  • monomers having at least two ethylenic unsaturations such as in particular, and without limitation, the group consisting of ethylene glycol dimethacrylate, trimethylolpropanetriacrylate, allyl acrylate, methylene-bis-acrylamide, methylene-bis-methacrylamide, tetrallyloxyethane, triallylcyanurate, ethers allylics obtained from polyols such
  • the invention also relates to the stable liquid polymeric aqueous composition.
  • optical brightener activator and water-retaining agent containing at least one PVA (alcohol polyvinyl) and at least one water-soluble polymer at neutral or alkaline pH, characterized in that the water-soluble polymer is a water-soluble polyurethane.
  • the invention also relates to the stable liquid polymeric aqueous composition.
  • optical brightener activator and water-retaining agent containing at least one PVA and at least a water-soluble polymer at neutral or alkaline pH, characterized in that the polymer water-soluble is a homopolymer or copolymer of a carboxylic acid used works in completely acidic form and in solution in water.
  • the invention relates to aqueous or slurry suspensions of mineral fillers containing the stable liquid polymeric aqueous composition according to the invention.
  • mineral fillers are the mineral fillers such as, for example, those chosen among the natural calcium carbonates such as in particular chalk, calcite, marble or synthetic calcium carbonates, dolomites, kaolins, talc, titanium dioxide, satin white, mica, calcined clay, hydroxide aluminum, calcium sulfate or mixtures thereof.
  • the coating sauces are prepared by a person skilled in the art by mixture in water, aqueous suspensions of mineral charges, of one or more binders of natural or synthetic origin such as for example casein, starch, carboxymethylcellulose, polyvinyl alcohols or latexes of the styrene-butadiene type or styrene-acrylate or acrylic or vinyl latex or the like.
  • binders of natural or synthetic origin such as for example casein, starch, carboxymethylcellulose, polyvinyl alcohols or latexes of the styrene-butadiene type or styrene-acrylate or acrylic or vinyl latex or the like.
  • the coating sauces can also contain additives in a known manner usual such as rheology modifiers, organic fillers, anti-foaming agents, optical brighteners, biocidal agents, lubricants, hydroxides alkaline and others.
  • the paper coating sauces containing one or more fillers, one or more polymeric binders, water retentants, pigments, brighteners optical, and various other papermaking additives are characterized in that the retention of water, activation of optical brighteners and viscosities of coating sauces paper mill are regulated by a polymer composition, according to the invention, containing at least one polyvinyl alcohol (PVA) and at least one water-soluble polymer at pH neutral or alkaline.
  • PVA polyvinyl alcohol
  • This example concerns the comparison of the effectiveness of activators of optical brighteners known, such as CMC or certain PVA, with the effectiveness of activating compositions according to the invention.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the polymeric composition of optical brightener activator and water-retaining, according to the invention is:
  • a polymer composition consisting of 70% by weight of a PVA of Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 39% by weight of methacrylic acid, 55% by weight of acrylate ethyl and 6% by weight of a precondensate of ethylene glycol methacrylate and toluene diisocyanate condensed on nonylphenol with 50 units of ethylene oxide.
  • the product according to the invention is named, in the rest of the application, product n ° 2.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid, 54% by weight of acrylate ethyl and 9% by weight of a precondensate of ethylene glycol methacrylate and toluene diisocyanate condensed on nonylphenol with 50 units of ethylene oxide.
  • a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid, 54% by weight of acrylate ethyl and 9% by weight of a precondensate of ethylene glycol methacrylate and toluene diis
  • the product according to the invention is named, in the rest of the application, product n ° 3.
  • a polymer composition consisting of 80% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 20% by weight of a copolymer composed of 42% by weight of methacrylic acid, 54.1% by weight of ethyl acrylate, 0.8% by weight of n-methylol acrylamide, of 1.6% of ethylene glycol dimethacrylate and 1.5% acrylamide.
  • the product according to the invention is named, in the rest of the application, product n ° 4.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid, 54% by weight of acrylate ethyl and 9% by weight of tristyrylphenol methacrylate with 25 oxide units ethylene.
  • the product according to the invention is named, in the rest of the application, product n ° 5.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight ethyl acrylate.
  • the product according to the invention is named, in the rest of the application, product n ° 6.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 44% by weight of methacrylic acid, 15% by weight of acrylate butyl and 41% by weight of styrene.
  • the product according to the invention is named, in the rest of the application, product n ° 7.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a polyurethane polycondensate of lauric alcohol, diisocyanate and polyalkylene glycol.
  • the product according to the invention is named, in the rest of the application, product n ° 8.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a polyurethane, polycondensate of octanol, diisocyanate and polyalkylene glycol.
  • the product according to the invention is named, in the rest of the application, product n ° 9.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a homopolymer of acrylic acid in solution in fully acidic form.
  • the product according to the invention is named, in the rest of the application, product n ° 10.
  • a polymer composition consisting of 70% by weight of a PVA Ostwald viscosity equal to 3.5 mPa.s and molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401), from 15% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of acrylate ethyl, and 15% by weight of another copolymer composed of 44% by weight of acid methacrylic, 15% by weight of butyl acrylate and 41% by weight of styrene.
  • the product according to the invention is named, in the rest of the application, product n ° 11.
  • the product according to the invention is named, in the rest of the application, product n ° 12.
  • the coating sauce is subjected to a pressure of 100 psi (7 bars) in a cylinder standardized, equipped with a filter paper type surface capable of letting water pass.
  • Each sheet of paper thus coated at 14-15 g / m 2 and then dried in a non-ventilated oven sold by the company JOUAN, for 5 minutes at 50 ° C. is then subjected to light radiation of wavelength equal to 457 nm. using an Elrepho 3000 spectrophotometer from ⁇ Data Color ⁇ (TM) to determine whiteness.
  • the accuracy of the whiteness result obtained is ⁇ 1.
  • the Brookfield viscosity of the coating sauces was also measured at 10 and 100 rpm at 25 ° C, using a Brookfield viscometer type DV-1 equipped with the mobile adequate.
  • Reading Tables Ia. and Ib. shows that only the coatings sauces according to the invention have both good whiteness and good retention and this by implementation of a single product according to the invention instead of two as in the art prior. Indeed test n ° 5 of the prior art, which uses only one product, has good water retention but poor whiteness.
  • Example I In a second group of tests (n ° 17 to n ° 32), we repeated, with the same mode procedure and the same material, the operations and measurements of Example I but in replacing the 100 dry parts of calcium carbonate of Example I with 70 parts by dry weight of an aqueous suspension of calcium carbonate Hydrocarb TM 90ME of Omya and 30 parts by dry weight of kaolin Hydragloss TM 90 from the company Huber.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the polymer composition according to the invention, called product No. 13, consists 70% by weight of a PVA with an Ostwald viscosity equal to 3.5 mPa.s and a percentage hydrolysis molar equal to 88 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • the product according to the invention is named in the rest of the product request n ° 13.
  • This test illustrates the invention and uses a coating sauce according to the invention by mixing the same constituents as in test No. 22 with the exception of the composition according to the invention.
  • the polymer composition, according to the invention, used is product n ° 6 according to the invention.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 70% by weight of a PVA of Ostwald viscosity equal to 3 mPa.s and of molar percentage hydrolysis equal to 83 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • the product according to the invention is called product n ° 14.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 70% by weight of a PVA of Ostwald viscosity equal to 5 mPa.s and of molar percentage hydrolysis equal to 88 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • This product of the invention is called product No. 15.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 70% by weight of a PVA of Ostwald viscosity equal to 4 mPa.s and of molar percentage hydrolysis equal to 88 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • This product of the invention is called product No. 16.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 70% by weight of a PVA of Ostwald viscosity equal to 4 mPa.s and of molar percentage hydrolysis equal to 98 measured from the ester index (DIN 53401) and 30% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • This product of the invention is called product No. 17.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 70% by weight of a PVA of Ostwald viscosity equal to 3.5 mPa.s and of molar percentage hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 30% by weight of a homopolymer of acrylic acid.
  • This product of the invention is called product No. 18.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 20% by weight of a PVA of Ostwald viscosity equal to 3.5 mPa.s and of molar percentage hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 80% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • This product of the invention is called product n ° 19.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 40% by weight of a PVA of Ostwald viscosity equal to 3.5 mPa.s and of molar percentage hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 60% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • This product of the invention is called product No. 20.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 60% by weight of a PVA of Ostwald viscosity equal to 3.5 mPa.s and of molar percentage hydrolysis equal to 87.5 measured from the ester index (DIN 53401) and 40% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight of ethyl acrylate.
  • This product of the invention is called product n ° 21.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 22 with the exception of the polymer composition according to the invention.
  • the polymer composition according to the invention consists of 70% by weight of a PVA of Ostwald viscosity equal to 3.5 mPa.s and of molar percentage of hydrolysis equal to 87.5 measured from the ester index (DIN 53401), of 15% in weight of a copolymer composed of 42% by weight of methacrylic acid, 54.1% by weight of ethyl acrylate, 0.8% by weight of n-methylol acrylamide, of 1.6% of ethylene glycol dimethacrylate and 1.5% acrylamide and 15% by weight of a copolymer composed of 37% by weight of methacrylic acid and 63% by weight ethyl acrylate.
  • This product of the invention is called product No. 22.
  • Example I In a third group of tests No. 33 to No. 43, we repeated, with the same mode procedure and the same material, the operations and measurements of Example I but in replacing the 100 dry parts of calcium carbonate of Example I with 70 parts by dry weight of an aqueous suspension of calcium carbonate Hydrocarb TM 90ME of Omya and 30 parts by dry weight of talc C10 from Mondo Minerals.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • the dry matter content is around 64% and the pH is around 8 to 9 per adjustment with aqueous sodium hydroxide solution.
  • This test illustrates the invention and uses a coating sauce according to the invention in mixing the same constituents as in test No. 38 with the exception of the polymer composition according to the invention.
  • the polymer composition, according to the invention, used is product n ° 3 according to the invention.
  • This test illustrates the invention and uses a coating sauce according to the invention by mixing the same constituents as in test No. 38 with the exception of the polymer composition according to the invention.
  • the polymer composition, according to the invention, used is product n ° 4 according to the invention.
  • This test illustrates the invention and uses a coating sauce according to the invention by mixing the same constituents as in test No. 38 with the exception of the polymer composition according to the invention.
  • the polymer composition, according to the invention, used is product No. 5 according to the invention.
  • This test illustrates the invention and uses a coating sauce according to the invention by mixing the same constituents as in test No. 38 with the exception of the polymer composition according to the invention.
  • the polymer composition, according to the invention, used is product n ° 6 according to the invention.
  • This test illustrates the invention and uses a coating sauce according to the invention by mixing the same constituents as in test No. 38 with the exception of the polymer composition according to the invention.
  • the polymer composition, according to the invention, used is product n ° 7 according to the invention.
  • Reading Tables IIIa. and IIIb. leads to the same conclusions as those Tables I or II but this time for a coating sauce comprising a charge composed of calcium carbonate and talc.
  • Examples 34 and 42 being differentiated by the use of a single product for test n ° 42 according to the invention while two products are used in the test No. 34 of the prior art.
  • This example concerns the tests on the variation of the type of optical brightener.
  • the different optical brighteners are:
  • optical brightener sold by the Clariant company under the name Leucophor TM CK.
  • optical brightener sold by the company Bayer under the name of Blankophor TM PSK.
  • optical brightener sold by the company 3V Sigma under the name of Optiblanc TM.
  • the optical brightener sold by the company Ciba under the name of Tinopal TM ABP.
  • the optical brightener sold by the company Ciba under the name of Tinopal TM STP.
  • the optical brightener sold by the company Ciba under the name of Tinopal TM SPP.
  • the optical brightener sold by the company Ciba under the name of Tinopal TM UP.
  • the optical brightener sold by the company Ciba under the name of Tinopal TM SK.
  • Reading Tables IVa. and IVb. shows that whatever the brightener optics used, the polymer composition according to the invention allows increase whiteness under UV while retaining water retention.
  • the proportion of composition is varied polymer based on the amount of optical brightener used in the sleeping.
  • the coating sauces to be tested are prepared according to the same procedure, with the same material and the same quantities of the various constituents as in the previous example, except for the amounts of optical brightener and composition polymer according to the invention which vary for the various tests.
  • This test illustrating the invention, uses 0.6 parts, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 0.6 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.6 parts, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 0.8 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.6 parts, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 1.0 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.6 parts, expressed as it is, of a brightener optical sold by the company Ciba under the name of Tinopal TM ABP and 1.2 parts of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.8 parts, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 0.6 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.8 parts, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 0.8 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.8 parts, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 1.0 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 0.8 parts, expressed as it is, of a brightener optical sold by the company Ciba under the name of Tinopal TM ABP and 1.2 parts of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 1.0 part, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 0.6 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 1.0 part, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 0.8 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 1.0 part, expressed as it is, of a brightener optical sold by Ciba under the name of Tinopal TM ABP and 1.0 part of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 1.0 part, expressed as it is, of a brightener optical sold by the company Ciba under the name of Tinopal TM ABP and 1.2 parts of the product No. 6 according to the invention.
  • This test illustrating the invention, uses 1.2 parts, expressed as is, of a optical brightener sold by Ciba under the name of Tinopal TM ABP and 0.6 part of the product n ° 6 according to the invention.
  • This test illustrating the invention, uses 1.2 parts, expressed as is, of a optical brightener sold by Ciba under the name of Tinopal TM ABP and 0.8 part of the product n ° 6 according to the invention.
  • This test illustrating the invention, uses 1.2 parts, expressed as is, of a optical brightener sold by Ciba under the name Tinopal TM ABP and 1.0 part of product n ° 6 according to the invention.
  • This test illustrating the invention, uses 1.2 parts, expressed as is, of a optical brightener sold by Ciba under the name Tinopal TM ABP and 1.2 parts of product n ° 6 according to the invention.
  • the coating sauces to be tested are prepared according to the same procedure, the same material and the same quantities of the various constituents as in Example IV, with the exception of the nature of the latex used in the various tests, as well as the products intended to act as water retentants and / or activators of optical brighteners.
  • This test which describes the invention, uses 1 part, expressed as dry matter, of product n ° 6 according to the invention, as well as 12 parts, expressed as dry matter, of a latex acrylic styrene sold under the name of Acronal TM S 360 D by the company BASF.
  • This test which describes the invention, uses 1 part, expressed as dry matter, of product n ° 6 according to the invention, as well as 12 parts, expressed as dry matter, of a latex styrene-butadiene sold under the name DL 980 by the company Dow Chemical and referenced here under the name styrene-butadiene 1.
  • This test which describes the invention, uses 1 part, expressed as dry matter, of product n ° 6 according to the invention, as well as 12 parts, expressed as dry matter, of a latex styrene-butadiene sold under the name Rhodopas TM SB 123 by the company Rhône-Poulenc and referenced here under the name styrene-butadiene 2.
  • Reading Table VI shows that it is possible to increase the whiteness under UV while retaining water retention whatever the latex used works in the coating sauce.
  • the invention also relates to the use, in the preparation of coating sauces paper mills, stable liquid polymeric aqueous compositions ensuring the function optical brightener activator, water retention and viscosity regulator coating sauces, containing at least one polyvinyl alcohol (PVA) and at least one water-soluble polymer at neutral or alkaline pH.
  • PVA polyvinyl alcohol
  • the invention also relates to papermaking coating sauces of the type containing a filler, a polymeric binder, water retentants, pigments, optical brighteners, and various other papermaking additives, and suitable mixtures of these additives according to the knowledge of a person skilled in the art, characterized in that water retention, activation of optical brighteners and viscosities are controlled by a composition stable liquid polymeric aqueous containing at least one polyvinyl alcohol (PVA) and at least one water-soluble polymer at neutral or alkaline pH.
  • PVA polyvinyl alcohol

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
EP99420217A 1998-11-10 1999-10-29 Composition polymérique rétentrice d'eau et activatrice d'azurants optiques, sauces de couchage pour papier, et papier couché Withdrawn EP1001083A1 (fr)

Applications Claiming Priority (2)

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FR9814299 1998-11-10
FR9814299A FR2785629B1 (fr) 1998-11-10 1998-11-10 Composition polymerique retenteur d'eau et activateur d'azurants optiques, sauces de couchage pour papier, et feuilles de papier couche ainsi obtenues

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JP (1) JP2000144037A (zh)
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FR (1) FR2785629B1 (zh)
ID (1) ID23758A (zh)
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AU2278401A (en) 1999-12-21 2001-07-03 Omnova Solutions Inc. Polyvinyl alcohol copolymer composition
EP1368347A1 (en) * 2001-02-21 2003-12-10 Ciba SC Holding AG Bis-triazinylaminobenzoxazole derivatives
EP1694759A1 (en) * 2003-12-09 2006-08-30 Celanese International Corporation Optical brightener and method of preparing it
WO2005056691A1 (ja) * 2003-12-12 2005-06-23 San Nopco Ltd. 蛍光増白増強剤
ITRM20040129A1 (it) * 2004-03-11 2004-06-11 Wittsun Sa Additivo per patina e relativo processo di produzione.
DE102004045171A1 (de) * 2004-09-17 2006-03-23 Basf Ag Verfahren zur Herstellung von ein- und/oder mehrfach gestrichenen Substraten
EP1712677A1 (en) * 2005-04-08 2006-10-18 Clariant International Ltd. Aqueous solutions of optical brighteners
US20070128460A1 (en) * 2005-12-07 2007-06-07 Miller Gerald D Paper coating composition
FR2894998A1 (fr) * 2005-12-16 2007-06-22 Coatex Sas Procede de fabrication de sauces de couchage a la retention d'eau et a la viscosite brookfield ameliorees mettant en oeuvre un polymere peigne avec au moins une fonction greffee oxyde de polyalkylene.
SE530020C2 (sv) * 2006-06-15 2008-02-12 Holmen Ab Förfarande för stabilisering av vitheten hos i ytbehandlingslim/smet för papper ingående fluroescerande vitmedel (FWA) och hos av detta/dessa formade ytbehandlingsskikt
FR2917091B1 (fr) * 2007-06-08 2009-08-28 Coatex S A S Soc Par Actions S Procede de fabrication d'une formulation aqueuse a base de solution d'un polymere peigne acrylique et d'emulsion epaississante acrylique, formulation obtenue et ses utilisations dans le couchage papetier
AU2012335825B2 (en) * 2011-11-07 2017-02-16 Safety Syringes, Inc. Contact trigger release needle guard
US9512569B1 (en) * 2016-01-26 2016-12-06 Li Meng Jun Formulation of optical brighteners for papermaking

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JP2000144037A (ja) 2000-05-26
NO995479L (no) 2000-05-11
FR2785629A1 (fr) 2000-05-12
TW500857B (en) 2002-09-01
TR199902780A2 (xx) 2000-06-21
FR2785629B1 (fr) 2000-12-22
US6297317B1 (en) 2001-10-02
CA2287805A1 (fr) 2000-05-10
ID23758A (id) 2000-05-11
US20030144408A1 (en) 2003-07-31
KR20000035317A (ko) 2000-06-26
PL336490A1 (en) 2000-05-22
TR199902780A3 (tr) 2000-06-21
US6521701B2 (en) 2003-02-18
NO995479D0 (no) 1999-11-09
US20020004550A1 (en) 2002-01-10

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