EP1590380B1 - Dispersions aqueuses contenant des cires de copolymere d'ethylene - Google Patents

Dispersions aqueuses contenant des cires de copolymere d'ethylene Download PDF

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Publication number
EP1590380B1
EP1590380B1 EP04702330A EP04702330A EP1590380B1 EP 1590380 B1 EP1590380 B1 EP 1590380B1 EP 04702330 A EP04702330 A EP 04702330A EP 04702330 A EP04702330 A EP 04702330A EP 1590380 B1 EP1590380 B1 EP 1590380B1
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EP
European Patent Office
Prior art keywords
molecular weight
butyl
low molecular
tert
ethylene copolymer
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Expired - Lifetime
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EP04702330A
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German (de)
English (en)
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EP1590380A1 (fr
Inventor
Wolfgang Gaschler
Andreas FECHTENKÖTTER
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BASF SE
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BASF SE
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Classifications

    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/44—Coatings with pigments characterised by the other ingredients, e.g. the binder or dispersing agent
    • D21H19/56—Macromolecular organic compounds or oligomers thereof obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D21H19/58—Polymers or oligomers of diolefins, aromatic vinyl monomers or unsaturated acids or derivatives thereof
    • D—TEXTILES; PAPER
    • D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
    • D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
    • D21H19/00—Coated paper; Coating material
    • D21H19/36—Coatings with pigments
    • D21H19/38—Coatings with pigments characterised by the pigments
    • D21H19/385—Oxides, hydroxides or carbonates

Definitions

  • the present invention relates to aqueous dispersions comprising at least one ethylene copolymer wax which comprises from 60 to 99.5% by weight of ethylene and from 0.5 to 40% by weight of at least one ethylenically unsaturated carboxylic acid in copolymerized form, and at least one hydrophobic low molecular weight organic substance.
  • hydrophobic substances are to be understood as meaning those organic substances which have a solubility of less than 0.5 g / l of water at room temperature.
  • Low molecular weight substances are to be understood as meaning substances having a molecular weight of up to 2000 g / mol, excluding polymer waxes. In the case of such low molecular weight substances which are present in molecular weight-disperse form, the molecular weight is to be understood as the number average M n .
  • EP-A 0 691 390 Progress in Organic Coatings 1995 , 26, 207 and Progress in Organic Coatings 1996 , 29, 201 disclose aqueous dispersions of fluorescent dyes obtainable by free-radical polymerization of, for example, acrylic acid, methyl methacrylate, n-butyl acrylate and Styrene in an organic solvent, for example isobutanol, in the presence of a fluorescent dye.
  • the copolymers thus obtainable have a weight-average molecular weight M w of from 20,000 to 500,000 g.
  • the solvent can be removed later, ie before or after the actual application of the dispersion.
  • the use of solvents is generally disadvantageous.
  • aqueous dispersions of dyes are known, for their preparation, two copolymers are used, which are also prepared by solution polymerization.
  • the solvent can later be removed, i. before or after the actual application of the dispersion.
  • solvents the above applies.
  • fluorescent dyes are used to give improved whiteness to articles such as plastics or fibers. It is generally desirable to use as possible fluorescent dyes which have a high quantum efficiency. Oil-soluble fluorescent dyes are generally superior to the polar and thus water-soluble fluorescent dyes. It is ever - but difficult to use oil-soluble fluorescent dyes in such processes that occur in an aqueous environment. So far, it has not been possible to use oil-soluble fluorescent dyes in papermaking, especially in paper coating.
  • the dispersions of the invention comprise at least one ethylene copolymer wax.
  • This is at least one ethylene copolymer wax which contains 60 to 99.9% by weight, preferably 65 to 85% by weight of ethylene and 0.1 to 40% by weight, preferably 15 to 35% by weight of at least one ethylenically unsaturated carboxylic acid contains polymerized.
  • the dispersions of the invention contain at least one hydrophobic low molecular weight organic substance.
  • hydrophobic substances are to be understood as meaning those organic substances which have a solubility of less than 0.5 g / l of water at room temperature.
  • Low molecular weight substances are to be understood as meaning substances having a molecular weight of up to 2000 g / mol, excluding polymer waxes. In the case of such low molecular weight substances which are present in molecular weight-disperse form, the molecular weight is to be understood as the number average M n .
  • Preferred low molecular weight substances are selected from oil-soluble dyes, in particular oil-soluble fluorescent dyes, so-called optical brighteners, biocides, fragrances and flavorings.
  • at least one low molecular weight hydrophobic substance contained in the dispersions of the present invention is an oil-soluble dye.
  • oil-soluble dyes of the general formula II b is the compound of the formula II b.1
  • the dispersions according to the invention contain from 0.001 to 10% by weight, preferably to 5% by weight and more preferably to 1% by weight, of one or more of the organic low molecular weight hydrophobic substances described above.
  • Ethylene copolymer waxes of ethylene and ethylenically unsaturated carboxylic acids can advantageously be prepared by free-radically initiated copolymerization under high pressure conditions, for example in stirred high-pressure autoclaves or in high-pressure tubular reactors. Production in stirred high pressure autoclave is preferred.
  • High pressure autoclaves are known per se, a description can be found in Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, keywords: Waxes, Vol. A 28, p 146 ff., Verlag Chemie Weinheim, Basel, Cambridge, New York, Tokyo, 1996 . In their case, the ratio length / diameter predominantly behaves at intervals of 5: 1 to 30: 1, preferably 10: 1 to 20: 1.
  • Suitable pressure conditions for the polymerization are 500 to 4000 bar, preferably 1500 to 2500 bar.
  • the reaction temperatures are in the range of 170 to 300 ° C, preferably in the range of 200 to 280 ° C.
  • the polymerization can be carried out in the presence of one or more regulators.
  • regulators one uses for example hydrogen or an aliphatic aldehyde or an aliphatic ketone of the general formula III or mixtures thereof.
  • R 8 and R 9 are covalently linked together to form a 4- to 13-membered ring.
  • R 8 and R 9 may be in common: - (CH 2 ) 4 -, - (CH 2 ) 5 -, - (CH 2 ) 6 , - (CH 2 ) 7 , -CH (CH 3 ) -CH 27 CH 2 -CH (CH 3 ) - or -CH (CH 3 ) -CH 2 -CH 2 -CH 2 -CH (CH 3 ) -.
  • regulators are alkylaromatic compounds, for example toluene, ethylbenzene or one or more isomers of xylene. Preference is given to the use of aldehydes and ketones of the general formula III as a regulator. With particular preference, no further regulators are metered, with the exception of the so-called phlegmatizers, which can be added to organic peroxides for better handling and can likewise have the function of a molecular weight regulator.
  • the customary free radical initiators such as organic peroxides, oxygen or azo compounds can be used. Also mixtures of several radical starters are suitable.
  • Peroxides of the general formulas IV a to IV c and processes for their preparation are known from EP-A 0 813 550.
  • di-tert-butyl peroxide, tert-butyl peroxypivalate, tert-butyl peroxyisononanoate or dibenzoyl peroxide or mixtures thereof are particularly suitable.
  • azo compound azobisisobutyronitrile ("AIBN") is exemplified. Free-radical initiators are metered in amounts customary for polymerizations.
  • phlegmatizers Many commercially available organic peroxides are added to so-called phlegmatizers before they are sold to make them easier to handle.
  • white oil or hydrocarbons in particular isododecane, are suitable as phlegmatizers.
  • phlegmatizers Under the conditions of high-pressure radical polymerization, such phlegmatizers may have a molecular weight-regulating effect.
  • molecular weight regulators should be understood as the additional use of further molecular weight regulators beyond the use of the phlegmatizers.
  • the monomers used are ethylene and at least one ethylenically unsaturated carboxylic acid.
  • at least one ethylenically unsaturated carboxylic acid is a carboxylic acid of the general formula I.
  • R 1 is hydrogen or methyl and R 2 is hydrogen.
  • the quantitative ratio of the monomers in the dosage usually does not correspond exactly to the ratio of the units in the ethylene copolymer waxes used according to the invention, because ethylenically unsaturated carboxylic acids are generally more readily incorporated into ethylene copolymer waxes than ethylene.
  • the monomers are usually dosed together or separately.
  • the monomers can be compressed in a compressor to the polymerization pressure.
  • the monomers are first brought by means of a pump to an elevated pressure of for example 150 to 400 bar, preferably 200 to 300 bar and in particular 250 bar and then with a compressor to the actual polymerization.
  • the polymerization may optionally be carried out in the absence and in the presence of solvents, with mineral oils, white oil and other solvents present in the reactor during the polymerization and used to quench the radical initiator or initiators not being considered as solvents in the context of the present invention.
  • the polymerization is carried out in the absence of solvents.
  • the dispersions according to the invention preferably contain from 0.05 to 40% by weight, preferably from 10 to 35% by weight, of one or more ethylene copolymer waxes. It is advantageous that the proportion by weight of or of the ethylene copolymer waxes in the dispersions according to the invention is that of the hydrophobic or low molecular weight organic Substances not below. Advantageously, the proportion by weight of or of the ethylene copolymer waxes in the dispersions according to the invention is more than twice as large as the proportion by weight of the hydrophobic or low molecular weight organic substances, particularly advantageously more than ten times as large.
  • the proportion by weight of or of the ethylene copolymer waxes in the dispersions according to the invention is more than a hundred times greater than the weight fraction of the hydrophobic low molecular weight organic substances more than two hundred times that size.
  • the dispersions of the invention usually contain one or more basic substances, for example hydroxides and / or carbonates and / or bicarbonates of alkali metals, ammonia, organic amines such as triethylamine, diethylamine, ethylamine, trimethylamine, dimethylamine, methylamine, ethanolamine, diethanolamine, triethanolamine, methyldiethanolamine , n-butyldiethanolamine, N, N-dimethylethanolamine.
  • the dispersions according to the invention preferably contain so much basic substance or basic substances that at least half, preferably at least three quarters of the carboxyl groups of the ethylene copolymer wax or copolymers are neutralized.
  • the dispersions according to the invention contain so much basic substance (s) that the carboxyl groups of the or the ethylene copolymer wax (s) are quantitatively neutralized.
  • the dispersions according to the invention usually have a basic pH, preferably pH values of 7.5 to 14, particularly preferably 8 or higher, and very particularly preferably 8.5 or higher.
  • the dispersions of the invention preferably contain no emulsifiers or protective colloids.
  • the dispersions according to the invention are stable even without such surface-active auxiliaries, ie at a shear stress of 100 cm -1 , the light transmittance does not change by more than 2%, measured with a dispersion having a solids content of 0.1% by weight with pure water Reference.
  • the invention Dispersions find numerous uses because of their good application properties.
  • Another object of the present invention is a process for the preparation of the aqueous dispersions of the invention.
  • the process according to the invention is characterized in that first one or more ethylene copolymer waxes are mixed with at least one hydrophobic low molecular weight organic substance and then dispersed in water.
  • a vessel such as a flask, autoclave or kettle.
  • one or more hydrophobic low molecular weight organic substances is added and the ethylene copolymer or ethylene waxes are heated to a temperature above its melting point.
  • the mixture is heated to a temperature which is at least 10 ° C., particularly advantageously to a temperature which is at least 30 ° C. above the melting point of the or the ethylene copolymer waxes.
  • the mixture is heated to a temperature which is above the melting point of the ethylene copolymer wax which melts at the highest temperature.
  • a temperature which is at least 10 ° C above the melting point of the melting at the highest temperature ethylene copolymer wax it is particularly advantageous to heat to a temperature which is at least 30 ° C. above the melting point of the ethylene copolymer wax which melts at the highest temperature.
  • the ethylene copolymer or ethylene copolymer waxes are first heated and give the hydrophobic or low molecular weight hydrophobic polymer (s) organic matter to the molten ethylene copolymer (s).
  • hydrophobic or low molecular weight organic substances during the heating process is conceivable.
  • water and one or more basic substances and optionally other ingredients such as ethylene glycol are added, wherein the order of addition of water and the addition of basic or basic acting substances and other ingredients is arbitrary. If the temperature is above 100 ° C, it is advantageous to work under elevated pressure and to choose the vessel accordingly. Homogenize the resulting emulsion, for example by mechanical or pneumatic stirring or by shaking. Subsequently, the aqueous dispersion thus prepared can be cooled.
  • Another aspect of the present invention is the use of the aqueous dispersions of the invention in the paper coating.
  • a further aspect of the present invention are paper coating slips comprising the dispersions according to the invention and a process for preparing the paper coating slips according to the invention using the dispersions according to the invention.
  • pigments for example barium sulfate, calcium carbonate, calcium sulfoaluminate, kaolin, talc, titanium dioxide, chalk or coating clay.
  • powdered plastics for example polystyrene.
  • the paper coating slips according to the invention contain at least one pigment.
  • the other constituents of the paper coating slips according to the invention are standardized to the proportion of pigment.
  • the paper coating slips according to the invention comprise one or more dispersions of the invention in an amount of from 0.5 to 95% by weight, based on the pigment (s), preferably from 1 to 50% by weight.
  • the paper coating slips according to the invention may contain further dispersants which may serve to disperse the pigment (s).
  • Suitable examples are aqueous polymer solutions.
  • the aqueous polymer solutions include, for example: aqueous solutions of polyalkali metal salts of poly (meth) acrylic acid, copolymers of (meth) acrylic acid and (meth) acrylic acid C 1 -C 10 -alkyl esters, where the copolymers completely or partially neutralized with basic alkali metal salts could be.
  • concentrations of the aqueous polymer solutions are usually in the range of 10 to 50 wt .-%.
  • the paper coating slips of the invention may further comprise one or more binders.
  • aqueous polymer dispersions of polymers or copolymers of one or more of the following monomers are suitable: butadiene, styrene, acrylonitrile, vinyl acetate, C 1 -C 10 -alkyl (meth) acrylate, (meth) -acrylic acid-hydroxy-C 1 - C 10 alkyl esters, acrylamide and N-methylolacrylamide.
  • the solids content is usually in the range of 30 to 70, preferably 40 to 60 wt .-%. Examples of polymer dispersions which can be added as binders to the paper coating slips according to the invention are described in US Pat. No.
  • binder When one wishes to add a binder, typical proportions are in the range of 0.1 to 50 wt .-%, preferably 2 to 20 wt .-%, particularly preferably 8 to 14 wt .-% aqueous polymer dispersion, based on the or Pigments, as a binder.
  • binder may be added, for example in the range from 0.1 to 14% by weight. based on the pigment (s), or omit the binder (s) altogether.
  • the paper coating slips according to the invention may furthermore contain co-binders.
  • co-binders examples of so-called natural co-binders are starch, casein, gelatine, almonds called modified starch.
  • synthetic co-binders are the customary synthetic co-binders, for example co-binders based on polyvinyl acetate or polyacrylate.
  • Co-binders can be contained in a proportion of 0.1 to 10 wt .-%, based on the proportion of pigment.
  • Another component of the paper coating slips according to the invention is water.
  • the content of water is usually adjusted to 25 to 75 wt .-%, based on the total mass of the paper coating composition according to the invention.
  • the paper coating slips according to the invention can then be applied to various materials, in particular to paper.
  • various materials in particular to paper.
  • inventive paper coating slip on paper By applying inventive paper coating slip on paper to obtain paper containing oil-soluble fluorescent dyes. It is characterized by particularly advantageous whiteness and can be prepared with small amounts of fluorescent dyes with high quantum efficiency. It has overall advantageous application properties.
  • the content of the paper to oil-soluble fluorescent dyes is generally 0.0001 to 5 wt .-%, preferably 0.001 to 3 wt .-%, particularly preferably 0.002 to 1 wt .-%, each based on paper.
  • a specific aspect of the present invention is paper treated with the paper coating slips of the invention.
  • Inventive paper are characterized by particularly advantageous whiteness and can be prepared with small amounts of fluorescent dyes at high quantum efficiency. It has overall advantageous application properties.
  • the content of the paper coated according to the invention with oil-soluble fluorescent dyes is in particular from 0.0001 to 5% by weight, preferably from 0.001 to 3% by weight, particularly preferably from 0.002 to 1% by weight.
  • the reaction temperature was 220 ° C.
  • the content of ethylene and methacrylic acid in the ethylene copolymer wax was determined by NMR spectroscopy or by titration (acid number).
  • the acid number of the ethylene copolymer wax was determined by titrimetry according to DIN 53402.
  • the KOH consumption corresponds to the methacrylic acid content in the ethylene copolymer wax.
  • the whiteness (R457) was determined to be 91.5% at 457 nm with UV light using a spectrometer of the Elrepho G-50-660 brand according to DIN 53 145, and 83.5% at 457 nm without UV light there was a difference of 8.0%.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paper (AREA)
  • Paints Or Removers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)

Claims (8)

  1. Dispersion aqueuse, contenant au moins une cire de copolymère d'éthylène qui contient à l'état copolymérisé 60 à 99,5 % en poids d'éthylène et 0,5 à 40 % en poids d'au moins un acide carboxylique éthyléniquement insaturé, ainsi qu'au moins une substance organique de faible poids moléculaire, hydrophobe, la substance de faible poids moléculaire, hydrophobe, présentant à la température ambiante, dans l'eau, une solubilité inférieure à 0,5 g/l et présentant un poids moléculaire de jusqu'à 2 000 g/mole, des cires polymériques étant exclues, et la moyenne numérique Mn étant à comprendre inférieure au poids moléculaire pour de telles substances de faible poids moléculaire hydrophobes qui se présentent sous une forme dispersée au niveau moléculaire.
  2. Dispersion suivant la revendication 1, caractérisée en ce que, pour ce qui concerne ledit au moins un acide carboxylique éthyléniquement insaturé, il s'agit d'un acide carboxylique de la formule générale I
    Figure imgb0010
     où les radicaux sont définis de la manière suivante :
    R1 est choisi parmi de l'hydrogène, ou des groupes alkyle en C1-C10 ramifiés ou non ramifiés,
    R2 est choisi parmi de l'hydrogène, des groupes alkyle en C1-C10 ramifiés ou non ramifiés ou COOH, COOCH3, COOC2H5.
  3. Dispersion suivant la revendication 1 ou 2, caractérisée en ce que ladite au moins une substance de faible poids moléculaire, hydrophobe, est un colorant oléosoluble.
  4. Dispersion suivant les revendications 1 à 3, caractérisée en ce que la substance de faible poids moléculaire, hydrophobe, est choisie parmi des composés distyrylique et des dérivés de benzoxazole.
  5. Procédé de préparation de dispersions aqueuses suivant l'une des revendications 1 à 4, caractérisé en ce que tout d'abord on mélange une ou plusieurs cires de copolymère d'éthylène avec au moins une substance organique de faible poids moléculaire, hydrophobe, et ensuite on disperse dans de l'eau.
  6. Utilisation de dispersions suivant l'une des revendications précédentes, dans l'enduction de papier.
  7. Masses d'enduction de papier, contenant des dispersions suivant l'une des revendications précédentes.
  8. Papier traité par des masses d'enduction de papier suivant la revendication 7.
EP04702330A 2003-01-27 2004-01-15 Dispersions aqueuses contenant des cires de copolymere d'ethylene Expired - Lifetime EP1590380B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10303170 2003-01-27
DE10303170A DE10303170A1 (de) 2003-01-27 2003-01-27 Wässrige Dispersionen, enthaltend Ethylencopolymerwachse
PCT/EP2004/000240 WO2004067587A1 (fr) 2003-01-27 2004-01-15 Dispersions aqueuses contenant des cires de copolymere d'ethylene

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EP1590380A1 EP1590380A1 (fr) 2005-11-02
EP1590380B1 true EP1590380B1 (fr) 2006-08-02

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US (1) US20060063877A1 (fr)
EP (1) EP1590380B1 (fr)
JP (1) JP2006519274A (fr)
AT (1) ATE335017T1 (fr)
DE (2) DE10303170A1 (fr)
ES (1) ES2270334T3 (fr)
WO (1) WO2004067587A1 (fr)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10326630A1 (de) * 2003-06-11 2005-01-05 Basf Ag Verwendung wässriger Dispersionen, enthaltend Ethylencopolymerwachse
US9650745B2 (en) * 2011-05-10 2017-05-16 Basf Se Oil-in-water emulsions
JP7128659B2 (ja) 2017-06-15 2022-08-31 ダウ グローバル テクノロジーズ エルエルシー 機能性ポリオレフィンフィルムでコーティングされた紙
CA3186663A1 (fr) 2020-05-05 2021-11-11 Alan M. PIWOWAR Papier revetu d'un film de polyolefine fonctionnel

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR1463256A (fr) * 1965-01-05 1966-12-23 Dow Chemical Co Nouveaux latex et compositions et articles obtenus à partir de ces latex
US3990080A (en) * 1975-07-21 1976-11-02 Bell Telephone Laboratories, Incorporated Antenna with echo cancelling elements
DE4423610A1 (de) * 1994-07-06 1996-01-11 Basf Ag Farbstoffe enthaltende wäßrige Dispersionen
DE19625773A1 (de) * 1996-06-27 1998-01-02 Hoechst Ag Dispersionen oder Lösungen von Polymeren und Polymermischungen in Wasser
DE19647564A1 (de) * 1996-11-18 1998-05-20 Basf Ag Verfahren zur Herstellung von Ethylen(Meth)acrylsäure-Copolymeren
FR2757054B1 (fr) * 1996-12-16 1999-01-15 Oreal Pigment melanique composite sous forme de particules comprenant un noyau spherique a base de cire, procedes de preparation et utilisations en cosmetique
DE19805121A1 (de) * 1998-02-09 1999-08-12 Basf Ag Verfahren zur Herstellung farbstoffenthaltender, wässriger Polymerisatdispersionen
DE19937261A1 (de) * 1999-08-06 2001-02-15 Basf Ag Wässrige, farbstoffhaltige Zubereitung

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Publication number Publication date
DE10303170A1 (de) 2004-07-29
WO2004067587A1 (fr) 2004-08-12
EP1590380A1 (fr) 2005-11-02
US20060063877A1 (en) 2006-03-23
JP2006519274A (ja) 2006-08-24
ATE335017T1 (de) 2006-08-15
ES2270334T3 (es) 2007-04-01
DE502004001099D1 (de) 2006-09-14

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