EP1874881A1 - Agents de revetement ayant une resistance a l'abrasion elevee, procede pour les preparer, et leur utilisation - Google Patents

Agents de revetement ayant une resistance a l'abrasion elevee, procede pour les preparer, et leur utilisation

Info

Publication number
EP1874881A1
EP1874881A1 EP06724188A EP06724188A EP1874881A1 EP 1874881 A1 EP1874881 A1 EP 1874881A1 EP 06724188 A EP06724188 A EP 06724188A EP 06724188 A EP06724188 A EP 06724188A EP 1874881 A1 EP1874881 A1 EP 1874881A1
Authority
EP
European Patent Office
Prior art keywords
monomers
silane
coating composition
vinyl
composition according
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06724188A
Other languages
German (de)
English (en)
Inventor
Ivan Cabrera
Harald Petri
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Celanese Sales Germany GmbH
Original Assignee
Celanese Emulsions GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Celanese Emulsions GmbH filed Critical Celanese Emulsions GmbH
Publication of EP1874881A1 publication Critical patent/EP1874881A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
    • C08F218/02—Esters of monocarboxylic acids
    • C08F218/04—Vinyl esters
    • C08F218/08—Vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
    • C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
    • C09D131/04—Homopolymers or copolymers of vinyl acetate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/02—Emulsion paints including aerosols
    • C09D5/024—Emulsion paints including aerosols characterised by the additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • C08L2312/08—Crosslinking by silane

Definitions

  • CH-A-436,721 describes a process for the preparation of latexes by emulsion polymerization of vinyl esters in the presence of an alpha-beta-unsaturated monocarboxylic acid.
  • Suitable anionic emulsifiers include, among others, salts of sulfosuccinic acid esters.
  • Coating agents such as emulsion paints, are used in building protection indoors and outdoors. Coatings must be abrasion resistant to ensure a long service life.
  • the coating composition according to the invention contains pigments and / or fillers. These are finely divided solids of inorganic or organic nature, which are colored or undyed.
  • pigments are inorganic pigments, such as inorganic oxides or inorganic sulfides, or carbon black or organic pigments.
  • Preferred examples of pigments are titanium dioxide, zinc oxide, zinc sulfide, iron oxides and / or carbon black or organic pigments. Particularly preferred is titanium dioxide.
  • these are vinyl esters of aliphatic, saturated carboxylic acids having a chain length of Ci-C 4 ,
  • the proportion of the monomers A2, if appropriate in combination with further comonomers from this group, is 0 to 45% by weight, preferably 5 to 45% by weight, particularly preferably 8 to 25% by weight, very particularly preferably 10 to 20% by weight .-%, based on the total amount of the monomers used.
  • the vinyl esters A3 of aliphatic saturated carboxylic acids of chain length C- 5 -C -I8 are vinyl esters of straight-chain or, preferably, branched aliphatic carboxylic acids, for example vinyl esters of ⁇ -branched carboxylic acids having 5 to 11 carbon atoms in the acid radical ( ® Versatic acids), the vinyl esters of pivalin, 2-ethylhexane, lauric, palmitic, myristic and stearic acid. Vinyl esters of versatic acids, in particular VeoVa® 9, VeoVa® 10 and VeoVa® 11, are preferred.
  • the vinyl esters A3 can also be present in the polyvinyl ester in combination of two or more of them next to one another.
  • ethylenically unsaturated silanes can as Monomeric A4 ethylenically unsaturated epoxy compounds, such as glycidyl methacrylate or glycidyl acrylate, are used.
  • Suitable comonomers of group A5 preferably have at least one stabilizing nonionic or ionic group, preferably an acid group in the molecule, which additionally stabilize the emulsion polymer via polymer-bound functional groups and / or charges.
  • comonomers A5 which can be used in the copolymer are any comonomers which do not belong to the groups A1, A2, A3 or A4.
  • Examples include esters of aliphatic carboxylic acids of chain length C 3 -C- I2 with unsaturated alcohols of chain length C 3 -C 8, the acrylic and methacrylic esters of monohydric saturated aliphatic alcohols, vinyl chloride, vinylidene chloride, acrylonitrile and methacrylonitrile, butadiene, isoprene, C 9 -C 16 alpha-olefins, 2-chlorobutadiene, 2,3-dichlorobutadiene, tetrafluoroethylene, styrene, vinyl ethers of monohydric aliphatic saturated alcohols of chain length Cr C 18 , divinyl and diallyl esters of saturated and unsaturated aliphatic dicarboxylic acids of chain length C 3 -C 18 , Vinyl and allyl est
  • nonionic emulsifiers E1 0.1 to 5 parts by weight, preferably 0.5 to 3.0 parts by weight, based on the vinyl ester polymer, of nonionic emulsifiers E1 are typically used. used. It is also possible to use mixtures of nonionic emulsifiers E1.
  • a salt of a bis-ester preferably a bis-C 4 -C 18 alkyl ester, a sulfonated dicarboxylic acid having 4 to 8 carbon atoms or a mixture of these salts is used.
  • Examples of particularly preferred emulsifiers of the E2 type are alkali salts of sulfosuccinic acid esters with aliphatic saturated monohydric alcohols of chain length C 4 -C 16 , sulfosuccinic acid 4-esters with polyethylene glycol ethers of monohydric aliphatic alcohols of chain length C 10 -C 12 (di-sodium salt) Sulfosuccinic acid 4-esters with polyethylene glycol nonyl phenyl ether (di-sodium salt) or sulfosuccinic acid bis-cyclohexyl ester (sodium salt).
  • the proportion of emulsifier, based on the vinyl ester polymer from 0.2 to 10 parts by weight, preferably 0.5 to 5.0 wt.%, Based on the vinyl ester polymer.
  • the proportion of component b) in the coating composition according to the invention is typically from 6 to 55% by weight, preferably from 15 to 30% by weight, based on the total solids content.
  • coating compositions in which the vinyl ester polymer is derived from monomers of the above-defined type A1, A3, A4 and optionally A5 and in which the monomer of type A3 is a vinyl ester of ⁇ - branched carboxylic acids having 9 to 11 carbon atoms in the acid radical ( ® versatic acid) and which has been modified with silane-containing monomers and / or with monomers containing epoxide groups.
  • the proportion of component c) in the coating composition according to the invention can be up to 25% by weight, preferably from 2 to 15% by weight, and in particular from 5 to 10% by weight, based on the total solids content.
  • the minimum film-forming temperature of the coating compositions according to the invention is typically less than 25 0 C, preferably below 15 0 C.
  • the film-forming temperature can be modifed by the addition of a known and coalescing agents are specifically set.
  • the invention also relates to a process for the preparation of the aqueous coating compositions described above.
  • This comprises preparing a polyvinyl ester dispersion copolymerized with ethylenically unsaturated and silane-containing monomers and / or with ethylenically unsaturated epoxy compounds and / or modified with aminosilanes or epoxysilanes by free radical emulsion polymerization in the presence of an emulsifier mixture comprising at least one nonionic emulsifier and at least one salt of a bis-ester, preferably a bis-C 4 -C 8 -alkyl ester, a sulfonated dicarboxylic acid having 4 to 8 carbon atoms, and mixing the above-defined components a), b) and optionally c) in a conventional manner, for example by stirring the described Kunststoffoffcopolymerdispersion together with a pigment / filler paste at 1500 U / min by means of a Lenardrlochers.
  • the combined batch / feed process or, more preferably, the feed process, wherein usually some of the monomers (from 1 to 15% by weight) are initially charged to start the polymerization.
  • the dosage of the monomers can be done either together or in separate feeds.
  • the emulsifier mixture used for the stabilization can likewise either be initially charged completely at the beginning of the polymerization or partially charged and partially metered or metered in completely during the polymerization.
  • the polymerization temperature is typically in the range of 20 to 120 0 C, preferably in the range of 30 to 11O 0 C and most preferably in the range of 45 to 95 ° C.
  • a further, preferably chemical aftertreatment in particular with redox catalysts, such as, for example, combinations of the abovementioned oxidizing agents and reducing agents, may be added for demonomerization.
  • redox catalysts such as, for example, combinations of the abovementioned oxidizing agents and reducing agents
  • residual monomer present be removed.
  • Particularly effective is a combination of physical and chemical methods, which allows a lowering of the residual monomers to very low levels ( ⁇ 1000 ppm, preferably ⁇ 100 ppm.
  • an aqueous solution consisting of the following constituents was added: 22000 g of water, 86 g of sodium acetate, 1440 g of a 70 wt.% Aqueous solution of a Oxoalkylethoxylats with 28 moles of ethylene oxide, 2160 g of a 10 wt.
  • Gusty aqueous polyvinyl alcohol (viscosity of 4 wt.% Aqueous solution 18 mPa * s ), 1127 g of a 15% by weight sodium lauryl sulfate solution, 577 g of a 30% by weight aqueous sodium vinylsulfonate solution and 8 g of a 1% by weight aqueous solution of Fe-II (SO 4 ) ⁇ 7H 2 O.
  • the pH of the solution was 7.2.
  • the apparatus was freed of atmospheric oxygen and ethylene was forced into the apparatus. At 20 bar ethylene pressure 1500 g of vinyl acetate were metered. It was heated to 60 ° C internal temperature while the ethylene pressure increased to 40 bar.
  • the polyvinyl ester dispersion used according to the invention is distinguished from a protective colloid-stabilized dispersion by a smaller average particle size and by a narrower particle size distribution.
  • paints were prepared in a solvent-free formulation (Table 3) and mixed with the hard dispersions in a solvent-containing formulation (Table 5).
  • the powdery methylhydroxyethyl cellulose was sprinkled into the water and dissolved with stirring, then the solutions of the NA salts of polyacrylic acid and polyphosphoric acid and the 10 wt% sodium hydroxide solution were added with stirring. To the resulting viscous solution was added the preservative and the defoamer. With stirring by means of a dissolver, aluminum silicate was first dispersed in at a stirring speed of 2000 rpm and then titanium dioxide and the calcium carbonate types were added while increasing the stirring speed to 5000 rpm. It was further dispersed at 5000 rpm for 20 minutes with the temperature of the pigment / filler paste rising to 60 ° C. It was allowed to cool to 30 ° C. The pH was 9.3.
  • the abrasion resistance of these colors was tested by means of the fleece method (ISO 11998). For this, the removal of the coating after 28 days of storage (28 d) on the mass loss of the paint film was determined. The color removal in ⁇ m was then calculated from the color density, the scrubbed areas and the mass loss of the color film.
  • the essential characteristics of the different emulsion paints are scrub resistance (ESR) and opacity. The test results are shown in Table 4.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Paints Or Removers (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

La présente invention concerne des agents de revêtement contenant au moins un pigment et/ou une charge, et au moins une dispersion aqueuse d'un copolymère d'ester de vinyle sélectionné, stabilisé par émulsifiant, qui contient un mélange d'au moins un émulsifiant non ionique en tant qu'agent de stabilisation, et au moins un sel d'un ester bis d'un acide dicarboxylique sulfoné contenant de 4 à 8 atomes de carbone. Les agents de revêtement formulés avec ces liants, se caractérisent par des résistances à l'abrasion élevées.
EP06724188A 2005-04-20 2006-04-10 Agents de revetement ayant une resistance a l'abrasion elevee, procede pour les preparer, et leur utilisation Withdrawn EP1874881A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102005018129A DE102005018129A1 (de) 2005-04-20 2005-04-20 Beschichtungsmittel mit hoher Scheuerbeständigkeit, Verfahren zu deren Herstellung und Verwendung
PCT/EP2006/003254 WO2006111290A1 (fr) 2005-04-20 2006-04-10 Agents de revetement ayant une resistance a l'abrasion elevee, procede pour les preparer, et leur utilisation

Publications (1)

Publication Number Publication Date
EP1874881A1 true EP1874881A1 (fr) 2008-01-09

Family

ID=36572180

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06724188A Withdrawn EP1874881A1 (fr) 2005-04-20 2006-04-10 Agents de revetement ayant une resistance a l'abrasion elevee, procede pour les preparer, et leur utilisation

Country Status (7)

Country Link
US (1) US20080214722A1 (fr)
EP (1) EP1874881A1 (fr)
CN (1) CN101163764A (fr)
CA (1) CA2605274A1 (fr)
DE (1) DE102005018129A1 (fr)
MX (1) MX2007013165A (fr)
WO (1) WO2006111290A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102007033596A1 (de) 2007-07-19 2009-01-22 Celanese Emulsions Gmbh Beschichtungsmittel mit hoher Bewitterungsbeständigkeit, Verfahren zu deren Herstellung und deren Verwendung
DE102007033595A1 (de) 2007-07-19 2009-01-22 Celanese Emulsions Gmbh Polyvinylesterdispersionen, Verfahren zu deren Herstellung und deren Verwendung
DE102010031339A1 (de) 2010-07-14 2012-01-19 Wacker Chemie Ag Verfahren zur kontinuierlichen Emulsionspolymerisation
WO2013170411A1 (fr) * 2012-05-14 2013-11-21 Celanese International Corporation Emulsion de copolymère d'acétate de vinyle-éthylène et composition de couchage de papier à base de celle-ci
EP2892718A4 (fr) * 2012-09-10 2016-06-08 Liants d'éthylène d'acétate de vinyle fonctionnalisés pour revêtements de papier et de carton
CN105377903B (zh) * 2013-07-18 2017-03-29 旭硝子株式会社 含氟聚合物水性分散液的制造方法、含氟聚合物水性分散液和含氟聚合物
CN106164372B (zh) * 2014-03-27 2018-07-27 瓦克化学股份公司 用于纸张涂层的水性乙酸乙烯酯乙烯共聚物分散体
CN104962162A (zh) * 2015-06-30 2015-10-07 黄一伦 一种含纳米碳酸钙的树皮保护涂层
CN105153881A (zh) * 2015-09-14 2015-12-16 安徽华润涂料有限公司 一种家用铝合金推拉门外层耐磨涂料的粘合剂及其制备方法
WO2019201695A1 (fr) * 2018-04-20 2019-10-24 Basf Se Composition d'additifs pour dispersions aqueuses de polymères hydrophobes

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EP0528479B1 (fr) * 1991-08-15 1995-12-06 Agfa-Gevaert N.V. Elément récepteur d'image de colorant pour utilisation dans le transfert thermique de colorant par thermosublimation
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US6080802A (en) * 1991-12-03 2000-06-27 Rohm And Haas Company Process for preparing an aqueous dispersion of composite particles including polymeric latex adsorbed to titanium dioxide
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Also Published As

Publication number Publication date
DE102005018129A1 (de) 2006-10-26
CA2605274A1 (fr) 2006-10-26
MX2007013165A (es) 2008-01-18
WO2006111290A1 (fr) 2006-10-26
US20080214722A1 (en) 2008-09-04
CN101163764A (zh) 2008-04-16

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