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WO2006007999A2 - Compositions aqueuses a base de copolymeres greffes vinyliques - Google Patents

Compositions aqueuses a base de copolymeres greffes vinyliques Download PDF

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Publication number
WO2006007999A2
WO2006007999A2 PCT/EP2005/007425 EP2005007425W WO2006007999A2 WO 2006007999 A2 WO2006007999 A2 WO 2006007999A2 EP 2005007425 W EP2005007425 W EP 2005007425W WO 2006007999 A2 WO2006007999 A2 WO 2006007999A2
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WO
WIPO (PCT)
Prior art keywords
vinyl monomer
vinyl
aryl
alkyl
macromonomer
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PCT/EP2005/007425
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English (en)
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WO2006007999A3 (fr
Inventor
Saskia Van Der Slot
Tijs Nabuurs
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Dsm Ip Assets Bv
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Priority to EP05768448A priority Critical patent/EP1769031A2/fr
Publication of WO2006007999A2 publication Critical patent/WO2006007999A2/fr
Publication of WO2006007999A3 publication Critical patent/WO2006007999A3/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J151/00—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers
    • C09J151/003—Adhesives based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Adhesives based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • 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
    • C08F265/00—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00
    • C08F265/04—Macromolecular compounds obtained by polymerising monomers on to polymers of unsaturated monocarboxylic acids or derivatives thereof as defined in group C08F20/00 on to polymers of esters
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • 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
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/04—Polymers provided for in subclasses C08C or C08F
    • C08F290/046—Polymers of unsaturated carboxylic acids or derivatives thereof
    • 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
    • C08F291/00—Macromolecular compounds obtained by polymerising monomers on to macromolecular compounds according to more than one of the groups C08F251/00 - C08F289/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/003—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • 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
    • C09D151/00—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers
    • C09D151/003—Coating compositions based on graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Coating compositions based on derivatives of such polymers grafted on to macromolecular compounds obtained by reactions only involving unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials

Definitions

  • the present invention relates to certain aqueous vinyl graft copolymer compositions, to a process for the production of such aqueous vinyl graft copolymer compositions and to their use.
  • aqueous vinyl polymer compositions are well known in the art for numerous applications, and in particular for the provision of a binder material in coating applications. It is also known to be advantageous in some applications to employ an aqueous vinyl graft copolymer composition.
  • EP 261 ,942 discloses compositions comprising at least 15 mol % of a macromonomer and processes for preparing the macromonomers using catalytic chain transfer agents. All the disclosed examples are to homo-macromonomers prepared using a single feed.
  • WO 93/22351 and WO 93/22355 disclose the use of a macromonomer prepared using a single vinyl monomer feed having terminal ethylenic unsaturation acting as a chain transfer agent for controlling the molecular weight of polymers prepared in the presence of the macromonomer.
  • US 6,248,826 discloses an aqueous dispersed copolymer formed by emulsion polymerisation of terminally unsaturated carboxylic acid oligomers with ethylenically unsaturated vinyl monomers so as to have low viscosities over a broad pH range.
  • WO 95/32228 and WO 95/32229 describe aqueous coating and lacquer compositions comprising a graft copolymer having carboxylic-acid functional macromonomers attached at a terminal end thereof to a polymeric backbone.
  • US 5,231 ,131 describes a pigment dispersion containing a graft copolymer dispersant having a hydrophobic backbone and hydrophilic macromonomer side chains. Both the macromonomer and backbone are prepared in solvent.
  • an aqueous composition comprising a vinyl graft copolymer and containing ⁇ 50 wt% of organic co-solvent by weight of the graft copolymer, said vinyl graft copolymer comprising: i) 20 to 95 wt% of a polymeric backbone; and ii) 80 to 5 wt% of a macromonomer(s) of Formula (1 ) grafted to the polymeric backbone:
  • R 1 optionally substituted aryl, -C(O)OR 2 or -C(O)NR 2 R 3 ;
  • R 2 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl
  • R 3 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl
  • X residue of vinyl monomer
  • n an integer in the range of from 2 to 50,000
  • the macromonomer(s) is obtained using at least two different vinyl monomer feeds
  • the at least two different vinyl monomer feeds comprise in the range of from 0 to 50 wt%, preferably 0 to 42 wt% and especially 0 to 20 wt% of vinyl monomers carrying anionic or potentially anionic water-dispersing groups; and where i) and ii) add up to 100%.
  • an aqueous composition comprising a vinyl graft copolymer and containing ⁇ 50 wt% of organic co-solvent by weight of the graft copolymer, said vinyl graft copolymer comprising: i) 20 to 95 wt% of a polymeric backbone; and ii) 80 to 5 wt% of at least two different macromonomers comprising: a) a first macromonomer of Formula (1 ); b) a second macromonomer of Formula (1); c) optionally further macromonomers of Formula (1);
  • R 1 optionally substituted aryl, -C(O)OR 2 or -C(O)NR 2 R 3 ;
  • R 2 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl, (alkyl)aryl;
  • R 3 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl, (alkyl)aryl;
  • X residue of vinyl monomer
  • n an integer in the range of from 2 to 50,000; grafted to the polymeric backbone; wherein the macromonomers are obtained using at least two different vinyl monomer feeds; where the at least two different vinyl monomer feeds comprise in the range of from 0 to 50 wt%, preferably 0 to 42 wt% and especially 0 to 20 wt% of vinyl monomers carrying anionic or potentially anionic water-dispersing groups; and where i) and ii) add up to 100%.
  • an aqueous composition comprising a vinyl graft copolymer and containing ⁇ 50 wt% of organic co-solvent by weight of the graft copolymer, said vinyl graft copolymer comprising: i) 20 to 95 wt% of a polymeric backbone; and ii) 80 to 5 wt% of at least two different macromonomers comprising: a) 0 to 99 wt% of a first macromonomer of Formula (1 ); b) 1 to 99 wt% of a second macromonomer of Formula (1 ); c) 0 to 80 wt% of further macromonomers of Formula (1 );
  • R 1 optionally substituted aryl, -C(O)OR 2 or -C(O)NR 2 R 3 ;
  • R 2 -H 1 -CH 3 or optionally substituted Ci to C 18 alkyl, cycloalkyl, aryl, (alkyl)aryl;
  • R 3 -H, -CH 3 or optionally substituted Ci to C 18 alkyl, cycloalkyl, aryl, (alkyl)aryl;
  • R 1 optionally substituted aryl, -C(O)OR 2 or -C(O)NR 2 R 3 ;
  • R 2 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl, (alkyl)aryl;
  • R 3 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl, (alkyl)aryl;
  • X residue of vinyl monomer
  • n an integer in the range of from 2 to 50,000
  • the macromonomer is obtained using at least two different vinyl monomer feeds
  • the at least two different vinyl monomer feeds comprise in the range of from 0 to 50 wt%, preferably 0 to 42 wt% and especially 0 to 20 wt% of vinyl monomers carrying anionic or potentially anionic water-dispersing groups.
  • a vinyl graft copolymer a vinyl monomer, a polymeric backbone and a macromonomer are intended to cover the singular as well as the plural.
  • the aqueous composition of the invention may be a solution, dispersion, emulsion or suspension of the vinyl graft copolymer in an aqueous carrier medium.
  • the macromonomer(s) is obtained using at least two different vinyl monomer feeds by which is meant that the macromonomer(s) is preferably prepared using a sequential polymerisation process or a gradient polymerisation process to give a gradient polymeric morphology.
  • the macromonomer(s) may also be obtained by a blend of at least two macromonomers where each macromonomer is obtained from a different vinyl monomer feed.
  • the macromonomers are each obtained by a solution polymerisation process, blended and then dispersed in an aqueous medium. This ensures an intimate blend of the macromonomers to be grafted to the polymeric backbone.
  • at least one of the macromonomers is obtained using at least two different vinyl monomer feeds.
  • Sequential polymerisations are well known in the art and are described in, for example, EP 492301 and are defined as polymerisations carried out using at least two feeds where the second vinyl monomer feed is added when most or all of the first vinyl monomer feed has been reacted.
  • the macromonomer prepared using a gradient process may be prepared by any of the process variations (also often described as a power feed process) as disclosed in US 3,804,881, US 4,195,167 and WO 97/12921 (incorporated herein by reference).
  • a typical gradient process for preparing a macromonomer comprises introducing a first vinyl monomer feed to a reactor, where the first vinyl monomer feed continually varies in its composition due to the addition of a different second vinyl monomer feed to the first vinyl monomer feed and polymerising the vinyl monomers introduced into the reactor.
  • the addition of the second vinyl monomer feed to the first vinyl monomer feed may be in parallel to the introduction of the first vinyl monomer feed to the reactor (i.e. both feeds start and end at the same time).
  • the start of the first vinyl monomer feed to the reactor may precede the start of the addition of the second vinyl monomer feed to the first vinyl monomer feed for example when preparing a macromonomer using a seeded polymerisation process, or both vinyl monomer feeds may be started simultaneously but the time taken for the addition of the second vinyl monomer feed to the first vinyl monomer feed may exceed the time taken for the introduction of the first vinyl monomer feed to the reactor.
  • the seed may comprise up to 20 wt%, more preferably up to 15 wt% and especially up to 10 wt% of the first vinyl monomer feed.
  • a gradient process may also comprise simultaneously introducing a first vinyl monomer feed and a different second vinyl monomer feed into a reactor where the rate of introduction of the first vinyl monomer feed varies with respect to the rate of introduction of the second vinyl monomer feed and polymerising the vinyl monomers introduced into the reactor.
  • the at least two vinyl monomer feeds used to prepare the macromonomer usually differ in composition.
  • the difference between the macromonomers resulting from the at least two vinyl monomer feeds may be any, including for example a difference in glass transition temperature (Tg), vinyl monomer functionality (for example the use of crosslinking, acid functional or adhesion promoting vinyl monomers), hydrophilicity, refractive index, molecular weight (by varying, for example, the amount or type of catalytic chain transfer agent used) or simply a variation in the concentration of the respective vinyl monomers in each vinyl monomer feed and any combinations thereof.
  • Tg glass transition temperature
  • vinyl monomer functionality for example the use of crosslinking, acid functional or adhesion promoting vinyl monomers
  • hydrophilicity for example the use of crosslinking, acid functional or adhesion promoting vinyl monomers
  • refractive index for example the amount or type of catalytic chain transfer agent used
  • the functional groups are selected from crosslinking groups, water-dispersing groups, fluorinated groups and adhesion promoting groups as described herein.
  • the first vinyl monomer feed is the vinyl monomer feed with the most hydrophilic composition, followed by a second vinyl monomer feed with a more hydrophobic composition.
  • the weight ratio of the first vinyl monomer feed to the second different vinyl monomer feed is in the range of from 10:90 to 90:10, more preferably 70:30 to 30:70.
  • the weight average molecular weight of the macromonomer is less than 500,000, more preferably less than 200,000, most preferably less than 100,000, and especially between 50,000 and 10,000 g/mol.
  • the weight % ratio of polymeric backbone to macromonomer is preferably between 25:75 to 90:10, more preferably between 30:70 to 85:15, most preferably between 35:65 to 80:20 and especially between 40:60 to 70:30.
  • the macromonomer and the polymeric backbone are derived from free-radically polymerisable olefinically unsaturated monomers, which are also usually referred to as vinyl monomers, and can contain polymerised units of a wide range of such vinyl monomers, especially those commonly used to make binders for the coatings industry.
  • a preferred polymeric backbone and/or macromonomer is defined herein as an acrylic polymeric backbone and an acrylic macromonomer respectively.
  • Particularly preferred acrylic monomers include butyl (meth)acrylate (all isomers), methyl (meth)acrylate, octyl (meth)acrylate (all isomers) and ethyl (meth)acrylate.
  • vinyl monomers include (meth)acrylic amides, (meth)acrylonitrile and vinyl acetate.
  • the other vinyl monomers in such acrylic polymeric backbones and/or macromonomers may include one or more of the other vinyl monomers mentioned above, and/or may include ones different to such other vinyl monomers.
  • the vinyl monomers may also include vinyl monomers carrying functional groups as exemplified below.
  • Such functional vinyl monomers may be introduced directly in the vinyl graft copolymer by free radical polymerisation, or alternatively the functional group may be introduced by a reaction of a reactive precursor into the macromonomer or polymeric backbone using a reactive compound carrying a functional group.
  • Water-dispersing functional groups provide the facility of self-dispersibility, stability, solubility in water and/or a substrate.
  • the water dispersing groups may be ionic, potentially ionic, non-ionic or a mixture of such water-dispersing groups.
  • Ionic water- dispersing groups need to be in their dissociated (i.e. salt) form to effect their water- dispersing action. If they are not dissociated they are considered as potential ionic groups which become ionic upon dissociation.
  • the ionic water-dispersing groups are preferably fully or partially in the form of a salt in the final composition of the invention.
  • Ionic water- dispersing groups include cationic water-dispersing groups such as basic amine groups, quaternary ammonium groups and anionic water-dispersing groups such as acid groups, for example phosphoric acid groups, sulphonic acid groups, and carboxylic acid groups. Conversion to the salt form is described below.
  • Preferred vinyl monomers providing anionic or potentially anionic water-dispersing groups include (meth)acrylic acid, itaconic acid, maleic acid, ⁇ -carboxyethyl acrylate, monoalkyl maleates (for example monomethyl maleate and monoethyl maleate), citraconic acid, styrenesulphonic acid, vinylbenzylsulphonic acid, vinylsulphonic acid, acryloyloxyalkyl sulphonic acids (for example acryloyloxymethyl sulphonic acid), 2-acrylamido-2-alkylalkane sulphonic acids (for example 2-acrylamido-2- methylethanesulphonic acid), 2-methacrylamido-2-alkylalkane sulphonic acids (for example 2-methacrylamido-2-methylethanesulphonic acid), mono(acryloyloxyalkyl)phosphates (for example, mono(acryloyloxyethyl)phosphate and mono(3-acryloyloxy
  • the polymeric backbone and/or macromonomer may comprise functional vinyl monomers that may become cationic upon addition of acid, such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide.
  • functional vinyl monomers that may become cationic upon addition of acid, such as dimethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, and dimethylaminopropyl (meth)acrylamide.
  • Such potentially ionic functional vinyl monomers may contribute to improved adhesion and may also improve stability or appearance on specific substrates such as wood.
  • the acid value of the macromonomer is in the range of from 0 to 300, more preferably 0 to 100 and especially 0 to 40 mgKOH/g.
  • the acid value of the polymeric backbone is in the range of from 0 to 80 mgKOH/g and especially in the range of from 10 to 50 mgKOH/g.
  • the acid value of the vinyl graft copolymer is ⁇ 160 mgKOH/g, more preferably in the range of from 0 to 75 mgKOH/g, especially in the range of from 0 to 40 mgKOH/g and most especially in the range of from 2 to 40 mgKOH/g.
  • Non-ionic water-dispersing groups may be in-chain, pendant or terminal groups.
  • Preferably non-ionic water-dispersing groups are pendant polyoxyalkylene groups, more preferably polyoxyethylene groups such as methoxy(polyethyleneoxide (meth)acrylate) or hydroxyalkyl (meth)acrylates such as hydroxyethyl (meth)acrylate (HE(M)A).
  • Preferred vinyl monomers providing non-ionic water-dispersing groups include alkoxy polyethylene glycol (meth)acrylates, hydroxy polyethylene glycol (meth)acrylates, alkoxy prolyproplene glycol (meth)acrylates and hydroxy polypropylene glycol (meth)acrylates, preferably having a number average molecular weight of from 350 to 3000.
  • vinyl monomers which are commercially available include ⁇ - methoxypolyethylene glycol (meth)acrylate.
  • Other vinyl monomers providing non-ionic water-dispersing groups include (meth)acrylamidemono(methacryloyloxethyl)phosphate).
  • Such non-ionic functional vinyl monomers may contribute to improved stability and improved pigment and substrate wetting.
  • the vinyl graft copolymer comprises 0 to 20 wt%, more preferably 0 to 15 wt%, most preferably 0 to 10 wt% and especially 0 to 5 wt% of vinyl monomers carrying non-ionic water-dispersing groups.
  • the macromonomer comprises 0 to 15 wt%, more preferably 0 to 10 wt% and most preferably 0 to 5 wt% of vinyl monomers carrying non-ionic water- dispersing groups.
  • the polymeric backbone comprises 0 to 20 wt%, more preferably 0 to 15 wt%, most preferably 0 to 10 wt% and especially 0 to 5 wt% of vinyl monomers carrying non-ionic water-dispersing groups.
  • Vinyl monomers carrying crosslinker groups include for example allyl, glycidyl or hydroxyalkyl (meth)acrylates, keto functional vinyl monomers such as acetoacetoxy esters of hydroxyalkyl (meth)acrylates, keto-containing amides such as diacetone acrylamide (DAAM), (meth)acrylamide, methylol (meth)acrylamides and silane functional (meth)acrylic monomers such as methacryloxy propyltrimethoxy silane.
  • keto functional vinyl monomers such as acetoacetoxy esters of hydroxyalkyl (meth)acrylates
  • keto-containing amides such as diacetone acrylamide (DAAM)
  • (meth)acrylamide, methylol (meth)acrylamides keto-containing amides
  • silane functional (meth)acrylic monomers such as methacryloxy propyltrimethoxy silane.
  • Preferred vinyl monomers carrying crosslinker groups are diacetone acrylamide, acetoacetoxy ethyl methacrylate (AAEM), glycidyl methacrylate and silane functional (meth)acrylic vinyl monomers.
  • AAEM acetoacetoxy ethyl methacrylate
  • silane functional (meth)acrylic vinyl monomers examples include Silquest A-2171 , Silquest A-174, CoatOSil 1757, Silquest A-151 and Silquest A-171 available from OSI Specialty Chemicals (Silquest and CoatOSil are trade marks). Also possible are combinations of AAEM and Silquest A-1100 or A-1101 or combinations of acid functional vinyl monomers and Silquest A-186 or A-187.
  • the polymeric backbone and/or macromonomer may optionally contain other functional groups to contribute to the optional crosslinking of the vinyl graft copolymer.
  • other groups include unsaturated groups such as those provided by maleic, fumaric, acryloyl, methacryloyl, styrenic, allylic and mercapto groups, these allow crosslinking through Michael Addition by using polyamines or UV crosslinkability to be introduced into the vinyl graft copolymer.
  • the polymeric backbone may comprise up to 5 wt% of olefinically polyunsaturated vinyl monomers.
  • the vinyl graft copolymer comprises 0 to 30 wt%, more preferably 0 to 25 wt%, most preferably 0 to 20 wt% and especially 2 to 10 wt% of vinyl monomers carrying crosslinker groups.
  • the macromonomer comprises 0 to 50 wt%, more preferably 0 to 40 wt%, most preferably 0 to 30 wt% and especially 2 to 15 wt% of vinyl monomers carrying crosslinker groups.
  • the polymeric backbone comprises 0 to 30 wt%, more preferably 0 to 20 wt%, most preferably 0 to 15 wt% and especially 0 to 10 wt% of vinyl monomers carrying crosslinker groups.
  • the vinyl monomer composition for preparing the macromonomer and/or polymeric backbone may comprise functional vinyl monomers that are capable of forming hydrogen bridging links, such as (meth)acrylamide, methylol (meth)acrylamide, butoxymethyl (meth)acrylamide and ureido vinyl monomers (such as Sipomer WAM available from Rhodia).
  • functional vinyl monomers that are capable of forming hydrogen bridging links, such as (meth)acrylamide, methylol (meth)acrylamide, butoxymethyl (meth)acrylamide and ureido vinyl monomers (such as Sipomer WAM available from Rhodia).
  • the polymeric backbone and/or macromonomer may also comprise functional vinyl monomers that induce a dipole moment, such as cyano functional vinyl monomers, such as (meth)acrylonitrile.
  • functional vinyl monomers contribute to improved mechanical properties, including toughness and elongation at break, a better hardness- MFFT balance and improved blocking properties.
  • the polymeric backbone and/or macromonomer may comprise functional vinyl monomers that include fluorinated groups, more preferably fluorinated groups having alcohol units of the formula: -O(CH 2 ) m -(CF 2 ) p F, where 0 ⁇ m ⁇ 4, and 1 ⁇ p ⁇ 4.
  • functional vinyl monomers may contribute to improved chemical resistances, better cleanability and improved scratch resistance.
  • the polymeric backbone and/or macromonomer may also comprise functional vinyl monomers that act as adhesion promoters, such as Sipomer WAM (ex. Rhodia), Cylink C4 (ex. Cytec), and Norsocryl 104 (ex. Atofina), or vinyl monomers with long alkyl chains, such as iauryl (meth)acrylate, and stearyl (meth)acrylate or adhesion promoters such as ⁇ -napthyl methacrylate.
  • functional vinyl monomers that act as adhesion promoters such as Sipomer WAM (ex. Rhodia), Cylink C4 (ex. Cytec), and Norsocryl 104 (ex. Atofina)
  • vinyl monomers with long alkyl chains such as iauryl (meth)acrylate, and stearyl (meth)acrylate or adhesion promoters such as ⁇ -napthyl methacrylate.
  • the macromonomer is prepared from at least a first vinyl monomer feed and a different second vinyl monomer feed where either the first vinyl monomer feed and/or the second vinyl monomer feed comprises composition (a): i) 10 to 100 wt%, more preferably 20 to 100 wt% and most preferably 25 to
  • first vinyl monomer feed and/or the second vinyl monomer feed comprises composition (b): i) 10 to 98 wt%, more preferably 20 to 95 wt% and most preferably 25 to
  • a process for the preparation of an aqueous composition comprising a vinyl graft copolymer and containing ⁇ 50wt% of organic co-solvent by weight of the graft copolymer, said process comprising the steps:
  • R 1 optionally substituted aryl, -C(O)OR 2 or -C(O)NR 2 R 3 ;
  • R 2 -H, -CH 3 or optionally substituted Ci to Ci 8 alkyl; cycloalkyl, aryl,
  • R 3 -H, -CH 3 or optionally substituted Ci to Ci 8 alkyl; cycloalkyl, aryl,
  • X residue of a vinyl monomer
  • n an integer in the range of from 2 to 50,000;
  • step a) polymerising i) 20 to 95 wt% of vinyl monomer in the presence of ii) 80 to 5 wt% of the macromonomer(s) prepared in step a) using an aqueous free radical polymerisation process, where i) and ii) add up to 100%.
  • the macromonomer and the polymeric backbone are preferably prepared by free radical polymerisation.
  • the free radical polymerisation can be performed by techniques well known in the art, for example, as emulsion polymerisation, solution polymerisation, suspension polymerisation or bulk polymerisation. Furthermore the free radical polymerisation may be carried out as a batch or as a semi-continuous polymerisation process.
  • the macromonomer may be prepared by any known technique including those discussed above and may include directly synthesising the macromonomer in the presence of water (for example by emulsion polymerisation, suspension polymerisation, micro-suspension polymerisation or mini emulsion polymerisation), or by solution polymerisation where the solution may be water or any organic solvent. If the solution is water the monomers are preferably soluble in water.
  • the macromonomer is prepared by solution polymerisation, emulsion polymerisation or suspension polymerisation.
  • the macromonomer is prepared in an aqueous process.
  • the continuous phase of the aqueous process comprises > 50 wt% , more preferably > 80 wt% and most preferably > 95 wt% of water.
  • the polymeric backbone is prepared in an aqueous process.
  • the polymeric backbone is prepared by solution polymerisation or emulsion polymerisation.
  • the process for preparing the vinyl graft copolymer may be carried out in a number of modes including but not limited to polymerising all of the macromonomer and vinyl monomers in one batch, pre-charging the macromonomer to a reactor and subsequently feeding in the vinyl monomers in one or more stages and/or using a gradient feeding technique (or vice versa), feeding both macromonomer and vinyl monomers to a reactor (optionally pre-charged with some macromonomer), preparing a graft copolymer by feeding the vinyl monomers to the macromonomer which is simultaneously fed into a reactor (optionally pre-charged with some macromonomer) or continuously feeding a mixture of macromonomer and vinyl monomers into a reactor.
  • the free-radical polymerisation is effected by heating the reactor contents to a temperature in the range of from 30 to 100 0 C and more preferably in the range of from 30 to 90 0 C.
  • a free-radical polymerisation of vinyl monomers will require the use of free-radical- yielding initiator to initiate the vinyl polymerisation.
  • Suitable free-radical-yielding initiators include inorganic peroxides such as K, Na or ammonium persulphate, hydrogen peroxide, or percarbonates; organic peroxides, such as acyl peroxides including e.g.
  • alkyl hydroperoxides such as t-butyl hydroperoxide and cumene hydroperoxide
  • dialkyl peroxides such as di-t-butyl peroxide
  • peroxy esters such as t-butyl perbenzoate and the like
  • 2,2'-azo-bis(2-methyl butane nitrile) (ANBN) mixtures may also be used.
  • the peroxy compounds are in some cases advantageously used in combination with suitable reducing agents (redox systems) such as Na or K pyrosulphite or bisulphite, and iso-ascorbic acid.
  • Metal compounds such as Fe.
  • EDTA ethylene diamine tetracetic acid
  • Azo functional initiators may also be used.
  • Preferred azo initiators include azobis(isobutyronitrile) and 4,4'-azobis(4-cyanovaleric acid). It is possible to use an initiator partitioning between the aqueous and organic phases, e.g. a combination of t-butyl hydroperoxide, iso-ascorbic acid and Fe.EDTA.
  • the amount of initiator or initiator system to use is conventional, e.g. within the range 0.05 to 6 wt% based on the total vinyl monomer(s) used.
  • Preferred initiators for preparing the macromonomers include ammonium persulphates, sodium persulphates, potassium persulphates, azobis(isobutyronitrile) and/or 4,4'-azobis(4-cyanovaleric acid).
  • Preferred initiators for preparing the polymeric backbone include redox systems and persulphates as described above. A further amount of initiator may optionally be added at the end of the polymerisation process to assist the removal of any residual vinyl monomers.
  • Macromonomers may be prepared by a number of processes including but not limited to the use of catalytic chain transfer agents, diarylethene or high temperature processes (such as those described in US 5710227).
  • a catalytic chain-transfer agent is preferably added to the free radical polymerisation process.
  • the macromonomer is in this invention a vinyl polymer with a terminal unsaturated group which is preferably prepared by free-radical emulsion polymerisation or suspension polymerisation of at least two different vinyl monomer feeds in the presence of a catalytic chain-transfer agent.
  • Use of a catalytic chain-transfer agent allows control over the molecular weight of the macromonomer as well as creating terminal unsaturated groups.
  • CCTP catalytic chain-transfer polymerisation
  • a free radical polymerisation is carried out using a free radical forming initiator and a catalytic amount of a selected transition metal complex acting as a catalytic chain transfer agent (CCTA), and in particular a selected cobalt chelate complex.
  • CCTA catalytic chain transfer agent
  • Various other publications, e.g. US 4,680,354, EP-A-0196783, EP-A-0199436 and EP-A-0788518 describe the use of certain other types of cobalt Il chelates as chain-transfer agents for the production of oligomers of vinyl monomers by free radical polymerisation.
  • WO-A-87/03605 claims the use of certain cobalt III chelate complexes for such a purpose, as well as the use of certain chelate complexes of other metals such as iridium and rhenium.
  • wt ppm of catalytic chain-transfer agents based on the weight of vinyl monomer required for the macromonomer is used, more preferably ⁇ 60 wt ppm, most preferably ⁇ 35 wt ppm and especially ⁇ 20 wt ppm is used.
  • the preferred process for preparing a macromonomer is using a free-radical- initiated aqueous emulsion polymerisation in a polymerisation reactor of at least one vinyl monomer, which process employs a hydrophobic Co chelate complex as a CCTA, a stabilising substance for the emulsion polymerisation process and a vinyl monomer feed stage wherein an aqueous pre-emulsified mixture, comprising at least part of the Co chelate employed, at least part of the stabilising substance employed and (i) a non- polymerisable organic solvent and/or (ii) a polymerisable vinyl monomer in unpolymerised or at least partially polymerised form, is contacted in the reactor with vinyl monomer feed stage at the beginning of and/or during the course of the vinyl monomer feed stage.
  • a hydrophobic Co chelate complex as a CCTA
  • a stabilising substance for the emulsion polymerisation process and a vinyl monomer feed stage wherein an aqueous
  • the cobalt chelate catalysts may be added in stages between the vinyl monomer feeds.
  • the ratio of acrylic to methacrylic vinyl monomers is in the range of from 40:60 to 100:0 for the polymeric backbone.
  • the ratio of acrylic to methacrylic vinyl monomers is in the range of from 0:100 to 40 : 60 for the macromonomer(s).
  • the macromonomer is prepared by the use of diarylethene.
  • diarylethene is described in detail in W. Bremser et al, Prog.Org.Coatings, 45, (2002, 95 and JP 3135151, DE 10029802 and US 2002/0013414, incorporated herein by reference.
  • Examples of diarylethene include but are not limited to diphenylethene. Preferably ⁇ 7.5 wt%, more preferably ⁇ 5 wt%, especially ⁇ 3 wt% and most especially 0.5 to 2.5 wt% of diarylethene, based on the weight of vinyl monomers required for the macromonomer, is used.
  • the complete vinyl monomer feed may take up to 4 hours. If a sequential polymerisation is carried out to obtain the macromonomer it is preferred that the vinyl monomer residue from the first feed is as low as possible. This is usually achieved by waiting for ah hour between the end of the first feed and the start of the second feed.
  • Molecular weight control additional to that provided by catalytic chain-transfer agents may be provided by using additional chain-transfer agents such as mercaptans and halogenated hydrocarbons as exemplified below.
  • chain-transfer agent such as mercaptans and halogenated hydrocarbons as exemplified below.
  • ⁇ 2 wt% by weight of chain-transfer agent based on vinyl monomers required for the macromonomer is used, more preferably ⁇ 1 wt%, most preferably ⁇ 0.5 wt% and especially 0 wt% is used.
  • the vinyl monomers required for the polymeric backbone are added to the macromonomer and are preferably polymerised by a free radical aqueous emulsion or suspension polymerisation in the presence of a conventional initiator.
  • a chain-transfer agent may be added to control the molecular weight of the polymeric backbone.
  • Suitable chain-transfer agents include mercaptans such as n-dodecylmercaptan, n-octylmercaptan, t-dodecylmercaptan, mercaptoethanol, iso-octyl thioglycolurate, C 2 to C 8 mercapto carboxylic acids and esters thereof such as 3-mercaptopropionic acid and 2-mercaptopropionic acid; and halogenated hydrocarbons such as carbon tetrabromide and bromotrichloromethane.
  • ⁇ 5% by weight of chain-transfer agent based on vinyl monomers required for the polymeric backbone is used, more preferably ⁇ 4 wt% and most preferably ⁇ 3 wt%.
  • Surfactants can be utilised in order to assist in the dispersion of the emulsification of the vinyl graft copolymer in water (even if it is self-dispersible).
  • Suitable surfactants include but are not limited to conventional anionic, cationic and/or non-ionic surfactants and mixtures thereof such as Na, K and NH 4 salts of dialkylsulphosuccinates, Na, K and NH 4 salts of sulphated oils, Na, K and NH 4 salts of alkyl sulphonic acids, Na, K and NH 4 alkyl sulphates, alkali metal salts of sulphonic acids; fatty alcohols, ethoxylated fatty acids and/or fatty amides, and Na, K and NH 4 salts of fatty acids such as Na stearate and Na oleate.
  • anionic surfactants include alkyl or (alk)aryl groups linked to sulphonic acid groups, sulphuric acid half ester groups (linked in turn to polyglycol ether groups), phosphonic acid groups, phosphoric acid analogues and phosphates or carboxylic acid groups.
  • Cationic surfactants include alkyl or (alk)aryl groups linked to quaternary ammonium salt groups.
  • Non-ionic surfactants include polyglycol ether compounds and preferably polyethylene oxide compounds as disclosed in "non-ionic surfactants - Physical chemistry" edited by M.J. Schick, M. Decker 1987.
  • the amount of surfactant used is preferably 0 to 15% by weight, more preferably 0 to 8% by weight, still more preferably 0 to 5% by weight, especially 0.1 to 3% by weight and most especially 0.3 to 2% by weight based on the weight of the vinyl graft copolymer.
  • aqueous composition of the invention can be used in combination with other polymer compositions which are not according to the invention.
  • the vinyl graft copolymer may comprise macromonomers that are not according to the invention such as macromonomers obtained using a single feed.
  • the vinyl graft copolymer comprises ⁇ 50 wt%, more preferably ⁇ 30 wt%, especially ⁇ 10 wt% and most especially ⁇ 1 wt% of macromonomer obtained using a single feed.
  • a process for preparing an aqueous composition comprising at least one vinyl graft copolymer as according to the present invention and containing ⁇ 50 wt% of organic co- solvent by weight of the graft copolymer and at least one additional vinyl polymer comprising the steps: a) polymerising at least two different vinyl monomer feeds where the at least two different vinyl monomer feeds comprise in the range of from 0 to 50 wt%, preferably 0 to 42 wt% and especially 0 to 20 wt% of vinyl monomers carrying anionic or potentially anionic water-dispersing groups; using an aqueous free radical polymerisation process to obtain a macromonomer(s) of Formula 1 :
  • R 1 optionally substituted aryl, -C(O)OR 2 or -C(O)NR 2 R 3 ;
  • R 2 -H, -CH 3 or optionally substituted Ci to Ci 8 alkyl, cycloalkyl, aryl, (alkyl) aryl;
  • R 3 -H, -CH 3 or optionally substituted C 1 to C 18 alkyl, cycloalkyl, aryl, (alkyl) aryl;
  • the aqueous composition of the present invention may be applied to a variety of substrates including wood, board, metals, stone, concrete, glass, cloth, leather, paper, plastics, foam and the like, by any conventional method including brushing, dipping, flow coating, spraying, flexo printing, gravure printing, ink-jet printing, any other graphic arts application methods and the like.
  • the aqueous carrier medium is removed by natural drying or accelerated drying (by applying heat) to form a coating.
  • a coating, a polymeric film, a printing ink and/or an overprint lacquer obtainable from an aqueous composition of the present invention.
  • aqueous composition of the invention is suitable for use as an adhesive, accordingly there is also provided an adhesive obtainable from an aqueous composition of the present invention.
  • adhesives include pressure sensitive adhesives, hot melt, contact and laminating adhesives.
  • the aqueous composition of the invention may contain conventional ingredients, some of which have been mentioned above; examples include pigments, dyes, emulsifiers, surfactants, plasticisers, thickeners, heat stabilisers, levelling agents, anti- cratering agents, fillers, sedimentation inhibitors, UV absorbers, antioxidants, drier salts, organic co-solvents, wetting agents and the like introduced at any stage of the production process or subsequently. It is possible to include an amount of antimony oxide in the dispersions to enhance the fire retardant properties.
  • the process for preparing an aqueous composition according to the invention is carried out in the presence of 0 to 50 wt%, more preferably 0 to 40 wt%, most preferably 0 to 35 wt%, especially 0 to 25 wt% and most especially 0 to 15 wt% of organic co-solvent by weight of the vinyl graft copolymer.
  • the aqueous composition of the invention comprises 0 to 50 wt%, more preferably 0 to 40 wt% and most preferably 0 to 35 wt% of organic co-solvent by weight of the vinyl graft copolymer.
  • Suitable organic co-solvents which may be added during the process or after the process during formulation steps are well known in the art and include xylene, toluene, butyl acetate and 1-methyl-2-pyrrolidinone.
  • an external crosslinking agent may be added to the aqueous composition of the invention to aid crosslinking during or after drying.
  • reactive functional groups on the polymeric backbone or macromonomer which may be utilised for reaction with an external crosslinking agents include but are not limited to hydroxyl functional groups reacting with isocyanate (optionally blocked), melamine or glycouril functional groups; keto, aldehyde and/or acetoacetoxy carbonyl functional groups reacting with amine, hydrazide, semi-carbazide or hydrazine functional groups; carboxyl functional groups reacting with aziridine, epoxy or carbodiimide functional groups; silane functional groups reacting with silane functional groups; epoxy functional groups reacting with amine or mercaptane groups as well as carboxyl functional groups undergoing metal ion (such as zinc) crosslinking.
  • the solids content of the aqueous composition of the invention is preferably within the range of from 20 to 60 wt%, and most preferably within the range of from 30 to 50 wt%.
  • Cobalt chelate complex Co Il (bis 4,4'-dimethylbenzildioxime diborondifluoride) as disclosed in US 5,962,609.
  • a hydrophilic oligomer for use as a stabilising substance in the invention process was prepared using the following procedure. In a round-bottomed flask equipped with a stirrer and reflux condenser, 1044.1 parts of water and 1.64 parts of SLS and 0.59 parts of APS were mixed and heated to 85 0 C. 5 weight % a pre-emulsified feed of 473.5 parts of MMA, 46.2 parts of MAA, 57.7 parts of AAEM, 238.5 parts of water, 9.3 parts of SLS and 15.6 parts of CTA (3-mercaptopropionic acid) was added to the reactor phase at 6O 0 C. At reaction temperature the remaining monomer feed was added over a period of 60 minutes.
  • An initiator feed of 1.37 parts of APS dissolved in 141.1 parts of water was added over a period of 70 minutes. When the initiator feed had been completed the reaction mixture was kept at 85 0 C for 20 minutes. After 20 minutes the temperature was reduced to 60°C.
  • the pH of the reactor phase was increased to 8 using a mixture of 45.48 parts aqueous NH 3 (25 wt% in water) and 36.25 parts of water.
  • a solution of 0.82 parts of sodium metabisulphite in 13.6 parts of water was fed to the reactor phase in 45 minutes, directly after the start of this feed a slurry of 0.78 parts of t-butyl hydroperoxide and 2.27 parts of water was added. This was repeated after 15 and 30 minutes after the start of the sodium metabisulphite feed.
  • the reactor phase was cooled to 30°C and filtered.
  • the molecular weight of the hydrophilic oligomer HO1 was 12,000 g/mol.
  • oligomer material HO1 (30% solids, example C2 to C9) or 28.3 parts of SLS (30% solids, example C1), or 16.7 parts of SLS (30% solids, example C10) were mixed with a preformed solution of 0.003 parts of cobalt chelate complex and 14.15 parts of MMA at room temperature. After mixing for 1 hour at room temperature the emulsified mixture was diluted with 1196 parts of water and heated to 75°C thereby forming a pre-emulsified mixture.
  • oligomer material HO1 (30% solids, example S2 to S9) or 28.3 parts of SLS (30% solids, example S1), or 16.7 parts of SLS (30% solids, example S10) were mixed with a preformed solution of 0.003 parts of cobalt chelate complex and 14.15 parts of MMA at room temperature. After mixing for 1 hour at room temperature the emulsified mixture was diluted with 1196 parts of water and heated to 75°C thereby forming a pre-emulsified mixture.
  • a vinyl monomer feed stage MF2 with a composition as described in table 1 and a separate APS initiator feed, comprising C parts of an APS solution (2.5% in water) (see Table 1) and 3.66 parts of SLS (30% solution in water) at a pH of 8.5, was fed to the reactor in D minutes (see table 1).
  • the vinyl monomer feed tank was rinsed with 53.8 parts of water.
  • the polymerisation mixture kept at 85°C for 90 minutes.
  • the emulsion was cooled to room temperature and filtered.
  • the specifications of the sequential macromonomers S1 to S10 are given in table 2 below.
  • oligomer material HO1 (30% solids, example P2 to P9) or 28.3 parts of SLS (30% solids, example P1), or 16.7 parts of SLS (30% solids, example P10) were mixed with a preformed solution of 0.003 parts of cobalt chelate complex and 14.15 parts of MMA at room temperature. After mixing for 1 hour at room temperature the emulsified mixture was diluted with 1196 parts of water and heated to 75°C thereby forming a pre-emulsified mixture.
  • the second vinyl monomer feed stage MF2 with a composition as displayed in table 1 was fed to vinyl monomer feed MF1 in 240 minutes. Following the addition of the vinyl monomer feed the vinyl monomer feed tank was rinsed with 53.8 parts of water. The polymerisation mixture kept at 85 0 C for 90 minutes. The emulsion was cooled to room temperature and filtered. The specifications of the gradient macromonomers P1 to P10 are shown in table 2 below.
  • the vinyl monomer feed tank was rinsed with 50 parts of water.
  • the polymerisation mixture kept at 85 0 C for 120 minutes.
  • the emulsion was cooled to room temperature and filtered.
  • the specifications of the final macromonomer S11 is given in table 2 below.
  • the example emulsions of the invention and the comparative example emulsions were formulated with coalescent and if necessary a wetting agent.
  • the pH of the emulsion was increased to a pH in the range of 7.0 to 7.5 with an ammonia solution (12.5%).
  • To each emulsion was added drop wise between 5 to 10 wt% on total emulsion of butyl diglycol and optionally 1 wt% of BYK 346 (wetting agent).
  • the butyl diglycol was adjusted to a pH of 7 using ammonia.
  • the formulated emulsions were allowed to stand at room temperature for 24 hours and then were cast with a blade roller (125 ⁇ m wet) on Leneta chart or (80 ⁇ m wet) on glass.
  • the resultant films were dried at room temperature after which they were annealed at 52°C for 16 hours (all the resultant films were tack-free) and then scratch resistance, K ⁇ nig Hardness, elongation at break and toughness were determined. The results are shown below in Table 5.
  • Konig Hardness as used herein is a standard measure of hardness, being a determination of how the viscoelastic properties of a film formed from the dispersion slows down a swinging motion deforming the surface of the film, and is measured according to DIN 53157 NEN 5319 using an Erichsen hardness equipment.
  • Scratch resistance was determined by scratching the surface with a finger nail in one swift motion. The damage to the film was assessed, a 0 being very poor (film was completely removed) and a 5 excellent (no damage to the film was observed).
  • Minimum film forming temperature of an aqueous composition as used herein is the temperature where the composition forms a smooth and crack free coating or film using DIN 53787 and applied using a Sheen MFFT bar SS3000.
  • Tensile tests A 400 micron wet film of the formulated aqueous coating composition of the invention was dried for 4 hours at room temperature, followed by 16 hours annealing at 52°C. A halter according to DIN 52 910-53 was prepared. Toughness (MPa) and elongation at break (%) of the free film were determined using an lnstron optical tension meter.
  • Sediment is unstabilised solid material (in the order of microns rather than nanometers) which is formed during dispersing or reaction and which will settle or precipitate upon storage and / or heating. It may be determined quantitatively by centrifuging. The sediment content was determined by taking 50cm 3 of the resultant dispersion of the examples prepared above, diluting this with water (1 :1) and centrifuging the diluted composition for 15 minutes at 1500rpm (276G) in a centrifuge tube.
  • Each division on the tube tip represents 0.05 cm 3 or 0.05% sediment.
  • the outcome, i.e. the level of solid sediment in the tube tip was then multiplied by 2 to take into account the dilution factor.

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Abstract

L'invention concerne une composition aqueuse comprenant un copolymère greffé vinylique et entre 0 et 50 % en poids d'un co-solvant organique en poids du copolymère greffé, le copolymère greffé vinylique comprenant entre 20 et 95 % en poids d'un squelette polymère et entre 80 et 5 % en poids d'un ou plusieurs macromonomères, ce ou ces macromonomères étant obtenus avec au moins deux alimentations différentes en monomères vinyliques comprenant entre 0 et 50 % en poids de monomères vinyliques supportant des groupes de dispersion aqueuse anioniques ou potentiellement anioniques.
PCT/EP2005/007425 2004-07-16 2005-07-08 Compositions aqueuses a base de copolymeres greffes vinyliques WO2006007999A2 (fr)

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006052983A1 (fr) * 2004-11-08 2006-05-18 E.I. Dupont De Nemours And Company Vernis à séchage rapide contenant des copolymères greffés à bras segmentés
WO2006052984A3 (fr) * 2004-11-08 2006-08-24 Du Pont Vernis-laques a sechage rapide contenant un additif de reglage rheologique ameliore
WO2007147561A1 (fr) * 2006-06-23 2007-12-27 Dsm Ip Assets B.V. Compositions aqueuses de copolymères greffés vinyliques réticulables
WO2023038147A1 (fr) * 2021-09-13 2023-03-16 三菱ケミカル株式会社 Feuille adhésive, composition adhésive, feuille adhésive avec film détachable, stratifié pour dispositif d'affichage d'image et dispositif d'affichage d'image souple

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IN2014DN05910A (fr) 2012-02-03 2015-06-05 Dsm Ip Assets Bv

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1313922C (fr) * 1986-09-23 1993-02-23 Andrew Henry Janowicz Compositions de macromonomeres
JPH0253803A (ja) * 1988-08-19 1990-02-22 Hitachi Chem Co Ltd スチレン系ミクロゲルの製造方法、塗膜性能向上剤．レオロジーコントロール剤及び熱可塑性樹脂の改質剤
JPH02151479A (ja) * 1988-12-02 1990-06-11 Toagosei Chem Ind Co Ltd 感熱記録体
US5231131A (en) * 1991-12-24 1993-07-27 E. I. Du Pont De Nemours And Company Aqueous graft copolymer pigment dispersants
JP2916554B2 (ja) * 1992-01-10 1999-07-05 富士写真フイルム株式会社 静電写真用液体現像剤
JP2855022B2 (ja) * 1992-02-27 1999-02-10 富士写真フイルム株式会社 静電写真用液体現像剤及びこれを用いた印刷版の製造方法
US5264530A (en) * 1992-05-01 1993-11-23 E. I. Du Pont De Nemours And Company Process of polymerization in an aqueous system
WO1995032229A1 (fr) * 1994-05-19 1995-11-30 E.I. Du Pont De Nemours And Company Compositions de revetement comprenant des latex auto-stabilises, preparees dans un vecteur aqueux
IL113600A0 (en) * 1994-05-19 1995-08-31 Du Pont Aqueous coatings comprising self-stabilized lattices
US5502113A (en) * 1994-08-22 1996-03-26 E. I. Du Pont De Nemours And Company Stable aqueous metallic flake dispersion using phosphated acrylic polymer dispersant
JPH09118858A (ja) * 1995-10-24 1997-05-06 Toagosei Co Ltd 塗料用水性樹脂分散体
JP4025852B2 (ja) * 1997-08-15 2007-12-26 Ｊｓｒ株式会社 放射線硬化性樹脂組成物
JPH11124536A (ja) * 1997-10-23 1999-05-11 Toagosei Co Ltd 水性コーティング剤
US6214958B1 (en) * 1999-07-21 2001-04-10 Arco Chemical Technology, L.P. Process for preparing comb-branched polymers

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006052983A1 (fr) * 2004-11-08 2006-05-18 E.I. Dupont De Nemours And Company Vernis à séchage rapide contenant des copolymères greffés à bras segmentés
WO2006052984A3 (fr) * 2004-11-08 2006-08-24 Du Pont Vernis-laques a sechage rapide contenant un additif de reglage rheologique ameliore
WO2007147561A1 (fr) * 2006-06-23 2007-12-27 Dsm Ip Assets B.V. Compositions aqueuses de copolymères greffés vinyliques réticulables
US20110196084A1 (en) * 2006-06-23 2011-08-11 Tijs Nabuurs Aqueous crosslinkable vinyl graft copolymer compositions
WO2023038147A1 (fr) * 2021-09-13 2023-03-16 三菱ケミカル株式会社 Feuille adhésive, composition adhésive, feuille adhésive avec film détachable, stratifié pour dispositif d'affichage d'image et dispositif d'affichage d'image souple

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