WO1999018157A1 - Latex resistants au frottement - Google Patents

Latex resistants au frottement Download PDF

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Publication number
WO1999018157A1
WO1999018157A1 PCT/US1998/021089 US9821089W WO9918157A1 WO 1999018157 A1 WO1999018157 A1 WO 1999018157A1 US 9821089 W US9821089 W US 9821089W WO 9918157 A1 WO9918157 A1 WO 9918157A1
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WO
WIPO (PCT)
Prior art keywords
vinyl
methacrylate
acid
polymer
latex composition
Prior art date
Application number
PCT/US1998/021089
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English (en)
Inventor
Gerald Anthony Vandezande
Victor Vincent Kaminski
Andrew Joseph Defusco
Original Assignee
Union Carbide Chemicals & Plastics Technology Corporation
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 Union Carbide Chemicals & Plastics Technology Corporation filed Critical Union Carbide Chemicals & Plastics Technology Corporation
Priority to EP98952117A priority Critical patent/EP1034218A1/fr
Priority to AU97889/98A priority patent/AU9788998A/en
Priority to BR9815391-9A priority patent/BR9815391A/pt
Priority to KR1020007003528A priority patent/KR20010015684A/ko
Priority to KR1020007003509A priority patent/KR20010030851A/ko
Priority to JP2000514962A priority patent/JP2001519451A/ja
Priority to CA002305566A priority patent/CA2305566A1/fr
Publication of WO1999018157A1 publication Critical patent/WO1999018157A1/fr

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Classifications

    • 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
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/12—Polymerisation in non-solvents
    • C08F2/16—Aqueous medium
    • C08F2/22—Emulsion polymerisation
    • 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
    • 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
    • C08F265/06—Polymerisation of acrylate or methacrylate esters on to polymers thereof

Definitions

  • the present invention generally relates to latex polymers and more specifically relates to latex polymers having enhanced wet adhesion characteristics.
  • Latex paint coatings are typically applied to substrates and dried to form continuous films for decorative purposes as well as to protect the substrate. Such paint coatings are often applied to architectural interior or exterior surfaces, where the coatings are sufficiently fluid to flow out, form a continuous paint film, and dry at ambient temperatures.
  • a latex paint ordinarily comprises an organic polymeric binder, i.e., latex polymer, pigments, and various paint additives.
  • the polymeric binder functions as a binder for the pigments and provides adhesion of the dried paint film to the substrate.
  • the pigments may be organic or inorganic and functionally contribute to opacity and color in addition to durability and hardness, although some paints contain little or no opacifying pigments and are described as clear coatings.
  • the manufacture of paints involves the preparation of a polymeric binder, mixing of component materials, grinding of pigments in a dispersant medium, and thinning to commercial standards. Latexes produced for architectural interior or exterior surfaces often require the property of wet adhesion.
  • Wet adhesion is typically tested by casting a 7-mil wet film of the latex paint over a gloss alkyd (oil based) paint film that has been allowed to dry for at least 3 weeks but no longer than 6 weeks.
  • the latex paint is allowed to dry for 24 hours, then the film is cross-hatched, placed in water for 30 minutes, then removed from water and placed on a scrub machine.
  • the cross- hatch section is scrubbed for 500 cycles using a 5% lava soap solution and standard scrub brush.
  • Optimum wet adhesion values are obtained when none of the paint film is removed during the test. The percent film remaining is recorded. Essentially this property allows the paint to adhere to surfaces previously painted with alkyd paints.
  • One latex polymer commonly used in latex paints which require wet adhesion contains acrylic or styrene / acrylic monomers. Many methods exist to produce latexes from these types of monomers.
  • One particular method utilizes a generic reaction scheme which produces two stage latexes.
  • the first stage is comprised of monomers and chain transfer agents, polymerized in the presence of water and optionally surfactants, to produce a latex polymer which is water soluble or slightly water soluble.
  • a second stage is then polymerized in the presence of the first stage to produce a more hydrophobic polymer.
  • the resultant polymer is referred to in the art as a composite latex with a hydrophobic inner second stage and water soluble or slightly water soluble/swellable outer first stage.
  • EP 0 587 333 A2 describes water-resistant multi-stage polymers having an alkali-insoluble polymer and an alkali-soluble polymer which are prepared by sequential emulsion polymerization of a monomer mixture having acid functionality in the alkali-soluble stage and an alkali-insoluble polymer having, optionally, an amine functionality to tie or link the first stage polymer to the second stage polymer.
  • Latex polymer compositions comprising blends of latex polymers with wet adhesion properties are disclosed in U. S. Pat. No. 5,208,285.
  • the patentees disclose relatively small amounts of carboxylic acid-containing monomers which are often desirable in latex compositions. Accordingly, latex polymer compositions polymerized from monomers having acid or anhydride functionality and wet adhesion properties, i.e., scrub resistance, are desired.
  • latex polymer compositions polymerized from monomers having acid or anhydride functionality and wet adhesion functionality are provided.
  • the process of the invention allows for the preparation of a first stage polymer which, upon addition of base, swells, partially dissolves or substantially dissolves the polymer thereby providing a medium for a second-stage polymerization of an alkali-insoluble polymer, providing stability for the alkali-insoluble polymer.
  • the polymer latexes of the of the present invention contain acid contents of up to 10% or higher based on the total weight of the polymer containing the acid or anhydride functionality. Surprisingly, when wet adhesion functionality is added it has been discovered that latex polymers of this type provide excellent wet adhesion when employed in coatings formulations despite the presence of the acid or anhydride functionality.
  • the present invention provides polymers which can be useful in compositions such as architectural coatings, industrial and automotive coatings, sealants, adhesives, paper coating compositions, inks, varnishes and the like. Detailed Description of the Invention
  • the latex compositions of the present invention can be prepared by a two stage polymerization of a first stage polymer and a second stage polymer.
  • the first stage polymer is an emulsion polymerization of a mixture of monomers comprising at least one carboxylic acid or anhydride functional monomer or monomer that imparts alkaline sensitivity to the first stage polymer, reacted with a variety of comonomers, optionally in the presence of a wet adhesion promoter.
  • Suitable acid or anhydride functional monomers include acrylic acid, methacrylic acid, ethacrylic acid, alpha- chloroacrylic acid, crotonic acid, citraconic acid, mesaconic acid, itaconic acid, maleic acid, fumaric acid, 3-acrylamido-3- methylbutanoic, acrylic anhydride, methacrylic anhydride, ethacrylic anhydride, crotonic anhydride, citraconic anhydride, mesaconic anhydride, itaconic anhydride, maleic anhydride, fumaric anhydride, p-styrene carboxylic acid, p-styrene sulfonic acids, vinyl sulfonic acid, 2-sulfoethyl methacrylate, 3- sulfopropyl methacrylate, 3-sulfopropylacrylate, 2-acrylamido- 2-methylpropane sulfonic acid, and the like including mixtures thereof.
  • the preferred acid monomer is selected from the group consisting of acrylic acid and methacrylic acid.
  • the amount of acid or anhydride functionality present in the first stage emulsion polymerization determines the degree of solubility of the first stage on addition of a base.
  • a minimum amount of acid or anhydride functionality is needed to solubilize the polymer depending on the hydrophobicity of the comonomers, molecular weight of the polymer, chemical nature of the acid or anhydride monomer and sequence distribution of monomers in the polymers.
  • Acid or anhydride modified polymers can improve or degrade adhesion, depending on the paint system and substrate. When used in excess, acid or anhydride groups render the paint film water sensitive, and thereby hurt wet adhesion.
  • the preferred weight of acid or anhydride functional monomers present in the first stage polymerization is at least about 2 weight percent, preferably at least 3 weight percent, more preferably about 5 weight percent to 50 percent; even more preferably from about 8 percent to 30 weight percent, and most preferably from about 10 percent to 20 weight percent, based on the total weight of monomers charged in the first stage reaction.
  • Illustrative of comonomers useful in the first stage polymerization are monomers such as methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, styrene, substituted styrene such as alpha methyl styrene, acrylonitrile, vinyl acetate, and other C1-C12 alkyl or hydroxy alkyl acrylates and methacrylates, vinyl 2-ethylhexanoate, vinyl propionate, vinyl neodecanoate, vinyl neononanoate, vinyl versatate, vinyl pivalate and the like, and/or mixtures thereof.
  • the first-stage polymer may have a variety of molecular weights.
  • the molecular weight is controlled by the addition of a suitable chain transfer agent as is known in the art.
  • suitable chain transfer agents include, for example, alkyl mercaptans such as octyl mercaptan and decyl mercaptan, esters of mercaptoacetic acid, such as an ethyl ester of mercaptoacetic acid and 2-ethylhexyl ester of mercaptoacetic acid, and esters of mercapto- propionic acid, such as isooctyl ester of mercaptopropionic acid.
  • the chain transfer agent may be selected from the group consisting of 2-ethylhexyl mercaptopropionate and iso-octyl mercaptopropionate or mixtures thereof.
  • the number average molecular weight Mn obtained typically ranges from 500 to 100,000.
  • a wet adhesion promoter is optionally incorporated in the first stage alkali-soluble polymerization to provide wet adhesion properties to the first stage polymer and final latex product.
  • the wet adhesion promoter comprises a monomer having nitrogen functionality effective to enhance the wet adhesion properties of the latex composition.
  • Preferred wet adhesion promoters include compounds having an amino, ureido or N-heterocyclic group, such as, for example, dialkylaminoalkyl esters and dialkylaminoalkyl amides of acrylic or methacrylic acid, and particularly those having from 1 to 5 carbon atoms in the alkyl groups, free radically polymerizable compounds of urea, ethylene urea, or propylene urea, and polymerizable imidazolidinones having a - NC(O)N - group as part of a cyclic five member ring structure.
  • an amino, ureido or N-heterocyclic group such as, for example, dialkylaminoalkyl esters and dialkylaminoalkyl amides of acrylic or methacrylic acid, and particularly those having from 1 to 5 carbon atoms in the alkyl groups, free radically polymerizable compounds of urea, ethylene urea, or propylene urea
  • wet adhesion promoters that provide the desired wet adhesion properties include dimethylaminoethyl acrylate, diethylamino acrylate, dimethylaminopropyl acrylate, 3-dimethyl- amino-2,2-dimethylpropyl-l-acrylate, 2-N-morpholinoethyl acrylate, 2- N-piperi-dinoethyl acrylate, N-(3-dimethylaminopropyl acrylamide (as used herein includes methacrylamide), N-(3-dimethyl-amino-2,2- dimethyl-propyl)acrylamide, N-dimethylaminomethyl acrylamide, N- (4-morpho-linomethyl) acrylamide, N-(2-methacryloyloxyethyl) ethylene urea, methacrylamidoethyl ethylene urea, N-(2-methacryl- oxyacetamidoethyl-N,N,N'
  • Preferred wet adhesion promoters include N-(2- methacryloyloxyethyl) ethylene urea, and methacrylamidoethyl ethylene urea.
  • propylene imine may be post-reacted with the first- stage alkali-soluble polymer to provide wet adhesion properties and act as a base to neutralize the first-stage alkali- soluble polymer. It can also be reacted to the first stage polymer after the second stage polymer has been formed.
  • the amount of wet adhesion promoter present in the first stage emulsion polymerization process typically ranges from about 0.1 to 20 weight percent, more preferably from about 1 to 10 weight percent, and most preferably from about 1.9 to 5 weight percent, based on the total weight of the monomer composition of the first stage charge.
  • At least one initiator or catalyst is used at a concentration sufficient to initiate or catalyze the polymerization reaction.
  • concentration of initiator and/or catalyst will vary based on the weight of monomers charged. The particular concentration used in any instance will depend upon the specific monomers mixture undergoing reaction and the specific initiator employed; as is well known to those skilled in the art, and is frequently from about 0.01 to 3 weight percent; more preferably from about 0.05 to 2 weight percent and most preferably from about 0.1 to 1 weight percent based on the weight of monomers charged. It is also known that traces of metal ions can be added as activators to improve the rate of polymerization, if desired.
  • initiators hydrogen peroxide, peracetic acid, t-butyl hydroperoxide, ammonium persulfate, potassium persulfate, sodium persulfate, as well as any of the other known initiators.
  • redox catalyst systems such as sodium persulfate-sodium formaldehyde sulfoxylate, cumene hydroperoxide-sodium metabisulfite, hydrogen peroxide- ascorbic acid, and the other known redox systems.
  • the polymerizable feed compositions can also contain any of the other known additives conventionally used in emulsion polymerization processes in the usual known quantities, such as crosslinkers, dispersion aids, emulsifiers, photosensitizers, colorants, bactericides, fungicides, etc.
  • a neutralizing agent or base is added to the first stage alkali- soluble polymer so as to swell, partially dissolve, or substantially dissolve the polymer.
  • Suitable bases include ammonia, triethylamine, monoethanolamine, dimethylaminoethanol, ammonium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide and all other Group I A and II A hydroxides and the like.
  • propylene imine may also be effective for neutralization of the first-stage alkali-soluble polymer, while at the same time providing wet adhesion properties to the final product.
  • the first stage latex polymer, as prepared, may be stored for later neutralization.
  • the first stage polymer can be neutralized and used as a dispersant medium for other latex polymers including the second stage emulsion polymerization process of the present invention.
  • the final product has been found to exhibit improved film forming properties, wet adhesion properties and other characteristics.
  • Monomers useful for polymerization in the second-stage include any alkali-insoluble monomers, i.e., those which are substantially free of carboxylic acid or anhydride functionality, such as, for example, those which have acrylic, styrenic, vinyl or versatic functionality.
  • substantially free means less than about 10 weight percent, preferably less than about 5 weight percent and more preferably less than about 2 weight percent, based on the total weight of the polymer.
  • Illustrative of such monomers are acrylate and methacrylate esters, styrene, alkyl styrenes, vinyl toluene, vinyl acetate, vinyl alcohol, acrylonitrile, vinylidene chloride, and vinyl ketones.
  • illustrative monomers useful in this invention include, for example, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, n- amyl methacrylate, sec-amyl methacrylate, hexyl methacrylate, lauryl methacrylate, stearyl methacrylate, ethyl hexyl methacrylate, crotyl methacrylate, cinnamyl methacrylate, oleyl methacrylate, ricinoleyl methacrylate, hydroxy ethyl methacrylate, hydroxy propyl methacrylate, vinyl propionate, vinyl butyrate, vinyl tert-butyrate, vinyl caprate, vinyl stearate, vinyl laurate, vinyl oleate, vinyl methyl ether, vinyl ethyl ether, vinyl n-propyl ether, vinyl isopropyl ether, vinyl n-butyl ether, vinyl is
  • Optional ingredients which may be included in the second stage polymerization of the alkali-insoluble polymers include, for example, other monomers such as vinyl esters, acid and/or anhydride functional monomers, crosslinkers, chain transfer agents, and others as known in the art.
  • the number average molecular weight can range from 500 to 500,000 or greater to infinity if the appropriate chain transfer or crosslinking agents are employed.
  • the wet adhesion promoter is also optionally incorporated in the second stage polymerization to provide wet adhesion properties to the final latex product; provided, however, that it is incorporated into at least one of the first stage polymer or the second stage polymer.
  • the desired ratio for polymerization of the second-stage monomer feed into the first stage polymer medium covers a wide range depending on the desired properties of the final latex composition, and the acid level in each stage.
  • the amount of first stage polymer incorporated into the second stage polymerization may be small when using a more highly carboxylated material [e.g., 10 parts per hundred resin, i.e., first stage plus second stage ("p.h.r.") of the first stage resin which contains 20% methacrylic acid] or larger amount when using a less carboxylated material [e.g., 20 p.h.r. of the first stage resin which contains 10% methacrylic acid].
  • Suitable ranges include from about 1:99 to about 99:1.
  • the weight ratio of second-stage monomer feed is from about 5:95 to 95:5, and most preferably from about 10:80 to 80:10.
  • the resulting final latex compositions may be used, for example, as binders for architectural coatings, industrial and automotive coatings, sealants, adhesives, paper coating compositions, inks, varnishes and the like.
  • the alkali-insoluble polymers dispersed in the first-stage neutralized polymer may be used at levels based on the weight of solids, ranging from about 5 percent to about 90 percent of the total weight of the paint formulation. Paint formulations prepared with these unique polymers have been found to exhibit excellent wet adhesion, high gloss and improved block resistance.
  • the paint formulations may, in addition to the polymers of this invention, contain conventional additives such as pigments, fillers, dispersants, wetting agents, coalescents, rheology modifiers, drying retarders, biocides, anti-foaming agents and the like.
  • the following description is a general description of an emulsion polymerization process for preparing alkali-insoluble polymers dispersed in substantially dissolved alkali-soluble polymer.
  • the mixture of acrylic or methacrylic acids, acrylate or methacrylate esters, and/or styrenic monomers, the wet adhesion monomer, and other optional ingredients are fed to a reactor where they are emulsion polymerized in the presence of a chain transfer agent and initiator.
  • the polymerization is carried out using a surfactant or emulsifying agent and in aqueous medium.
  • the temperature can vary from about 35°C to about 90°C or higher; the preferred temperature is from about 70°C to about 85°C.
  • the pressure is not critical and is dependent on the nature of monomers being employed, normally gaseous monomers requiring superatmospheric pressures.
  • the reaction is held at reaction temperature until the residual monomer level is less than about 5000 ppm, followed by addition of the desired neutralizing agent until the first-stage polymer is swollen, partially dissolved, or substantially dissolved.
  • the second- stage monomers including optional ingredients such as wet adhesion monomers, are then fed into the first-stage polymer medium at the temperatures described above.
  • the reactor is held at temperature for about one (1) hour, cooled and the latex product collected. Optionally the latex may be further neutralized at this time.
  • a monomer mixture was prepared by charging 100 grams of styrene, 70 grams of methyl methacrylate (Aldrich), 30 grams of methacrylic acid (Aldrich), and 7 grams of 2 - ethylhexyl mercapto propionate (Hampshire Chemicals) to a one 1-liter monomer feed cylinder.
  • a second monomer mixture was prepared by charging 210 grams of styrene, 250 grams of methyl methacrylate (Aldrich), 330 grams of butyl acrylate (Union Carbide), and 50 grams of a 25 weight percent of N-(2- Methylacryloyloxyethyl) in methyl methacrylate (ROHAMERE 6844-0) (Rohm Tech) into a second one-liter monomer feed cylinder.
  • a two liter jacketed resin flask equipped with a four - bladed stainless steel mechanical stirrer, Claisen connecting tube, Friedrichs water condenser, nitrogen sparge and bubble trap, thermometer, and monomer addition inlets was used to charge 925 grams of water, 2.5 grams of GR-9M (Union Carbide).
  • An initial oxidizer solution prepared by dissolving 2.5 grams of ammonium persulfate in 20 grams of water, was prepared in a separate container.
  • a delayed oxidizer solution prepared by dissolving 5 grams of ammonium persulfate in 100 grams of water, was also prepared in a separate container. Under nitrogen purge, the reactor was heated to 80°C by circulating temperature controlled water through the reactor jacket.
  • the initial oxidizer solution was added to the reactor. Two minutes later, the monomer feed was conveyed to the reaction vessel over a 40 minute period by FMI pumps using 1/8" Teflon tubing with continuous stirring while the reaction temperature was held between 79 - 81°C. The reaction was allowed to proceed at 80°C for an additional fifteen minutes after completion of the monomer feed. To the product was added 20 grams of a 15 weight percent ammonium hydroxide solution. After a further 15 minutes the second monomer mix was fed to the reactor concurrently with the delayed oxidizer solution over 2 hours. The product is held at 80 for 1 hour. To the resulting product was added a further 20 grams of 15 weight percent ammonium hydroxide solution.
  • the product was then cooled to room temperature.
  • the resulting 48% solids content latex has a pH of 8, and a volume average particle diameter of 252 nanometers("nm") as measured with an Microtrac particle size analyzer (Leeds-Northrop).
  • Three samples were made according to the procedure described above with styrene contents of 30 wt % (Al), 10 wt % (A2) and 20 wt % (A3).
  • a pigment grind was prepared by mixing the following ingredients in sequence: 30 grams of water, 40 grams of propylene glycol, 9.0 grams of Tamol 165 dispersant (Rohm and Haas), 2.5 grams of Triton® CF-10 surfactant (Union Carbide Corp.), 1.5 grams of Strodex PK-90, (Dexter), 1.0 grams of AMP-95 (Angus), 2.0 grams Nuosept 145 preservative (Huls), 2.0 grams of Foamaster AP defoamer (Henkel), and 225 grams of TiONA RCL-535 titanium dioxide (SCM). The mixture was ground on a high speed disperser for 20 minutes to provide a fineness of grind of 6+ Hegman Scale.
  • a paint was prepared by mixing, under moderate agitation the following ingredients in order: 550 grams of latex from Example A, 313 grams of the pigment grind made above, 26 grams Texanol coalescing solvent (Eastman), 10.5 grams Polyphase P-20-T mildewcide (Troy), 13.0 grams Acrysol RM-2020 (Rohm & Haas), 10 grams Butyl Carbitol solvent (Union Carbide Corp.), and 134 grams water.
  • Example C Wet Adhesion Testing
  • the 24 hour wet adhesion value is at least 90%, more preferably 95% and most preferably 100%.

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

Abstract

L'invention concerne des compositions de latex, polymérisées à partir de monomères présentant une fonction acide ou anhydride et des propriétés d'adhérence à l'état humide. Ces compositions de latex sont préparées par une polymérisation en deux étapes d'un premier polymère et d'un second polymère respectivement, au cours de laquelle un monomère servant à augmenter l'adhérence à l'état humide de la composition est introduit dans le premier ou dans le second polymère, ou dans les deux.
PCT/US1998/021089 1997-10-03 1998-10-01 Latex resistants au frottement WO1999018157A1 (fr)

Priority Applications (7)

Application Number Priority Date Filing Date Title
EP98952117A EP1034218A1 (fr) 1997-10-03 1998-10-01 Latex resistants au frottement
AU97889/98A AU9788998A (en) 1997-10-03 1998-10-01 Scrub resistant latexes
BR9815391-9A BR9815391A (pt) 1997-10-03 1998-10-01 Látex resistente ao esfregamento
KR1020007003528A KR20010015684A (ko) 1997-10-03 1998-10-01 스크러브 저항성 라텍스
KR1020007003509A KR20010030851A (ko) 1997-10-03 1998-10-01 스크럽 내성 라텍스
JP2000514962A JP2001519451A (ja) 1997-10-03 1998-10-01 擦り耐性ラテックス
CA002305566A CA2305566A1 (fr) 1997-10-03 1998-10-01 Latex resistants au frottement

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US6104997P 1997-10-03 1997-10-03
US60/061,049 1997-10-03

Publications (1)

Publication Number Publication Date
WO1999018157A1 true WO1999018157A1 (fr) 1999-04-15

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PCT/US1998/021089 WO1999018157A1 (fr) 1997-10-03 1998-10-01 Latex resistants au frottement

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EP (1) EP1034218A1 (fr)
JP (1) JP2001519451A (fr)
KR (2) KR20010015684A (fr)
CN (1) CN1280594A (fr)
AU (1) AU9788998A (fr)
BR (1) BR9815391A (fr)
CA (1) CA2305566A1 (fr)
ID (1) ID24431A (fr)
PL (1) PL339615A1 (fr)
WO (1) WO1999018157A1 (fr)

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EP1193273A1 (fr) * 2000-09-25 2002-04-03 Rohm And Haas Company Composition aqueuse à base de polymères acryliques en émulsion
US6797328B2 (en) * 2001-02-23 2004-09-28 Rohm And Haas Company Coating composition
US6887933B2 (en) 2000-09-25 2005-05-03 Rohm And Haas Company Aqueous acrylic emulsion polymer composition
CN100445331C (zh) * 2000-10-17 2008-12-24 国家淀粉及化学投资控股公司 水性聚合物溶液
US8193278B2 (en) 2009-08-07 2012-06-05 Rohm And Haas Company Plasticizer free caulks and sealants having improved aged wet adhesion
US8440752B2 (en) 2001-02-22 2013-05-14 Valspar Sourcing, Inc. Coating compositions containing low VOC compounds
US11136468B2 (en) 2011-12-15 2021-10-05 Swimc Llc Rheological methods for high block, tack and scrub resistant coating composition
US11168230B2 (en) 2011-12-15 2021-11-09 Swimc Llc High block, tack and scrub resistant coating composition

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Publication number Priority date Publication date Assignee Title
KR100418999B1 (ko) * 2001-10-22 2004-02-14 삼화페인트공업주식회사 자외선 차단용 아크릴수지 조성물 및 이를 포함하는아크릴도료
MX370386B (es) * 2011-12-15 2019-12-11 Swimc Llc Composicion de revestimiento altamente resistente al bloqueo, refregado y adherencia.
KR20160106675A (ko) 2014-01-08 2016-09-12 애버리 데니슨 코포레이션 선택적으로 점착성이 제거된 접착제를 사용한 물품, 조성물, 시스템 및 방법
CA3015489C (fr) 2016-02-22 2019-05-21 Craig W. Potter Etiquette de contenu etendu transparente avec adhesif detackifie selectivement

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EP0587333A2 (fr) * 1992-09-03 1994-03-16 Rohm And Haas Company Polymères fabriqués en plusieurs étapes, ayant des étapes de formation de polymères solubles et non-solubles en milieu alcalin
EP0609756A2 (fr) * 1993-01-28 1994-08-10 National Starch and Chemical Investment Holding Corporation Compositions de peintures latex à base de polymères multistage sans solvant organique
US5468800A (en) * 1993-02-03 1995-11-21 Roehm Gmbh Chemische Fabrik Binder which is crosslinkable at room temperature

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US5073591A (en) * 1989-07-21 1991-12-17 S. C. Johnson & Son, Inc. Polymeric thickeners and methods of producing the same
EP0587333A2 (fr) * 1992-09-03 1994-03-16 Rohm And Haas Company Polymères fabriqués en plusieurs étapes, ayant des étapes de formation de polymères solubles et non-solubles en milieu alcalin
EP0609756A2 (fr) * 1993-01-28 1994-08-10 National Starch and Chemical Investment Holding Corporation Compositions de peintures latex à base de polymères multistage sans solvant organique
US5468800A (en) * 1993-02-03 1995-11-21 Roehm Gmbh Chemische Fabrik Binder which is crosslinkable at room temperature

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EP1193273A1 (fr) * 2000-09-25 2002-04-03 Rohm And Haas Company Composition aqueuse à base de polymères acryliques en émulsion
US6887933B2 (en) 2000-09-25 2005-05-03 Rohm And Haas Company Aqueous acrylic emulsion polymer composition
US7241834B2 (en) 2000-09-25 2007-07-10 Rohm And Haas Company Aqueous acrylic emulsion polymer composition
CN100445331C (zh) * 2000-10-17 2008-12-24 国家淀粉及化学投资控股公司 水性聚合物溶液
US8440752B2 (en) 2001-02-22 2013-05-14 Valspar Sourcing, Inc. Coating compositions containing low VOC compounds
US6797328B2 (en) * 2001-02-23 2004-09-28 Rohm And Haas Company Coating composition
US8193278B2 (en) 2009-08-07 2012-06-05 Rohm And Haas Company Plasticizer free caulks and sealants having improved aged wet adhesion
US11136468B2 (en) 2011-12-15 2021-10-05 Swimc Llc Rheological methods for high block, tack and scrub resistant coating composition
US11168230B2 (en) 2011-12-15 2021-11-09 Swimc Llc High block, tack and scrub resistant coating composition
US11649368B2 (en) 2011-12-15 2023-05-16 Swimc Llc Rheological methods for high block, tack and scrub resistant coating composition

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AU9788998A (en) 1999-04-27
KR20010030851A (ko) 2001-04-16
BR9815391A (pt) 2001-08-21
JP2001519451A (ja) 2001-10-23
PL339615A1 (en) 2001-01-02
ID24431A (id) 2000-07-20
KR20010015684A (ko) 2001-02-26
EP1034218A1 (fr) 2000-09-13
CN1280594A (zh) 2001-01-17
CA2305566A1 (fr) 1999-04-15

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