• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    cleaning solvent and paint thinner, solvent based composition, and method for cleaning or diluting a solvent based polymeric composition - this invention relates to a cleaning solvent and a paint thinner for coatings and resins based on solvents selected from compositions of formula (i). wherein r1 is a C1-6 alkyl, phenyl or benzyl group, R2 is carbon atoms, and n = 1-4; and mixtures thereof. The invention also relates to a solvent-based composition including a solvent-based polymer and the zero or low VOC composition of the present invention; and a method for cleaning or diluting a solvent based composition.
    公开号:BR102012007682B1
    申请号:R102012007682-9
    申请日:2012-04-03
    公开日:2019-08-06
    发明作者:Linda A. Adamson；Michael C. Becker；Felipe A. Donate；David M. Fasano；Sarah E. ITTNER；Thomas R. Tepe；Rebeca J. Wachowicz
    申请人:Rohm And Haas Company；Dow Global Technologies, Llc；
    IPC主号:
    专利说明:

    “GLYCOL ETHER-ESTER, WATER COATING COMPOSITION, AND, METHOD FOR FORMING A COATING” [0001] This invention relates to glycol ether-ester compositions with zero or low VOC content suitable for use as coalescing agents for aqueous polymeric dispersions. This invention particularly relates to the glycol ether-esters coalescing agents of Formula (I)
    [0002] in which Ri is a C1-C10 alkyl, phenyl or benzyl group, R2 is either hydrogen or methyl, R3 is a carbon chain including 4-6 carbon atoms, and n = 2-4; of Formula (II)
    [0003] in which R1 and R4 are independently C1-C10 alkyl, phenyl or benzyl groups, R2 is either hydrogen or methyl, R3 is a carbon chain including 1-2 carbon atoms, and n = 1-4; and their mixtures. The invention also relates to certain glycol ether esters, certain glycol ether coalescing agents having a boiling point greater than 450 ° C at 101.325 kPa, to compositions including an aqueous polymeric dispersion and to zero or VOC of the invention, and a method for forming a coating.
    [0004] Coalescing agents are typically added in compositions such as, for example, aqueous polymeric dispersions and water-based coatings or paints including aqueous polymer dispersions to facilitate the formation of a continuous polymeric binder or film as the water evaporates from composition. Without the addition of coalescing agents, polymeric dispersions may not act as effective binders for pigments in the paint and adhesion to a substrate may be impaired. For many years, these
    Petition 870190017178, of 02/20/2019, p. 12/80
    2/37 coalescence have been relatively volatile solvents such as 2,2,4-trimethyl-1,3 pentanediol monoisobutyrate.
    [0005] Volatile organic compound emissions (VOC) contribute to the formation of ozone, a major constituent of dry fog. In the U.S., VOC regulations established by the US Environmental Protection Agency (EPA) and required at the state level dictate the maximum concentration of volatile solvents in paints, cleaning solvents, and other products. In Europe, VOC limits are defined by “2004/42 / EC Solvents Directive for Decorative Paints”. VOC regulations have become increasingly stringent and have affected the use of volatile coalescing agents.
    [0006] The present invention serves to obtain certain glycol ether esters and certain compositions with zero or low VOC content including glycol ether esters which are particularly suitable for use in compositions which include aqueous polymeric dispersions such as, for example, decorative and protective coatings for various substrates.
    [0007] U.S. Patent Number 4,489,188 discloses coating compositions including aqueous latex polymers and an amount of 5 to 50 parts by weight of certain ether-ester solvents per 100 parts of polymer. Glycol ether-esters coalescing agents of the present invention are not disclosed.
    [0008] US Patent Application Publication Number 20090198002A1 discloses coalescing compositions for aqueous coating compositions including mixtures of dibasic esters such as glycol bis-ether esters of C4-C6 diacids specifically, succinic, glutaric, and adipic acids, with maximum boiling points up to 450 ° C. Glycol ether-esters coalescing agents of the present invention are not disclosed.
    [0009] There remains a need for low or zero VOC coalescing agents for aqueous polymeric dispersions.
    [0010] In a first of the present invention a glycol ether-esters selected from the group consisting of: triethylene glycol n-pentyl-benzoate is obtained; triethylene glycol n-hexyl ether benzoate; tripropylene glycol n-butyl-benzoate ether;
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    3/37 tripropylene glycol n-pentyl ether benzoate; dipropylene glycol n-butyl-ether benzoate; dipropylene glycol 2-ethylhexyl-ether benzoate; dipropylene glycol phenyl ether benzoate; ethylene glycol n-hexyl-levulinate ether; diethylene glycol n-hexyl-levulinate ether; diethylene glycol phenyl ether levulinate; triethylene glycol n-butyl-levulinate ether; dipropylene glycol phenyl ether levulinate; tripropylene glycol methyl-levulinate ether; tripropylene glycol n-propylether levulinate; and tripropylene glycol n-butyl-levulinate ether.
    [0011] In a second aspect of the present invention, a glycol ether-ester coalescing agent selected from the group of compositions of Formula (I) is obtained
    [0012] in which Ri is a C1-C10 alkyl, phenyl or benzyl group, R2 is either hydrogen or methyl, R3 is a carbon chain comprising 4-6 carbon atoms, and n = 2-4; of Formula (II)
    [0013] in which R1 and R4 are independently C1-C10 alkyl, phenyl or benzyl groups, R2 is either hydrogen or methyl, R3 is a carbon chain comprising 0-2 carbon atoms, and n = 1-4; and their mixtures.
    [0014] In a third aspect of the present invention, a glycol ether-ester coalescing agent selected from the group of Formula (II) compositions is obtained
    [0015] in which R1 and R4 are independently C1-C10 alkyl, phenyl or benzyl groups, R2 is either hydrogen or methyl, R3 is a carbon chain
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    4/37 comprising 3-4 carbon atoms, and n = 1-4; and their mixtures; the boiling point of said coalescing agent being greater than 450 ° C at 101.325 kPa. [0016] In a fourth aspect of the present invention an aqueous coating composition comprising an aqueous polymeric dispersion and from 0.1% to 40% by weight, based on the solids weight of the aqueous polymeric dispersion, of said ether coalescing agent is obtained glycol ester of the second or third aspects of the present invention.
    [0017] In a fifth aspect of the present invention there is provided a method for forming a coating comprising (a) forming said aqueous coating composition of the fourth aspect of the present invention; (b) applying said aqueous coating composition to a substrate; and (c) drying, or allowing drying, said aqueous coating composition.
    [0018] The present invention relates to a glycol ether-esters selected from the group consisting of: triethylene glycol n-pentyl-benzoate ether; triethylene glycol n-hexyl ether benzoate; tripropylene glycol n-butyl-benzoate ether; tripropylene glycol n-pentyl ether benzoate; dipropylene glycol n-butyl-ether benzoate; dipropylene glycol 2-ethylhexyl-ether benzoate; dipropylene glycol phenyl ether benzoate; ethylene glycol n-hexyl-levulinate ether; diethylene glycol n-hexyl-levulinate ether; diethylene glycol phenyl ether levulinate; triethylene glycol n-butyl-levulinate ether; dipropylene glycol phenyl ether levulinate; tripropylene glycol methyl-levulinate ether; tripropylene glycol n-propyl-levulinate ether; and tripropylene glycol nbutyl-levulinate ether. Furthermore, the invention relates to a glycol ether coalescing agent including a composition of glycol ether esters selected from the group of compositions of Formula (I)
    [0019] in which Ri is a C1-C10 alkyl, phenyl or benzyl group, R2 is either hydrogen or methyl, R3 is a carbon chain including 4-6 carbon atoms, and n = 2-4; of Formula (II)
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    [0020] in which Ri and R4 are independently C1-C10 alkyl, phenyl or benzyl groups, R2 is either hydrogen or methyl, R3 is a carbon chain including 0-2 carbon atoms, and n = 1-4; and their mixtures.
    [0021] Furthermore, the invention relates to a glycol ether-ester coalescing agent selected from the group of Formula (II) compositions
    [0022] in which R1 and R4 are independently C1-C10 alkyl, phenyl or benzyl groups, R2 is either hydrogen or methyl, R3 is a carbon chain including 3-4 carbon atoms, and n = 1-4; and their mixtures; the boiling point of said coalescing agent being greater than 450 ° C at 101.325 kPa.
    [0023] In each case here R3 is a chain of carbons including a certain number of carbon atoms; the chain may be / be, for example, saturated, unsaturated, substituted, part of a ring structure, or combinations thereof. The individual carbon atoms in the chain can have substituent groups such as, for example, -OH, -Cl, = 0, -NH2, and the like.
    [0024] Examples of glycol ether esters described by Formula I are diethylene glycol phenyl ether benzoate, dipropylene glycol phenyl ether levulinate, and tripropylene glycol nbutyl ether isopentanoate. Examples of bis-ether-glycol esters described by Formula II are bis-diethylene glycol n-butyl-ether malonate, bis-diethylene glycol n-butyl-ether glutarate, and bis-dipropylene glycol methyl-ether maleate.
    [0025] "Coalescent composition" means a composition that facilitates the film formation of an aqueous polymeric dispersion, particularly an aqueous coating composition that includes a polymer dispersion in an aqueous medium such as, for example, a polymer prepared by techniques in
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    6/37 emulsion polymerization. An indication of film facilitation is that the minimum film formation temperature ("MFFT") of the composition including the aqueous polymeric dispersion is measurably lowered by the addition of the coalescing agent.
    The glycol ether esters of the present invention are esters of monocarboxylic acids or dicarboxylic acids and glycol ethers, the latter obtained by the reaction of alcohols or phenol with either ethylene oxide or propylene oxide. Any of several synthetic methods known to those skilled in the art can be used to prepare the aforementioned esters. For example, stoichiometric amounts of the glycol-ether and the desired carboxylic acid can be heated in the presence of a catalytic amount of a strong acid such as, for example, concentrated sulfuric acid and p-toluenesulfonic acid and a solvent such as example, heptane, and water removed azeotropically to give the desired product. Another method of preparation uses acid monochloride (or dichloride) in place of dicarboxylic acid as a reagent. In this case, hydrogen chloride gas is released instead of water during the reaction and the acid chloride with glycol-ether. Hydrogen chloride can be captured using a water purifier. Yet another method of preparation involves the transesterification of a simple alkyl ester of the desired acid with a glycol ether in the presence of a titanium catalyst such as tetraisopropyl titanate. Yet another method of esterification uses acid anhydride as a reagent in combination with the azeotropic removal of water. This method is aimed at producing diesters. Ether-ester of glycols obtained by any of the aforementioned methods can be purified by flash distillation under high vacuum.
    [0027] The structural requirements of the glycol ether esters of the cleaning solvent and the paint thinner for solvent-based coatings and resins of the invention have been presented in Formulas I and II. Glycol ether esters are typically liquid in the 0-25 ° C temperature range to facilitate their use as diluents and cleaning solvents. These products are deliberately
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    7/37 less than 10% volatile by Method 24, preferably less than 5% volatile, and much more preferably less than 1% volatile to be useful as low VOC coalescing auxiliaries in the USA To be classified as free from VOC in Europe, solvents need to boil above 250 ° C and preferably above 280 ° C.
    [0028] Glycol-ether-monoesters described by Formula 1 were prepared from benzoic acid (or benzoyl chloride), ethyl levulinate, isopentanoic acid and valeric acid. Bis-ether-glycol esters described by Formula 2 were prepared from malonic acid, succinic acid, and maleic anhydride. Glycol ethers used in these preparations were ethylene glycol n-hexyl ether, triethylene glycol nhexyl ether, dipropylene glycol 2-ethyl hexhexyl ether, diethylene glycol n-hexyl ether, diethylene glycol ether, diethylene glycol n -butyl ether, dipropylene glycol phenyl ether, tripropylene glycol n-pentyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, dipropylene glycol n-butyl ether, dipropylene glycol n-propyl ether , tripropylene glycol npropyl ether, propylene glycol n-butyl ether, tripropylene glycol n-butyl ether, triethylene glycol n-butyl ether, propylene glycol methyl ether, triethylene glycol n-pentyl ether , and ethylene glycol n-pentyl ether. Ethylene glycol phenyl ether and propylene glycol phenyl ether were used to prepare benzoates and succinates but the resulting glycol ether esters were solid melting within the range of 50-100 ° C which limits their usefulness as coalescing agents.
    [0029] The aqueous coating composition of the present invention includes an aqueous polymeric dispersion and from 0.1% to 40% by weight, based on the solids weight of the aqueous polymeric dispersion, of the coalescing agent of the present invention. In one embodiment when the MFFT of the aqueous polymeric dispersion is from -5 ° C to 100 ° C, 0.1% to 30% coalescing agent can be used, by weight based on the solids weight of the polymeric aqueous dispersion. Alternatively, when the MFFT of the aqueous polymeric dispersion is from -20 ° C to 30 ° C, 0.1% to 5% coalescing agent can be used, by weight based on the solids weight of the polymeric aqueous dispersion. MFFTs of the aqueous polymeric dispersions here are those measured using ASTM D 2354 and a 127 micrometer bar on the MFFT. MFFT values
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    8/37 are indicative of how efficient a coalescing agent is for a given polymeric aqueous dispersion; it is desirable to achieve the lowest possible MFFT with the lowest amount of coalescing agent. The aqueous polymeric dispersion can be a dispersion of a polymer, oligomer, or prepolymer in an aqueous medium. In some embodiments, the aqueous polymeric dispersion may be reactive before, during, or subsequent to film formation. "Aqueous medium" here means a medium including at least 50%, by weight based on the weight of the medium, water. Typical aqueous polymeric dispersions are aqueous dispersions of epoxides, urethanes, acrylic polyols, polyesters, and hybrids of these and other chemical compounds; and emulsion polymers.
    [0030] In some embodiments, aqueous polymeric dispersions are part of reactive systems. For example, in a 2k system such as an epoxide dispersion system the coalescing agent can be added either to the component including the epoxide dispersion or, alternatively, to the curing agent component or divided between both components of the system.
    The emulsion polymer, an aqueous polymer dispersion formed by emulsion polymerization techniques, includes at least one ethylenically unsaturated monomer copolymerized by addition such as, for example, styrene or substituted styrenes; vinyl toluene; butadiene; (met) acrylonitrile; a (meth) acrylic ester monomer such as, for example, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, hydroxy-ethyl (meth) acrylate, hydroxy-propyl (meth) acrylate, and (met ) ureido-functional acrylates; vinyl acetate or other vinyl esters; vinyl monomers such as vinyl chloride, vinylidene chloride, and n-vinyl pyrrolidone. The use of the term "(met)" followed by another term such as (met) acrylate, as used throughout the disclosure, refers to both acrylates and methacrylates.
    [0032] In certain embodiments the emulsion polymer includes 0% to 6%, or alternatively, 0% to 3% by weight or 0% to 1%, by weight based on the weight of the polymer, of a multiethylenically unsaturated monomer copolymerized. It is important to select the level of multiethylenically unsaturated monomer so as not to interfere materially with the integrity and formation of the film.
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    Multiethylenically unsaturated monomers include, for example, allyl (meth) acrylate, diallyl phthalate, 1,4-butylene glycol di (meth) acrylate, 1,2-ethylene glycol di (meth) acrylate, 1,6hexanediol di (meth) acrylate, and divinyl-benzene.
    [0033] The emulsion polymer includes from 0% to 15%, preferably from 0.5% to 5%, of a copolymerized monoethylenically unsaturated acid monomer, based on the weight of the polymer. Acid monomers include carboxylic acid monomers such as, for example, (meth) acrylic acid, crotonic acid, itaconic acid, fumaric acid, maleic acid, monomethyl itaconate, monomethyl fumarate, monobutyl fumarate, maleic anhydride, 2-acrylamide-2- methyl-propane-sulfonic acid, vinyl-sulfonic acid, styrene-sulfonic acid, 1-allyl-oxy-2-hydroxy-propanesulfonic acid, alkyl-allyl-sulfo-succinic acid, sulfo-ethyl (meth) acrylate, phospho-alkyl ( met) acrylates such as phospho-ethyl (met) acrylate, phospho-propyl (met) acrylate, and phospho-butyl (met) acrylate, phospho-alkyl crotonates, phospho-alkyl maleates, phospho-alkyl fumarates, phospho-dialkyl (met ) acrylates, phospho-dialkyl crotonates, and allyl phosphate.
    [0034] The polymer in aqueous emulsion is typically formed by an emulsion polymerization process by addition polymerization as known in the art. Conventional mixtures and surfactants can be used including, for example, anionic and / or nonionic emulsifiers such as, for example, alkali metal or ammonium alkyl sulfates, alkyl sulfonic acids, fatty acids, and oxyethylated alkyl phenols, and their mixtures. Polymerizable surfactants that include at least one ethylenically unsaturated carbon-carbon bond that can undergo polymerization by addition of free radical can be used. The amount of surfactant used is usually 0.1% to 6% by weight, based on the total weight of the monomer. Initiation processes either thermal or redox can be used. Conventional free radical initiators can be used such as, for example, hydrogen peroxide, t-butyl hydroperoxide, t-amyl hydroperoxide, ammonium and / or alkali metal persulfates, typically at a level of 0.01% to 3.0 % by weight, based on the total monomer weight. Redox systems using the same initiators together with a suitable reducer such as, for example, sodium formaldehyde sulfoxylate, sodium hydrogen sulfide, isoascorbic acid,
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    10/37 hydroxylamine sulfate and sodium bisulfite can be used at similar levels, optionally in combination with metal ions such as, for example iron and copper, optionally additionally including complexing agents for the metal. Chain transfer agents such as mercaptans can be used to lower the molecular weight of the polymer. The monomer mixture can be added pure or as an emulsion in water. The mixture of monomers can be added in a single addition or more additions or continuously during the reaction period using a uniform or varied composition. Additional ingredients such as, for example, free radical initiators, oxidants, reducing agents, chain transfer agents, neutralizers, surfactants, and dispersants can be added prior to, during, or subsequent to the addition of monomers. Processes giving distribution of polymodal particle sizes such as those disclosed in U.S. Patent Nos. 4,384,056 and 4,539,361, for example, can be used. The emulsion polymer can be formed in a multistage emulsion polymerization process as is well known in the art. It is also contemplated that the emulsion polymer is formed in two or more stages differing in molecular weight. Mixing of two different emulsion polymers is also contemplated.
    [0035] The average particle diameter of the emulsion polymer particles is typically 40 nm to 1,000 nm, preferably 40 nm to 300 nm. Particle diameters here are those measured by dynamic light scattering on a Brookhaven BI-90 Plus particle size analyzer.
    [0036] The aqueous coating composition of the invention is prepared by techniques that are well known in the coating art. First, pigment (s), if any, are well dispersed in an aqueous medium under high shear as supplied by a COWLES ™ mixer or pre-dispersed dye (s), or mixtures thereof are used. Then the emulsion polymer is added under low shear stirring along with the coalescing composition and other coating adjuvants as desired. The aqueous coating composition may include, in addition to the aqueous polymeric dispersion and the
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    11/37 optional pigment (s), adjuvants of conventional coatings such as, for example, extenders, emulsifiers, coalescing agents other than the coalescing composition of the present invention, plasticizers, antifreeze agents, curing agents, buffers, neutralizers, thickeners , rheology modifiers, humectants, wetting agents, UV absorbers, fluorescent brighteners, stabilizers against light or heat, biocides, chelating agents, dispersants, colorants, waxes, and water repellents.
    [0037] Examples of suitable pigments and extenders include titanium dioxide such as anatase and rutile titanium dioxides; zinc oxide; iron oxide; magnesium silicate; calcium carbonate; organic and inorganic colored pigments; aluminosilicates; silica; various clays such as kaolin and delaminated clay; and lead oxide. It is also contemplated that the aqueous coating composition may also contain opaque polymer particles, such as, for example, Ropaque ™ Opaque Polymers (Dow Chemical Co.). Also included are encapsulated or partially encapsulated opacifying pigment particles; and polymer polymers or emulsions by adsorbing or bonding on the surface of pigments such as titanium dioxide; and hollow pigments, including pigments having one or more voids.
    [0038] Titanium dioxide is the main pigment used to achieve hiding power in architectural paints. This pigment is expensive and of limited supply. One way to achieve hiding power while decreasing the amount of T1O2 is to include polymers in multistage emulsion that provide opacity to the paint film, commonly known as "opaque polymers". These polymers are emulsion polymer particles (mostly styrene) filled with water with a high T g . These particles fill with air during film formation and spread light producing opacity. Typically an aqueous coating composition including an opaque polymer will also include an aqueous polymeric dispersion; desirably a coalescing agent will facilitate the formation of a film of the aqueous polymeric dispersion, but will not cause the collapse of the opaque polymer. However, some coalescing agents
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    12/37 attack the opaque polymer causing the particles to collapse which results in less light scattering and decreased opacity. TEXANOL ™, for example, attacks opaque polymers when used at 15% by weight based on resin solids while OPTIFILM ™ 400 plasticizer with low VOC content attacks the polymer at much lower levels (about 6% by weight based on resin solids). Certain glycol ether-ester esters coalescing agents of the invention were useful because of their ability to retain the opacity provided by certain commercial opaque ROPAQUE ™ polymers. Dipropylene glycol phenyl ether benzoate (DiPPh Benzoate), bis-dipropylene glycol n-butyl adipate (DPnB Adipate), bis-dipropylene glycol n-propyl ether adipate (DPnP Adipate), bis-dipropylene glycol n are preferred -butyl-ether maleate (DPnB Maleate), and tripropylene glycol pentyl-ether benzoate (TPP Benzoate).
    [0039] The amounts of pigment and extender in the aqueous coating composition range from a pigment volume concentration (pigment volume concentration, PVC) from 0 to 85 and thus encompass coatings other than those described in the art, for example, as transparent coatings , paints, uniform coatings, satin coatings, semi-gloss coatings, glossy coatings, background coatings, textured coatings, and the like. The aqueous coating composition here expressly includes architectural, maintenance, and industrial coatings, caulks, sealants, and adhesive. The volume concentration of pigment is calculated using the following formula:
    PVCt ’') - deextenaai; (ea) * 100 total dry volume · of the ink.
    [0040] The solids content of the aqueous coating composition can be from 10% to 70% by volume. The viscosity of the aqueous coating composition can be 50 millipascals.second to 50,000 millipascals.sec, as measured using a Brookfield viscometer; Viscosities suitable for different application methods vary considerably.
    [0041] In the method of forming a coating of the invention the aqueous coating composition is typically applied to a substrate such as, for example, wood, metal, plastics, marine and civil engineering substrates, substrates of
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    13/37 cement such as, for example, concrete, stucco, and mortar, surfaces previously painted or coated with background paint, and surfaces aged by the weather. The aqueous coating composition can be applied to a substrate using conventional coating application methods such as, for example, by brush, roller, caulk applicator, roller coating, curtain coating and spraying such as, for example, atomized spraying by air, air-assisted spraying, airless spraying, low pressure and high volume spraying, and air-assisted airless spraying.
    [0042] Drying of the aqueous coating composition to obtain a coating may be allowed to occur under environmental conditions such as, for example, from 5 ° C to 35 ° C, or the coating may be dried at elevated temperatures such as, for example, for example, from 35 ° C to 150 ° C.
    [0043] The invention in some of its modalities will now be described below with reference to the following examples:
    Test methods:
    Methods used in Example 5 [0044] All tests below have the same preparation steps as defined:
    [0045] 254 micrometer wet film applied to Bonderite 1000 treated steel panels (except for Initial Water Resistance, which was made on untreated aluminum).
    [0046] Drying / curing time was for 7 days for chemical resistance, impact resistance and flexibility to bend in mandrel.
    [0047] Drying / curing times for Konig and Pencil hardnesses are provided in a data table (test has been done on numerous curing times).
    [0048] Early Water Resistance (EWR) was performed on separate panels that were dried for 4 or 6 hours, as noted in the data table.
    Test methods that are from ASTM:
    [0049] Dry to Touch and Handling = ASTM D1640
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    14/37 [0050] Chemical Resistance = Spot test according to ASTM D1308. Chemical agents are as listed in the table and have been allowed to remain in contact for either 24 hours or 48 hours as noted in the data table.
    [0051] Konig hardness = ANS / ISO1522 (formerly ASTM D4366) [0052] Pencil hardness = ASTM D3363 [0053] Impact resistance = ASTM D2794 [0054] Mandrel flexibility = ASTM D522 [0055] EWR test method - After application with an extension bar, the panel was allowed to dry for the established time (4 or 6 hours) at 25 ° C / 50% RH. Panels were then left in a fog box for at least 18 hours, then they were removed, dried and immediately evaluated for the degree of blistering formation, as per ASTMD714.
    Methods used in Example 6:
    [0056] Low temperature film formation (LTFF) at 4.4 ° C / 40% RH: This is a procedure for determining the ability of an ink film to form a continuous film at low temperatures . Aqueous coating compositions were applied, in a room conditioned at 4.4 ° C / 40% RH, with a block extension bar (straight) for the thickness of 254 micrometers, on a Leneta B&W wallet with varnish and area without varnish. Inks were dried for 24 hours and then evaluated for cracking.
    [0057] Brightness for 1 day: Paints were applied in CTR (constant temperature room conditions) with a Bird extender bar for a thickness of 76.2 micrometers. After 12 hours, the brightness was measured at 20 and 60 degrees.
    [0058] Flow of paint: Test inks were painted at natural spreading speed over a Spreading Rate portfolio and allowed to dry. Flow was rated on a scale of 1-10, with 10 being the best.
    [0059] Contrast Ratio (Contrast Ratio, C) - Contrast ratio is the proportion of the reflectance of a dry paint film on a black substrate of
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    15/37 reflectance 2% or less for the reflectance of the same paint, equivalently applied and dry, on an 80% reflectance substrate (ASTM D-2805.88). C is a function of film thickness and toner concentration.
    [0060] Color Acceptance: This is a measurement of how well a colorant is accepted by the ink base. Good color acceptance is required for the purpose of combining color inserts and giving a uniform color appearance. Color acceptance of paints is required under various conditions of shear and paint aging during application. We add 30 grams / liter of pre-dispersed phthalate blue colorant to the base tinting paint and then follow this procedure:
    1. A film was applied with a Bird applicator bar for a thickness of 76.2 micrometers on a 1B Penopac holder supported on a vacuum plate.
    2. Two small sections approximately 2.54-5.98 cm in diameter (one in the varnish area and one in the varnish area) were rubbed in a circular motion with clean, dry fingertips.
    o The area rubbed over the lower third, without varnish, was rubbed until almost dry or 100 cycles, so that a high degree of shear was achieved.
    o The area rubbed over the middle third, containing varnish, was rubbed for approximately 100 cycles and represents a low shear state.
    3. The three portfolios were dried on the CTR 24 hours before the evaluation.
    4. Evaluation scale: no change in various degrees of possible color (dark) or flocculation of T1O2 (light).
    [0061] Yellowing: After thermal aging of the aqueous coating composition for 10 days at 140 ° F (60 ° C), the composition was balanced for 24 hours then applied by an extension bar over a white wallet side by side with its non-aging thermal maintained. After drying overnight, any changes in color with the thermally aged ink system were
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    16/37 registered.
    [0062] Abrasive Rubbing Resistance: This test measures the rubbing resistance of a paint film for the numerous cycles required to erode the paint film on the substrate. Penetration indicates an area of removed film that is the width of the area applied by the extension bar of the original dry film. Aqueous coating compositions were applied by spreading bar over a white vinyl cover, allowed to dry for 5-7 days, and then were rubbed using a Gardner Abrasive Friction machine. To speed up the failure, a plate with a brass wedge (wedge, 254 micrometers x 1.27 cm x 16.51 cm) was used.
    [0063] Stain Removal: This method describes the procedure for assessing the ease of removing common household stains from a paint film with a non-abrasive detergent. Aqueous coating compositions were applied by spreading bar over a black vinyl cover and allowed to dry for 5-7 days. Ordinary household stains were applied to the film and allowed to dry for 60 minutes before being placed on a Gardner Friction Tester and "washed" with coarse cotton gauze that had been saturated with 1% Tide solution for 200 rubbing cycles. Stains include:
    [0064] Hydrophobic: lipstick, pencil # 2, ballpoint pen, colored pencil, red highlighter marker, red china marker.
    [0065] Hydrophilic: tea, mustard, grape juice, coffee, ketchup or spaghetti sauce, red wine, black Flair.
    [0066] Hot Block for 1 day: This test measures the tendency of the painted surfaces to adhere to each other (block formation) when stacked or placed in mutual contact under pressure. Tack is the noise produced during the separation of the block's surfaces; Seal (permanent adhesion) is the physical damage to a paint film caused by the separation. The procedure is as follows:
    1. The aqueous coating composition to be tested was applied to a pouch using a Bird extender applicator for a thickness of 76.2 micrometers. The panels were conditioned in the CTR (25 ° C; 50% RH) for 7 days.
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    17/37
    2. Weights and lids were balanced in the oven overnight before the test. Cut four 3.81 cm x 3.81 cm sections (to perform the test twice) from the white area of each conditioned panel.
    3. The cut sections were positioned with the paint surfaces face to face.
    4. The specimen face to face was left in an oven at 50 ° C (120 ° F) on a flat metal plate. Each individual specimen was covered with a solid, heated number 8 rubber cap, with a narrow side down and a heated weight of 1,000 g positioned over each cap. The calculated force for this configuration is 127 g / cm 2 (12.4 kPa).
    5. After exactly 30 minutes (± 1 min.), The covers and weights were removed and the test sections were removed from the oven. The test specimens were allowed to cool for 30 minutes at room temperature.
    6. After cooling, the sections were separated with slow and uniform force. The parts were separated at an angle of approximately 180 ° while listening to the tack. The samples were evaluated for resistance to block formation on a scale of 0 to 10.
    [0067] Impression Resistance: This test measures the ability of a coating to resist impression by another surface positioned on it. The procedure is as follows:
    1. The aqueous coating composition to be tested was applied on an aluminum panel using a block extension bar (straight) with an opening of 127 micrometers. The coated aluminum panels were conditioned at CTR (25 ° C, 50% RH) for 1, 3, and 7 days.
    2. After the panels have been conditioned 1, 3 or 7 days, aluminum panels of approximately 3.81 cm x
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    3.81 cm, and 3.81 cm pieces of coarse cotton gauze, two pieces for each test panel. (Note: coarse cotton gauze was used as supplied with all 4 layers intact)
    3. Weights and covers were left in an oven at 60 ° C to balance (previous day).
    4. A piece of coarse cotton gauze (one at the top, one at the bottom) was placed on top of each test specimen and capped with a cap number 8 and a weight of 500 grams, using a cap and weight for each area a be tested in the oven for 60 minutes.
    5. After 60 minutes, the covers and weights were removed and the test specimens were removed from the oven. The specimens were allowed to cool (about 1 hour) before removing the coarse cotton gauze and evaluating for printing.
    6. Coarse cotton gauze was removed and the paint film under the coarse cotton gauze was carefully examined. The depth and print quantity of the coarse cotton gauze pattern that was left imprinted on the paint film surface were assessed on a scale of 0 to 10.
    [0068] Konig's Hardness: The Pendulum Hardness Tester by Byk Mallinckrodt Konig measures how hard a film is by using a pendulum. The longer the film surface lasts, the longer the pendulum will oscillate and thus the higher the recorded count. The softer the film, the more friction the pendulum will experience and therefore will swing freely less often. This will result in a lower recorded count.
    [0069] Lab DPUR (Dirt Pick Up Resistance): This test measures the ability of a paint film to resist the deposit of foreign matter consisting of dirt, soot, or stain present on the surface of coated panels exposed to the external environment. This test method provides visual comparison as well as Y reflectance readings before and after
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    19/37 exposure, and the difference is considered to be the accumulation of dirt. The procedure is as follows:
    1. The aqueous test coating compositions were applied with a Bird extender bar to the thickness of 127 micrometers on an aluminum panel and allowed to dry overnight.
    2. The test panels were exposed to the environment for 5-7 days (preferred S-45 direction). The panels were brought in and allowed to air dry.
    3. Mapico 422 iron oxide slurry was applied by brush in% of the test paint. The slurry was allowed to dry completely (minimum 4 hours).
    4. The slurry was removed by washing under water using a clean piece of coarse cotton gauze and consistent, gentle pressure.
    5. The panels were allowed to dry. Reflectance readings were taken from both treated and untreated areas. The higher the number, the better the DPUR.
    EXAMPLE 1 - Preparation of glycol ether esters using maleic anhydride [0070] Reactions were conducted in a 250 mL flask from a mouth equipped with a magnetic stirrer, a heating blanket, a built-in thermocouple hole, a connected heating blanket in a temperature controller equipped with control and high-limit thermocouples, and a Dean-Stark collector connected to a condenser with a nitrogen adapter with outlet for a bubbler. Glycol-ether, maleic anhydride, heptane solvent, and sulfuric acid catalyst were added to the flask. The apparatus was left under an atmosphere of nitrogen and the contents were heated to 60 ° C to melt the maleic anhydride and react it with the glycol-ether. After the initial ring opening reaction and subsequent exotherm, the reaction mixture was heated to about 118 ° C to establish a constant reflux of heptane through the collector where the esterification water was collected. The reaction was allowed to continue until the theoretical volume of water was collected. A typical synthesis of Example 1 is as follows:
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    20/37 [0071] 106.72 g (0.56 mol) of dipropylene glycol n-butyl ether, 25.11 g (0.26 mol) of maleic anhydride, 60 ml of heptane and 4 drops of concentrated sulfuric acid. The reactor was left under a nitrogen atmosphere. The contents were heated to about 60 ° C to melt maleic anhydride and react with glycol-ether. After observing the exotherm, the reaction mixture was heated to about 118 ° C to establish a constant reflux of heptane. The reaction was allowed to continue for a total of 15 hours, at which point the amount of theoretical water was collected. The reaction mixture was cooled to 25 ° C and analyzed pure on a gas chromatograph on a Fenomenex ZB-5 capillary column of 30 mm x 0.25 mm internal diameter x 0.25 micrometer film thickness. The area percentage of the GC chromatogram showed about 16% residual glycol-ether and about 83% of a product tentatively identified as bis-dipropylene glycol n-butyl ether maleate (solvent was excluded from the total area of the chromatogram). The reaction mixture was then filtered through a small bed of basic alumina to neutralize the catalyst. The filtrate was added in a boiling fraction and the heptane was removed on a Buchi rotary evaporator. The residue was subjected to flash distillation under vacuum to isolate the product in 92% purity boiling at 195 ° C @ 13 Pa. It was confirmed that the product is bis-dipropylene glycol n-butyl-ether maleate by its infrared spectra and Nuclear Magnetic Resonance. The boiling point at reduced pressure was corrected to normal boiling using a computer program that adjusts the vapor pressure data to an Antoine equation in the form logP = A-B / (T + C). The calculated normal boiling point was 476 ° C. A sample of the product was then tested as specified by the EPA Method 24 and was found to contain only 0.1 percent volatiles.
    [0072] Another product sample was subsequently evaluated in the standard MFFT test as a coalescing agent for an acrylic emulsion polymer (RHOPLEX ™ SG-30) at a concentration of 5% by weight based on the resin solids. The MFFT value obtained was 5 ° C, a value 24% less than the MFFT obtained for pure latex and 6% less than the MFFT obtained with TEXANOL ™. (See Table 1.2)
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    EXAMPLE 2. Preparation of glycol ether esters using acid chlorides [0073] Reactions were conducted in a 250 mL three-necked round-bottom flask equipped with an addition funnel with a pressure equalizing side arm, a cooling condenser, a thermocouple bore, a Teflon magnetic stir bar, and a heating mantle connected to a temperature controller equipped with control and high-limit thermocouples. The addition funnel was equipped with an adapter connected to a low pressure nitrogen line. The condenser was equipped with an adapter connected to a glass collector filled with water. In a typical reaction, glycol-ether was added to the flask and a stoichiometric amount of acid chloride was added slowly to control exotherm and HCI generation. The reactions were followed by gas chromatography and the products were checked for their infrared and nuclear magnetic resonance spectra. A typical synthesis of Example 2 is as follows:
    [0074] In a fraction 50.0 g (0.28 mol) of diethylene glycol phenyl ether were added. Benzoyl chloride (31.8 ml, 38.58g, 0.28 mol) was added to the addition funnel, the nitrogen adapter was positioned over the funnel, and a slow flow of nitrogen was initiated as evidenced by the bubbling in the Water. A magnetic stir bar was positioned below the blanket to initiate stirring. Benzoyl chloride was added in drops over a period of one hour during which time the temperature was allowed to rise to about 80 ° C. Hydrogen chloride gas emitted was captured in the collector. Once the addition was complete, the temperature was adjusted to about 112 ° C and maintained for two hours. The reaction mixture was then allowed to cool to room temperature so that a small sample could be withdrawn with a syringe. The sample was diluted with tetradecane containing isopropanol as an internal standard and analyzed by gas chromatography on a Restek RTX200 capillary column of 30 mm x 0.25 mm internal diameter x 0.25 micrometer film thickness. The analysis showed that the reaction mixture contained 0.28% residual diethylene glycol phenyl ether and 95.5% larger component tentatively
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    22/37 identified as diethylene glycol phenyl ether benzoate. The reaction mixture was subjected to flash distillation under reduced pressure to recover 72.6 g of 99.1% pure product boiling at 180 ° C @ 66.7 Pa. The product was confirmed to be diethylene glycol phenyl ether benzoate by their Infrared and Nuclear Magnetic Resonance spectra. The boiling point obtained under reduced pressure was adjusted to the Antoine equation of the form logP = AB / (T + C) restricted using the Thompson rule and a Trouton constant of 22 to obtain a normal boiling point of about 440 ° C. The product was evaluated in the MFFT test and by the EPA Method 24 as described in Example 1. (Results in Table 1.2) EXAMPLE 3. Preparation of glycol ether levulinates by transesterification [0075] Various glycol ether levulinates were prepared by transesterification of ethyl levulinate . In these syntheses, the glycol-ether was added in a 100 ml round-bottomed flask, with 3 mouths, equipped with a built-in thermocouple hole, a 50 ml addition funnel with a pressure equalizer arm equipped with a nitrogen adapter, a distillation head with condenser, vacuum / nitrogen adapter, and a 25 mL graduated collector, a Teflon stir bar, a glass cover, and a heating mantle connected to a temperature controller equipped with control thermocouples and upper limit. The distillation head was connected to a nitrogen bubbler via the nitrogen adapter. The entire device was secured on top of a magnetic stirring plate. The device was subjected to nitrogen flow from the addition funnel to the bubbler. The titanium tetraisopropoxide transesterification catalyst (DuPonfs Tyzor® TPT) was added and the mixture was heated to activate the catalyst. An equimolar amount of ethyl levulinate was then added slowly and the ethanol was collected in the graduated collector. Eventually, the nitrogen purge was replaced by a vacuum aspiration after cooling the graduated collector with dry ice. The ethanol removed was monitored throughout the reaction. A typical synthesis of Example 3 is as follows:
    [0076] After purging the apparatus with nitrogen, 42.6 g (0.17 mol) of tripropylene glycol n-butyl ether were added to the reaction flask. About 1 mL of
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    23/37 titanium tetraisopropoxide catalyst was loaded into a syringe (into a nitrogen chamber) and then added to the glycol-ether in the flask to momentarily lift the glass stopper.
    [0077] The mixture was heated to 150 ° C. At this point, 27.8 g (0.19 mol) of ethyl levulinate was loaded into the addition funnel. Once the reaction mixture had stabilized at 150 ° C, the ester was added in drops over a period of 40-60 minutes. As ethanol formed, it was harvested from the graduated collector and the temperature was gradually raised to 175 ° C. About half of the theoretical ethanol was removed during the first 3 hours. At this point, the nitrogen purge and the addition funnel were replaced by a glass cover and the connection to the bubbler was replaced by a vacuum line. The graduated collector was replaced by a small cold collector surrounded by dry ice. The pressure was slowly lowered to about 5.3 kPa (from either a water aspirator or a vacuum pump) over the course of 4 to 5 hours. At this point, the reaction was discontinued. The total ethanol harvested was recorded and the reaction product was sampled and analyzed pure in a gas chromatograph on a Fenomenex ZB-5 capillary column of 30 mm x 0.25 mm internal diameter x 0.25 micrometer film thickness . The percentage by area of the GC chromatogram showed the presence of residual ethanol, unknown components, and about 20% of unreacted glycol-ether, and about 61% of the product tentatively identified as tri-propylene glycol n-butyl-ether levulinate.
    [0078] The catalyst was neutralized with ~ 0.25 g of deionized water and about 50 ml of methyl ethyl ketone (methyl ethyl ketone, MEK) was added to the flask while the reaction mixture was stirred. A glass column measuring 30.48 cm x internal diameter of 2.54 cm equipped with a deep-fried glass bottom and Teflon tap was filled with approximately 7.62 centimeters of neutral alumina. The reaction mixture was added slowly to the column and then a gentle pressure of nitrogen was applied over the top of the column through an adapter to accelerate the flow of material through the alumina. Additional MEK was added to recover any product adhered to the alumina. The MEK solution was then
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    24/37 evaporated in a Buchi rotary evaporator with the water bath at 40 ° C and the pressure was slowly reduced to 26.7 Pa until no dripping from the dry ice condenser was observed. The residue was vacuum distilled in a small flash distillation apparatus equipped with a Cow fraction cutter. Fraction # 2 weighed 24.0 g and boiled at 150-160 ° C @ 53.3 Pa. This product (94.5% pure) was positively identified as tripropylene glycol n-butyl-levulinate ether by its Infrared and Nuclear magnetic resonance. The boiling point obtained under reduced pressure was adjusted to the Antoine equation of the form logP = AB / (T + C) restricted using the Thompson rule and a Trouton constant of 22 to obtain a normal boiling point of about 403 ° C. The product was evaluated in the MFFT test and by the EPA Method 24 as described in Example 1. (Results in Table 1.2)
    EXAMPLE 4. Preparation of glycol ether esters by direct esterification with carboxylic acids [0079] Glycol ether esters were prepared by directly esterifying glycol ether with monocarboxylic or dicarboxylic acids in the presence of concentrated sulfuric acid and an azeotropic solvent such as example, heptane. In a typical reaction, glycol-ether, carboxylic acid, heptane, and catalyst were loaded into a single-mouthed flask equipped with a Teflon magnetic stir bar, a built-in thermocouple hole, and a heating mantle connected to a temperature controller equipped with control and upper limit thermocouples. The flask was coupled to a Dean-Stark collector that was connected to a reflux condenser having a nitrogen adapter with outlet for a bubbler. A magnetic stirring plate was under the blanket. The entire apparatus was attached to a support structure within the chapel. After establishing a nitrogen atmosphere, the reaction mixture was stirred and heated to 120-130 ° C to establish a constant reflux of heptane through the collector where the esterification water was collected. The reaction was allowed to continue until the theoretical volume of water was collected. A typical synthesis of Example 4 is as follows:
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    25/37 [0080] In a 2 L reaction flask, 298.1 g (2.04 mol) of adipic acid, 775.8 g (4.08 mol) of dipropylene glycol n-butyl ether were added, 352 mL of heptane, and 1.35 g (0.0138 mol) of concentrated sulfuric acid. After establishing a nitrogen atmosphere and activating the stirrer, the reaction mixture was heated to 121 ° C to initiate a constant reflux of heptane. After 5 hours, 45.7g of water had been drained from the collector. The flask temperature was raised to 130 ° C and the reaction was allowed to continue overnight for a total of about 30 hours at which point heating was discontinued. A total of 70.85 g (3.94 moles) of water was collected (about 97% of theory). A sample of the reaction mixture was analyzed by gas chromatography in a capillary column ZB-5 from Fenomenex of 30 mm x 0.25 mm internal diameter x 0.25 micrometer of film thickness. The area percentage of the GC chromatogram showed about 1.8% residual glycol-ether and about 93.3% of a product tentatively identified as bis-dipropylene glycol n-butyl-adipate (the solvent was excluded from the total chromatogram area). The reaction mixture was then filtered through a small bed of activated basic alumina to neutralize the catalyst. The filtrate was added to a boiling flask and the heptane was removed at low pressure on a Buchi rotary evaporator. The residue was subjected to flash distillation under vacuum to isolate 806.4 g of product (80% yield) boiling at 204-211 ° C @ 26.7 Pa (95.5% purity). It was confirmed that the product is adipate bis-dipropylene glycol n-butyl-ether due to its Infrared and Nuclear Magnetic Resonance spectra. The boiling point The reduced pressure boiling point was corrected to normal boiling using a computer program that adjusts the vapor pressure data to an Antoine equation of the form logP = A-B / (T + C). The calculated normal boiling point was 485 ° C. The product was evaluated in the MFFT test and by the EPA Method 24 as described in Example 1. (Results in Table 1.2)
    Table 1.1 Synthesis of glycol ether esters
    Glycol-Ether Ester or AcidUsed Carboxylic Used Solvent Used Catalyst Mixture CompositionGross Reaction (Area%) Distilled Product Preparation Method
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    Abbreviation Grams Name Grams(Grams or mL) GlycolEther Product Area% by GC Example Method DiEPh 32.00 Ethyl Levulinate 24.5 none 1 mL of TYZOR ™ TPT 24.6 67.7 97.5 3 HxCb 33.40 Ethyl Levulinate 24.5 none 1 mL of TYZOR ™ TPT 17.8 76.7 94.5 3 HxCs 26.40 Ethyl Levulinate 24.5 none 1 mL of TYZOR ™ TPT 8.8 82.9 95.9 3 DiPPh 37.40 Ethyl Levulinate 24.5 none 1 mL of TYZOR ™ TPT 27.9 66.6 94.3 3 TPM 35.50 Ethyl Levulinate 24.5 none 1 mL of TYZOR ™ TPT 13.9 73.8 96.7 3 TPnP 39.73 Ethyl Levulinate 26.2 none 1 mL of TYZOR ™ TPT 20.1 69.9 95.3 3 BTG 36.60 Ethyl Levulinate 26.70 none 1 mL of TYZOR ™ TPT 14.5 76.1 94.3 3 TPnB 42.60 Ethyl Levulinate 27.80 none 1 mL of TYZOR ™ TPT 20.3 60.9 94.5 3 DiEPh 97.60 Ethyl Levulinate 82.40 none 1 mL of TYZOR ™ TPT 18.0 50.8 94.6 3 TPnB 262.00 Levulinic Acid 121.50 heptane 1.02 g H2SO4 6.2 85.6 > 97 4 DiEPh 198.10 Levulinic Acid 124.00 heptane 1.02 g H2SO4 0.9 97.7 > 95 4 BuCb 45.70 Adipic Acid 20.20 heptane 0.11 g H2SO4 5.1 85.6 88.2 4 DPnP 77.10 Adipic Acid 31.80 heptane 0.2 g of H2SO4 11.7 77.1 > 98 4 DPM 74.60 Adipic Acid 35.90 heptane 0.2 g of H2SO4 5.2 70.0 > 99 4 HxCs 74.60 Adipic Acid 36.30 heptane 0.23 g of H2SO4 3.7 92.9 > 97 4 PM 186.21 Adipic Acid 50.59 none 0.27 g of H2SO4 2.0 96.9 99.0 4 DPnB 775.80 Adipic Acid 298.10 heptane 1.35 g H2SO4 1.8 93.3 95.5 4 HxCs 86.80 Succinic Acid 31.80 heptane 0.21 g of H2SO4 5.4 90.5 > 97 4 BuCb 108.80 Succinic Acid 36.30 heptane 0.22 g of H2SO4 7.2 91.7 > 98 4 DiEPh 143.00 Isopentanoic Acid 51.00 heptane 0.25 g of H2SO4 23.4 75.6 > 98 4 BTG 103.70 Isopentanoic Acid 51.00 heptane 0.26 g H2SO4 4.0 89.8 > 98 4
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    Glycol-Ether Ester or AcidUsed Carboxylic Used Solvent Used Catalyst Mixture CompositionGross Reaction (Area%) Distilled Product Preparation Method Abbreviation Grams Name Grams(Grams or mL) GlycolEther Product Area% by GC Example Method HTG 117.00 Isopentanoic Acid 51.00 heptane 0.26 g H2SO4 1.9 96.2 > 98 4 TPnB 124.20 Isopentanoic Acid 51.00 heptane 0.2 g of H2SO4 8.7 86.9 > 98 4 HTG 117.00 Valeric Acid 51.00 heptane 0.2 g of H2SO4 0.9 96.1 > 99 4 BTG 103.60 Acetyl Chloride 47.00 none none 2.1 85.9 > 86 2 BuCs 59.00 Benzoic acid 61.00 heptane 0.12 g H2SO4 1.4 95.3 > 95 4 PentCs 66.00 Benzoic acid 61.00 heptane 0.12 g H2SO4 1.2 96.2 78.0 4 HxCb 206.83 Benzoic acid 132.66 heptane 0.37 g of H2SO4 3.9 89.8 97.5 4 PM 218.70 Malonic Acid 42.08 none 0.30 g H2SO4 1.5 86.2 98.2 4 DiEPh 50.00 Benzoyl Chloride 38.58 none none 0.3 95.5 99.1 2 EPh 30.00 Benzoyl Chloride 30.51 none none 0.6 98.8 n / solid 2 HxCb 50.00 Benzoyl Chloride 36.93 none none 1.6 95.8 98.1 2 DiPPh 40.00 Benzoyl Chloride 26.78 none none 1.3 96.9 99.0 2 HTG 40.00 Benzoyl Chloride 30.30 none none 9.0 88.0 96.7 2 TPPent 40.00 Benzoyl Chloride 25.45 none none 1.0 89.8 97.3 2 DP2EH 40.00 Benzoyl Chloride 25.45 none none 0.0 91.7 94.8 2 DPnB 50.00 Benzoyl Chloride 36.36 none none 4.3 92.7 98.6 2 TPnB 35.00 Benzoyl Chloride 19.39 none none 4.7 90.2 93.8 2 EPh 44.60 Succinyl Chloride 24.77 none none n / solid n / solid n / solid 2 HxCs 44.00 Succinyl Chloride 23.39 none none 1.7 91.7 96.5 2 BuCb 44.00 Succinyl Chloride 20.64 none none 1.9 92.5 94.4 2 TPM 45.00 Succinyl Chloride 16.51 none none 2.6 71.5 91.4 2 DPnP 40.00 Succinyl Chloride 17.20 none none 8.6 84.1 95.3 2 DPnB 40.00 Succinyl Chloride 15.82 none none 7.4 84.7 93.8 2
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    Glycol-Ether Ester or AcidUsed Carboxylic Used Solvent Used Catalyst Mixture CompositionGross Reaction (Area%) Distilled Product Preparation Method Abbreviation Grams Name Grams(Grams or mL) GlycolEther Product Area% by GC Example Method BuCb 44.00 Adipoil Chloride 23.92 none none 0.2 93.0 98.3 2 DPM 35.00 Adipoil Chloride 21.34 none none 0.0 93.1 94.5 2 TPM 35.00 Adipoil Chloride 15.69 none none 2.6 88.8 95.9 2 DPnB 35.00 Adipoil Chloride 16.32 none none 0.1 98.4 98.6 2 DPnP 35.00 Adipoil Chloride 18.18 none none 1.1 97.5 98.5 2 PnB 35.00 Adipoil Chloride 18.70 none none 0.0 80.1 94.8 2 TPM 107.15 Maleic Anhydride 25.05 heptane 0.14 g of H2SO4 27.2 66.0 93.1 1 BuCb 85.51 Maleic Anhydride 25.07 heptane 0.16 g H2SO4 10.5 85.0 96.8 1 HxCs 75.53 Maleic Anhydride 25.00 heptane 0.14 g of H2SO4 6.4 87.7 99.0 1 DPnB 106.72 Maleic Anhydride 25.11 heptane 0.14 g of H2SO4 16.3 82.8 99.2 1 PM 139.09 Maleic Anhydride 37.80 heptane 0.21 g of H2SO4 1.5 72.9 98.6 1
    Key for Glycol-Ether abbreviations DiEP h Diethylene glycol phenyl ether TPnB Tripropylene glycol ether n-butyl- BuCs Ethylene glycol nbutyl-ether HxC b Diethylene glycol nhexyl-ether BuCb Diethylene glycol n-butyl ether PentCs Ethylene glycol n-pentyl ether HxCs Ethylene glycol nhexyl ether DPnP Dipropylene glycol propyl ether n- EPh Ethylene glycol phenyl ether DiPP h Dipropylene glycol phenyl ether DPM Dipropylene glycol ether methyl- TPPent Tripropylene glycol n-pentylether TPM Tripropylene glycol methyl ether PM Propylene glycol methyl ether DP2EH Dipropylene glycol 2-ethyl-hexyl ether TPn P Tripropylene glycol n-propyl ether DPnB Dipropylene glycol ether n-butyl- PnB Propylene glycol n-butyl ether BTG Triethylene glycol nbutyl-ether HTG Triethylene glycol ether n-hexyl-
    Table 1.2 Glycol ether-esters coalescing agents, their properties and MFFTs of aqueous polymeric dispersion compositions including them (Compounds 1 and 2 are not of the present invention, but are included for comparison purposes)
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    Type of coalescing agent Chemical name Percentage Volatilide I (EPAMethod 24) Boiling Point (° C @101.3 kPa) MFFT (° C) of RHOPLEX ™ SG-30 with 5% coalescing agent based on polymeric solids)None (pure polymeric dispersion) none at at > 12 (pure emulsion polymer) 1 Alcohol ester 2,2,4-trimethyl-1,3pentanediol monoisobutyrate (Texanol®) 99.8 255 6.7 2 Glycol-diester Triethylene glycol bis-2ethylhexanoate (Optifilm® Enhancer400) 1.1 422 3.9 3 Bis-alkyl ester Bis (2-ethyl hexyl) adipate 0.8 417 > 10 4 Glycol ether-ester Triethylene glycol n-hexylether benzoate 0.4 441 5.0 5 Glycol ether ester Dipropylene glycol 2-ethylhexyl-ether benzoate 4.3 420 4.4 6 Glycol ether ester Diethylene glycol n-hexyl ether benzoate 3.5 390 3.3 7 Glycol ether ester Ethylene glycol phenyl ether benzoate 2.6 (solid) 370 untested 8 Glycol ether ester Diethylene glycol phenyl ether benzoate 0.7 440 7.2 9 Glycol ether ester Tripropylene glycol n-pentyl ether benzoate 2.2 425 4.4 1 0 Glycol ether ester Dipropylene glycol phenyl ether benzoate 1.5 422 4.4 11 Glycol ether ester Dipropylene glycol n-butyl ether benzoate 10.7 375 6.1 12 Glycol ether ester Tripropylene glycol n-butyl ether benzoate 4.3 410 6.1 13 Glycol ether ester Ethylene glycol n-pentylether benzoate 45.6 305 5.0 14 Glycol ether ester Ethylene glycol n-butyl-ether benzoate 78.1 290 5.0 15 Glycol ether ester Triethylene glycol n-pentylether benzoate 1.7 425 at 16 Glycol ether ester Dipropylene glycol phenylether levulinate 2.6 414 7.8 17 Glycol ether ester Ethylene glycol n-hexyl-levulinate ether 37.4 332 5.6 18 Glycol ether ester Diethylene glycol n-hexylether levulinate 10.6 383 4.4 19 Glycol ether ester Diethylene glycol phenyl ether levulinate 1.2 420 4.4 20 Glycol ether ester Tripropylene glycol methyl ether levulinate 6.9 367 untested
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    Type of coalescing agent Chemical name Percentage Volatilide I (EPAMethod 24) Boiling Point (° C @101.3 kPa) MFFT (° C) of RHOPLEX ™ SG-30 with 5% coalescing agent based on polymeric solids) 21 Glycol ether-ester Tripropylene glycol n-propyl ether levulinate 7.2 385 untested 22 Glycol ether ester Triethylene glycol n-butyl ether levulinate 3.6 403 7.2 23 Glycol ether ester Tripropylene glycol n-butyl-ether levulinate 3.1 403 4.4 24 Glycol ether-ester Tripropylene glycol n-butyl ether isopentanoate 27.5 390 6.1 25 Glycol ether ester Diethylene glycol phenyl ether isopentanoate 10 382 7.2 26 Glycol ether ester Triethylene glycol n-hexylether isopentanoate 8.1 396 4.4 27 Glycol ether ester Triethylene glycol n-butyl ether isopentanoate 20.6 360 5.0 28 Glycol ether ester Triethylene glycol n-hexyl ether valerate 5.8 398 7.2 29 Glycol Bis-Ether-Ester Bis-Ethylene glycol phenyl ether succinate solid 485 untested 30 Bis-ether-glycol esters Bis-Diethylene-glycol nbutyl-ether succinate 0.4 452 4.4 31 Bis-ether-glycol esters Bis-Propylene glycol phenyl-ether succinate 0.3 (solid) 483 untested 32 Bis-ether-glycol esters Bis-Ethylene glycol n-hexyl ether succinate 0.8 430 5.0 33 Bis-ether-glycol esters Bis-T ripropylene glycol methyl ether succinate 1.6 464 5.6 34 Bis-ether-glycol esters Bis-Dipropylene glycol npropyl-ether succinate 1.8 450 5.0 35 Bis-ether-glycol esters Bis-Dipropylene glycol nbutyl-ether succinate 1.0 460.0 5.0 36 Bis-ether-glycol esters Bis-Diethylene-glycol nbutyl-maleate ether 0.5 476.0 6.1 37 Bis-ether-glycol esters Bis-Ethylene glycol n-hexylether maleate 0.8 456.0 6.1 38 Bis-ether-glycol esters Bis-T ripropylene glycol methyl ether maleate 4.3 449.0 7.8 39 Bis-ether-glycol esters Bis-Dipropylene glycol nbutyl-maleate ether 0.1 476.0 5.0 40 Bis-ether-glycol esters Bis-Propylene glycol methyl-ether maleate 33.1 380.0 8.3 41 Bis-ether-glycol esters Bis-Diethylene-glycol nhexyl-ether malonate 1.7 440 untested 42 Bis-ether-glycol esters Bis-Propylene glycol methyl-ether malonate 72.5 330 8.3 43 Bis-ether-glycol esters Bis-Diethylene glycol nbutyl-adipate ether 0.5 479 4.4
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    Type of coalescing agent Chemical name Percentile Volatilide 1 (EPAMethod 24) Boiling Point (° C @101.3 kPa) MFFT (° C) of RHOPLEX ™ SG-30 with 5% coalescing agent based on polymeric solids) 44 Bis-ether-glycol esters Bis-T ripropylene glycol methyl adipate ether 0.9 471 5.0 45 Bis-ether-glycol esters Bis-Dipropylene glycol nbutyl-adipate ether 0.2 485 4.4 46 Bis-ether-glycol esters Bis-Dipropylene glycol npropyl-adipate ether 0.5 470 5.0
    EXAMPLE 5 - Evaluation of diethylene glycol phenyl ether benzoate and dipropylene glycol phenyl ether benzoate as coalescing agents for an aqueous epoxy dispersion.
    [0081] Glycol-ether benzoates of the invention were added in an aqueous dispersion of an aqueous epoxide having a particle size of approximately 500nm. The aqueous polymeric dispersion is part of a 2k system, typically combined with amine-based curing agents for ambicure coatings at concentrations. The coalescing agents were added at 4% by weight based on the resin solids and the MFFT values were compared with those obtained without a coalescing agent and with commercially available coalescing agents such as DOWANOL ™ PPh. The MFFT of the coating compositions containing the glycol ether benzoates of the invention (Coating Compositions 1-2) were similar to the MFFT obtained with DOWANOL ™ PPh (about 6 ° C) and considerably lower than the MFFT obtained without aids. coalescence (about 12 ° C). Aqueous compositions of shiny enamel coating were prepared with either the glycol-ether benzoates or the comparative coalescing agents at the level of 4% based on the resin solids. See Table 5.1 below. There was no significant loss of useful life in the presence of benzoates. Evaluation of extender bar applications of the cured formulations did not show harmful effects of the plasticizer, nor loss of gloss as a function of the useful life, nor loss of chemical or water resistance in coatings prepared with benzoates (Tables 5.2 and 5.3). Hardness and
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    Table 5.1 - Aqueous composition of a shiny enamel epoxy coating
    Comparative Coating Composition A Comparative Coating Composition B Coating Composition 1 Coating Composition 2 Ingredients (in kg)Grinding Part AEpoxide90,718 90,718 90,718 90,718 Water13,222 13,222 8,958 8,958 Sodium nitrite (15%)4,082 4,082 4,082 4,082 Disperbyk ™ 19413,336 13,336 13,336 13,336 BYK-0190.907 0.907 0.907 0.907 Ti-Pure ™ R-706 TiO 2 109,044 109,044 109,044 109,044 Dilution of Part AEpoxide151,654 151,654 151,654 151,654 DiPP Benzoato0.00 0.00 4,536 0.00 DiEPh Benzoato0.00 0.00 0.00 4,536 TegoAirex ™ 902W1.996 1.996 1.996 1.996 Part BAP Anquamine ™ 40145,559 45,559 45,559 45,559 Arcosolv ™ PM4,037 0.00 0.00 0.00 Dowanol ™ PPh4,037 0.00 0.00 0.00 Dowanol ™ PnP0.00 17.90 0.00 0.00 Water44,729 43.726 52,912 52,912 properties Units Total volume L 378.54 378.54 378.54 378.54 Total weight kg 483,321 482,364 483,702 483,702 Total PVC without addition Percent 18.00% 18.00% 18.00% 18.00% Volume of solids without addition Percent 40.00% 40.00% 40.00% 40.00% % By weight of solids without addition Percent 52.73% 52.83% 52.69% 52.69% VOC M 50 50 2 2
    Table 5.2 - Drying test results for epoxy coating composition
    Composition ofCoating 0Comparative A Composition ofCoating 0Comparative B Composition ofCoatings0 1 Composition ofCoating o2 Dry to the Touch 60 60 90 60 Dry to Handling 300 270 300 330 Initial Water Resistance
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    (about Al)dry 4 h, Blistering Assessment 10 10 10 10 6 h dry, Blister Evaluation 10 10 10 10
    Table 5.3 - Resistance to chemical attack of the epoxy coating
    Coating Comparative Coating A Coating 1 Coating 2 Compare asset B Chemical Resistance 24 hours Spot Test 48 hours Spot Test 24 hours Spot Test 48 hours Spot Test 24 hours Spot Test 48 hours Spot Test 24 hours Spot Test 48 hours Spot Test Rating scale 1-5, 5 = no damage to the film, 1 = dissolved film,delaminated H 2 S04 10% 2 1.5 2 1.5 2 1.5 2 1.5 10% HCI 3 1.5 3 1.5 3 1.5 3 1.5 ammonia 30% 4.5 5 4.5 5 4.5 5 4.5 5 15% NaOH 5 4 5 4.5 5 4 5 4 MEK 4 3.5 4 3.5 4 3.5 4 4 gasoline 4 4 4.5 4 4 4 4 4 Brake Fluid 3 3.5 3 3.5 3 3.5 3 3.5 Water 4.5 5 4.5 5 4.5 5 4.5 5 fluidstreaming 5 4 5 4 5 4 5 4 WD-40 5 5 5 5 5 5 5 5 Motor oil 5 4 5 4 5 4 5 4 Coffee 3.5 4 3.5 4 3.5 4 3.5 4 Mustard 2.5 2 2.5 2 2.5 2.5 2.5 2.5 50% Ethanol 4.5 4 4.5 4 4.5 4 4.5 4 Skydrol ™ 5 4 5 4 4.5 4 5 4 IPA 5 4 5 4 5 4.5 5 4.5
    Table 5.4 - Epoxy coating hardness / flexibility performance
    Comparative Coating Composition B Comparative Coating Composition A Coating Composition 1 Coating Composition 2 Konig's hardness(seconds) 1 day 104 83 83 79 7 days 136 117 120 118 14 days 134 117 121 118 30 days 131 118 127 124 Pencil Hardness 1 day 2H 2H 2H H
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    7 days 4H 5H 5H 3H 14 days 6H 6H 5H 6H 30 days 6H 6H 7H 6H Impact resistance direct, in kg 4,536 9,072 9,072 13.608 inverse, in kg <1.814 <1.814 <1.814 <1.814 Chuck flexibility Baton diameter 1.270 cm F P P P 0.635 cm F P P P 0.318 cm F F F F
    EXAMPLE 6 - Performance of glycol ether esters and diesters in an aqueous coating composition including an emulsion polymer [0082] A standard batch of aqueous coating was prepared having the composition in Table 6.1 and all test coalescing agents were subsequently added to 8% by weight based on the resin solids. A total of 14 formulations were evaluated including controls with TEXANOL ™, DOWANOL ™ DPnB, and OPTIFILM ™ 400. A series of typical paint tests were conducted in spreader applications for each formulation. These tests were gloss, low temperature film formulation (LTFF), yellowing, hot block for 1 day, oven printing for 1 day, Konig hardness, wet-dry alkyd resin adhesion for 1 day, resistance to dirt accumulation (DPUR) and color acceptance. The results of these tests showed that the glycol ether and diester esters of the invention performed well in fully formulated Coating Composition (Tables 6.2 and 6.3).
    Table 6.1- Semi-gloss formulation of acrylic polymer in emulsion RHOPLEX ™ SG-10M
    Component Kilograms LitersMilling TI-PURE ™ R-746 154,811 66,472Water 13.608 13,590Propylene glycol 12.701 12,265TAMOL ™ 165A 3,946 3.710TRITON ™ GR-7M 0.953 0.908KATHON ™ LX 1.5% 0.816 0.795Subtotal grinding 186,835 97,739Dilution FOAMASTER ™ VL 0.907 0.946RHOPLEX ™ SG-10M 224,433 212,021
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    Water 47,337 47,318ACRYSOL ™ RM 2020 9,072 8.706NPRACRYSOL ™ RM-8W 2.404 2.309Coalescing agent 8,977 7,949-9,842 (8% on polymeric solids) Totals -> 479,964 376,989-378,882 (volume, a density factor ofcoalescing solvent) % By weight of solids -> 48.05%PVC 23%
    Table 6.2 - Results of tests with aqueous coating composition
    LTFF (40/40) Brightness for 1 day Paint Flow Proportion ofContrast Color appearance Yellowing HA film Texanol ™ 99/97 34/73 8 0.9518 Good Great Dowanol ™ DPnB 99/99 26/65 7+ 0.9259 clear Great Optifilm ™ 400 99/99 37/75 7+ 0.9432 Suavement and Clara Great Butyl Carbitol ™ Adipate 99/97 37/75 7 0.9353 Suavement and Clara Great DPnB Adipato 99/97 32/75 7 0.9465 Suavement and Clara Great DPnP Adipato 99/99 36/74 7+ 0.9454 Suavement and Clara Great Butyl Carbitol ™Succinate 99/99 37/75 6 0.9363 Suavement and Clara Great Hexyl Cellosolve ™Maleate 99/99 38/75 7 0.9453 Suavement and Clara Great Butyl Carbitol Maleato 99/97 38/76 6+ 0.9432 Suavement and Clara Great Hexyl Carbitol Benzoate 99/99 35/73 7+ 0.9408 Suavement and Clara Great DPnB Maleato 99/97 37/75 7 0.9432 Suavement and Clara Great DiEPh BenzoatoTechnician 99/97 38/76 6+ 0.9463 Suavement and Clara Great TPP Benzoato 99/99 38/75 6+ 0.9400 Suavement and Clara Great PTG Benzoate 99/99 38/76 6 0.9453 Suavement and Clara Great
    Table 6.3 - Results of tests with coatings
    Abrasive Friction Hydrophobic / Hydrophilic Stain Removal. Hot Block for 1 day Oven printing for 1 day Konig hardness (1/7/14 days) Lab DPUR% retained Texanol ™ 1073 77/53 8+ 8+ 13/20 99.8
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    Dowanol ™ DPnB 793 65/53 8+ 9+ 15/32 99.6 Optifilm ™ 400 1127 71/53 8+ 6+ 9/11 98.5 Butyl Carbitol ™ Adipate 1065 57/73 8+ 6 9/11 98.9 DPnB Adipato 1178 56/63 8+ 6 10/13 97.2 DPnP Adipato 1059 57/53 8+ 6 12/10 98.6 Butyl Carbitol ™ Succinate 1222 56/53 8+ 6 9/11 98.4 Hexil Cellosolve ™ Maleate 1040 68/53 8+ 6 9/11 97.6 Butyl Carbitol ™ Maleate 1172 69/53 8+ 7 12/10 99.2 Hexyl Carbitol Benzoate 1072 63/53 8+ 6 9/11 98.3 DPnB Maleato 1027 71/53 8+ 7 11/13 99.3 DiEPh Benzoato Técnico 872 73/53 8+ 5+ 12/14 98.1 TPP Benzoato 1309 68/53 8+ 6 10/13 98.2 PTG Benzoate 1154 68/53 8+ 6 9/11 99.4
    EXAMPLE 7 - Performance of glycol ether esters and -dieters with opaque polymers [0083] Certain glycol ether esters and -desters were compared with TEXANOL ™ and OPTIFILM ™ 400 as coalescing agents in their ability to preserve the opacity provided by various commercial opaque polymers ROPAQUE ™ (multistage emulsion polymers including, when dry, a void) in a standard formulation. All coalescing agents were evaluated at 10% by weight based on the resin solids. In Table 7.1, high values represent high opacity preservation and scattering. It can be seen that glycol ether esters and diesters such as dipropylene glycol phenyl ether benzoate (DiPPh Benzoate), bis dipropylene glycol n-butyl ether adipate (DPnB Adipate), bisdipropylene glycol n-propyl ether adipate (DPnP Adipate), bis-dipropylene glycol n-butyl ether maleate (DPnB Maleate), and tripropylene glycol pentyl-ether benzoate (TPP Benzoate) performed similarly to TEXANOL ™ with ROPAQUE ™ Dual and better performance with ROPAQUE ™ Dual, ROPAQUE ™ Ultra, and / or ROPAQUE ™ Ultra E than OPTIFILM ™ 400.
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    Table 7.1 - Performance with opaque polymers
    Coalescent Agent Opaque Polymer - Relative Scattering ROPAQUE ™ ULTRAE ROPAQUE ™ ULTRA ROPAQUE ™ DUAL TEXANOL ™ 100 100 100 DiPP Benzoato AT 81 102 DPnB Adipato 7 AT 102 DPnP Adipato 26 AT 99 DPnB Maleato 69 AT 98 TPGPE Benzoato 8 59 97 OPTIFILM ™ 400 3 19 84 Hexyl CELLOSOLVE ™Maleate 13 AT 76 Butyl CARBITOL ™ Maleate 36 AT 75
    [0084] Certain glycol ether esters and diesters such as dipropylene glycol phenyl ether benzoate (DiPPh Benzoate), bis-dipropylene glycol n-butyl adipate ether (DPnB Adipate), bis-dipropylene glycol n-propyl ether adipate (DPnP Adipate), bisdipropylene glycol n-butyl-ether maleate (DPnB Maleate), and tripropylene glycol pentyl-ether benzoate (TPP Benzoate) of the invention performed similarly to TEXANOL ™ with ROPAQUE ™ Dual and performed better with ROPAQUE ™ Dual, ROPAQUE ™ Ultra, and / or ROPAQUE ™ Ultra E than OPTIFILM ™ 400.
    权利要求:
    Claims (6)
    [1]
    1. Glycol ether-ester, characterized by the fact that it is selected from the group consisting of: tripropylene glycol n-butyl-benzoate ether; tripropylene glycol n-pentyl-benzoate ether; dipropylene glycol 2-ethylhexyl-ether benzoate; dipropylene glycol phenyl ether benzoate; ethylene glycol n-hexyl-levulinate ether; diethylene glycol n-hexyl-levulinate ether; diethylene glycol phenyl ether levulinate; triethylene glycol n-butyl-levulinate ether; dipropylene glycol phenyl ether levulinate; tripropylene glycol methyl-levulinate ether; tripropylene glycol n-propyl-levulinate ether; and tripropylene glycol n-butyl-levulinate ether.
    [2]
    2. Aqueous coating composition, characterized by the fact that it comprises an aqueous polymeric dispersion and from 0.1% to 40% by weight, based on the weight of solids of said polymeric aqueous dispersion, of said glycol ether-ester as defined in claim 1.
    [3]
    Aqueous coating composition according to claim 2, characterized in that said aqueous polymeric dispersion is selected from the group consisting of an epoxide emulsion and an emulsion polymer.
    [4]
    Aqueous coating composition according to claim 2, characterized in that said polymeric aqueous dispersion has an MFFT, measured using ASTM D 2354 and a 127 micrometer bar in the MFFT, from -5 ° C to 100 ° C, said coating composition comprising from 0.1% to 30% by weight, based on the weight of solids of said polymeric aqueous dispersion, said glycol ether-ester as defined in claim 1.
    [5]
    Aqueous coating composition according to any one of claims 2, or 3 or 4, characterized in that it additionally comprises a multistage emulsion polymer which, when dry, includes a void.
    [6]
    6. Method for forming a coating, characterized by the fact that it comprises:
    (a) forming said aqueous coating composition as defined in claim 2 or claim 3 or claim 4 or claim 5;
    (b) applying said aqueous coating composition to a substrate; and (c) drying, or allowing drying, said aqueous coating composition.
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    同族专利:
    公开号 | 公开日
    EP2508577A2|2012-10-10|
    CN105669458B|2019-03-26|
    CA2771735A1|2012-10-08|
    CN102732077B|2017-07-04|
    BR102012007682A2|2015-04-07|
    EP3178891B1|2020-10-21|
    CA2829715A1|2012-10-08|
    CA2829715C|2017-11-21|
    IN2012DE00888A|2015-09-11|
    EP2508577B1|2017-01-18|
    ES2618654T3|2017-06-21|
    CA2771735C|2014-09-09|
    EP3178891A1|2017-06-14|
    US20120258249A1|2012-10-11|
    ES2841978T3|2021-07-12|
    CN105669458A|2016-06-15|
    BR102012007682B8|2019-12-24|
    CN102732077A|2012-10-17|
    EP2508577A3|2014-08-20|
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    法律状态:
    2015-04-07| B03A| Publication of a patent application or of a certificate of addition of invention [chapter 3.1 patent gazette]|
    2018-03-27| B15K| Others concerning applications: alteration of classification|Ipc: C09D 163/00 (2006.01), C07C 69/716 (2006.01), C07C |
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2018-05-15| B15K| Others concerning applications: alteration of classification|Ipc: C07C 69/716 (2006.01), C07C 69/78 (2006.01), C09D |
    2018-12-11| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|
    2019-06-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2019-08-06| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/04/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 03/04/2012, OBSERVADAS AS CONDICOES LEGAIS |
    2019-12-24| B16C| Correction of notification of the grant|Free format text: REFERENTE A RPI 2535 DE 06/08/2019,QUANTO AO ITEM (72) INVENTOR. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201161473243P| true| 2011-04-08|2011-04-08|
    US61/473243|2011-04-08|
    US201161503647P| true| 2011-07-01|2011-07-01|
    US61/503647|2011-07-01|
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