Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
  • C08G18/765—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group alpha, alpha, alpha', alpha', -tetraalkylxylylene diisocyanate or homologues substituted on the aromatic ring
• • 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
  • C09D121/00—Coating compositions based on unspecified rubbers
  • C09D121/02—Latex
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/2805—Compounds having only one group containing active hydrogen
  • C08G18/2815—Monohydroxy compounds
  • C08G18/283—Compounds containing ether groups, e.g. oxyalkylated monohydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate

Definitions

• the present invention relates to an improved paint compositions and, more particularly, to an additive composition to be used in water-borne latex paints to reduce the disruption of an associative thickener network upon the addition of colorants, as well as a novel process for producing the improved paint compositions.
• this invention relates to improved paint compositions containing an additive to reduce the effect of viscosity loss caused by the addition of colorants.
• One aspect of the invention relates to a water-borne latex paint system, comprising a base paint, at least one associative thickener, a colorant compound, and at least 0.1 % dry weight of a block copolymer ABLBA composition.
• the block copolymer acts as a viscosity stabilizer in the presence of associative thickeners.
• the A component includes a monomer unit containing a moiety such as an alkyl group, an aryl group or an alkyl aryl group.
• the B component includes a polyethylene oxide polymer or a polyethylene-polypropylene oxide copolymer.
• the L component includes a dianhydride unit or a diisocyanate unit.
• Another aspect of the invention relates to a method of formulating a water-borne latex paint system, comprising adding to a base paint, an associative thickener and a colorant compound and further adding at least 0.1% dry weight of a block copolymer ABLBA composition.
• the polymer chemical is prepared by reacting a monomer unit containing a moiety such as an alkyl group, an aryl group or an alkyl aryl group, a polyethylene oxide polymer or a polyethylene- polypropylene oxide copolymer; and an L component such as a dianhydride unit and a diisocyanate unit.
• Figure 1 illustrates the concentration effect of a viscosity stabilizer upon the addition of a colorant to a paint formulation for an embodiment of the present invention.
• the viscosity drop is related to the composition of the tinting formulation. This is most likely due to the quantity and type of surfactants used to stabilize the pigment in the colorant. In most cases, carbon black requires the most surfactant and therefore is the most troublesome color.
• the present invention provides for a system and method to formulate a water-borne latex paint system which reduces the viscosity drop until the addition of tint to the base paint formulation.
• the water-borne latex paint system includes a base paint, at least one associative thickener, a colorant compound, and at least 0.1% dry weight of a block copolymer ABLBA composition.
• the ABLBA-type polymer includes: an A component comprising a hydrophobic group A; a B component comprising a hydrophilic polymer B; and an L component comprising a linking group.
• the ABLBA copolymer functions as a viscosity stabilizer in the water-borne latex paint systems.
• the hydrophobic group A component, of the ABLBA polymer includes a monomer unit containing a moiety such as an alkyl group, an aryl group or an alkyl aryl group.
• the hydrophobic group A component includes linear Ci 0 -C 22 alcohols, branched Ci 2 - C 24 alcohols and mixtures thereof.
• the hydrophobic group A component includes 2-butyl-octanol, 2-hexyl- decanol, 2-octyl-dodecanol, 2-isoheptyl-7-methyl-undecanol, 2-(2,4,4-trimethylbutyl)-6,8,8- trimethyl-nonanol, and mixtures thereof.
• the hydrophobic group A component includes 2-hexyl decanol.
• the B component, of the ABLBA polymer includes a polyethylene oxide polymer or a polyethylene-polypropylene oxide copolymer.
• the polyethylene oxide polymer has from 25 to 100 ethylene oxide repeat units.
• the polyethylene-polypropylene oxide copolymer has a total number of repeat units ranging from 25 to 75 and up to 10 propylene oxide units.
• the polyethylene-polypropylene oxide copolymer has a number average molecular weight less than 2500.
• the B component includes polyethylene oxide having 50 ethylene oxide units.
• the AB ethoxylate may be synthesized by reacting the A and B components in a basic solution or in the presence of a metal catalyst.
• the AB ethoxylate has a number average molecular weight below 3000 g/mole. In another embodiment, the AB ethoxylate has a number average molecular below less than 2500 g/mole.
• the L component, of the ABLBA polymer includes one or more linking units such a diisocyanate unit.
• the diisocyanate linking unit is generated from compounds such as hexamethylene diisocyanate ("HDI”), trimethyl hexamethylene diisocyanate (“TMDI”), isophorone diisocyanate (“IPDI”), tetramethyl xylene diisocyanate (“TMXDI”), and 4,4-m ethylene bis(cyclohexylisocyanate).
• the diisocyanate linking unit is generated from hexamethylene diisocyanate.
• the L component, of the ABLBA polymer includes linking unit such as a dianhydride unit.
• the dianhydride is generated from compounds such as benzophenone tetracarboxylic dianhydride (BTD) or pyromellitic dianhydride (PMA) to give the corresponding diester polymer.
• the synthetic procedure for the dianhydride is similar to the diisocyanate procedure with an amine (triethylamine, DABCO, etc.) used as a catalyst.
• the resulting polymers have an anionic nature to them, which can be useful in some applications.
• the ABLBA polymer has number average molecular weight below 10,000 g/mole. In another embodiment, the ABLBA polymer has a number average molecular weight less than 7000 g/mole.
• the ABLBA has a hydrophobe-lipophile balance (HLB) value of greater than 15.
• the base paint formulation also includes a resin.
• the resin includes a hydrophobic resin.
• Representative hydrophobic resins include an acrylic resin, a styrene acrylic resin or a styrene resin.
• the resin includes a hydrophilic resin.
• Representative examples of hydrophilic resins include a vinyl acrylic resin or a vinyl acetate ethylene resin.
• the resin has a substantially spherical shape and a large particle size or low surface area. In one embodiment, the particle size may be greater than 200 tun. In another embodiment, the particle size ranges from 220 nm to 650 nm.
• the resin has a substantially spherical shape and small particle size or high surface area.
• the particle size may be less than 200 nm.
• the particle size ranges from 80 nm to 180 nm.
• the resin has a multilobe shape.
• Representative resins includes Optive 130 (BASF, acrylic, 160 nm), UCAR 300 (Dow, vinyl acrylic, 260 nm), UCAR 625 (Dow, acrylic, 340 nm), Rhoplex ML-200 (Rohm & Haas, acrylic, 590 nm multilobe), and Neocryl XK-90 (DSM Neoresins, acrylic, 90 nm).
• the water borne latex paint system may also include at least one associative thickener.
• Associative thickeners are water soluble or water swellable polymers that have chemically attached hydrophobic groups.
• the ABLBA stabilizer is effective in improving the viscosity stability to colorant addition for paints containing at least one associative thickener.
• the associative thickeners includes nonionic hydrophobically modified materials such as polyether and/or polyurethane associative thickeners or ionic associative thickeners such as hydrophobically modified alkali swellable (or soluble) emulsions (HASE) and hydrophobically modified hydroxyethyl cellulose and mixtures thereof.
• the number average molecular weights of the associative thickeners may range from 10,000 to 150,000 g/mole.
• two associative thickener compositions a low shear thickener and a high shear thickener, may be used in combination with the ABLBA stabilizer.
• the two associative thickeners may both have a composition of polyether polyurethane.
• the two associative thickeners may both have a composition of polyether polyacetal.
• one associative thickener has a composition of polyether and the second associative thickener has a composition of polyether polyurethane.
• Representative associative thickener pairs include Rohm & Haas Acrysol RM 825/ RM 2020 NPR, Rohm & Haas Acrysol SCT 275 / RM 2020 NPR, Aqualon NLS 200 / NHS 300, Elementis Rheolate 255 / 350 and Cognis DSX 1514 / DSX 3075.
• a high shear thickener composition may be used in combination with the ABLBA stablizer.
• the associative thickener has a composition of hydrophobically modified polyether polyurethane.
• the associative thickener has a composition of a hydrophobically modified polyether polyacetal.
• the associative thickener has a composition of hydrophobically modified polyether.
• the ABLBA stabilizing polymers may be used in combination with a high shear thickener and act as a low shear thickener. In certain embodiments where the resin has a particle size greater than 200 nm, the ABLBA stabilizing polymers may be used in combination with a high shear thickener and a low shear thickener.
• the water borne latex paint system may contain less than 0.01 wt. % of a second polymer containing at least one hydrophilic group having a number average molecular weight of at least 1000 and only one hydrophobic group.
• the ABLBA stabilizer may be added to the paint as a solid or as a liquid solution with other solvents and surfactants. In certain embodiments, the co-solution of the ABLBA stabilizer with other surfactants may make the ABLBA stabilizer less effective and therefore greater quantities of ABLBA stabilizer may be required to obtain the same performance.
• the ABLBA stabilizer is added to the paint formulation with the colorant and then the material is dispersed for example with a high speed disperser or on a Red Devil shaker.
• the ABLBA stabilizer is added at any stage of the paint preparation. In one embodiment, the ABLBA stabilizer is added to the base paint formulation. In another embodiment, the ABLBA stabilizer is added to the colorant.
• the solid additive can be put into solution with butyl carbitol and water.
• a typical additive formulation is a 25 weight % solution of the polymer with 10-15% butyl carbitol and 60-65% water.
• the resins used span a range of hydrophobicity and particle size which is related to the surface area.
• Representative resins include Optive 130 (BASF, acrylic, 160 nm), UCAR 300 (Dow, vinyl acrylic, 260 run), UCAR 625 (Dow, acrylic, 340 nm), Rhoplex ML-200 (Rohm & Haas, acrylic, 590 nm multilobe), and Neocryl XK-90 (DSM Neoresins, acrylic, 90 nm).
• the relative composition of low shear to high shear thickener in each paint was formulated to obtain a final approximate Stormer viscosity of between 90-100 KU and an ICI viscosity of 1-2 Poise (as per ASTM D562 and D4287).
• the ABLBA stabilizing polymer was added to the paint as a viscosity stabilizer.
• the stabilizing additive was added to the paint formula at the same time that a high shear associative thickener and a low shear associative thickener were added.
• Various pairs of associative thickeners in combination with the ABLBA stabilizing polymer were tested.
• the pair thickeners were Rohm & Haas Acrysol RM 825/ RM 2020 NPR, Rohm & Haas Acrysol SCT 275 / RM 2020 NPR, Aqualon NLS 200 / NHS 300, Elementis Rheolate 255 / 350 and Cognis DSX 1514 / DSX 3075.
• the ABLBA stabilizing additive was based on the reaction of 2-hexyl-decyl/EO (50) with HDI.
• the thickeners and concentrations are listed for each resin systems having large particle sizes.
• the concentration of the stabilizer was 0.5 wt. %. and the colorant was Colortrend 888 Lampblack @ 12 fl.oz/gal. No attempt was made to optimize the stabilizer concentration.
• the ABLBA stabilizing polymer reduced the amount of viscosity decrease upon the addition of colorant to the paint formulation compared to formulations without the ABLBA stabilizing polymer.
• the ABLBA stabilizing polymer slightly increased the base viscosity of the paint but reduced the degree of viscosity decrease on colorant addition.
• viscosity color stability means the difference in Stormer viscosity between the 24 hours color tinted formulation and the formulation before tinting after the addition of up to 12 fl. oz. of Colortrend 888 Lampblack per gallon of paint.
• the viscosity color stability may range from -10 KU units up to + 10 KU units.
• the viscosity color stability may range from -10 KU units up to -5 KU units.
• the viscosity color stability may range from -5 KU units up to 5 KU units.
• the viscosity color stability may range from 0 KU up to 10 KU units.
• Table 3 shows the results of the ABLBA stabilizing additive to paints for a small particle resin, Optive 130.
• the concentration of the stabilizer was 0.5 wt. %. and the colorant was Colortrend 888 Lampblack @ 12 fl.oz per gallon of paint.
• the formulations also contain a commercial high shear associative thickener and a commercial low shear associative thickener.
• the pair thickeners were Rohm & Haas Acrysol RM 825/ RM 2020 NPR, Rohm & Haas Acrysol SCT 275 / RM 2020 NPR 3 Aqualon NLS 200 / NHS 300, and Cognis DSX 1514 / DSX 3075.
• the results in Table 3 illustrate that for formulations having small particle resins, the ABLBA stabilizing polymer increased the viscosity of the base paint upon addition of the stabilizing polymer and the addition of colorant resulted in a decrease in viscosity.
• the viscosity color stability may range from -35 KU units up to -15 KU units. In one embodiment, the viscosity color stability may range from -30 KU units up to - 20 KU units. In another embodiment, the viscosity color stability may range from -25 KU units up to -20 KU units.
• the ABLBA polymer may be used as a low shear associative thickener, in conjunction with a high shear associative thickener, while also providing color stabilization.
• Table 4 compares the results in two small particle resin paints using the polymer of 2-hexyl-decyl/EO (50) linked with HDI at the quantities shown in the table.
• a commercial low shear thickener, DSM XK-90 was used.
• the colorant was Colortrend 888 Lampblack used at 12 fl.oz. per gallon of paint.
• the viscosity color stability may range from -15 KU units up to 0 KU units. In one embodiment, the viscosity color stability may range from -10 KU units up to 0 KU units.
• Table 5 compares the effect of the diisocyanate group on the stabilization of an ABLBA additive where A is 2-hexyl-deca ⁇ ol and B is ethylene oxide having 40 EO units.
• Deep tint base Case 1 was studied with Rheolate 255 without/with stabilizing additive.
• the stabilizing additive was used at a concentration of 0.75 wt.
• the colorant was Colortrend 888 Lampblack used at 12 fl.oz. per gallon of paint. The data shows that the coupling agent has minimal impact when the polymer is used as a stabilizer in a large particle latex paint.
• HDI Hexamthylene diisocyanate
• TMDI Trimethylhexamethylene diisocyanate
• TMXDI Tetramethylxylyl diisocyanate
• FPDI Isophorone diisocyanate
• Table 6 shows the results of the addition of the stabilizer based on the benzophenone tetracarboxylic dianhydride.
• the Deep tint base Case 1 was studied with Rheolate 255 without/with stabilizing additive.
• the ABLBA stabilizing additive based on 2-hexyl-decanol with 50 EO units at a concentration of 0.75 wt. %.
• the colorant was Colortrend 888 Lampblack used at 12 fl.oz. per gallon of paint.
• the ABLBA polymer appears to provide slightly less viscosity color stability than the diisocyanate linked polymers which may be due to the diacid in the product.
• BTD benzophenone tetracarboxylic dia ⁇ hydride
• the structure and molecular weight of the stabilizing polymer has an effect on the rheology of the paint and the stabilizing effect.
• ABLBA polymers based on A components which are straight chain, branched or cyclic aliphatic compounds all provide viscosity color stabilization. Higher AB molecular weights lead to viscosity build in the base paint. Hydrophobe length is also important where shorter lengths reduce base paint viscosity. Furthermore, the low and high shear viscosity can be influenced differently based on the structure.
• Table 9 and Figure 1 illustrate the effect of stabilizing additive concentration on the degree of viscosity change upon addition of colorant.
• the latex paint case 2 was thickened with Rheolate 255 (3%) with and without additives.
• the additive concentration was 0.75%.
• the colorant was Colortrend 888 Lampblack used at 12 fl.oz. per gallon of paint.
• the data show that amount of viscosity stabilization is proportional to the amount of stabilizer; increasing the amount of ABLBA stabilizer polymer decreases the effect of the colorant on the viscosity of the paint.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Medicinal Chemistry (AREA)
• Polymers & Plastics (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Wood Science & Technology (AREA)
• Paints Or Removers (AREA)
• Polyurethanes Or Polyureas (AREA)
• Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
• Inks, Pencil-Leads, Or Crayons (AREA)

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• 2007
  • 2007-06-07 EP EP07795910A patent/EP2029652A1/de not_active Withdrawn
  • 2007-06-07 JP JP2009514401A patent/JP2009540056A/ja not_active Withdrawn
  • 2007-06-07 RU RU2008152317/04A patent/RU2008152317A/ru not_active Application Discontinuation
  • 2007-06-07 KR KR1020097000222A patent/KR20090035512A/ko not_active Application Discontinuation
  • 2007-06-07 MX MX2008014810A patent/MX2008014810A/es unknown
  • 2007-06-07 WO PCT/US2007/013538 patent/WO2007146142A1/en active Application Filing
  • 2007-06-07 CA CA002651424A patent/CA2651424A1/en not_active Abandoned
  • 2007-06-07 BR BRPI0712118-0A patent/BRPI0712118A2/pt not_active IP Right Cessation

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