WO2015157929A1 - Sorbate ester or sorbamide coalescent in coatings formulation - Google Patents
Sorbate ester or sorbamide coalescent in coatings formulation Download PDFInfo
- Publication number
- WO2015157929A1 WO2015157929A1 PCT/CN2014/075446 CN2014075446W WO2015157929A1 WO 2015157929 A1 WO2015157929 A1 WO 2015157929A1 CN 2014075446 W CN2014075446 W CN 2014075446W WO 2015157929 A1 WO2015157929 A1 WO 2015157929A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coalescent
- composition
- polymer particles
- ester
- group
- Prior art date
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Classifications
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/10—Esters; Ether-esters
- C08K5/101—Esters; Ether-esters of monocarboxylic acids
- C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/20—Carboxylic acid amides
Definitions
- the present invention relates to a composition
- a composition comprising a stable aqueous dispersion of polymer particles (that is, a latex) and a sorbate ester or sorbamide coalescent.
- VOCs volatile organic chemicals
- Paint formulations comprise either a low T g polymer latex that forms film with little or no coalescent, or a high T g latex that forms film with the aid of a coalescent.
- Formulations containing low T g polymers generally give coatings having a soft and tacky feel and poor durability.
- Formulations using high-T g polymers require either permanent (nonvolatile) coalescents or volatile coalescents; permanent coalescents are known to adversely affect the hardness performance of the consequent coating; volatile coalescents such as Texanol, on the other hand, may give acceptable hardness performance - for example, a Konig hardness of ⁇ 20 s at 28 days for a typical semigloss paint - but are undesirable for their volatility.
- WO 2007/094922 describes the use of a bis-allylic unsaturated fatty acid ester as a reactive coalescent. Unfortunately, the described coalescent does not yield the desired hardness performance properties for the consequent coating.
- the present invention addresses a need in the art by providing a composition comprising a stable aqueous dispersion of polymer particles and from 0.5 to 35 weight percent of a sorbate ester or sorbamide coalescent, based on the weight of the polymer particles, wherein the coalescent is imbibed in the polymer particles.
- the composition of the present invention provides a way to enhance film formation of coatings at or even below room temperature, prepared using relatively high T g latexes without the aid of high volatile organic content (VOC) coalescents.
- VOC volatile organic content
- the present invention is a composition
- a composition comprising a composition comprising a stable aqueous dispersion of polymer particles and from 0.5 to 35 weight percent of a sorbate ester or sorbamide coalescent, based on the weight of the polymer particles, wherein the coalescent is imbibed in the polymer particles.
- the coalescent is preferably a liquid at 20 °C and preferably characterized by the following formula:
- R is a C 1 -C 20 linear or branched alkyl group optionally functionalized with an ether, thioether, amine, hydroxyl, ester, phenyl, alkyenyl groups, or combinations thereof; and C(0)X is an ester group or an amide group.
- R is -(CH 2 -CH(R 1 )-0) n -R 2 ,-CH(R 1 )-CH 2 -0-R 2 , or linear or branched -R 3 -OR 2 ; where RHS H, Ci-C 6 -alkyl ,-CH 2 OH, or phenyl;
- the coalescent preferably has a molecular weight in the range of 126 g/mol to 2000 g/mol, more preferably to 1000 g/mol, and most preferably to 500 g/mol. It is possible that the coalescent includes more than one sorbate ester or amide groups, or combinations thereof.
- a preferred coalescent is a sorbate ester wherein the ester portion (the R group) is
- coalescent of the composition of the present invention can be prepared in a variety of ways such as those set forth in the following schemes where R is as previously defined and Y is OH or CI: Scheme 1
- EDC is l-ethyl-3-(3-dimethylaminopropyl)carbodiimide
- DMAP is 4-dimethylamino pyridine
- TEA is triethylamine.
- the sorbate ester coalescent can also be prepared, for example, by way of transesterification of an alcohol and the sorbic acid or by reaction of the alcohol with an acid halide or an anhydride of the sorbic acid.
- Suitable sorbate ester and sorbamide coalescents include:
- the word "imbibed” means that at least 60% of the coalescent in the composition is incorporated into the polymer particles, that is, less than 40% of the coalescent is present in the aqueous phase of the latex. Preferably, at least 90%, more preferably at least 95, and most preferably at least 98% of the coalescent is imbibed into the polymer particles.
- the extent of imbibing can be determined by proton NMR spectroscopy, as discussed in the section of this text titled "Determination of Imbibing of Coalescent into the Latex Particle.”
- the coalescent preferably has a boiling point at atmospheric pressure of greater than 250 °C; as such, the preferred embodiment of the present invention promotes hardening of a coating prepared from the composition without the use of volatile coalescents.
- the coalescent gives surprisingly useful low temperature film formation (LTFF) properties in the formulated paint, that is, it provides excellent mechanical strength for films that are formed at 4 °C.
- the coalescent is preferably used at a concentration in the range of from 1 to 20, more preferably to 12 weight percent, based on the weight of the polymer particles and the coalescent.
- the coalescent is a sorbate ester.
- Suitable stable aqueous dispersions of polymer particles include acrylic, styrene-acrylic, vinyl ester-acrylic, polyurethane, alkyd, and vinyl-ester polyethylene latexes.
- the solids content of the latex is preferably in the range of 30 to 60%, and the T g of the polymer particles is preferably in the range of from 0 °C, more preferably from 20 °C, to 100 °C, more preferably 60 °C.
- the composition may be pigmented or non-pigmented.
- a preferred pigmented coating contains Ti0 2 .
- the polymer particles mays also include structural units of other monomers, particularly a post-crosslinking monomer (that is, a monomer that causes significant crosslinking after onset of film formation of the composition when applied to a substrate).
- a post-crosslinking monomer that is, a monomer that causes significant crosslinking after onset of film formation of the composition when applied to a substrate.
- suitable post-crosslinking monomers include acetoacetoxyethyl methacrylate (AAEM) and diacetone acrylamide (DAM).
- composition advantageously further includes one or more of the following materials: rheology modifiers; opaque polymers; fillers; colorants; pigments, including encapsulated or partially encapsulated pigments; dispersants; wetting aids; dispersing aids; anti-oxidants; dispersant adjuvants; chelating agents; surfactants; co-solvents; additional coalescing agents and plasticizers; defoamers; preservatives; anti-mar additives; flow agents; leveling agents; slip additives; and neutralizing agents.
- Coatings with suitable hardness can be prepared from the composition of the present invention without the use of a high VOC coalescent. Examples
- a reactor equipped with a stirrer and a cooling condenser was charged with sorbic acid (45.0 g), xylene (150.0 g), FeCl 3 (0.65 g) and phenothiazine (0.04 g). After a nitrogen purge, the mixture was heated with stirring to 75 °C, at which time liquid propylene oxide (24.4 g) was added at 2 mL/min. The obtained liquid product was cooled to 45 °C.
- Sorbic acid (98.56 g), triethylene glycol (135.36 g), p-toluenesulfonic acid (TsOH) (2.00 g), and butylated hydroxytoluene (BHT) (1 g) were dissolved in xylene (200 mL). This resulting mixture was allowed to react at 140 °C (oil bath) using a Dean-Stark apparatus. After 7 h, the contest of the reactor were cooled to room temperature and neutralized by washing through an aqueous solution containing 10% of NaCl and 7% of Na 2 C0 3 . The suspense was further filtrated through celite and dried over Na 2 S0 4 . The product was filtrated and evaporated to afford a colorless oil (122.5 g).
- Example 1 is the paint formulation using Intermediate 1; Examples 2 and 3 and Comparative Example 1 used the identical formulation except that Intermediate 2 (37.8 g) was used to prepare Example 2,
- TRITON, TAMOL, RHOPLEX, and ACRYSOL are all Trademarks of The Dow Chemical Company or its affiliates.
- the HG-95P emulsion polymer contains ⁇ 8 weight percent structural units of AAEM.
- Drawdowns of the paints (10 mil wet on aluminum panels, 25 g base paint with 0.85 g coalescent) were prepared for Konig testing. All drawdowns were stored in the controlled temperature room until use. Konig testing was done using the TQC Pendulum Hardness Tester SP0500. Each Konig value reported is the average of three measurements.
- Table 3 illustrates Konig hardness and LTFF (Low Temperature Film Formation at 4.5 °C) rating for the three formulation examples (Ex. 1, Ex. 2, Ex. 3) and the Comparative Example formulation (Comp. Ex.), which contains sorbic acid.
- LTFF Low Temperature Film Formation at 4.5 °C
- the formulations containing the sorbate ester coalescents showed adequate Konig hardness, even when compared to Texanol, which has a boiling point of 254 °C, as well as a top rating for LTFF.
- the formulation using sorbic acid although showing adequate Konig Hardness, showed no coalescence of the film at 4.5 °C and 40% relative humidity, as indicated by the lowest LTFF rating.
- the results demonstrate the remarkable and surprising difference in the film-forming enhancement of coatings formulations imparted by sorbate esters as compared to sorbic acid. The results further demonstrate that sorbic acid is not functioning as a coalescent.
- the latex containing the coalescent was placed as is in an NMR tube and resonances associated with the coalescent were monitored in the aqueous phase of the of the emulsion latex.
- signals from the aqueous phase were the only ones detected because the molecules in the latex particles are partly immobilized, leading to extremely broad signals that are not detected within the spectral width for aqueous phase materials.
- the spectra revealed only slight traces of the coalescent ( ⁇ 1% by weight) in the aqueous phase.
- sorbic acid was detected quantitatively or nearly quantitatively in the aqueous phase, which demonstrates that it does not partition into the latex particles.
- Minimum film formation temperature The minimum film formation temperature (MFFT) of a latex is the lowest temperature at which the latex forms a practical film. MFFT is typically measured using ASTM standard D2354-10. In this test method, the MFFT is determined by visual observation of cracking or whitening in films that have dried over a substrate having a controlled temperature gradient. In addition to the visual MFFT, a mechanical MFFT can also be determined by locating the minimum temperature at which the latex formed a film with some mechanical strength.
- the MFFT is measured determined at various coalescent levels. Typically reported in AMFFT (°C)/coalescent level (weight % coalescent based on solid polymer), the AMFFT is a direct measurement of the coalescent efficiency. Table 4 shows the visual MFFT of RHOPLEX HG-95P Binder with different coalescents at various levels. The percent coalescent level is based on binder solids. Similar behavior was observed for the mechanical MFFT.
- MFFT data for the comparative sorbic acid was not obtainable because of poor colloidal stability of the latex and the sorbic acid.
- Table 4 shows that MFFT decreases for each formulation with increasing sorbate level concentration. At 12% levels, the MFFT is less than 5 °C in each case, which is of particular interest to formulators who require that their formulations pass such as test.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Paints Or Removers (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Adhesives Or Adhesive Processes (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2014391006A AU2014391006A1 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
PCT/CN2014/075446 WO2015157929A1 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
BR112016024069A BR112016024069A2 (en) | 2014-04-16 | 2014-04-16 | sorbate or coalescing ester of sorbamide in coating formulation |
EP14889391.0A EP3131961A4 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
CN201480078034.0A CN106459485A (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
US15/303,752 US20170037266A1 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in a coatings formulation |
KR1020167030673A KR20160147792A (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
CA2945512A CA2945512A1 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCT/CN2014/075446 WO2015157929A1 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
Publications (1)
Publication Number | Publication Date |
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WO2015157929A1 true WO2015157929A1 (en) | 2015-10-22 |
Family
ID=54323366
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2014/075446 WO2015157929A1 (en) | 2014-04-16 | 2014-04-16 | Sorbate ester or sorbamide coalescent in coatings formulation |
Country Status (8)
Country | Link |
---|---|
US (1) | US20170037266A1 (en) |
EP (1) | EP3131961A4 (en) |
KR (1) | KR20160147792A (en) |
CN (1) | CN106459485A (en) |
AU (1) | AU2014391006A1 (en) |
BR (1) | BR112016024069A2 (en) |
CA (1) | CA2945512A1 (en) |
WO (1) | WO2015157929A1 (en) |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3070129A1 (en) * | 2015-03-17 | 2016-09-21 | Dow Global Technologies LLC | Sorbic acid ester containing coatings composition |
WO2017139965A1 (en) * | 2016-02-19 | 2017-08-24 | Rohm And Haas Company | High purity disorbate ester of triethylene glycol |
WO2017139966A1 (en) * | 2016-02-19 | 2017-08-24 | Rohm And Haas Company | Preparation of high purity disorbate ester of triethylene glycol |
CN109153874A (en) * | 2016-04-08 | 2019-01-04 | 陶氏环球技术有限责任公司 | Coating composition containing sorbate and photochemical catalyst |
EP3470474A1 (en) | 2017-10-11 | 2019-04-17 | Dow Global Technologies Llc | Waterborne damping composition |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CA2912291A1 (en) * | 2014-12-01 | 2016-06-01 | Dow Global Technologies Llc | Sorbic acid ester composition |
JP6417953B2 (en) * | 2015-01-15 | 2018-11-07 | オムロン株式会社 | Display device |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2133375A1 (en) * | 2008-06-11 | 2009-12-16 | Rohm and Haas Company | Low VOC aqueous compositions of phosphorus acid functional polymers and polyurethanes |
US20090318596A1 (en) * | 2008-06-11 | 2009-12-24 | Zhenwen Fu | Aqueous compositions comprising a blend of emulsion vinyl copolymer and polyurethane dispersion |
Family Cites Families (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL263266A (en) * | 1960-08-01 | |||
EP0026982A1 (en) * | 1979-09-07 | 1981-04-15 | Rohm And Haas Company | Coating compositions containing mono- or diester coalescing agents and a substrate coated therewith |
WO2007094922A2 (en) * | 2006-01-20 | 2007-08-23 | Archer-Daniels-Midland Company | Levulinic acid ester derivatives as reactive plasticizers and coalescent solvents |
US20080182929A1 (en) * | 2006-10-30 | 2008-07-31 | Velsicol Chemical Corporation | Aqueous Coating Compositions Exhibiting Increased Open Time With Reduced Levels Of Volatile Organic Compounds |
BRPI1102456B1 (en) * | 2011-05-26 | 2021-03-30 | Oxiteno S/a Industria E Comércio | COMPOSITION OF COALESCENCE AGENTS, AND, USE OF THE COMPOSITION OF COALESCENCE AGENTS |
-
2014
- 2014-04-16 AU AU2014391006A patent/AU2014391006A1/en not_active Abandoned
- 2014-04-16 KR KR1020167030673A patent/KR20160147792A/en not_active Application Discontinuation
- 2014-04-16 BR BR112016024069A patent/BR112016024069A2/en not_active IP Right Cessation
- 2014-04-16 CN CN201480078034.0A patent/CN106459485A/en active Pending
- 2014-04-16 EP EP14889391.0A patent/EP3131961A4/en not_active Withdrawn
- 2014-04-16 WO PCT/CN2014/075446 patent/WO2015157929A1/en active Application Filing
- 2014-04-16 US US15/303,752 patent/US20170037266A1/en not_active Abandoned
- 2014-04-16 CA CA2945512A patent/CA2945512A1/en not_active Abandoned
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2133375A1 (en) * | 2008-06-11 | 2009-12-16 | Rohm and Haas Company | Low VOC aqueous compositions of phosphorus acid functional polymers and polyurethanes |
US20090318596A1 (en) * | 2008-06-11 | 2009-12-24 | Zhenwen Fu | Aqueous compositions comprising a blend of emulsion vinyl copolymer and polyurethane dispersion |
Non-Patent Citations (1)
Title |
---|
See also references of EP3131961A4 * |
Cited By (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3070129A1 (en) * | 2015-03-17 | 2016-09-21 | Dow Global Technologies LLC | Sorbic acid ester containing coatings composition |
US20160272825A1 (en) * | 2015-03-17 | 2016-09-22 | Dow Global Technologies Llc | Sorbic acid ester containing coatings composition |
US9828510B2 (en) | 2015-03-17 | 2017-11-28 | Rohm And Haas Company | Sorbic acid ester containing coatings composition |
WO2017139965A1 (en) * | 2016-02-19 | 2017-08-24 | Rohm And Haas Company | High purity disorbate ester of triethylene glycol |
WO2017139966A1 (en) * | 2016-02-19 | 2017-08-24 | Rohm And Haas Company | Preparation of high purity disorbate ester of triethylene glycol |
CN108603047A (en) * | 2016-02-19 | 2018-09-28 | 罗门哈斯公司 | Two sorbate of high-purity of triethylene glycol |
CN109153874A (en) * | 2016-04-08 | 2019-01-04 | 陶氏环球技术有限责任公司 | Coating composition containing sorbate and photochemical catalyst |
EP3440141A4 (en) * | 2016-04-08 | 2019-10-09 | Dow Global Technologies, LLC | Coating composition containing sorbic acid ester and photocatalyst |
EP3470474A1 (en) | 2017-10-11 | 2019-04-17 | Dow Global Technologies Llc | Waterborne damping composition |
Also Published As
Publication number | Publication date |
---|---|
KR20160147792A (en) | 2016-12-23 |
CN106459485A (en) | 2017-02-22 |
CA2945512A1 (en) | 2015-10-22 |
EP3131961A1 (en) | 2017-02-22 |
US20170037266A1 (en) | 2017-02-09 |
AU2014391006A1 (en) | 2016-11-24 |
BR112016024069A2 (en) | 2017-08-15 |
EP3131961A4 (en) | 2018-01-10 |
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