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    • 专利摘要:
    new dibenzoate plasticizer/coalescent blends for low you coatings. A novel, low volatility, non-phthalate plasticant/coalescent combination for use in tubs and other polymeric coatings is disclosed comprising a triple blend of diethylene glycol dibenzoate, dipropylene glycol dibenzoate and 1,2-propylene glycol dibenzoate. the triple mix used in a paint or other coatings provides a low-voice paint or coating with stable viscosity after three freeze/thaw cycles and equivalent or greater runtime/wet edge coefficients, gloss coefficients, frictional resistance and toughness blocking as compared to traditional coalescents including, but not limited to, high voc coalescents, low voc non-dibenzoate coalescents and other dibenzoate mixtures. the triple blend can be employed as a substitute or alternative coalescent in acrylic and latex emulsion coatings, among others, in order to achieve a lower content of you without sacrificing performance properties.
    公开号:BR112013016920B1
    申请号:R112013016920-6
    申请日:2011-12-28
    公开日:2021-06-29
    发明作者:Willian D. Arendt；Emily MCBRIDE
    申请人:Emerald Kalama Chemical, Llc；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION
    [0001] This invention is directed to novel film-forming aids for use in formulating paints and other coating compositions. In particular, this invention is directed to a new triple combination dibenzoate composition having low VOC content and improved performance characteristics over traditional plastic/coalescent compositions, including low VOC plasticizer compositions, thus facilitating , use in well-known emulsion systems for formulating paints and other coatings. The new film-forming aid of the invention is compatible, efficient and works well in common emulsions, including, but not limited to, latex paints and coatings. BACKGROUND OF THE INVENTION
    [0002] Volatile organic compounds ("VOC") are carbon-containing compounds, which easily vaporize or evaporate into air, where they can react with other elements or compounds to produce ozone. Ozone, in turn, causes air pollution and a host of health problems, including respiratory problems, headaches, burning, watery eyes and nausea, just to name a few. Some VOCs have also been linked to cancer, as well as kidney and liver damage.
    [0003] VOCs are of particular concern in the paint and coatings industry in the manufacture and application of products using VOC. The use of VOCs in the manufacture of paints and coatings results in poor facility air quality and worker exposure to harmful chemicals. People who are exposed to VOCs can suffer from a number of health problems, including, but not limited to, various types of cancers, impaired brain function, kidney dysfunction and other health problems.
    [0004] Likewise, painters and other users of paints and coatings containing VOCs who are regularly exposed to the harmful vapors of VOCs can suffer from health problems. Products containing VOC release harmful VOCs into the air as they dry, especially with indoor applications. Indoor VOC levels are routinely 10 times higher than outdoor levels and can be up to 1000 times higher immediately after painting. Also, although VOC levels are highest during and shortly after painting, they continue to leak for several years. In fact, only 50 percent of VOCs can be released in the first year.
    [0005] Thus, regulations were implemented to protect manufacturing workers and end users.
    [0006] Paints and coatings with high VOC content are also considered environmental hazards. They are the second largest source of VOC emissions to the atmosphere after automobiles, which account for roughly 11 billion pounds each year.
    [0007] Consumers are demanding safer alternatives and coating formulators will continue to be faced with the challenge of reducing VOCs, while at the same time providing a coating with the required performance characteristics. Most of the time, formulators reduce the amount of components, or replace the more volatile components used in paints, which reduces VOC seizures to some extent and can nevertheless result in compromised performance. Desirably, a low VOC paint or coatings should have a minimum performance equivalent to higher VOC paints or coatings. To this end, raw material suppliers continue to develop new products, with low VOC's content for use in paints and coatings, which do not compromise performance.
    [0008] A volatile component, typically very necessary, but often used in coating compositions is the film-forming aid, that is, coalescent, which allows a formulator to use conventional latex emulsions and well recognized lower cost. Coalescents facilitate film formation by softening the dispersed polymers and allowing them to liquefy or form a continuous film. The coalescent will partially or completely volatilize out of the film, allowing it to recover from its original physical properties, such as gloss and peel resistance. Coalescents are selected to improve paint film/coat properties such as gloss, peel resistance and blockage resistance. Coalescents are also selected based on a range of properties, including, without limitation, volatility, miscibility, stability, compatibility, ease of use and cost. Traditional coalescents are highly volatile and can significantly contribute to the VOC content of a paint or coating.
    [0009] As an alternative to obtain a lower VOC content, polymeric emulsion systems that do not require these highly volatile film-forming aids are being developed. The polymers used in these newer emulsion systems tend to be soft enough to allow a low TMFP (minimum film forming temperature), however certain performance parameters can sometimes suffer, and these emulsion systems more -ves are, more often than not, expensive.
    [00010] Film-forming aids are known in the art. Hydrophobic film-forming aids such as industry standard 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate (TXMB), splitting the polymer into the emulsion and softening the dispersed particles of the emulsion during the phase of application coalescence. The coalescent then partially or completely evaporates from the film. By its nature, this coalescent that "leaks" significantly contributes to the film's VOCs, starting with the coalescence phase and lasting for a prolonged period afterward. This fact may affect the air quality around the film and manifest as an unpleasant odor.
    [00011] Due to these problems, there has been a trend towards the development and use of less volatile and more stable film-forming aids, such as plasticizers, for the coatings industry.
    [00012] Plasticizers have been known and used for years as excellent coalescents for latex paints and other coatings. In some cases, they are also desired for their plasticizing function, because softening of a more rigid base polymer in the coating is often desired. It is further known that plasticizers can improve other paint performance characteristics such as slurry cracking, wet edge and run time. Plasticizers have a higher degree of permanence than other traditional coalescents, and in some cases plasticizer permanence can be a disadvantage. For coalescents, a balance must be struck between greater permanence and therefore less VOC's and good final film properties.
    [00013] Phthalate plasticizers, such as di-n-butyl-phthalate (DBP), diisobutyl phthalate (DIBP), butyl benzyl phthalate (BBP), have traditionally been used in the coatings industry, when a true plasticizer is needed, as is the case when polymers with high Tg of (glass transition temperatures) are employed in one application or another. DPB and DIBP have a lower VOC content than traditional coalescents, but are still somewhat volatile, while BBP has a very low VOC content. In addition to the VOC content, however, the use of phthalate ester has some disadvantages, as the use of DBP and BBP in particular are restricted due to regulatory concerns.
    [00014] Dibenzoate plasticizers have been recognized for a number of applications since circa 1938. Their usefulness in coatings is also well recognized. Dibenzoates by their nature are non-phthalates and do not have the restrictions or health problems associated with phthalates.
    [00015] Monobenzoate ester coalescing technology has been developed and evolving since the 1980s, when isodecyl benzoate (IDB) was introduced in the coatings industry as a new coalescent with lower VOC content. IDB has compatibility with a wide variety of polymers which has been found to be an effective form of low odor coalescents in latex paint formulations as compared to the traditional use of TXMB as the coalescent.
    [00016] U.S Patent No. 5,236,987 to Arendt discloses the use of isodecyl benzoate, decyl benzoate, isooctyl benzoate, nonylbenzoate, and dodecyl benzoate as coalescents for latex paints.
    [00017] At the beginning of the 21st century, 2-ethylhexyl benzoate (2-EHB), was created as a new film-forming aid with lower VOC content. 2-EHB was seen to have greater efficacy than TXMB in many formulations, as well as a lower odor. Isononylbenzoate (INB) was introduced in 2009 as a coalescent with a formulated evaporation rate and efficiency comparable to 2 EHB, while at the same time exhibiting more effective MFFT reduction behavior than IDB.
    [00018] The second generation of benzoate ester coalescing technology was developed with the less volatile dibenzoate esters. Dibenzoates can satisfy low VOC requirements where volatilities of monobenzoate esters are considered to be very high. Dibenzoate technology has traditionally been based on mixtures of dipropylene glycol dibenzoate (DPGDB) and diethylene glycol dibenzoate (DEGDB). Films formulated with these blends were considered to have performance properties comparable to those formulated with TXMB, with improved friction resistance and chemical resistance with increased run times.
    [00019] Mixtures of dibenzoates together with other components for use in aqueous polymeric coating compositions with lower VOC and other film-forming coating compositions are described in the art.
    [00020] U.S. Patent Publication No. 2008/0182929 to Strepka et. al., discloses aqueous low VOC coating compositions containing dipropylene dibenzoates and diethylene glycol in combination with at least one of the corresponding monoesters for the primary purpose of prolonging the operating time exhibited by aqueous polymer compositions and partially to replace at least a part of the more volatile organic compounds typically used as coalescents.
    [00021] U.S. Patent Publication No. 2008/0076861 to Strepka et. al., discloses a film-forming composition comprising at least one acrylic or vinyl acetate polymer or a copolymer as a film-forming ingredient and a benzoate blend of a 6-carbon monohydric alcohol, dibenzoate. diethylene glycol, diethylene glycol monobenzoate to be used in floor polishing.
    [00022] Patent publication No. 2011/0218285 describes a low VOC coating additive employing a water-dispersible polymer, a water-insoluble plasticizer, cyclohexanedimethanol, and, optionally, an amphiphilic component for coatings in order to improve at least one coating performance characteristic, such as wet edges, run time, friction resistance, wet grip and water resistance. Among the plasticizers described are diethylene glycol dibenzoate, dipropylene glycol dibenzoate and tripropylene glycol dibenzoate.
    [00023] Still, there is a need to continue efforts in plasticizer/coalescent technology in order to achieve the minimum possible VOC's, improving performance properties. A newer next generation triple blend of dibenzoate esters has been developed, which works just as well as traditional plasticizers or low VOC coalescents in coating applications, by achieving unexpectedly better performance benefits in gloss and friction resistance compared to with the current generation of low VOC coalescing technology, including some improvements over traditional dibenzoate blends.
    [00024] A new triple-blend dibenzoate plasticizer for use in low VOC paints and coatings has been developed. The present invention is directed to a blend of three plasticizers of dibenzoate, DEGDB, DPGDB and 1,2-propylene glycol dibenzoate (PGDB), which allows for low VOC coalescence, while yielding unexpectedly better properties over tra-dibenzoate blends. additionals. The inventive triple blend is an improvement over existing dibenzoate plasticizer technology used in paints and coatings, and has not previously been known or used in paint and coating applications. The propylene glycol 1,2-dibenzoate component was previously known for its use as a plasticizer, but not in the inventive mixture disclosed herein. More specifically, propylene glycol 1,2-dibenzoate has become known as a flavoring agent for beverages as described in the US Patent. No. 3,652,291 to Bedoukian.
    [00025] The inventive triple blend is particularly useful in latex and acrylic coating applications and provides improved gloss, freeze/thaw stability, friction resistance, and chemical resistance and run times comparable to traditional blends of dibenzoate plasticizer. The new triple mix is compatible with a wide variety of materials used in paints and other coatings. The new triple blend of DPGDB, DEGDB, and PGDB has not been used in paints and other coatings in the past.
    [00026] The focus of the present invention lies in the use of the inventive mixture for the formulation of paints and other architectural and industrial coatings, however, the invention is not limited to these applications. The inventive triple plasticizer blend can be used, alone or in combination with other plasticizers in applications including, but not limited to: adhesives, sealants, OEM coatings, plastisol, sealants over printing varnishes, polishes, inks, vinyl compounds in melting, polyurethanes, polysulfides, epoxies, styrene acrylics and combinations thereof.
    [00027] It is an object of the invention to provide a film-forming aid that has a low VOC content, efficiency and compatibility when used in traditional latex emulsions or other polymeric coatings,
    [00028] It is yet another object of the invention to provide a polymeric emulsion paint or coating with a low VOC content and better performance properties, including, without limitation, gloss, chemical resistance and peel resistance, than achieved with current low VOC emulsion paints and coatings.
    [00029] It is yet another object of the invention to provide a polymeric emulsion paint or coating with low VOC content, which is low cost and effective for production, and yet environmentally harmless and safe to handle, not subject to control regulatory. SUMMARY OF THE INVENTION
    [00030] Plasticizer combinations of the present invention comprise the original formulations of three dibenzoate esters: diethylene glycol dibenzoate, (DEGDB), dipropylene glycol dibenzoate (DPGDB), and 1,2-propylene glycol dibenzoate (PGDB). In one embodiment, the plasticizer is a novel triple blend comprising from about 10% to about 90% by weight DEGDB, from about 1% by weight to about 50% by weight DPGDB%, and from about 10% by weight to about 90% by weight PGDB%, based on the total weight of the mixture.
    [00031] The plasticizers/coalescents identified above are compatible with each other and with various polymers used in paints and coatings, such as, for example, polyvinyl chloride and its copolymers, various polyurethanes and its copolymers; various polyacrylates and copolymers thereof; various polysulfides, various epoxies and their copolymers, and vinyl acetate and their copolymers. In particular, the new triple blend of the invention is particularly compatible with latex and other polymeric emulsions used in the paint and coatings industry.
    [00032] The inventive plasticizer/coalescent triple dibenzoate blend has low volatility and compares favorably with the industry standard film forming aid TXMB and the current triethylene glycol bis-(2-ethylhexanoate) (TEGDO). In particular, the inventive triple dibenzoate blend provides equivalent, and in some cases even better, performance benefits in gloss and peel resistance compared to some current low VOC standard coalescent alternatives, including blends traditional dibenzoate. The inventive triple blend particularly shows a significant benefit in using the most demanding acrylic copolymer gloss system, where it provides superior advantages of both peel resistance and blockage resistance. The formulations of the invention provide an alternative to paint and coating formulators by improving the current landscape of low VOC coalescents, including traditional dibenzoate coalescents. They also offer options for using harder polymers (Tg > 10 °C) in paints and coatings. The inventive triple blend can also be used with softer polymers intended for low VOC coatings as it will help the coating form a better film. BRIEF DESCRIPTION OF THE DRAWINGS
    [00033] FIGURE 1 is a graph that reflects the volatility of both plasticizers and coalescents non-dibenzoate and dibenzoate.
    [00034] Figure 2 is a graph reflecting the viscosity stability of smooth acrylic paint after three freeze/thaw cycles for various low VOC coalescents.
    [00035] Figure 3 is a graph that reflects the viscosity stability of the semi-gloss acrylic paint, after three freeze/thaw cycles for various coalescents.
    [00036] Figure 4 is a graph reflecting runtime/wet tip evaluations of a smooth vinyl acrylic paint for various coalescents.
    [00037] Figure 5 is a graph reflecting running time/wet tip evaluations of an acrylic paint being semi-gloss for various coalescents.
    [00038] Figure 6 is a graph reflecting runtime/wet tip ratings of an acrylic paint with copolymer gloss for various coalescents.
    [00039] Figure 7 is a graph reflecting gloss ratings of a semi-gloss acrylic paint for various coalescents.
    [00040] Figure 8 is a graph reflecting gloss ratings of a semi-gloss acrylic paint for various low VOC coalescents.
    [00041] Figure 9 is a graph reflecting gloss ratings of an acrylic copolymer gloss paint for various low VOC coalescents.
    [00042] Figure 10 is a graph reflecting the friction resistance of a smooth vinyl acrylic paint and a semi-gloss paint for various low VOC coalescents.
    [00043] Figure 11 is a graph reflecting the frictional resistance of an acrylic copolymer gloss paint for various coalescents.
    [00044] Figure 12 is a graph reflecting the blocking resistance of a semi-gloss acrylic paint for various low VOC coalescents.
    [00045] Figure 13 is a graph reflecting the blocking resistance of an acrylic copolymer gloss paint for various low VOC coalescents. DETAILED DESCRIPTION OF THE INVENTION
    [00046] The present invention is directed to a triple blend of plasticizers DEGDB, DPGDB and PGDB in the relationships discussed herein. The plasticizers of the present invention can generally be used as a plasticizer/coalescent, with numerous thermoplastic, thermoset or elastomeric polymers and polymer emulsions, often as a substitute or alternative to conventional plasticizers/coalescents, provided with a content of superior VOC. Any known polymers that can be formulated into a paint or coating can be used in combination with the new triple blend to prepare a low VOC paint or coating in accordance with the present invention.
    [00047] Useful polymers include, but are not limited to, the various latex polymers and vinyl polymers, including vinyl acetate, vinylidene chloride, diethyl fumarate, diethyl maleate, or polyvinyl butyral, a variety of polyurethanes and its copolymers; various polysulfides, cellulose nitrate, polyvinyl acetate, ethylene vinyl acetate, and copolymers thereof, and various polyacrylates and their copolymers.
    [00048] Acrylates in particular constitute a large group of polymers of different degrees of hardness for use with the triple blend of the present invention and, include without limitation, the various polyalkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, or allyl methacrylate; various aromatic methacrylates such as benzyl methacrylate; various alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate, or 2-ethylhexyl; various acrylic acids such as methacrylic acid, vinyl acrylics, styrene acrylics, and epoxy-acrylic hybrids.
    [00049] Other polymers include, without limitation, epoxies, phenol-formaldehyde types; melamines and the like.
    [00050] The present invention is not limited to any particular polymer. Other polymers useful in paint and coating applications will be known to one of skill in the art.
    [00051] The present invention is described herein in terms of latex or other emulsions, such as acrylics, also having utility with a wide variety of polymers.
    [00052] Preferred dibenzoates comprising the triple mixture of plasticizer/binder include DEGDB, DPGDB and propylene glycol 1,2-dibenzoate (PGDB).
    [00053] The amount of individual dibenzoates in the triple mixture of the invention can vary widely depending on the particular end use, and the desired properties. Thus, the amount of DEGDB can range from about 10% to about 90% by weight based on the total weight of the dibenzoate triple blend composition, preferably greater than about 60% by weight. Higher amounts of DEGDB are preferred than either of the other two plasticizers, due to cost considerations. DEGDB is much less expensive than PGDB and DPGDB. The amount of DPGDB generally can range from about 1% to 50% by weight based on the total weight of the triple mixture, preferably greater than about 15%. The amount of PGDB can vary as widely as from about 10% to about 90% by weight based on the total weight of the triple mixture of dibenzoates, but is preferably present in amounts of about 20% by weight. . PGDB is also less expensive than DPGDB.
    [00054] A preferred embodiment is shown below: a. 1,2-PGDB 20% by weightb. DEGDB / DPGDB 80/20 80% by weight The new triple mixture of dibenzoates of the present invention can be used as a substitute or acceptable plasticizer/coalescent for various low VOC paints and architectural and industrial coatings in interior and exterior applications, such as by example, gloss paint, semi-gloss and eggshell paints.
    [00055] The amounts of the triple mixture of dibenzoates used in paints and coatings may vary depending on the composition of the particular paint or coating, the characteristics, its application or use and the desired results. As a target objective, the inventive triple plasticizer/binder mixture is used in an amount sufficient to form a film that will not crack at 4.44°C (40°F). Exemplary amounts can range from about 0.5 to about 1.5% per 3.8 liters (1 gallon) of architectural paint/coating. Luminous industrial coatings or other coatings may require a greater range.
    [00056] Other useful quantities are given in the examples. It is expected that one skilled in the art will be able to arrive at additional acceptable values based on the intended use and desired performance of the particular coating application. The amount of binder/plasticizer required is based on the MFFT of the base emulsion. The harder the polymer (higher TMFP and Tg), the more plasticizer/binder you will need. In some applications, as much as 20% or more plasticizer, based on resin solids, may be required.
    [00057] The new triple plasticizer/binder blends of the present invention provide a low VOC content, viscosity stability, i.e. good freeze/thaw performance, better or equivalent runtime/edge performance wet, better shine and unexpectedly improves exfoliation and blocking resistance. In many cases, the inventive triple blend has outperformed industry standard coalescents regardless of VOC content, including traditional and newer dibenzoate blends. The inventive triple blend is particularly useful as a coalescent when considering the use of harder polymers as alternatives to softer polymers for low VOC formulations.
    [00058] The invention is further described by means of the following examples: Experimental Methodology Tested Coatings:
    [00059] Two common architectural latex paint emulsions and one emulsion commonly used in light industrial paint applications were selected to perform a series of tests on the inventive triple blend. The vinyl acrylic emulsion (TMFP = 12°C, Tg = 19°C) shown in Table 1, below, was chosen as the polymer for a smooth interior formulation, and the acrylic emulsion (TMFF <12°C) shown in Table 2, it was chosen as the polymer for a semi-gloss interior formulation. In addition, a harder acrylic copolymer gloss emulsion (MFFT = > 30°C) shown in Table 3 was selected to provide further validation of performance. It is recognized that hard acrylic copolymer is not intended for architectural paint applications particularly, rather it is designed for light industrial applications. However, this emulsion was chosen to explore the compatibility of the inventive plasticizer/binder triple blend.
    [00060] The chosen test methodology was the same for all paint/coating formulations in order to allow for appropriate comparisons when considering the use of harder polymers with plasticizers, as alternatives to the softer polymers in low-content formulations. YOU Using harder polymers is an alternative way to achieve lower VOC coatings than using soft polymers and provides more options for paint formulators considering the development of low VOC paints and coatings. Below are the main parameters of the coatings: Smooth acrylic vinyl paint - Solids volume = 34.8% and PVC = 58% Semi-gloss acrylic paint - Solids volume = 33.7% and PVC = 29.8% Acrylic copolymer bright - Solids volume = 18% and PVC = 35%.
    [00061] Generic starting formulations are listed in the tables below.
    [00062] With the exception of a certain adequate level of coalescent required, no attempt has been made to optimize the formulation for any coalescents.Table 1 - Vinyl Acrylic Flat Paint Formulations

    Formulation of Acrylic Copolymer Gloss Paint Tested components: plasticizer/coalescent
    [00063] The following plasticizers/coalescents in Table 4 were evaluated: Table 4 - Coalescent abbreviations


    [00064] TXMB - 2,2,4-trimethyl-1,3-pentanediol monoisobutyrate, is a widely used product, and it is an industry standard, despite the fact that it is considered 100% volatile by the method Test EPA 24 ASTM D-2369 triethylene glycol di-2-ethylhexanoate (TEGDO) is a commercial low VOC coalescent (CLVOC), which is the latest low VOC non-dibenzoate coalescent used as a primary control.
    [00065] Both K-FLEX 850S and BENZOFLEX LA-705 are the latest commercially available blends of two dibenzoates, K-FLEX 500 is an older traditional blend of two dibenzoate esters.
    [00066] The formulations of the invention include X10 and X20, which are mixtures of three dibenzoate esters in accordance with the present invention, differing only in the proportions of the esters used. Methods: Ink Preparation
    [00067] Raw materials for milling were mixed for 20 minutes in a high speed disperser. The resin was then added, and the master mix was divided into smaller batches. For each small batch, coalescent, defoamer and additional water were added. The ink was then mixed for an additional 10 minutes and allowed to settle overnight prior to testing. test oven
    [00068] ASTM D2369. As the invention is directed to low VOC coalescents, a first main test was the determination of the VOC of each tested coalescent. ASTM D2369, as described in EPA Method 24, is the procedure of choice for determining volatiles in coatings for the purpose of calculating the volatile organic matter content in coatings under specified test conditions. This information is useful to the paint producer and user and to environmental concerns in determining the volatiles emitted by coatings. For this example, 1/3 of a gram of each coalescent was placed in a weighing pan, and 3 ml of toluene was added. The coalescents were heated for one hour at 110°C + 5°C. The weight percent solids content (non-volatile matter) can be determined by the difference. Ink/Coating Test
    [00069] Ink evaluations consisted of the following determinations:
    [00070] Wet ink and film formation - pH, viscosity, KU and ICI, freeze/thaw, flow and leveling, running time/wet edge, dry to touch, spatter, low temperature film formation, touch ( room temperature and low temperature) and mud cracks.
    [00071] Dry films - friction resistance, blocking resistance, contrast ratio, color and brightness.
    [00072] Details of the test methods are presented in Table 5 below: Table 5 - Summary of Test Methods Employed


    Example 1 - Plasticizer/Coalescent Volatility
    [00073] Although the amount of coalescent used in a gallon of paint is not too large, minimizing all components contributing to the VOC content is essential. Even a raw material, usually used at a relatively low level, can be altered to reduce VOC significantly. Oven testing is a standard method to compare the VOC contribution of volatile and semi-volatile components. Oven tests as described above were performed on the plasticizers/coalescents listed in Table 4 and DIBP, BBP and DBP.
    [00074] Figure 1 illustrates the volatility of coalescents based on the results determined by the furnace test. As seen in Figure 1, the inventive formulation X20 had a comparable low volatility when compared to mixtures of the two dibenzoates (K-FLEX 850S (newer) and K-FLEX 500 (traditional), despite the values for K-FLEX 500 were slightly higher. X20 also had a favorable volatility profile when compared to the newer, low VOC non-dibenzoate coalescent used as the primary control (TEGDO).The values obtained for X10 were substantially the same as for X20, no being shown, however, in Figure 1. The values for BENZOFLEX LA-705 were comparable to the K-FLEX 500 and are also not shown in Figure 1. In general, the K-FLEX 850S, X10 and X20 produced the same values of low volatility.
    [00075] Figure 1 states that all low VOC coalescents were seen to be very low in volatility compared to TXMB, the industry standard, and as such were considered to be acceptable low VOC alternatives. Among the non-dibenzoate plasticizers, DIBP is the most volatile. The rest of the low VOC coalescents/plasticizers will contribute very little to the VOC of a coating, especially at low levels of employment. Example 2 - Coalescent Efficiency
    [00076] Before starting the paint evaluation, the efficiency of each coalescent was determined in the basic paint formulations described in Tables 1, 2 and 3 above. The determination of the efficiency of a coalescent is often made on the binary pair, determining the MFFT of the mixture of coalescent and base emulsion. In this case, each coalescent efficiency level was established by determining the amount of coalescent (in pounds) needed to obtain adequate film formation at (40°F) 4.44°C in each of the paints/coatings described. above. For this test, TXMB was used as the primary control for efficiency as it is still considered a benchmark in this type of test. For low VOC coalescents, the best comparison is TEGDO, a commercially available low VOC coalescent.
    [00077] For every 380 liters (100 gallons), smooth paint required 2.7216 kg (6 pounds), semi-gloss 1.587 kg (3.5 pounds), and gloss paint 17.23 kg (38 pounds) , in addition to the propylene glycol methyl ether present) of each binder for proper coalescence (film formation). Each coalescent was determined to have equivalent efficiency based on this test. Example 3 - Wet and Dry Film Characteristics
    [00078] Tables 6 to 8 reflect performance data obtained for wet paint or dry paint using various coalescents as described above. As can be seen from the tables, performance was similar for each paint in all cases, including pH, initial viscosity (Stormer and ICI), thermal stability, flow and leveling, mud cracks (flat only, ambient and low temperature temperature), retouching (room temperature and low temperature), color acceptance, spatter resistance and low temperature film formation (on sealed and unsealed substrates). Most of these parameters are considered very important, as the choice of coalescent has the potential to degrade performance in all these areas. For the most robust acrylic copolymer gloss formulation (Table 8), data is provided for KF850S, X20 and TEGDO only. Table 6 - Wet and Dry Ink Data for Acrylic Semi-Gloss Formulations




    Example 4 - Freeze/Thaw Resistance
    [00079] A paint attribute that can pass on paints or coatings with lower VOC content is freeze/thaw resistance. Figures 2 and 3 illustrate the results obtained for three freeze/thaw cycles in plain vinyl acrylic paints and semi-gloss acrylic paints. Plain paints with dibenzoate coalescents had better freeze/thaw characteristics than those with the new low VOC coalescent TEGDO. For the semi-gloss formulation, all paints using dibenzoate coalescents were superior to the TEGDO control, but similar to the TXMB alcohol ester control. In the glossy acrylic copolymer formulation, all systems studied failed after three freeze/thaw cycles. Based on these results, the inventive triple blend offers some advantages in smooth and semi-gloss formulations. Example 5 - Running Time/Wet Edge
    [00080] Coalescent type may affect wet edge/ink runtime. Plasticizers are known to prolong the wet edge better than volatile coalescents. Figures 4, 5 and 6 present the data obtained to describe this characteristic for the plasticizers/coalescents described herein. The test used to consider the wet edge or running time for the formulations evaluated is shown in Table 5 and was slightly different from those other current tests being considered, such as the one that the ASTM D01 committee considers to describe this paint attribute .
    [00081] The data obtained indicated that all low VOC coalescent paints have a slightly wetter edge than the high VOC coalescent (TXMB) in smooth paint; however, the inventive triple-blend X20 formulations outperformed both TEGDO and KF850S dibenzoate control in smooth paint. In acrylic copolymer gloss coating systems and semi-gloss acrylic paint, the wet edge characteristics for all low VOC coalescents appeared to be equivalent. Example 6 - Dry Film Characteristics
    [00082] Gloss is a good indicator of the quality of film formation of a coating. The data shown in Figure 7 indicate that, with the exception of TEGDO, all the low VOC coalescents had a slightly higher gloss in the semi-gloss formulation compared to TXMB. In the case of TEGDO, its brightness was lower than that of other low VOC dibenzoate coalescents and TXMB coalescent. Figure 8 shows the results for the semi-gloss formulation, comparing only KF850S (control), X20 (inventive triple mix) and TEGDO coalescents. The data indicate that the low VOC dibenzoate coalescents KF850S (control) and X20 (inventive triple blend formulation) yielded a slightly better gloss in the semi-gloss formulation than TEGDO. In the acrylic copolymer gloss system, the X20 dibenzoate blend imparted a slightly superior gloss to TEGDO as shown in Figure 9. Example 7 - Friction Resistance
    [00083] The work of a coalescent in a latex (or any) coating composition - be it a highly volatile organic compound or a true plasticizer for the polymer - is to assist in the film formation process, particularly at low temperatures. The binder should also have a minimal impact on coating performance after the film is dried. It can be assumed that, due to their relative permanence, plasticizers can reduce the properties of the film, such as friction, however, this need not necessarily be the case. Figure 10 illustrates that the dibenzoates tested had slightly better resistance to friction than coatings formulated with TEGDO on smooth paint. KF850S and TEGDO have similar friction resistance in semi-gloss paints, and the inventive X20 triple blend outperforms both of these low VOC coalescents in semi-gloss paint.
    [00084] In Figure 11, the improvement of low VOC friction strength coalescents over TXMB is unexpectedly and significantly better in the acrylic copolymer gloss formulation, with the KF850S dibenzoate system, demonstrating a further improvement over TEGDO. This indicates that the inventive triple blend is useful for low VOC paint formulations and coatings that contain harder polymers, while still achieving excellent friction resistance. Example 8 - Blocking resistance
    [00085] Another indicator of film performance with plasticizers is the blocking resistance. Figure 12 illustrates the data obtained for the blocking resistance of semi-gloss paints containing low VOC coalescents. Notably, the low VOC benzoate plasticizers outperformed TEGDO at both room temperature and at elevated temperatures in seven days of blocking testing. As stated above, there has been no attempt to modify the formulations to optimize performance. Instead, this trial demonstrated the feasibility of using the new generation of triple plasticizer/coalescent blends as a substitute or alternative to low VOC film-forming aids, including other dibenzoate blends.
    [00086] In Figure 13, the acrylic copolymer gloss system formulated with the X20 inventive formulation has a distinct advantage of blocking resistance at elevated temperatures over both TEGDO and the KF850S dibenzoate control after seven days of exposure, as well as a advantage over TEGDO after seven days at room temperature.
    [00087] The data presented above indicate that the inventive dibenzoate triple blend works well both as a plasticizer and as a low VOC coalescent for coatings applications. In addition, the test indicated that the new triple dibenzoate blend provides superior performance benefits in gloss and peel resistance over some of the current low VOC and standard coalescent choices. X20 particularly shows a significant benefit in use in the most demanding glossy acrylic copolymer system, where it provides both frictional and blocking strength advantages. The formulations of the invention provide an alternative for paint and coating formulators to improve the current landscape of low VOC coalescents, including traditional dibenzoate coalescents.
    [00088] In accordance with the patent statutes, the best mode and preferred embodiments have been described; the scope of the invention being not limited thereto, but by the scope of the appended claims.
    权利要求:
    Claims (9)
    [0001]
    1. Low VOC triple blend coalescing additive for use in a polymeric coating composition, CHARACTERIZED by the fact that it comprises: a. diethylene glycol dibenzoate present in amounts ranging from 10 to 90% by weight, b. dipropylene glycol dibenzoate present in amounts ranging from 1 to 50% by weight, ec. 1,2-propylene glycol dibenzoate present in amounts ranging from 10 to 90% by weight, based on the total weight of the triple blend composition.
    [0002]
    2. Triple mix additive for use according to claim 1, CHARACTERIZED by the fact that diethylene glycol dibenzoate is present in amounts of at least 60% by weight, dipropylene glycol dibenzoate is present in amounts of at least 15 % by weight, and 1,2-propylene glycol dibenzoate is present in amounts of at least 20% by weight.
    [0003]
    3. Triple mix additive for use according to claim 1, CHARACTERIZED by the fact that the mixture comprises 80% by weight of a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate, wherein the ratio of DEGDB to DPGDB is 4:1, and 20% by weight 1,2-propylene glycol dibenzoate based on the total weight of the triple plasticizer blend.
    [0004]
    4. Low VOC coating composition, CHARACTERIZED by the fact that it comprises: a. an aqueous polymeric emulsion; and b. a non-phthalate low VOC coalescent comprising the low VOC triple blend coalescent additive as defined in claim 1, wherein the coalescent has low volatility and achieves an operating time/wet edge and equivalent or better gloss coefficients, equivalent or better attrition resistance and blocking resistance over traditional low VOC coalescents, and where the viscosity of the coating composition remains stable after three freeze/thaw cycles.
    [0005]
    5. Low VOC coating composition according to claim 4, CHARACTERIZED by the fact that diethylene glycol dibenzoate is present in an amount ranging from 10% by weight to 90% by weight; dipropylene glycol dibenzoate is present in an amount ranging from 1% by weight to 50% by weight; and 1,2-propylene glycol dibenzoate is present in an amount ranging from 10% by weight to 90% by weight, based on the total weight of the triple mixture.
    [0006]
    6. Low VOC coating composition according to claim 5, CHARACTERIZED by the fact that diethylene glycol dibenzoate is present in an amount greater than 60% by weight; dipropylene glycol dibenzoate is present in a greater amount than that 15% by weight; and 1,2-propylene glycol dibenzoate is present in an amount greater than 20% by weight, based on the total weight of the triple mixture.
    [0007]
    7. Low VOC coating composition according to claim 4, CHARACTERIZED by the fact that the polymer emulsion is a glossy acrylic copolymer, acrylic semi-gloss, vinyl acrylic or latex emulsion.
    [0008]
    8. Low VOC coating composition, according to claim 4, CHARACTERIZED by the fact that the polymeric aqueous emulsion comprises vinyl acetate, polyvinyl acetate, ethylene vinyl acetate, and their copolymers; vinylidene chloride; diethyl fumarate; diethyl maleate; polyvinyl butyral; polyurethanes and their copolymers; polysulfides; cellulose nitrate; polyalkyl methacrylates such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate or allyl methacrylate; various aromatic methacrylates such as benzyl methacrylate; various alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; various acrylic acids such as methacrylic acid; vinyl acrylics; styrene acrylics; acrylic-epoxy hybrids; epoxies, phenol-formaldehyde polymer; melamines; or mixtures thereof.
    [0009]
    9. Low VOC coating composition, CHARACTERIZED by the fact that it comprises: a. a polymeric emulsion comprising latex, a vinyl acrylic or an acrylic copolymer; and b. a non-phthalate triple coalescing mixture comprising: i. 80% by weight of a mixture of diethylene glycol dibenzoate and dipropylene glycol dibenzoate, wherein the ratio of DEGDB to DPGDB is 4:1; eii. 20% by weight 1,2-propylene glycol dibenzoate, based on the total weight of the triple mixture.
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    同族专利:
    公开号 | 公开日
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    WO2012092366A1|2012-07-05|
    KR101652891B1|2016-08-31|
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    EP2658728B1|2016-06-22|
    BR112013016922B1|2020-12-15|
    CA2823206A1|2012-07-05|
    MX344323B|2016-12-13|
    HUE030481T2|2017-05-29|
    CA2823204A1|2012-07-05|
    US20160053085A1|2016-02-25|
    US9193843B2|2015-11-24|
    EP2658728A4|2014-09-10|
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    CN103687732A|2014-03-26|
    CN103649196B|2015-09-30|
    EP2658911B1|2016-02-24|
    CA2823206C|2016-05-24|
    BR112013016920A2|2020-12-08|
    RU2013135055A|2015-02-10|
    MX2013007626A|2014-03-12|
    SI2658728T1|2017-01-31|
    MX347161B|2017-04-18|
    KR101761288B1|2017-07-25|
    SG191373A1|2013-08-30|
    KR20150123345A|2015-11-03|
    KR20130108656A|2013-10-04|
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    KR101598089B1|2016-02-26|
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    WO2012092370A1|2012-07-05|
    RU2013135053A|2015-02-10|
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    JP5705998B2|2015-04-22|
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    JP2014507514A|2014-03-27|
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    法律状态:
    2020-12-22| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2021-01-19| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-05-25| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-06-29| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 28/12/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US201061460330P| true| 2010-12-30|2010-12-30|
    US201061460329P| true| 2010-12-30|2010-12-30|
    US61/460,329|2010-12-30|
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    US201161464731P| true| 2011-03-08|2011-03-08|
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