HK1195537B - Blends of dibenzoate plasticizers - Google Patents

Description

Mixtures of dibenzoate plasticizers

Technical Field

The present invention relates to a non-phthalate plasticizer triblend comprising dibenzoate plasticizers that are compatible with each other in specific proportions and that are useful in a variety of polymer applications where plasticizers are traditionally needed, including but not limited to plastisols, adhesives, caulks, architectural coatings, industrial coatings, OEM coatings, inks, polishes, other coatings, polishes, and the like. The plasticizer blends of the present invention improve the performance properties of the polymer, such as processability and resistance to staining and extraction. The present invention is also directed to polymeric compositions, such as plastisols and adhesives, comprising a tri-mixture of plasticizers.

Background

Plasticizers, such as polymer additives, are used as mainline additives (main line additives) and have been known for over a century. A number of high capacity plasticizers have been developed over the last seventy years, primarily for use with ethylene and other polymeric materials. Plasticizers are sold in attractive quantities and are used much more than any kind of polymer additive, especially for polyvinyl chloride (PVC) applications. Polyvinyl chloride can be manufactured into a large number of products and used in myriad applications. Plasticizers provide polyvinyl chloride versatility and are key raw materials and tools for the formulation of ethylene. It is used to adjust stiffness (or softness), impart stain resistance, change tensile properties (e.g., strength, elongation or flexibility), and processability, as needed in a variety of applications including but not limited to applications of flexible vinyl. Although many plasticizers have been produced, only some have acceptable performance properties when combined with ethylene or other polymeric materials.

There are several different classes of plasticizers: 1) general use, 2) specific type (e.g. high solvating agent), 3) secondary form (oil) and type of diluent (e.g. isodecyl benzoate). Plasticizer additives are widely used as replacements for chemicals.

Plasticizers are classified and distinguished by their ability to dissolve dispersed solid polymers and/or their temperature of gelation and melting in plastisols, in addition to chemical form. The gelling and fusing temperatures determine the production rate and are influenced by the solvating power of the plasticizer. For example, plastisols comprising dibenzoate plasticizers will have lower gelation and melting temperatures than plastisols comprising a general phthalate ester, thereby accelerating the process in a particular application.

Plasticizers are used as vehicles for dispersing resin (polymer) particles, such as polyvinyl chloride. The dispersion starts from two phases, a heterogeneous system. The use of plasticizers in the polymeric dispersion promotes the formation of a homogeneous system and results in polymer fusion upon heating. The higher the solvating power, the lower the temperature at which the homogeneous system is fused, which in turn reduces residence time and increases speed as the polymeric composition can be made into an end product, resulting in a faster, more efficient and economical process.

A general purpose plasticizer.

Current plasticizers offer a good compromise between performance and economics for most applications. Some examples include: di (2-ethylhexyl) phthalate (bis (2-ethylhexyl) phthalate (DEHP or DOP)), di (isononyl) phthalate (DINP)), di (n-octyl) phthalate (DNOP), di (isodecyl) phthalate (DIDP), di (2-propylheptyl) phthalate (DPHP), di (2-ethylhexyl) terephthalate (DOTP or DEHT), and di (isononyl-1, 2-cyclohexyldicarboxylate (DIDC or DEHT)) 1, 2-cyclohexanedicarboxylic acid diisononyl ester (diisononyl-1, 2-cyclohexanedicarboxylate (DIDC or dopc or DOP))) (as described in U.S. patent No. 7855430). Universal phthalates account for the predominant amount of plasticizers purchased annually and are most often selected for the synthesis of flexible ethylene.

The plasticizer production in the annual field is in the range of 120 hundred million pounds and despite the pressure of the universal phthalate ester from health and environmental issues, the universal phthalate ester DOP accounts for about half of the plasticizer consumption.

In view of the continued control over the use of phthalates, a need has developed for alternative phthalates. Both DOTP and DIDC are competitors to the substituted phthalate esters on the general market. The two plasticizers are considered "new generation" generic "non-phthalate" plasticizers. Even though DOTP is chemically a phthalate rather than an o-phthalate, its use is increasingly regulated. These "new generation" phthalate alternatives are feasible; however, it is not always possible to impart the desired properties in ethylene compositions, especially in plastisols (i.e.which have low compatibility, slow speed, high gel temperature, low gel strength). Although there are some limitations to this approach, a mixture of plasticizers can be used to tune the properties.

In addition to DOTP and DIDC, sustainable "green" type plasticizers are also competing for the general plasticizer market. Examples include plasticizers based on castor oil (castor oil) and soybean oil (soybean oil).

However, some applications require properties that cannot be achieved by the use of a general purpose plasticizer alone. One example is the use of more oil and solvent resistance, and the general purpose phthalate esters are easily extracted by using a non-polar solution such as hexane, making it a better choice to replace plasticizers. There is also a need for plasticizers for solvating agents that are higher than those used for polyvinyl chloride and other polymers.

A special type of plasticizer.

Specific types of plasticizers have been developed to meet the demand for high solvating agents, the most popular being low molecular weight phthalates. An example of such a plasticizer is Butyl Benzyl Phthalate (BBP), which is commonly used as a high solvating plasticizer. Dibutyl phthalate (DBP) and diisobutyl phthalate (DIISOBUTYL phthalate (DIBP)) are also useful high solvating agents, a special class of plasticizers. Other examples of non-phthalate esters, high solvating plasticizers include some citrates (citric acid ester), alkyl sulfonates (alkyl sulfonic acid ester) and certain phosphates (certain phosphate). Dibutyl terephthalate (DBTP) and N-alkyl pyrrolidone (N-alkyl pyrrolidone) have also been proposed as a special class of high solvating agent plasticizers.

All high solvating agent plasticizers (regardless of type) add value to the conventional general purpose plasticizers for ethylene compositions. Even so, many high solvating agent plasticizers are phthalates for which safer alternatives should be considered.

Benzoic acid ester plasticizer.

Benzoate plasticizers have also been developed as a special class of plasticizers. Benzoic acid plasticizers have been considered as useful plasticizers for polyvinyl chloride applications since the 1940 s, and then some of such benzoic acid plasticizers have been commercialized. Benzoic acid plasticizers have been perfected and are now used for several decades in polyvinyl chloride applications. Benzoate plasticizers are, by their nature, non-phthalates; however, they have not been created or specifically established on this basis and have been used until there is a need for phthalate alternatives. The benzoate plasticizers include monobenzoates (monobenzoates) and dibenzoates (dibenzoates).

Monobenzoates useful as plasticizers include: isodecyl benzoate (isodecyl benzoate), isononyl benzoate (isononyl benzoate), 2-ethylhexyl benzoate (2-ethylhexyl benzoate). "half ester" (Halfester) monobenzoate includes dipropylene glycol benzoate (diethylene glycol monobenzoate) and diethylene glycol benzoate (diethylene glycol monobenzoate), which are byproducts of making dibenzoate esters, but most of the time is not a production target. Monoformates are generally not noted as highly solvating agents, although they may be used in combination therewith. The monoformates are also not used as dibenzoate plasticizers because of their poorer compatibility with polyvinyl chloride than the corresponding dibenzoates. However, half-esters are compatible with latex polymers, such as acrylic and/or vinyl ester polymers.

Typically, dibenzoate plasticizers work well as high solvating agent plasticizers and are now considered to be some of the best high solvating agents in polyvinyl chloride applications. Historically, diethylene glycol dibenzoate (DEGDB) and dipropylene glycol dibenzoate (DPGDB) have been widely known and used in many applications including the ethylene industry. DEGDB is a very good plasticizer, but because of its high freezing point, blends with DPGDB have also been developed to make full use of and reduce costs. For many years, a mixture of DEGDB, DPGDB and triethylene glycol dibenzoate (TEGDB) was introduced as a high solvating agent dibenzoate mixture.

The state of the field.

Benzoate plasticizers are commercially available and described in the literature and prior patents, either alone or in combination with other plasticizers. It is also known in the art to include benzoate plasticizers in plastisol and organosol (organosol) compositions, adhesives, caulks, polishes, inks, and various coatings.

By way of example, U.S. Pat. No. 4,950,702 to Arentt discloses plastisol compositions comprising a polyethylene resin plasticized with dipropylene glycol monomethyl ether benzoate (dipropylene glycol monomethyl ether benzoate) or tripropylene glycol monomethyl ether benzoate (tripropylene glycol monomethyl ether benzoate).

Us patent No. 5,236,987 to arret discloses the use of isodecyl benzoate as a coalescent agent for the preparation of coating compositions and plastisols.

U.S. patent No. 5,319,028 to zhongmura et al describes a plastisol composition comprising a polyvinyl chloride resin, and a plasticizer, alone or in combination, which may comprise, among other plasticizers, ethylene glycol derivatives (glycoderitive), such as DEGDB, DPGDB, and triethylene glycol diisooctanoate (TEG di- (2-ethylhexoate)).

The use of dibenzoates, alone or in combination with their corresponding monobenzoates, is described in U.S. Pat. No. 5,676,742 to Allentet al, which discloses plasticized waterborne polymer compositions as latex caulks.

Dibenzoate plasticizer mixtures for use as primary plasticizers for plastisol compositions are described in U.S. patent No. 5,990,214 to alente et al, which discloses mixtures comprising DEG and triethylene glycol (triethylene glycol) formate esters for plastisol applications.

U.S. patent No. 7,812,080 to arret et al describes plastisols having a dispersed phase and a liquid phase comprising a blend of dibenzoate plasticizers having hydroxyl numbers of about 30 or greater, representing a higher half-ester monobenzoic acid content. The plastisols provided are described as being effective in providing foamed compositions having improved color.

U.S. patent No. 6,583,207 to stannoprop (Stanhope), et al, describes adding at least about 30% by weight of DEG or DPG half-ester monobenzoate to DEG dibenzoate to form a liquid mixture at about 28 ℃. Likewise, U.S. patent No. 7,056,966 to stanop et al describes adding 20% by weight of at least one half ester monobenzoate to at least one dibenzoate to form a liquid mixture at about 28 ℃. These liquid mixtures are described as effective plasticizers for waterborne polymer compositions, such as adhesives and caulks.

U.S. patent No. 7,071,252 to stannop et al describes the use of half ester monobenzoates as secondary plasticizers for non-aqueous and solvent-free plastisols comprising a primary plasticizer.

U.S. patent No. 7,872,063 to streppa (strepaka), et al, describes a film-forming composition, such as a polish, coating, adhesive, or ink, comprising at least one acrylic or vinyl acetate polymer as a film-forming ingredient, in combination with a plasticizer mixture comprising an aromatic dibenzoate plasticizer, DEGDB, and DEGMB.

Godwin et al, U.S. Pat. No. 7,629,413, describes polyvinyl chloride plastisol compositions comprising C9-C11 alkyl benzoates in combination with phthalate plasticizers to reduce viscosity and reduce contamination issues with phthalate esters.

U.S. Pat. No. 8,034,860 to Allent et al describes organosol plastisol compositions comprising diesters of acids with glycols (dihydric alcohols) in combination with an organic diluent. Monoesters of benzoic acid with monohydric alcohols (monohydralcohols) are also described as co-plasticizers.

U.S. patent publication No. 2009/0036581 to Joshi et al describes plasticizers for polymers based on a mixture of mono and dibenzoate esters of 2,2,4-trimethyl-1,3-pentanediol (2,2,4-trimethyl-1,3-pentanediol), which contain a minimum of 87 weight percent dibenzoate esters, which can be used in conjunction with dipropylene glycol benzoate (dipropylene glycol benzoate).

In summary, benzoate esters, including mixtures of DPGDB and DEGDB, have been used in a number of applications. The dibenzoate plasticizers provide improved processability, among other attributes that are beneficial for many polymer applications, accelerated fusion and stain resistance.

The present invention is directed to non-phthalate, high solvating agent plasticizers because the general phthalate plasticizers-although widely used, are effective and economical for ethylene-are ineffective solvating agents. In addition, the use of phthalates is under increasing scrutiny by governmental agencies as a result of environmental, health, and safety concerns regarding their use. And although the special phthalate plasticizer Butyl Benzyl Phthalate (BBP) has been widely regarded as a difficult target in plasticizers because it is a good (high) solvating agent with low viscosity and ideal rheological profile, it also defeats its purpose as a potential teratogen and toxin.

Thus, there is a continuing need for alternatives to the currently available highly solvatable phthalate plasticizers, and thus benzoate plasticizers and mixtures thereof are viable alternatives due to their highly solvating characteristics.

Of particular interest in the present invention are dibenzoate plasticizers whose high solvating characteristics are known and used in a variety of applications, as discussed above. Even so, dibenzoates used in plastisols may be limited by high plastisol viscosity over time and desirable rheology as the plasticizer continues to dissolve. As the plastisol composition ages, it exhibits increasingly higher viscosity. Additionally, high solvating plasticizers may be low heat and Ultraviolet (UV) light stable. It is also denser than general plasticizers and has higher migration than general types when used in polymeric products such as plastisols.

These limitations are described in the above-mentioned' 860 to alenter et al. The' 860 patent describes plastisols comprising dispersed polymers and DEG/DPG dibenzoate blends that result in a 25-fold increase in plastisol viscosity, which are too viscous for processing using conventional equipment. The publication further discloses plastisols comprising dispersed polymer, a dibenzoate plasticizer (etc.) and an organic diluent (solvent), wherein the increase in viscosity is avoided or reduced by selecting and matching ingredients based on a specific difference between a) the Hildebrand solubility parameter of the polymer and b) a weighted average of the Hildebrand solubility parameters of the organic diluent (solvent), plasticizer and any other liquid ingredients present in the plastisol. The difference between a and b needs to be within a specified range, on the one hand to avoid an excessively high viscosity of the plastisol or on the other hand to avoid the possibility of liquid exudation from the article formed from the plastisol. Plasticizers are selected from the group consisting of oligomers (oligomeric) comprising benzoic acid and glycols, such as propylene glycol and ether glycol, such as diesters of diethylene glycol, triethylene glycol, dipropylene glycol and 1,3-butanediol, and diesters of phthalic acid monohydric alcohols.

In response to the continuing need of the polyvinyl chloride industry, new tri-blend platforms of dibenzoates have been developed which can be optimized for performance and operation in polymeric compositions and which can provide some conventional benzoate plasticizers and blend improvements, particularly in plastisol rheology. The novel blend contains three dibenzoate plasticizers with unexpectedly lower viscosity limits than predicted based on the viscosity of the individual ingredients. Mixtures of dibenzoate plasticizers, i.e., specific ratios of DEGDB to DPGDB, in combination with 1, 2-propanediol dibenzoate (PGDB) form the basis of a tri-mixture of plasticizers of the present invention. 1,2-propylene glycol dibenzoate is a known ingredient that is currently used with polyvinyl chloride alone or in plasticizer blends that are not related to the triblend of the present invention. 1, 2-propanediol dibenzoate is also known as a flavoring agent for beverages described in U.S. Pat. No. 3,652,291 to Bidao gold (Bedoukian).

The tri-blend of the present invention is a highly solvating plasticizer for plastisol applications and unexpectedly provides a lower viscosity in the plastisol and improved rheology beyond that expected based on the rheology of the individual components of the tri-blend. The novel triblend is compatible and efficient when used in plastic adhesive formulations and provides improved processability, whether as a primary plasticizer or as a blended plasticizer in combination with a low solvating plasticizer. The novel triple-mixture of DPGDB, DEGDB and PGDB has not been used in the past.

The focus of the present invention is the use of the mixture to form new plastisol compositions for flooring applications. However, the invention is not limited to flooring applications. The plasticizer triblend of the present invention may be used alone or in combination with other plasticizers in applications including, but not limited to, adhesives, caulks, architectural coatings, industrial coatings, OEM coatings, other types of plastisols, sealants, polishes, polish inks, melt compounded vinyl, polysulfide, polyurethane, epoxy, styrene acrylic, and combinations thereof. Other applications will be apparent to those skilled in the art based on the disclosure herein.

The main applications of the tri-mixture of the present invention include:

polyvinyl chloride: the tri-blends of the present invention have been shown to have unexpectedly low viscosities of high solvating plasticizers compared to what would be expected based on the viscosities of the individual ingredients.

Coating: the triblend of the present invention has been shown to be useful in coating science, primarily as a low VOC coalescent with good compatibility with polymers used in the architectural and industrial coating industries. This application is the subject of a co-pending application. The triblend of the present invention can also be used in other coating and film forming compositions such as polishes, inks, and polishes.

Adhesive: the inventive triblend is highly compatible and has good viscosity response and Tg (glass transition temperature) inhibition.

Sealants and caulks.

It is an object of the present invention to provide polymer compositions that are useful as conventional plasticizers in need thereof, including but not limited to polyvinyl chloride applications, primary plasticizers or non-phthalate plasticizer compositions used as a specific type of plasticizer.

It is another object of the present invention to provide non-phthalate plasticizer compositions that are compatible with a wide range of polymer compositions, have high solvating characteristics, and are useful as special blend plasticizers to improve the compatibility and processability of poor solvating plasticizers.

It is a further object of the present invention to provide a non-phthalate plasticizer composition for plastisols that has high solvating characteristics while minimizing the disadvantages of high viscosity and differential rheology associated with the use of high solvating agents in the plastisol.

It is another object of the present invention to provide plastisol formulations utilizing non-phthalate plasticizers that achieve faster processing speeds and economic efficiencies.

It is another object of the present invention to provide plastisol formulations utilizing non-phthalate plasticizers that provide higher tensile strength and resistance to staining and pull-out.

Another object of the present invention is to provide adhesive formulations and polishes utilizing the non-phthalate plasticizer triblend of the present invention.

Other objects of the present invention will be apparent from the description herein.

Disclosure of Invention

The plasticizer triblend of the present invention comprises a unique mixture of three dibenzoates: diethylene glycol dibenzoate (DEGDB), dipropylene glycol dibenzoate (DPGDB), and 1, 2-propanediol dibenzoate (PGDB). These plasticizers are compatible with each other and with various polymers, such as elastomers, thermoplastics, and thermosets; such as polyvinyl chloride and its copolymers; various polyurethanes and their copolymers; various polyacrylates and copolymers thereof; various polysulfides and copolymers thereof; various epoxy resins and copolymers thereof, and vinyl acetate and copolymers thereof.

The plasticizer triblend of the present invention acts as a high solvating agent in polyvinyl chloride applications, but has unexpectedly lower viscosity and improved rheological properties based on the individual triblend components.

In one embodiment, the present invention is directed to novel plastisol compositions comprising a polymer dispersed in a liquid phase comprised of a triple mixture of the present invention, wherein the viscosity of the plastisol is lower than when PGDB is used in combination with a 4:1 ratio of DEGDB/DPGDB mixture.

In other embodiments, the invention is directed to adhesive compositions comprising a liquid phase polymer dispersed in a triblend of the invention, wherein the Tg of the adhesive is unexpectedly lower than that achieved with PGDB alone, and compared to that achieved with a polymer blend of 4: the Tg achieved for the 1-ratio DEGDB/DPGDB mixture was similar. The triblend of the present invention is more efficient than PGDB in softening the binder polymer for efficient manufacturing and cost reduction.

In other embodiments, the present invention is directed to conventional coating compositions comprising a liquid phase polymer dispersed in a tri-blend of the present invention, wherein the VOC content of the coating is substantially reduced compared to other conventional coalescents and plasticizers.

In a further embodiment, the present invention is directed to a screen ink or polish composition comprising a polymer dispersed in a liquid phase comprised of a triblend of the present invention.

The improvement in properties is attributed to the use of the plasticizer triblend described herein, including effective Tg suppression (for adhesives), accelerated processing times over conventional plasticizers, reduced plasticizer set point, low gel and fuse temperatures, low VOC content, unexpectedly lower application viscosity over conventional phthalates, higher tensile strength, and good stain and extraction resistance.

Drawings

FIG. 1 shows a triple mixture of the invention with DINP, DIDC or DIDC at 23 ℃ reflecting a rotation speed of 20 rpmGraph of BBP, dibenzoate bis-mixture (DEGDB/DPGDB), and PGDB compared Brookfield viscosities.

FIG. 1A is a graph reflecting the 7 day/initial viscosity ratio of the triblend of the present invention compared to DINP, DIDC, BBP, dibenzoate doublet, and PGDB.

FIG. 2 is a 1 day shear rate scan reflecting the results obtained for the triple mixture, DINP, DIDC, BBP, dibenzoate double mixture (DEGDB/DPGDB), and PGDB of the present invention.

FIG. 3 is a graph reflecting the gel/fusion curves of the triblend, DINP, DIDC, BBP, dibenzoate double mix (DEGDB/DPGDB), and PGDB of the present invention.

FIG. 4 is a graph reflecting Shore A hardness data for the triblend, dibenzoate double-cocktail (DEGDB/DPGDB), DINP, DIDC, and BBP of the present invention.

FIG. 5a is a graph reflecting the triple blend, dibenzoate double blend (DEGDB/DPGDB), PGDB, DINP, DIDC, and BBP tensile Strength pounds per square inch (psi) data of the present invention.

FIG. 5b is a graph reflecting the% elongation of the triblend, dibenzoate double mix (DEGDB/DPGDB), PGDB, DINP, DIDC, and BBP of the present invention.

FIG. 5c is a graph reflecting the 100% coefficients of the triblend, dibenzoate double mix (DEGDB/DPGDB), PGDB, DINP, DIDC, and BBP of the present invention.

FIG. 6 is a graph reflecting volatility data for the triblend, dibenzoate double mix (DEGDB/DPGDB), DINP, DIDC, and BBP of the present invention.

FIG. 7 is a graph reflecting the pull-out resistance of the triblend, dibenzoate double blend (DEGDB/DPGDB), DINP, DIDC, and BBP of the present invention in heptane, peanut oil, and 1% ivory soap.

FIG. 8 is a graph reflecting Brookfield viscosity (megapascals) of typical base coat formulations comprising a triblend, dibenzoate double blend (DEGDB/DPGDB), PGDB, DINP, or BBP of the present invention.

FIG. 9 is an initial shear rate sweep reflecting viscosity (megapascals) versus various shear rates (1/sec) for a typical base coat formulation comprising a triblend of the present invention, dibenzoate double blend (DEGDB/DPGDB), PGDB, DINP, or BBP.

FIG. 10 is a graph reflecting the gel/fusion curves of a typical base coat formulation comprising a triblend of the present invention, a dibenzoate double blend (DEGDB/DPGDB), PGDB, DINP, or BBP.

FIG. 11 is a graph reflecting the use of asphalt,Comparative stain resistance (Δ E) study of stain resistance in resilient floor plastisol formulations for DINP, BBP, dibenzoate bis-mixture (DEGDB/DPGDB), PGDB, and tri-mixture of the present invention on brown shoe polish, mustard and 1% oil palm stains.

FIG. 12 is a graph reflecting the results of a base rheology screen for a base plastisol formulation comprising a triblend, dibenzoate double mix (DEGDB/DPGDB), PGDB, DINP, DIDC, BBP, DBT or DOTP of the present invention.

FIG. 13 is a graph reflecting the gel fusion curves of base plastisol formulations comprising a triblend of the present invention, a dibenzoate bis-mixture (DEGDB/DPGDB), PGDB, DINP, DIDC, BBP, DBT, DOTP or alkyl pyrrolidone (300).

FIG. 14 is a chart reflecting the base rheology screens of the three mixtures of the present invention in the base coating formulations at 1 hour and 1 day.

FIG. 15 is a graph reflecting the gel/fusion curve of a triblend of the present invention in a base coating formulation.

FIG. 16 is a graph reflecting the stain resistance of vinyl and PGDB, dibenzoate bis-mixture (DEGDB/DPGDB), triblend of the present invention, DINP/DIHP mixtures, and BBP.

FIG. 17 reflects a ternary mixture comprising the invention, DINP, and ternary mixture of the invention with DINP 50: 50 and BBP.

FIG. 18 reflects a ternary mixture comprising the invention, DINP, and ternary mixture of the invention with DINP 50: 50 of the mixture of plastisol screen inks.

FIG. 19 shows a commercial dibenzoate bis-mixture comprising a triblend of the present invention: (850S) or PGDB, respectively, a polyvinyl acetate (PVAc) homopolymer.

FIG. 20 shows a commercial dibenzoate bis-mixture comprising a triblend of the present invention: (850S) or PGDB, respectively.

FIG. 21 is a graph reflecting the degree of plasticizer use of 10% or 15%, including a tri-blend, commercial dibenzoate bis-blend of the present invention (R850S) or PGDB at 1 day.

FIG. 22 is a graph reflecting the degree of plasticizer use of 5% or 10%, including a tri-blend, commercial dibenzoate bis-blend of the present invention (R850S) or PGDB, at 1 day.

FIG. 23 is a graph reflecting Konig hardness data on aluminum panels for a polish formulation comprising a tri-mixture of the present invention (6% loading), DEGDB, diethylene glycol monomethyl ether, 2-EHB, monobenzoates, dipropylene glycol monomethyl ether, diethylene glycol monobutyl ether, or no coalescent.

Detailed Description

The present invention is directed to a new plasticizer tri-blend: DEGDB, DPGDB, and 1, 2-propanediol dibenzoate (PGDB) in the amounts and/or ratios discussed herein. The plasticizers of the present invention are generally utilized with many thermoplastic, thermoset or elastomeric polymers as a replacement for conventional plasticizers. In particular, according to the invention, the triblend can be used to prepare polyvinyl chloride or acrylic plastisols of reduced solubility.

In addition to polyvinyl chloride and acrylic plastisols, the triblend of the present invention may be used in other polymeric compositions including, but not limited to, various vinyl polymers such as polyvinyl chloride and its copolymers, vinyl acetate, vinylidene chloride (vinylidene chloride), diethyl fumarate (diethyl fumarate), diethyl maleate (diethyl maleate) or polyvinyl butyral (polyvinyl butyral); various polyurethanes and their copolymers; various polysulfides; cellulose nitrate (cellulose nitrate); polyvinyl acetate and copolymers thereof; and various polyacrylates and copolymers thereof.

Acrylic polymer compositions for various applications may also be used with the triblend of the present invention and include various polyalkylmethacrylates (polyalkylmethacrylates), such as methyl methacrylate, ethyl methacrylate, butyl methacrylate, cyclohexyl methacrylate, or allyl methacrylate; or various aromatic methacrylates (e.g., benzyl methacrylate); or various alkyl acrylates such as methyl acrylate, ethyl acrylate, butyl acrylate or 2-ethylhexyl acrylate; or various acrylic acids such as methacrylic acid (methacrylic acid) and styrenated acrylic acid (styrenated acrylic).

Other polymers for the tri-blends of the present invention that can be used as plasticizers include epoxy resins, phenol-formaldehyde type; melamine (melamine); and the like. There are other polymers that will be apparent to those skilled in the art.

For the purposes of the present invention, "plastisol" means a liquid polymeric composition comprising at least one non-crosslinked (non-crosslinked) organic polymer in the form of particles dispersed in a liquid phase comprising a plasticizer for the polymer. While the invention may be described in terms of ethylene polymers, the invention is not limited to any particular polymer.

As used herein, "organosol" means a plastisol that includes, in addition to a plasticizer, a liquid hydrocarbon, ketone, or other organic liquid in an amount greater than about 5 weight percent to achieve a desired processing viscosity.

As used herein, "high solvating agent" or "high solvation" is a term describing the penetration of the plasticizer and the efficiency of softening the polymer, "higher" solvating agents soften the polymer faster, thus favoring the formation of a homogeneous phase.

Preferred dibenzoates of the present invention are DEGDB, DPGDB and 1, 2-propanediol dibenzoate (PGDB). The use of PGDB alone or in combination with other plasticizer materials unrelated to the disclosure herein as a high solvating agent polymer for ethylene compositions is currently known. The use of PGDB (defined as 1, 2-propanediol dibenzoate) in the dibenzoate triblend of the present invention is critical because the use of other propanediol dibenzoates does not provide the lower freezing points discussed below.

The plasticizer triblend of the present invention is further characterized by a lower freezing point as compared to some of the currently commercially available DEGDB-containing dibenzoate blends. Almost all new commercial dibenzoate mixtures contain DEGDB as the basis for the mixture due to its good solvation and cost-saving drive. However, pure DEGDB solidified above normal room temperature (28 ℃), thereby preventing its use. The freezing points (onset of condensation) of the tri-mixture of the present invention are as follows compared to typical dibenzoate mixtures currently available:

the three mixtures of the invention: +6 deg.C

Typical dibenzoate ester mixtures: +12 ℃.

Handling of dibenzoate blends containing DEGDB can be a problem compared to typical plasticizers such as phthalate esters. Thus, the lower freezing point achieved by the tri-mixture of the present invention provides a distinct advantage over currently available dibenzoate mixtures.

While not wishing to be bound by any particular theory, it is believed that the addition of PGDB to the DEGDB/DPGDB mixture will greatly lower the freezing point (-12 ℃ to-6 ℃), which provides considerable advantages for handling some dibenzoate mixtures in cold weather not currently contemplated.

The amount of plasticizer alone in the inventive mixture can vary widely depending on the end use and the desired properties. Thus for the triblend, the amount of DEGDB can vary from about 10% to about 90% by weight, but is preferably greater than about 60% by weight, based on the total weight of the composition of the triblend. For cost reasons, it is preferred that the amount of DEGDB be higher than either of the other two plasticizers, DEGDB being much cheaper than PGDB and DPGDB. The amount of DPGDB may generally vary from about 1% to about 50% by weight based on the total weight of the triblend, but is preferably present in an amount greater than about 15% by weight. The amount of PGDB may generally vary from about 10% to about 90% by weight based on the total weight of the dibenzoate triblend, but is preferably present at about 20% by weight. PGDB is also cheaper than DPGDB.

One preferred embodiment is presented below:

jia, 1,2-PGDB 20% by weight

B, DEGDB/DPGDB 80/2080% by weight

The triblend may be prepared by any conventional method known to those skilled in the art, including by simply mixing the three components together or forming the three components together in situ.

DPGDB manufactured by Emerald Kalama Chemical industryDP, produced by Unitex Chemical Corp988. Manufactured by Froude (Ferro)9100 and manufactured by Finetex, IncPG-22 is commercially available. DEGDB asDE and245 are commercially available. PGDB as284, sold in the market, and previously used asMP manufacture.

The triblend of the present invention can be used with many different types of polymers and used in different applications where plasticizers are required. The total amount of the triblend of dibenzoates, for example, is generally from about 1 to about 300, desirably from about 10 to about 100, and preferably from about 20 to about 80 parts by weight per 100 parts by weight of the total weight of the one or more thermoplastic, thermoset or elastomeric polymers, including but not limited to those defined above, depending on the application, and is wide ranging. A particularly preferred embodiment of the plastisol contains 70 parts by weight plasticizer or about 40 parts by weight per 100 total parts by weight of the polymer.

The tri-mixture composition of the present invention can be used in coatings, in systems at levels up to about 20% plasticizer solids, depending on the nature of the coating.

The triblend of the present invention can be used in liquid adhesives in amounts up to 50% by weight, based on the total weight of the adhesive.

The triblend of the invention may be used in the polish in amounts up to 20% by weight, based on the total weight of the polish.

The triblend of the present invention may, but need not, be blended with various other conventional plasticizers to enhance or enhance the polymeric composition properties, including but not limited to improving plastisol compatibility and processability. Conventional plasticizers include, but are not limited to, phthalate esters, phosphate esters, adipate salts, azelate salts, oleate salts, succinate salts, and sebacate salts, terephthalate esters, such as DOTP, 1,2-cyclohexane dicarboxylate esters (1,2-cyclohexane dicarboxylate ester), epoxy plasticizers, fatty acid esters, glycol derivatives, sulfonamides, and hydrocarbons and hydrocarbon derivatives commonly used as secondary plasticizers. Monobenzoates such as isononyl benzoate, isodecyl benzoate, 2-ethylhexyl benzoate and 2,2,4-trimethyl-1,3-pentanediol diisobutyrate may also be mixed with the triblend of the present invention. In particular, the triblend of the present invention is useful as a blending plasticizer with the addition of poor solvating plasticizers such as DIDC and DOTP to improve compatibility and processability in plastisol applications.

The tri-mixtures of the present invention may also contain conventional additives such as antioxidants, heat stabilizers, flame retardants, surfactants, and the like, in various amounts. The amount of additive can generally vary widely and typically ranges from about 0.1 to about 75 parts by weight per 100 parts by weight of the mixture.

The dibenzoate blends of the present invention may be used wherever conventional plasticizers are currently used. Desirably, it is utilized in adhesives, caulks, architectural and industrial coatings, plastisols, polishes, inks, melt compounded vinyls, polysulfides, polyurethanes, epoxies, or any combination thereof. Other uses will be apparent to those skilled in the art.

The invention is further described in the following examples.

Examples

Experimental methods

Preparation of plastisol and vinyl

The plastisols used for the base scan were prepared in a Habert Square (Hobart Model) N-50 mixer. Mix for 10 minutes using speed one (1). The plastisols were then prepared for further evaluation using a high speed disperser with a 1000 rpm mixing time of ten minutes. All plastisols were degassed at 1 mm Hg until completely free of air as possible.

The vinyl used for the base scan was fused in a closed mold at a thickness of 1.2 mm in a Blue M oven at 177 ℃ for 25 minutes. The vinyl used for the contamination test was fused in a massesis (Mathis) oven at 204 ℃ for 2.5 minutes at a thickness of 0.5 mm. The airflow was set at 1500 rpm.

Testing/evaluating

Unless otherwise indicated in specific examples, the following general tests and/or methods were used to evaluate the performance of the plasticizers of the present invention over currently available plasticizers. Tests and methods are known to those skilled in the art.

Outgassing-the degree and ease of outgassing (ease) was determined after mixing the plastisol. About 10 ml was placed in a vacuum jar and a vacuum of 1 mm hg was applied. The height of the raised ml was divided by the starting volume and the value recorded. The time to break the foam was recorded.

Viscosity and rheological properties: low shear-Brookfield RVT, 20 rpm, number of reading cycles 10 (re)volumionreading). ASTM D1823. High shear-use of TA AR2000 ex. The parallel plates were mounted at appropriate intervals (350 microns). Shear at 1000 seconds^-1。

Gel/fusion: TA AR2000ex in oscillation mode. The parallel plates were mounted at appropriate intervals (600 microns). The test temperature was started at 40 ℃ and heated at 220 ℃ at a rate of 5 ℃/min.

Gel temperature-Hot plate type (Hot bench type) test, in which a small droplet of plastisol is applied to a temperature gradient plate (temperature gradient plate) and sheared across the droplet after three minutes. The temperature at which the cuts in the plastisol do not re-fuse is the gel temperature, i.e., plastisol gelation.

Compatibility: cycle-ASTM D3291. Nip roll-one compact cycle of vinyl rolling with absorbent paper, then placed in an oven at 60 ℃ for three days. Compatibility was judged by the degree of the sum of bleeding.

efficiency-Shore A-ASTM D2240; tensile-ASTM D638, model IV die, 50.8 cm/min pull speed.

Durability-resistance to extraction, ASTM D1239. Extract-peanut oil (24 hours exposure at room temperature); 1% ivory soap solution (24 hours at 50 ℃ C. and 4 hours at 50 ℃ C.); heptane was dried at room temperature (24 hours, 4 hours at 50 ℃). Activated carbon volatility, ASTM D1203, was evaluated at 1,3, 7, 14, 21 and 28 days.

The thermal stability test was carried out in a Mathis oven at 195 ℃ at a blowing speed of 1500 rpm at the indicated test intervals. Note the time to yellow first and then brown.

And (3) dyeing test: a 1% brown dye solution in mineral spirits was used as the staining agent. Stain was applied to the vinyl and held there with toilet paper for 30 minutes. The stain was wiped off from ethylene, which was wiped clean with mineral oil and photographed to record the results.

Examples 1 to 6

With respect to examples 1-6, a tri-blend dibenzoate plasticizer (X20) of the present invention was evaluated to determine basic performance parameters for orientation relative to a standard control, comprising 20 wt.% 1, 2-propanediol dibenzoate and 80 wt.% of a 80/20DEG/DPG dibenzoate blend. The control group used for the evaluation of examples 1-6 comprised Butyl Benzyl Phthalate (BBP), diisononyl phthalate (DINP), and diisononyl 1, 2-cyclohexanedicarboxylate (DIDC). In addition to the inventive triblend, the DEGDB/DPGDB doublet plasticizers (X250; 4:1 DEG dibenzoate: DPG dibenzoate ratio) and PGDB (X100> 98%), both of which are ingredients of the inventive triblend, were evaluated separately.

The tests performed in examples 1-6 included: compatibility (circulation and rolling spray); efficiency (Shore a, tensile properties); persistence (extractability and volatility); and processability (viscosity, viscosity stability, shear rate/rheology and gelling/fusing).

The base plastisol formulations evaluated in examples 1-6 are presented in table 1 below:

TABLE 1 basic plastisol formulations

Material	PHR
		Dispersing resin, K76	100
Plasticizer agent	70
		Ca/Zn stabilizer	3

The use of the base plastisol formulation showed that the plasticizer interaction with the polyvinyl chloride did not come from interference from other additives than the desired heat stabilizer.

Example 1 Brookfield viscosity

The brookfield viscosity test exhibited the expected higher initial viscosity for the individual ingredients of the high solvating plasticizer, i.e., the DEGDB/DPGDB double blend (X250) and PGDB (X100) exhibited higher viscosities at the beginning of the entire control group and on day 1. The overall DINP to DIDC control group also had a higher 7-day/initial ratio of X250 to X100 components alone, but the BBP was reversed. It is expected that the viscosities of the triblend (X20), i.e. the combination of DEGDB/DPGDB and PGDB, will add up, i.e. between the viscosities of the individual components (based on the proportions of the admixtures). Surprisingly, the 7 day/initial viscosity ratio of the triple blend of the present invention was lower compared to the BBP or DEGDB/DPGDB (X250) alone versus the PGDB (X100) component and compared to that obtained from DINP versus DIDC. The lower the ratio, the more stable the plasticizer viscosity. Generally, high solvating agents are not expected to have lower proportions but are the case with the inventive triblend.

Example 2-One Day Shear Rate Scan (One-Day Shear Rate Scan).

The results of the one-day shear rate scan (70PHR) are presented in fig. 2. Higher and higher viscosities are expected as the shear rate increases. For the control group, the viscosity of DINP and DIDC remained level while BBP slightly increased and stabilized. For DEGDB/DPGDB (X250) and PGDB (X100), the viscosity of X100 rises rapidly and falls rapidly, while X250 rises slightly and decreases rapidly and decreases slightly at higher shear rates. Also unexpectedly, the one day shear rate scan of the triple blend (X20) was preferred over the individual ingredients (i.e., DEGDB/DPGDB (X250) blend and PGDB (X100)) and had BBP-like profiles, albeit at higher viscosities. Overall, PGDB (X100) has poorer rheological properties compared to the triple mixture of the present invention, as reflected in figure 2.

Example 3 gel/fusion

The gel fusion data illustrates the relative solvent properties of the various plasticizers. Fig. 3 and table 2 present the results of the gel/fusion assessment, which reflects the results of the individual components (X250 and X100) and the triblend (X20) compared to the BBP control group considered as an industry standard. The results also show that the novel triblend (X20) is a preferred solvating agent for DEGDB/DPGDB (X250) compared to PGDB (X100).

TABLE 2 gel fusion data

Fused vinyl character

Example 4 compatibility testing

Cycle testing, ASTM D3291 was used to determine plasticizer compatibility with polyvinyl chloride. The test temperature was 23 ℃ and the evaluation was obtained after 1,3 and 7 days. No plasticizer exhibited any bleed except for DIDC. All plasticizers were considered compatible by this test.

Roll testing was performed on plasticizers. The test temperature was 60 ℃,3 days, and evaluations were obtained after 1,2, and 3 days. All plasticizers that pass this test are compatible, except for DIDC. DIDC exhibits severe bleeding.

Example 5 efficiency testing

Shore a hardness data were obtained for the entire control (BBP, DINP and DIDC), X250 double mix and X20 triple mix at 1 second and 10 seconds. The results are presented in fig. 4 and show that the triple mix (X20) and double mix (X250) are as effective as the control.

The tensile data obtained for the control, the double blend (X250), PGDB (X100) and the triple blend (X20) are presented in fig. 5a (tensile at break); FIG. 5b (% elongation); fig. 5c (100% factor). The results show that the X20 triblend exhibited better elongation than the dibenzoate blend and most of the control, and greater tensile strength than the control.

Example 6 durability test

The volatility data obtained for the control, the two-mix (X250) and the three-mix (X20) are presented in figure 6. The results show that the X20 cocktail has a slower volatility than the control.

The extraction resistance data obtained for the control, the double mixture (X250) and the triple mixture (X20) in heptane, peanut oil and 1% ivory soap solution are presented in figure 7. The results show that the X20 triblend has superior resistance to extraction in both heptane and peanut oil compared to the control. Although the triple blend was less resistant to extraction in ivory soap solution than the control, it was still slightly better than the double blend.

The above results demonstrate that the triblend of the present invention, like the dibenzoate double-cocktail, is a highly solvating agent with similar compatibility to the control. Both the tri-blend and the di-blend of the present invention exhibited a higher viscosity in the plastisol than the conventional plasticizer control. Overall, the dibenzoate blends are more volatile than general purpose plasticizers, but exhibit preferred resistance to extraction with solvents and oils. The dibenzoate blend exhibited much better fusing properties than the plasticizer.

Example 7-properties in coating-type formulations.

Performance characteristics in a typical base coat type formulation were also evaluated. The base formulation is presented in table 3 below.

TABLE 3 typical base coat type formulation

Raw materials	PHR
		Dispersing resin, K76	85
Mixed resin	15
		Plasticizer agent	40
2,2,4-trimethyl-1,3-pentanediol diisobutyrate	10
		Solvent(s)	3
Epoxidized soybean oil	2
		Ca/Zn stabilizer	3

The individual components of the control plasticizers, DINP and BBP and the double mixture (X250) and PGDB (X100) were compared with the triple mixture of the invention (X20). The brookfield viscosity, initial shear rate scan, and gel fusion results obtained are presented in fig. 8, 9, and 10. The gel fusion data obtained are described in table 4.

TABLE 4

Example 8 stain resistance

Stain resistance studies were conducted comparing the stain resistance of DINP, BBP, X250 (double mix), X100(PGDB) and X20 (triple mix) in the formulations of table 3 to various stains: asphalt,Brown shoe polish, mustard and 1% Oil palm (Oil Brown). Oil palm is an industry standard for simulating high flow pollution (traffic staining). All stains except oil palm were placed on the sample and left for about 2 hours; the oil palm stain was left for 30 minutes. The stain was then removed with clean mineral spirits. The change in color was assessed using delta E measurements (Δ E or dE), which presented differences between colors numerically. The triblend of the present invention exhibited good soil resistance to asphalt, mustard and 1% oil palm. For theBrown shoe polish, the inventive triblend was better than the control. The stain resistance results are presented in figure 11.

Examples 9 to 11

The following plasticizers were evaluated in examples 9-11:

diisononyl phthalate (DINP);

butyl Benzyl Phthalate (BBP);

bis (2-ethylhexyl) terephthalate (DOTP);

1,2-cyclohexane dicarboxylic acid diisononyl ester (DIDC);

dibutyl terephthalate (DBTP);

N-C8-10 alkyl pyrrolidone (300);

x-20 dibenzoate triblend of the invention;

x-250 is a dibenzoate double mixture customized for the polyvinyl chloride industry;

x-1001, 2-propanediol dibenzoate (98%).

In addition to evaluating the basic performance data of the above plasticizers in simple plastisols, two other evaluations of the plasticizer were also made-one in the floor wear layer or typical coating starting formulation and the other in the starting formulation of the plastisol screen ink. As mentioned above, the basic screening of plastisols takes into account four basic performance parameters: compatibility, efficiency, durability and processability. The following example identifies the fundamental characteristics used to demonstrate performance.

Determining the viscosity, rheology, gelation/fusion and staining of the coating formulation; and determining the gel/fusion and rheology of the plastic adhesive screen ink formulation.

Table 5 below presents a simple plastisol formulation used to evaluate plasticizers. Table 6 below presents the coating formulations used to evaluate the plasticizer and table 7 below presents the evaluated plastisol screen ink formulations.

TABLE 5 simple plastisol formulation, basic screening

TABLE 6 coating initiation formulation

Raw materials	PHR	％
			Dispersion resin (Geon 121A)	75	44.9
Mixed resin (Geon 217)	25	15
			Plasticizer agent	45	26.9
Isodecyl benzoate	10	6
			Viscosity control additives	5	3
Heat stabilizer (Mark 1221)	3	1.8
			Epoxidized soybean oil	4	2.4

TABLE 7 plastisol Screen inks, starting formula

Example 9 basic screening plasticizer

The results obtained in the basic screening using a simple plastisol formulation are presented in tables 8 and 9 below and are further reflected in fig. 12 and 13.

TABLE 8 Performance characteristics, base recipe (from TABLE 5)

TABLE 9 gel/fusion Curve data, base recipe (from TABLE 5)

The above data show that the dibenzoate blends of the present invention are more compatible with ethylene than the generic non-phthalate esters, as illustrated by the cycle test and nip roll test data. It is known that dibenzoate blends have lower viscosity/rheology than conventional plasticizers. Surprisingly, however, the tri-blend of the present invention is a high solvating agent, exhibiting lower viscosity than expected (fig. 12), which provides a viable solution for formulating plastic glues requiring high solvating formulation plasticizers, while minimizing the viscosity/rheology limitations of the standard blend of dibenzoate plasticizers known to date.

The properties of the solvating agent were evaluated using a TA AR2000ex rheometer in oscillatory mode to produce gel/fusion properties. Table 9 lists the data obtained and figure 13 illustrates the curves developed on the basis of this data. Based on this data, it is evident that dibenzoates, BBP, DBTP and 300 are better solvating agents than all the general type plasticizers. This shows that with the mixture of the invention it is possible to obtain sufficient strength at lower temperatures, which translates into accelerated production. Classical gel point data also verifies this. 300 is the most drastic high solvating agent, but a very low gel strength is developed.

With respect to efficiency, the resulting data show that the dibenzoate blends are somewhat more efficient than DINP, but other phthalates and high solvating agents are somewhat more efficient than dibenzoates. X100 is the least efficient.

With respect to extractability and volatility, the data indicate that the universal plasticizer is extracted in large amounts by solvents and oils but has good resistance to aqueous solutions. This opposite face is true for high solvating agents. Meanwhile, general purpose plasticizers are less volatile than high solvating agents. 300 was very volatile compared to DBT compared to other tested high solvating agents, while the volatility of BBP was the lowest. The triblend X20 of the present invention was similar in volatility to the doublet X250 and was less volatile than BBP, respectively. Volatile activated carbon tests are generally performed for only one day. For this example, the test was extended to 28 days to determine plasticizer development under long term exposure. Dibenzoate plasticizers invariably contain residual reaction products that tend to flake off over time, which is supported by the data. X100 is more stable than the dibenzoate mixture.

Dibenzoate-based plasticizing vinyls and, indeed, all high solvating agents plasticizing vinyls exhibit poorer thermal stability than general plasticizing vinyls. 300 has very poor thermal stability.

Overall, dibenzoates perform quite well compared to other high solvating agents. Especially compared to the newer non-phthalate plasticizers, N-alkylpyrrolidones (300).

Example 10 coating starting formulation Properties

The plasticizers evaluated in the coating starting formulations are reflected in table 6. Figure 14 illustrates that good rheology and viscosity were demonstrated in the formulations through the triple mixture X20 of the present invention. Figure 15 illustrates the good gel/fusion properties obtained for X20.

FIG. 16 presents stain resistance compared to BBP for vinyl and DINP, mixtures of DINP and DIHP, with X100, X250, and X20. All benzoates exhibit good stain resistance against oil-brown dyes (an indicator of kinetic line contamination). By visual inspection, X20 plasticized vinyl was the most resistant to staining of the dibenzoates.

Example 11 plastisol Screen ink Properties

An evaluation of the performance of the starting plastisol screen inks is presented in table 7. X20, X20 and DINP 50: 50 mixtures and DINP alone were evaluated as plasticizers in ink formulations. The excellent rheology and viscosity obtained with X20 are reflected in fig. 17 and 18. The gel/fusion properties of X20 were also superior. The blend (X20 with DINP) also exhibited improved properties, indicating that the booster X20 enhanced the performance of the general purpose plasticizer.

Based on the above, the inventive triblend of dibenzoates and new grade (grade) of glycol dibenzoate provide a new option as a high solvating agent for vinyl applications. Dibenzoates have been non-phthalates by their nature and are safe-to-use products with good performance records. The triblend X20 of the new benzoate class exhibits good handling characteristics and good performance as a high solvating agent. Plastisol rheology was good and the resistance to soiling of vinyl plasticized from X20 exceeded the available general purpose plasticizers and their double blends.

X250, a bis-mixture, is highly efficient in vinyl.

X100, propylene glycol dibenzoate, provides an excellent high solvating agent alternative for the vinyl group, although somewhat less effective than the tri-and di-mixtures of the present invention. Its high coefficient may be advantageous in some applications.

The triblend of the present invention has presented an excellent alternative for use as a non-phthalate high solvating agent plasticizer replacement. It can also be used in mixtures with other poor solvating plasticizers to improve compatibility and processability in plastisols or as a mixed plasticizer with a variety of other plasticizers to tailor the needs of the application.

Example 12 adhesive evaluation

The performance of the novel triblend X20 was evaluated in a commonly used latex adhesive compared to a given plasticizer. The formulations evaluated included:

polymer (b):

polyvinyl acetate homopolymer, protected by PVOH (polyvinyl acetate (PVAc))

Polyvinyl acetate/ethylene copolymer, Tg 0 ℃ protected by PVOH (polyvinyl alcohol/ethylene (PVA/E))

Plasticizer:

x20, triblend of dibenzoates of the invention.

Commercial bis-mixtures of DEG/DPG dibenzoates (K-FLEX 850S).

X100，PGDB

The plasticizer levels in PVAc were evaluated at 5, 10, 15 and 20% on a wet adhesive basis. The plasticizer level in PVA/E was evaluated at 5, 10 and 15% on a wet adhesive basis. VOC content testing was performed on neat plasticizer. Viscosity response and stability, compatibility (dry film), reduced moisture, rheology, set and open times, wet tack (rheology determination), T and 180 ° peel bonds were performed on the adhesive.

PVAc is a standard industrial binder polymer. Once added, the plasticizer is incorporated into the polymer as part of the gum. Plasticizer glues have a lower glass transition, which results in a more flexible PVAc polymer, making the glue more efficient. The Tg obtained at various levels is presented in fig. 19 and 20. The inhibition of Tg by PGDB is less efficient than that of the triple mixture of the invention. The Tg inhibition ratio of the triblend of the invention is 4: the PGDB content in the combination of the 1 DEGDB/DPGDB double mixture is expected to be low. The suppression of Tg of the tri-mixture of the present invention provides a viable option for use in adhesives, compared to that achieved with commercially available K-FLEX 850S.

The viscosity results obtained are presented in fig. 21 and 22. The triblend of the invention exhibits good viscosity response.

Overall, the above results show that the novel triblend of dibenzoate is compatible and functions similarly to typical latex binder polymers. And in some cases better than the standard binary blend (double blend) of dibenzoates.

Example 13 glazing agent evaluation

The triblend of the invention was evaluated in an aqueous polish (OPV) for graphic art applications. Many polymers used in the industrial panels are non-film forming agents at room temperature; plasticizers and/or coalescents are therefore needed to help properly form the film to ensure that these hard polymers fully develop their performance characteristics. Coalescents used in the graphic arts industry have typically been of the volatile type. Traditionally, glycol ethers (glycol ethers), phthalates (e.g., BBP), and benzoates (2-EHB) have been used as plasticizers and coalescents for OPV. Although it works well, VOC is a problem. Typically, phthalates such as DBP or BBP have been used in the graphic arts industry but alternatives are recently being considered.

The triblend of the present invention is evaluated in OPV formulations with other conventional or coalescent agents based on its broad base of compatibility with the polymers used for this application.

First, the volatility characteristics of the plasticizer and/or coalescent were determined (data not shown). The volatility of both the trimix X20 and the bimix X250 of the present invention was determined to be lower than 2,2,4-Trimethyl-1,3-pentanediol monoisobutyrate (2,2,4-Trimethyl-1, 3-cationic monobutyrate (TMPDMB)) (a historical coalescent selection for paints and other coatings), BBP, 2-EHB, and several ethers (diethylene glycol monobutyl ether), diethylene glycol monomethyl ether (diethylene glycol monomethyl ether), ethylene glycol monobutyl ether (ethylene glycol monobutyl ether), and dipropylene glycol monomethyl ether (dipropylene glycol monomethyl ether)), making them acceptable low VOC alternatives.

The base polish formulations for viscosity response, Minimum Film Forming Temperature (MFFT), and coni-g hardness evaluations are presented in table 10 below, which reflects the addition of 4% plasticizer/coalescent.

TABLE 10 basic glazing agent formulation

Raw materials	Non-coalescence (%)	Coalescence (%)
			Styrene acrylic emulsion, high Tg	64	60
Dispersed polyethylene wax in cream form, 26% solids	4	4
			Resin solution, 34%, high Tg	20	20
Wetting surfactants	4	4
			Defoaming agent	0.1	0.1
Water (W)	7.9	7.9
			Plasticizer/coalescent	0	4

The viscosity response of the base emulsion is an indicator of the compatibility of the plasticizer/coalescent test. Viscosity data was obtained by one day aging. The viscosity response of the OPV with 4% plasticizer/coalescent was in the range contemplated by the present invention for tri-blend X20 and di-blend X250, and was similar to that of DEGDB (at 00-150 mpa). The viscosity reaction of diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether and diethylene glycol monomethyl ether is low.

The viscosity response of dibenzoates selected in the OPV formulation with 6% coalescent rather than 4% was also measured. Both X-250 and X-20 OPV have viscosities of 250 MPa, which indicates that the addition of a relatively low level (2% increase) of this type of plasticizer/coalescent has a significant effect on the OPV viscosity.

Table 11 lists MFFT for various OPV formulations with 4% and 6% addition levels. The data show that all formulations formed good films at room temperature. The water soluble coalescent type is more effective in inhibiting MFFT. When the MFFT inhibition for dibenzoates was somewhat less than for ethers, MFFT with OPV loaded at 6% humidity on X20 and X250 was also determined. The results show that less than an additional 2% addition is required to achieve ether-like MFFT inhibition results. Most likely, the additional amount is not necessary to achieve development of the desired adequate performance characteristics.

TABLE 11 minimum film formation temperature

A problem with using true plasticizers but non-volatile coalescents is the effect on parameters such as drying time. The OPV finger pressure drying time (dry-to-touch time) of the trimix X20, the bis-mixture X250, DEGDB, 2-EHB, diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether of the present invention was determined. It is indicated that there is no significant difference in the tack-free time between volatile and non-volatile plasticizers or coalescents.

The gloss values of OPVs were also determined and found to be similar to the trimix X20, the bimix X250, DEGDB, 2-EHB, diethylene glycol monobutyl ether, and dipropylene glycol monomethyl ether of the present invention.

FIG. 23 shows Konig hardness data obtained for an OPV formulation with a plasticizer comprising a triblend X20 of the present invention and a coalescing agent conventionally used for OPVs. Plasticizers are generally not favored for use in OPVs based on the belief that they are longer lasting than coalescents and thus will remain and soften the film resulting in inferior performance. As shown in fig. 23, the Konig hardness data overrules the commonly held idea. The 6% plasticizer films (X20 and X250) were somewhat softer than the other coalescents, but they may be too coalesced as shown in the MFFT above. The 4% plasticizer films were all similar to the more volatile polymerized OPV.

Overall, OPV evaluation shows that the triblend of the present invention has low volatility, good compatibility and comparable dry times, gloss and hardness and is, for example, suitable for use as a replacement in OPV applications.

Best mode and preferred embodiments are described according to the patent statutes; the scope of the invention is not limited thereto but rather by the scope of the appended claims.

Claims (14)

1. A plasticizer triblend composition, wherein said composition comprises:

a. diethylene glycol dibenzoate, present in an amount ranging from 10 to 90 weight percent,

b. dipropylene glycol dibenzoate present in an amount ranging from 1 to 50 weight percent, and

c. 1, 2-propanediol dibenzoate, present in an amount ranging from 10 to 90 weight percent,

based on the total weight of the plasticizer tri-mixture composition,

wherein the triblend is used as a primary plasticizer alone or as a special blend plasticizer to improve compatibility and processability of poorly solvated plasticizers.

2. The plasticizer triblend composition of claim 1, wherein the composition is

Diethylene glycol dibenzoate is present in an amount of at least 60 weight percent,

dipropylene glycol dibenzoate is present in an amount of at least 10 weight percent,

the 1, 2-propanediol dibenzoate is present in an amount of at least 20 weight percent.

3. The plasticizer triblend composition of claim 1, wherein the mixture comprises 80 weight percent of the diethylene glycol dibenzoate and dipropylene glycol dibenzoate mixture, wherein the ratio of diethylene glycol dibenzoate to dipropylene glycol dibenzoate is 4: 1. and 20 weight percent 1,2-propylene glycol dibenzoate based on the total weight of the plasticizer triblend composition.

4. The plasticizer triblend composition of claim 1, wherein the plasticizer triblend composition further comprises: selected from the group consisting of phthalate esters; phosphoric acid esters; adipate, azelate, oleate, and sebacate compounds; a succinate salt; esters of terephthalic acid; 1, 2-cyclohexanedicarboxylic acid esters; an epoxy plasticizer; a fatty acid ester; a diol derivative; sulfonamides; cellulose esters; a phenolic resin; an amino resin; amide and protein plastics; hydrocarbons and hydrocarbon derivatives; monobenzoates; 2,2,4-trimethyl-1,3-pentanediol diisobutyrate and mixtures thereof.

5. A plastisol composition, wherein said composition comprises:

a. an organic polymer which is a dispersed phase; and

b. a liquid phase, non-phthalate, high solvating plasticizer triblend composition comprising diethylene glycol dibenzoate, dipropylene glycol dibenzoate and 1,2-propylene glycol dibenzoate,

wherein the plastisol composition has a processing viscosity that is better than expected when comparing the viscosities of the ingredients, and at least that which is comparable to the viscosity achieved with conventional dibenzoate-based double blends, and wherein the plastisol has excellent stain resistance compared to phthalate-based plasticizers.

6. The plastisol composition of claim 5, wherein the composition comprises

The organic polymer in the dispersed phase is present in 100 parts by weight, and

the plasticizer triblend composition is present at 1 to 300 parts by weight per 100 parts by weight of the polymer.

7. The plastisol composition of claim 6, wherein the plasticizer triblend composition is present at 70 parts by weight per 100 parts by weight of the polymer.

8. A coating composition, said composition comprising:

a. acrylic, Vinyl Acetate Ethylene (VAE), or styrene acrylic polymers or any combination thereof,

b. the plasticizer triblend composition of claim 1, and

c. at least one additive selected from the group consisting of antioxidants, heat stabilizers, flame retardants, and surfactants.

9. The coating composition of claim 8, wherein the coating composition further comprises a conventional plasticizer or coalescent.

10. An adhesive composition, said composition comprising:

a. polyvinyl acetate, polyvinyl acetate ethylene copolymers or mixtures thereof;

b. the plasticizer triblend composition of claim 1; and

c. at least one binder additive.

11. An underfill or sealant, characterized in that said underfill or sealant comprises: a latex polymer, the plasticizer of claim 1, and at least one additive selected from the group consisting of antioxidants, heat stabilizers, flame retardants, surfactants.

12. The underfill or sealant of claim 11 wherein said underfill or sealant further comprises a filler

A plastisol screen ink composition, wherein the composition comprises the plasticizer according to claim 1.

13. An overprint varnish for graphic arts applications, said overprint varnish comprising the plasticizer triblend composition of claim 1.

14. A method of preparing a plastisol composition, said method comprising the steps of:

a. mixing together diethylene glycol dibenzoate, dipropylene glycol dibenzoate, and 1,2-propylene glycol dibenzoate to form a plasticizer tri-mixture composition; and

b. polyvinyl chloride (PVC) or acrylic polymers are dispersed in the plasticizer tri-blend composition.