MXPA99007092A - Water dispersible/redispersible hydrophobic polyester resins and their application in coatings - Google Patents

Abstract

This invention relates to the synthesis from PET (virgin, recycled, post consumer, or precursor raw materials) of novel water dispersible or water emulsifiable polyester resins having improved hydrophobicity or non-polar characteristics. These characteristics give the applied film of these dispersions or emulsions much improved water repellency while at the same time retaining their redispersible or reemulsifiable properties. Such resins can be used for many applications in the paper, textile, coatings, paint, construction, and other industries.

Description

HYDROPHOBIC POLYESTER RESINS THAT CAN BE DISPERSED / REDISPERSED IN WATER AND ITS APPLICATION IN COATINGS FIELD OF THE INVENTION This invention relates to the synthesis of polyethylene terephthalate (PET) with, for example, virgin PET, recycled PET, post-consumer PET or precursor raw materials of polyester resins emulsifiable in water or dispersible in water. novel water having improved hydrophobicity or non-polar characteristics. The present invention relates to resins having an excellent hydrophobic character, and also a good ability to orient the hydrophobic groups away from substrates on which they are applied and high contact angles with water drop of the coated surface. The above characteristics provide the applied film of these dispersions or emulsions with a highly improved water repellency characteristic while retaining their I redispersion or re-emulsification properties. Such resins can be used for many applications in the paper, textile, coatings, paint, construction and other industries. BACKGROUND OF THE INVENTION AND DESCRIPTION OF THE TECHNIQUE PREVIOUS Several patents were written regarding the synthesis of water-soluble polyester resins, which can be dispersed in water or emulsifiable in water. For example, Altenberg, in U.S. Patent No. 4,604,410, proposed the manufacture of etherified aromatic polyols by digestion of waste polyethylene terephthalate with a low molecular weight polyhydroxy compound, containing from 3 to 8 hydroxyl groups. A resulting intermediate is alkoxylated with 1-4 moles of moles of ethylene oxide and / or propylene oxide. The final product is useful for making polyisocyanurate and polyurethane foams. Sperenza et al, U.S. Patent No. 4,485,196, reported the reaction of recycled polyethylene terephthalate residue with an alkylene oxide, such as, for example, propylene oxide. The product can be used to make rigid foams. Other methods for reacting polyalkylene terephthalate residue with glycols or polyols appear in Svoboda et al, in U.S. Patent 4,048,104; and Altenberg et al, in U.S. Patent No. 4,701,477. In the applicant's prior invention (US Pat. No. 4,977,191 to Salsman), a water-soluble or water-dispersible polyester resin suitable for applications in the preparation of textiles is presented. of the reaction of 20-50% by weight of residual terephthalate polymer, 10-40% by weight of at least one glycol and 5-25% by weight of at least one oxyalkylated polyol. Preferred compositions also comprise from 20 to 50% by weight of isophthalic acid. A resin soluble in water or that can be dispersed in additional water comprises a reaction product of 20-50% by weight of residual terephthalate polymer, 10 to 50% by weight of at least one glycol and 20-50% by weight. isophthalic acid weight. U.S. Patent No. 5,252,615 to Rao et al discloses coating compositions derived from the alcoholysis of polyethylene terephthalate (PET). More preferably, PET is recycled or recovered from plastic articles. Dale et al, in U.S. Patent No. 4,104,222, proposed the preparation of a dispersion of linear polyester resins by mixing linear polyester resin with a surfactant agent of higher alcohol addition type / ethylene oxide, the melting of the mixing and dispersing the resulting melt in an aqueous alkaline solution. The products are used as coating and impregnating agents. References proposing the use of copolymers containing terephthalic units and units derived from alkylene glycols and polyoxyalkylene glycols for the treatment of fibers or fabrics include Hayes (U.S. Patent No. 3,939,230), Nicol et al (U.S. Patent No. 3,962,152), Wada et al (U.S. Patent). No. 4,027,346), Nicol (U.S. Patent No. 4,125,370) and - >; Bauer (U.S. Patent No. 4,370,143). Marshall et al, in U.S. Patent No. 3,814,627, proposed the application of an ester, based on polyethylene glycol, on polyester yarn. In our other North American patent number 5,281,630 (Salsman), we present sulfonated polyester resin compositions soluble in water or that can be dispersed in water made by treating a product of polyester glocolysis with an alpha, beta ethylenedically unsaturated dicarboxylic acid and then with a sulfite. The following North American patents describe polyester resins containing fatty acid portions: 4,080,316; 4,179,420; 4,181,638; 4,413,116; 4,497,933; 4,517,334; 4,540,751; 4,555,564; 4,686,275; 5,075,417 and 5,530,059. None of the aforementioned patents disclose the resins of the present invention which have excellent hydrophobic characteristics and high contact angles when a drop of water is applied on surfaces coated with said resins. The resins described in the prior art have found applications in textiles, coatings, adhesives. All these resins however have a weakly polar nature which limits their use to adhesion promoters or coating applications where water resistance is not a main factor or where water resistance is supplied by means of other additives. No mention of water rejection properties has been associated with being polyester resins. In some cases, large amounts of oils and fatty acids are employed to provide crosslinking and heat setting properties to the polyester resins. This chemistry has been known as% alkyd chemistry. "Crosslinking occurs between chains during the drying phase, and the applied coating becomes insoluble.To date, the inventor has no knowledge of prior art polyester wherein the resins of polyester emulsifiable or that can be dispersed in water, sufficient non-polar groups are incorporated to provide a hydrophobic character or hydrophobic properties to the substrate in which these dispersions are applied and / or at the same time retain the redispersion capacity in water. Most non-polar materials that have reactive condensation sites are that these materials have only one reactive site (eg, stearic acid, oleic acid, palmitic acid, behenic acid, etc. these are more likely to be isolated from triglycerides than occur in nature, such as vegetable and animal fats and oils.) This means that In the polyester condensation reaction they become chain terminators and the amounts that can be used have strict limitations because the higher the amount, the lower the molecular weight of the resin. In the chemistry of alkyds, the unsaturation in oils is used and crosslinking reactions can be used. However, a reaction through unsaturation does not expose sufficient areas of the oil-modified chain to provide hydrophobic or water rejection properties to the coatings produced from this chemistry. The resins described in this invention have overcome the problem of chain termination using a highly modified polyester structure. In this way, polyester resins - containing 30% or more of monofunctional monomers, such as stearic acid, can be made to provide a much improved non-polar nature. Thus, by using the reactions mentioned in our prior patents, these resins can be transformed into dispersions or emulsions in water. Due to the large amount of hydrophobic or non-polar functionality, these resins can not be considered as water soluble as certain previous sulfonated resins have been qualified. When these dispersions or emulsions are applied to most substrates and dried, an orientation of the hydrophobic areas of the chain occurs and the surface of the substrates becomes water repellent, with a degree of rejection of water corresponding to the thickness and concentration of the initial coating. This characteristic of repelling water is evident from the high contact angle of a drop of distilled water placed on the substrate. This high contact angle is not evident in previous water dispersible resins. The prior art does not mention the novel polyester resins which can be dispersed in water of the present invention which are derived from polyethylene terephthalate and which has a high characteristic of being water repellent in accordance with what is evidenced by high contact angles. OBJECTS OF THE INVENTION It is a primary object of the present invention to provide water-soluble or water-dispersible polyester resin compositions having improved hydrophobicity. It is a further object of the present invention to provide water-soluble or water-dispersible polyester resin compositions having improved hydrophobicity and non-polar characteristics. It is a further object of the present invention to provide water-soluble or water-dispersible polyester resin compositions that have an improved water repelling characteristic. It is another object of the present invention to provide water-soluble or water-dispersible polyester resin compositions that have improved oil and water repellency characteristics. A further object of the present invention is the use of residual polyester material in the production of polyester resins having non-polar characteristics and improved hydrophobicity. It is another object of the present invention to employ polyester compositions that can be dispersed in water as coatings for fiber, paper or cloth. It is a further object of the present invention to produce water-soluble or water-dispersible polyester coating compositions that have improved water and oil repellency characteristics. SUMMARY OF THE INVENTION "In summary, the present invention relates to hydrophobic polyester resins that can be dispersed in water / and dispersed again derived typically from PET, especially from recycled PET having improved hydrophobicity and non-polar characteristics. it focuses on polyester resins having the following general formula ln- -Ain where I is the ionic group; n is an integer in the range of 1 to 3 and defines the number of ionic groups; P is a polyester structure, A is an aliphatic group; and m is an integer in the range of 3 to 8 and defines the number of aliphatic groups. The ionic groups I that are required for dispersibility in water are typically derived from the carboxylic acid group which is introduced into the resin by the polyacid monomers. The percentage weight of ionic monomers in the resin is from 1% to 20%, with 5 to 10% of ionic monomers being preferred. The structure P of the polymer consists of polyester groups. It can be any linear or branched polyester made by the use of polyacids and polyalcohols. The preferred method is the generation of the structure through the use of polyester from recycled sources. The percentage by weight of the ingredients of the polyester structure is within a range of 30 to 80% of the whole resin, with a range of 50 to 60% by weight being preferred. The aliphatic groups A consist of chain fatty acids of 6 to 24 straight or branched carbon atoms, or triglycerides thereof. The percentage weight of the aliphatic portion can be from 10 to 60%, with a range of from 20 to 40% by weight being preferred. The hydrophobic and water dispersible polyester resins of the present invention have excellent water repellency properties in accordance with what is evidenced by their contact angle measurements when used as coatings. The contact angles achieved when the resins are applied to paper are of the order of 98 or more. The present invention also focuses on a hydrophobic polyester resin and can be dispersed in water, comprising a reaction product of 30-70% by weight of terephthalate polymer; from 5 to 40% by weight of a hydroxy-functional compound having at least two hydroxyl groups; from 1 to 20% by weight of a carboxy functional compound having at least two carboxyl groups, and from 10 to 60% by weight of a compound selected from the group consisting of C6-C24 straight or branched chain fatty acid or triglycerides thereof, wherein said resin is further characterized in that the hydroxy functional compound is present at 1-3 times the equivalents of the hydrophobic portion. The present invention also focuses on substrates such as paper, cardboard, food packaging, textiles, concrete, and the like, coated with a polyester resin comprising a reaction product of 30-70% by weight of a polymer of terephthalate; from 5 to 40% by weight of a hydroxy functional compound having at least two hydroxyl groups; from 1 to 20% by weight of a carboxy-functional compound having at least two carboxyl groups and from 10 to 60% by weight of a hydrophobic compound selected from the group consisting of a straight-chain C6-C24 fatty acid or branched or triglycerides thereof. The present invention also focuses on an article of manufacture comprising a substrate coated with a water-dispersible and hydrophobic polyester coating composition comprising a reaction product of 40-60% by weight of polyethylene terephthalate polymer.; 1-10% by weight of neopentyl glycol; from 5 to 10% pentaerythritol; from 3 to 15% by weight of trimellitic acid or trimellitic anhydride; and from 10 to 45% by weight of stearic acid. The invention is also characterized by a water repellent polyester coating composition, comprising a reaction product of 30-70% by weight of a terephthalate polymer; from 5 to 40% by weight of a hydroxy-functional compound having at least two hydroxyl groups; from 1 to 20% in weight of a compound having carboxy functionality having at least two carboxyl groups and from 10 to 60% by weight of a hydrophobic compound selected from the group consisting of a straight chain C6-C24 fatty acid or branched or triglycerides thereof. Another novel aspect of the present invention is a water repellent polyester coating composition, comprising a reaction product of 40-60% by weight polyethylene terephthalate polymer.; from 1 to 10% by weight of neopentyl glycol; from 5 to 10% by weight of pentaerythritol; from 3 to 15% by weight of trimellitic acid or trimellitic anhydride; and from 10 to 45% by weight of stearic acid. The invention also relates to a method for providing a water repellency characteristic to selected substrates within the group csting of fibrous substrates and leather, comprising the application to said substrates of a composition comprising the reaction product of the invention. -70% by weight of a terephthalate polymer; from 5 to 40% by weight of a hydroxy-functional compound having at least two hydroxyl groups; from 10 to 20% by weight of a carboxy-functional compound having at least two carboxyl groups and from 10 to 60% by weight of a hydrophobic compound selected from the group csting of straight or branched chain C6-C24 fatty acid or well triglycerides thereof. The invention also discloses polyester resins that can be made which contain 30% or more of monofunctional monomers, such as for example stearic acid, in order to provide a highly improved non-polar nature. DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The objects of the present invention and many of the expected advantages of the present invention will be readily realized as the present invention is better understood with reference to the following detailed description. The resins that can be dispersed in novel water of the present invention can be represented by the following structure: In- - "m where I is the ionic group; n = 1-3 defines the number of ionic groups, P is polyester; A is an aliphatic group; and m = 3-8 represents the number of aliphatic groups. There are three requirements necessary for the polyester chemistry of the present invention: 1. A polyester structure. 2. A multifunctional glycol in the structure that provides an additional hydroxyl functionality present in 1-3 times the equivalents of group 3. 3. A hydrophobic portion, such as for example saturated fatty acid, but not limited thereto. This portion is present in a proportion of one third to two thirds of the equivalents of component number 2 and must be present in the total formula at a rate of 10 to 50% by weight, the preferred level being between 15 and 40% by weight according to the required degree of water repellency characteristic. 4. An ionic portion either in the structure or located at extremes, present in 5-20% by weight, the preferred amount is 10 to 15% by weight. This portion can be neutralized with base, if necessary, to supply a dispersion capacity in water. These physical properties that make the resins of the present invention unique are: 1. Hydrophobic character. 2. The ability of these resins to guide the hydrophobic groups away from the substrates on which they are applied. 3. Evidence of hydrophobic orientation as characterized by high contact angles with water droplets on the coated surface. 4. The "s" hydrophobic and water dispersible polyester compositiof this invention provide desirable water and oil repellency character to substrates treated with such compositiwithout adversely affecting other desirable properties of the substrate, such as for example smoothness. The composition of the present invention can be used to provide a water and oil repellency characteristic to fibrous substrates such as textiles, papers, nonwovens, or leather or to other substrates such as plastic, wood, metals, glass, stone and concrete. The resins that can be dispersed in water of the present invention are synthesized by means of condensation polymerization with original or recycled PET or polyacid-polyalcohols (monofunctional acids or alcohols) used to make polyesters together with aliphatic acids or animal or vegetable triglycerides hydrogenated or not hydrogenated. Resins soluble in water or that can be dispersed in water are made from residual terephthalate polymers, including bottles, sheet material, textile waste and the like. Residual terephthalate plastics can be purchased from recyclers and include, but are not limited to, materials identified as "PET rock." The residual terephthalate can be characterized by the unit formula OROOCCO to: where R is the residue of an aliphatic or cycloaliphatic glycol of 2-10 carbon atoms or of oxygenated glycol of the formula H O (C? H 2? O) nC? H 2XO H (2) where x is an integer from 2 to 4 and is from l to l0. Preferably, the residual terephthalate polymer is a polyalkylene terephthalate, such as for example polyethylene terephthalate and polybutylene terephthalate, polycyclohexanedimethate terephthalate or a mixture of the same. Other suitable polyester polymers that can be employed in the practice of the present invention include polyl, 2 and polyl, 3 propylene terephthalate as well as polyethylene naphthanate. It will be understood that, for reasons of economy, the use of residual terephthalates is preferred. However, the use of virgin terephthalate resins may be included within the scope of the presentation and the appended claims. The ionic group In required for dispersibility in water can be a carboxylic acid introduced into the resin by polyacid monomers such as trimellitic anhydride, trimellitic acid, or maleic anhydride or sulfur groups which contain monomers such as example dimethyl 5-sulfoisophthalate (DMSIP or 5-sulfo, 1,3-dimethylbenzenedicarbonate), ethylene glycol sulfoisophthalate (SIPEG or 5-sulfo, 1,3-benzenedicarboxylic acid dioxyethyl ester, or from sulphonated end groups) Alcanically unsaturated according to that described in Salsman, patent number 5,281,630 The polyacid is preferably selected from the group consisting of isophthalic acid, terephthalic acid, ophthalmic anhydride (acid), adipic acid, etc. other preferred polyacids, but not limited to to them, they are ophthalmic anhydride (acid), isophthalic and terephthalic acids, adipic acid, fumaric acid, 2, 6-naft acid alendicarboxylic acid and glutaric acid. Mixtures of the above acids and anhydrides thereof can be employed in the practice of the present invention. The weight percentage of ionic monomers in the resin is from 1% to 20%, but from 5 to 10% is preferred. The structure of the polymer consists of polyester groups. It can be any linear or branched polyester made using polyacids and polyalcohols. The preferred method is the generation of the structure using polyester from recycled sources. The percentage by weight of the ingredients of the polyester structure is within a range of 30 to 80% of the whole resin, with 50 to 60% being especially preferred. Said structure is typically derived by the reaction of PET such as for example residual PET with a hydroxy functional compound containing at least two hydroxyl groups. The hydroxy functional compound having at least two hydroxyl groups is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, propylene glycol, 1,2-propylene glycol, 1,3-propanediol, 1,2-butylene glycol, 1,3 -butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol, or a monosaccharide. In another embodiment, other hydroxy compounds having at least two hydroxyl groups include derivatives of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol or an oxyalkylated monosaccharide with 5-30 moles of ethylene oxide, propylene oxide or a mixture thereof. , by hydroxyl of the hydroxy functional compound. The aliphatic groups consist of chain fatty acids of 6-24 carbon atoms or triglycerides thereof, such as for example stearic, oleic, palitic, lauric, linoleic, linolenic, behenic acid or mixtures thereof. They can come from hydrogenated or non-hydrogenated animal or vegetable oil, such as beef bait, lard, corn oil, soybean oil, etc. if fatty acids or highly unsaturated triglycerides are used, care must be taken to avoid cross-linking through the unsaturated group. The percentage by weight of the aliphatic portion can be from 10 to 60%, with 20 to 40% being preferred. 7 There are two basic routes for making resins. These routes are presented below: via 1 (1) aliphatic acids + esters + ultifunctional glycol - >esterification or transesterification = hydrophobic glycol (2) hydrophobic glycol + PET (or diacid with dialcohol) - > esterification or transesterification = hydrophobic polyester (3) Hydrophobic polyester _ + ionic monomer - > esterification or transesterification = hydrophobic polyester resin and that can be dispersed in water Route 2 (1) Di-acid or PET + multifunctional glycol - > esterification or transesterification = graft polyester with hydroxyl groups through chain and / or as end groups (2) Graft polyester + aliphatic acids or esters - > esterification or transesterification = hydrophobic polyester resin (3) Hydrophobic polyester + ionic monomer - > esterification or transesterification = hydrophobic polyester resin or that can be dispersed in water The following steps are used in the process to produce the resin of the present invention: 1. Incorporation of a non-polar group or non-polar groups that can be chosen from the following : fatty acids of stearic acid, behenic acid, palitic acid, lauric acid, oleic acid, linoleic acid, etc .; triglycerides from animal or vegetable sources of the type of beef bait, corn oil, soybean oil, peanut oil, safflower oil, hydrogenated versions of these oils, etc .; reactive silicones, blown paraffins or mineral oils, hydrophobic urethanes, etc. This group must be present at a rate of 10-50% by weight. The incorporation by esterification or transesterification of a multifunctional hydroxyl component or of several components of this type such as for erythritol, sorbitol, glycerol, etc., at consistent levels but not limited to 1 to 3 times the reactive equivalent of the components of group 1. Esterification or transesterification of typical ingredients of the employees "to make polyester polymers These ingredients can be chosen from polyethylene terephthalate or similar terephthalates and / or difunctional acids such as terephthalic acid, isophthalic acid, ophthalmic acid or anhydride combined with difunctional alcohols such as ethylene glycol, diethylene glycol, neopentyl glycol, propylene glycol, etc. The incorporation of an ionic group or of several ionic groups required for dispersion of the resin in water Examples of these groups are trimellitic anhydrides, anhydride maleic, sulfosuccinate, ac gone sulfonated isophthalic or its esters, etc. 5. The dispersion of the resin in water containing a quantity of base, if required, to neutralize the pending acid groups. In practice, the process of the present invention, steps 1-3 can be carried out in any order but the processing order listed above is preferred. The polyester resins are usually manufactured and preferably by the use of an ester exchange catalyst. These catalysts are metal carboxylates and well-known organometallic compounds, particularly tin or titanium compounds. Preferred catalysts include manganese acetate, sodium acetate, zinc acetate, cobalt acetate, or calcium acetate, tetraalkyl titanates wherein the alkyl has up to 8 carbon atoms as well as alkylstanoic acid or dialkyltin oxides, such as for example monobutylstanoic acid or dialkyltin oxide. Preferred catalysts include monobutylstanoic acid as well as tetrapropyl or tetrabutyl titanate, or a mixture thereof. The resulting resinous products obtained are generally collected in relatively concentrated aqueous solutions of ammonium or alkali metal hydroxides or carbonates. The concentration used can be determined by routine experiments. However, if the shipment of the concentrated aqueous solutions to a point of use is contemplated, it is preferred to produce highly concentrated solutions. Within the scope of the present invention is the production of initial solutions or dispersions containing from 20% to 30% or more of solids in resin. The resins of the present invention find the production of initial solutions or dispersions containing from 20 to 30% or more of solids in resin. The resins of the present invention typically have average molecular weights within the range of 3000 to 50,000. Preferably, the resins typically have a molecular weight of about 4, 000 to approximately 8,000. Obviously, the expected end use will determine which molecular weight will be optimal. The average molecular weight of the resins is typically determined by GPC either by viscosity measurements, or by other methods well known in the art of polymer chemistry. EXAMPLES The following examples are presented for the purpose of illustrating the invention in greater detail. The examples are intended to illustrate the invention and should not be construed as limiting the present invention in any way. All parts, proportions, percentages, etc., in the examples and in the rest of the specification, are provided by weight unless otherwise indicated. Among all the examples described below, a 1,000-ml, 4-neck flask reactor suitable for high temperature firing is used for the reactions. The bottle is equipped with a condenser, a nitrogen inlet, a thermometer, and an agitator The chemical products and their proportion are shown below in the following examples: Example 1 Ingredients% by weight Recycled PET Grams 56.29 598.8 Pentaerythritol 6.71 71.4 Neopeñti1glicol 2.6 27.7 Tetrapropyl Titanate (TPT) 0.08 0.8 Stearic Acid 28.24 300.4 Monobutyl Static Acid 0.08 0.9 Trimellitic Anhydride 6 63.8 PET, pentaerythritol, neopentyl glycol, and TPT are added to the reactor and heated to a temperature of 200- 270 ° C under a nitrogen atmosphere. The transesterification reaction takes 30 to 180 minutes and is monitored by the presence of a clear pill. Then the stearic acid and the monobutylstanoic acid are added and reacted until the acid value is less than 10.

Then trimellitic anhydride is added which reacts at a temperature of 160-180 ° C for 30 minutes. The entire reaction lasts from 5 to 12 hours. The resin obtained is dispersed in a diluted ammonium solution. The amount of ammonium hydroxide used depends on the pH of the final resin in dispersion. By using this method a white dispersion or emulsion of the resin is obtained. Using this solution with or without clay, and with or without dye to coat paper or cardboard, you get a shiny surface finish and water repellent on paper or cardboard. The strength of coated paper or carbon is also increased. When the coated paper or paperboard is vigorously stirred in a dilute solution of sodium hydroxide at room temperature or at a temperature higher than room temperature, the resin is removed and redispersed and the paper again forms a pulp. Example 2 Ingredients% by weight Grams PET recycled 56.29 598.8 Pentaerythritol 6.71 71.4 Neopeñtilglicol 2.6 27.7 Tetrapropyl Titanate (TPT) 0.08 0.8 Pleic / stearic acid 28.24 300.4 Monobutyl-sodium acid 0.08 0.9 Maleic anhydride 6.0 63.83 PET, pentaerythritol, neopentyl glycol and TPT are added to the reactor and heated to a temperature of 200 to 270 ° C under a nitrogen atmosphere. The reaction lasts from 30 to 180 minutes and is monitored by the presence of a clear pill. Stearic acid and monbutylstanoic acid are then added and the whole is esterified until an acid value of less than 10 is obtained. Maleic anhydride is added which reacts for 15 minutes at a temperature of 150 to 180 ° C. The entire reaction lasts from 5 to 12 hours. The final resin is emptied into a sodium sulphite solution - where the amount of sodium sulphite has the same molar ratio, or a slightly lower molar ratio "to maleic anhydride." Using this method, a white dispersion or emulsion is obtained. the resin The resin dispersed in water is applied to the paper and cardboard which causes the same results as example 1. Example 3 A "recipe containing a triglyceride is shown below: Ingredients% by weight Grams PET recycled 48.80 480 Pentaerythritol 6.83 67.17 Neopeñtilglicol (NPG) 2.65 26.04 Tetrapropyl Titanate (TPT) 0.08 0.8 Hydrogenated Bait 24.98 245.7 Monobutyl Sodium Acid 0.08 0.8 Trimelitic Anhydride or 9.83 96.67 Maleic anhydride Isophthalic acid 6.76 66.45 Hydrogenated bait triglycerides react first with pentaerythritol at a temperature of 180 at 270 ° C, then PET, NPG, and TPT are added to the reactor and transesterified with the triglyceride alcoholized Isophthalic acid or ophthalmic acid is then added to increase the molecular weight of the resin. Finally, trimellitic anhydride or maleic anhydride reacts to provide a neutralizable end group. With this formula, other polyalcohols and polyacids can be used. The final resin is diluted in a solution of ammonium sulfite or sodium sulfite at a temperature of 50 to 90 ° C. The final resin dispersed in water is a stable emulsion. The coated paper or cardboard surface exhibits the same water rejection properties as the previous examples. The paperboard is reshaped to a point and the gloss, strength, print maintenance properties of the coated paper as well as other properties are significantly improved. EXAMPLE 4 In this example, the same formula as in Example 3 is used, except that the hydrogenated bait triglycerides are replaced by corn oil or soybean oil. Precautions should be taken to avoid the occurrence of crosslinking reactions. The properties of the resin are similar to the properties of. Example 3, except that the presence of unsaturated groups in the oil makes the resin less firm. The application on paper or cardboard has a slightly higher brightness than that produced with hydrogenated triglycerides. Example 5 The formula is presented below: Ingredients% by weight Gram < you Pentaerythritol (PE) 7.07 67.7 Neoprene glycol 19.18 182.26 Diethylene glycol 3.35 31.84 Stearic acid 24.98 245.7 Monobutyl aminic acid 0.1 0.96 Trimelitic anhydride (TMA) 10.17 96.67 Oral maleic anhydride (MA) Isophthalic acid 34.27 325.64 Stearic acid, monobutylstanoic acid, and pentaerythritol they are added to the vessel and react at a temperature 160 to 270 ° C until the acid value is less than 100. The isophthalic acid, neopentyl glycol and diethylene glycol are added to the reactor and the polymerization proceeds until the acid value 1 be less than 10. Finally, TMA or MA is added at reduced temperature to ensure control. The final resin is dispersed in a solution of ammonium sulfite or sodium sulfite as in the previous examples. The resin dispersion has the appearance of a stable emulsion. The coated paper or paperboard exhibits high water repellency properties. The gloss is also increased in the case of coated papers.

Example 6 The same formula as in Example 5 was used, except that terephthalic acid was used instead of isophthalic acid with the same results. Example 7 The same formula as in Example 5 was used, except that ophthalic acid was used instead of isophthalic acid, with similar results. Example 8 The formula is presented below: Ingredients% by weight Grams Pentaerythritol (PE) 7.07 67.7 Neopehti1glycol 19.18 182.26 Diethylene glycol 3.35 31.84 Stearic acid 24.98 245.7 Monobutyl sodium acid 0.1 0.96 Trimellitic anhydride (TMA) 10.17 96.67 Oral maleic anhydride (MA) Ophthalmic acid 34.27 325.64 Stearic acid, monobutylstanoic acid and pentaerythritol are added to the container and they react at a temperature of 160 to 270 ° C until the acid value is less than 100. Ophthalmic acid, neopentyl glycol, and diethylene glycol are added to the reactor and the polymerization proceeds until the acid value is less than 10. Finally, TMA or MA is added at reduced temperature to ensure control. The final resin is dispersed in a solution of ammonium sulfite or sodium sulfite as in the previous examples. The resin dispersion has the appearance of a stable emulsion. Coated paper or cardboard shows great water repellency properties. The gloss is also increased for papers / coated. Example 9 The same formula is used as in Example 5, except that instead of TMA or MA, DMSIP or SIPEG is filled and reacted as a polyacid or polyol. A resin with good dispersion property in water is obtained and the resin shows similar properties as described above. The hydrophobic and water dispersible novel polyester resins of the present invention can be used to coat substrates such as cellulosic or synthetic substrates such as paper. More particularly, polyester resins are used as coatings in the following industrial applications: I. PAPER Since these resins contain a high concentration of hydrophobic groups and have a much improved ability to orient these hydrophobic groups away from paper or paperboard, the surface of paper or cardboard covered with these resins shows a surprising effect of rejection to water. This water rejection effect produces surfaces that have higher contact angles with water droplets than other resins currently used. Accordingly, these resins can make the paper or cardboard surface effectively waterproof or water repellent at much lower concentrations than the other resins usually employed. In addition, resins described herein can be easily removed from paper, cardboard, or another substrate by washing with water that has become basic by the addition of ammonium hydroxide, sodium hydroxide, or other basic additives commonly employed. The advantages of using these resins in the paper and paperboard industry are threefold. An advantage is the use of smaller amounts of materials in paper or cardboard, a second advantage is the recycling of residual PET (possibly from bottle sources) back into packaging materials, and the third advantage is that all materials coated in this way can be easily formed into pulp again and therefore recycled. In relation to paper coating applications, the following are especially preferred: A. Paper or cardboard for packaging food Some food packages (fresh products, frozen products, dry products, dairy products, etc.) require high hydrophobic properties of the Packing box surface to ensure a shelf life of the package under high humidity conditions. In addition to plastic packaging, paper or carbon is usually used. The coating of this paper or carbon is generally very hydrophobic. The resins most widely used in paper or cardboard coating are a mixture of polyethylene / and vinyl acetate copolymers (commonly known as EVA which represent the initials of ethylene vinyl acetate) in combination with paraffin wax. This type of coating system produces hydrophobic coatings that are insoluble in water and therefore very difficult to remove from paper or cardboard during pulp reformation. This difficulty in re-forming pulp inhibits a recycling of these paper products. The resins described in this invention can easily form pulp again using basic additives in accordance with what is described above. The resins described in this invention are composed of raw materials which have the reputation of being generally considered safe and non-toxic. This fact coupled with the great need for water repellent coatings in the paper industry for packaging food, etc., and the economic nature of these resins that can be produced from recycled PET, make these resins highly desirable for the coating of paper or cardboard intended to pack food. In the frozen food industry, paper containers are used to store food for use in instant-firing microwave ovens. These containers must be resistant to moisture to handle the freezing and thawing conditions to which they are subjected. The resins presented, due to their FDA status for contact with food are ideal candidates for the connection of these paper containers. B. Paper for printing The paper intended for printing or magazine paper has a coating consisting of a rubber latex of styrene butadiene (SBR), polyvinyl acetate latex, rosin and / or other materials such as clay and starch. . The coating is used to provide properties such as smooth surface, hard surface, gloss, ink retention, and water resistance. The new resins presented in this patent can also be used to provide these properties at lower coating weights. For example, a printing paper coated with these resins alone has excellent characteristics of water repellency and ink retention as well as increased strength and gloss. C. Paper or cardboard for storage or transport Paper bags for carrying purchased items, for example, present a problem in that if they get wet they lose their strength and break easily. Making these bags water repellent or just water resistant would help solve this problem. Letters, envelopes, and packaging for messages must be waterproof to protect dry contents during shipment by mail or boarding. Envelopes or packages coated with these presented resins offer sufficient protection. D. Release paper _ Release liners are used when an adhesive material must be fixed on a surface but not to the point of tearing the surface when it comes off. Nowadays silicones are used for this purpose. The resins described herein can also be used for this purpose since the hydrophobic properties make said resins ideally suited as adhesive release agents E. various paper articles F. Other paper products that could benefit from an economical waterproofing system they would be fiber drums, book covers and notebooks, popcorn bags, paper plates, paper cups, paper raincoats, such as disposable clothing, paper construction materials (such as wallpaper, dry wall, sound insulation, or forms of construction of concrete), and other paper products for external use that could be damaged by rain, water or high humidity level. II. TEXTILES In the textile industry, there are several needs to make the finishes waterproof or water resistant. Resins currently used can be expensive and difficult to apply. The resins described here can find applications in several areas in the textile industry. Some of these application areas include: fiber or thread finishes, clothing in general, tarpaulins, raincoats, non-woven articles, nylon microdenier fabrics, bedding, mail bags, reapplication of waterproofing agents, and footwear. III. WOOD Wood products, especially those used in external applications, should be protected against rain and weather. The resins described here can be used to waterproof wood products. Some examples of wood products where the resins described can be used are: furniture, wood floors, wood for construction, plywood, wood for concrete molds, house booths, telephone poles, roof tiles, panels for internal walls, wooden boxes, and boxes for shipping and storage, as well as wooden boats or boat parts. IV. CONCRETE In some concrete applications it is desirable to have a water resistant seal or finish applied to the concrete after setting. This finish provides increased durability and longer life to the concrete surface and also allows rainwater to run more effectively. The products described in this invention can be used for this purpose. Some examples are: bridges over roads, high traffic areas such as stadium floors, etc., outside seats for stadiums, roads, and concrete houses. V. PAINT In some, it is desirable that a paint (or protective coating) present a certain amount of water repellency. Some examples: paint for transit to replace alkyd resins based on currently used solvents and latex for general purposes. In the case of latex, the resins of the present invention can be used as additives. SAW . LEATHER Leather products can be treated to repel water. In this case, the additional brightness is also desired. Typical leather products include shoes, bags, coats, and gloves. VII. INKS In the market of the inks resins are used so that the ink adheres on a substrate. Once dry, they must resist moisture and abrasion. Many resins currently used are based on water. The resins described here would be ideal as resins for inks, or additives since the resins are very adhesive, especially on cellulose surfaces, and once dry they are very resistant to water. VIII. GLASS Fiberglass is used as sculptural material for a large number of commonly used items such as showers, boats, kitchen sinks and bathroom sinks. The resin described can be used as part of the formulation to make these products repel water more effectively. The containment dispersions can also be used to treat the glass fibers themselves, as preparation elements for a greater water rejection or for a higher resin solubility.

IX. METAL COATINGS Metal coils are frequently coated with a resin to prevent oxidation caused by moisture in the air. The products usually used are resins usually dissolved in some solvent. The resins described herein could be used as replacements for these coatings. They can be applied to carts, channels and devices that can be coated with the resins of the present invention. The amount of the composition that is applied on a substrate in accordance with the present invention is chosen in such a way as to provide an ability to repel water and oil sufficiently high or desirable to the substrate surface, said amount is usually from 0.01% to 10% by weight, preferably from 0.05 to 5% by weight, based on the weight of the substrate "" of the polyester present in the treated substrate.The amount that is sufficient to provide a desired rejection can be determined empirically and can be increased as necessary or desired Fiber substrate treatment using the composition that provides the water and oil repelling feature of the present invention is carried out by the use of well-known methods including immersion, spraying, filling, knife application, and roller coating The drying of the substrate is carried out at a temperature of 120 ° C, or at a temperature or, including ambient temperature, for example, at a temperature of about 20 ° C, with optional thermal treatment of the textile products in the same manner as in the case of conventional textile processing methods. The effectiveness of the coatings resulting from the resins of the present invention is illustrated in example 10. EXAMPLE 10 Contact angle comparisons The following example illustrates the effectiveness of polyester resins of the applicant as water repellent coatings for paper or paperboard. The test is carried out using a Kernco Model G-I Contact Angle Goniometer used to measure the contact angle between the surface of a piece of paper or cardboard and a drop of distilled water placed on the paper. PROCEDURES A sample of 0.1 ml of distilled water was placed on the surface of a piece of uncoated cardboard (control) and coated using a microsyringe. The initial angle of the drop was measured with the cardboard surface. A time of 5 minutes was allowed to pass and a second contact angle was measured. The test was carried out 10 times and the average values were calculated. The difference between the two average values was calculated as angle loss. Results The following table reflects the results using uncoated paper and several coating formulas. Test sample initial angle angle a Loss of 5 min. Angle. Control: not reversed 78.2 64.3 13.9 Ti. Graph paper: 91.3 84.4 6.9 Polyurethane finish. PE-230: finish of - 68.5 52.7 15.8 Hydrophilic polyester. LB-100 (30%): poly- 68.0 53.3 14.7 Eastman Ester. Stretch polymer-95.0 77.7 17.3 non-maleic. 2161: XWP with 43.27% 110.3 N / A N / A fatty acid. 2160: XWP with 37.94% 112.0 103.8 8.2 fatty acid. 2148: XWP with 28.82% 107.5 N / A N / A fatty acid. 2141. XWP with 25.86% 104.3 96.6 7.7 fatty acid. 2180: XWP with 20.00% 102.0 94.3 7.7 fatty acid. 2086: XWP with 15.00% 98.8 1 81.0 17.8 fatty acid. In the above table, the resin compositions of the present invention are defined as follows: Resin 2161: this resin is the product of the reaction of: 38.57% by weight of PET, 43.17% by weight of fatty acid (6.50% by weight of stearic acid, 10.22% by weight of oleic acid and 26.45% by weight of hydrogenated bait glyceride), 8.10% by weight of pentaerythritol and 10% by weight of trimellitic anhydride. Resin 2160: this resin is the product of the reaction of: 42.84% by weight of PET, 37.94% by weight of fatty acid (18.97% by weight of stearic acid and 18.97% by weight of hydrogenated bait glyceride), 9.08% by weight weight of pentaerythritol and 9.96% by weight of trimellitic anhydride. Resin 2148: this resin is the product of the reaction of: 48.08% by weight of PET, 28.82% by weight of fatty acid (14.41% by weight of stearic acid and 14.41% by weight of soybean oil), 6.89% by weight of pentaerythritol, 1.58% by weight of neopentyl glycol, 9.96% by weight of trimellitic anhydride and 3.68% by weight of isophthalic acid.

Resin 2141: this resin is the product of the reaction of: 34.27% by weight of isophthalic acid, 25.86% by weight of stearic acid, 7.07% by weight of pentaerythritol, 19.18% by weight of neopeñtilglicol, 3.35% by weight of diethylene glycol and 10.17 % by weight of trimellitic anhydride. Resin 2180: this resin is the product of the reaction of: 61.72% by weight of PET, 20.00% by weight of stearic acid, 4.75% by weight of pentaerythritol, 2.46% by weight of neopentyl glycol, 0.91% by weight of diethylene glycol , 10.00% by weight of trimellitic anhydride Resins 2086: this resin is the product of the reaction of: 74.90% by weight of PET, 15.0% by weight of stearic acid, 4.50% by weight of pentaerythritol, 3.47% by weight of neopentyl glycol, 1.96% by weight of diethylene glycol. The physical properties that make this resin unique are: 1. Hydrophobic character. 2. The ability of these resins to guide the hydrophobic groups away from the substrates on which they are applied. 3. Evidence of hydrophobic orientation in accordance with characterized by high contact angles with water drop of the coated surface. It will be apparent from the foregoing that many other variations and modifications can be carried out with respect to the hydrophobic polyester resins described herein, without departing substantially from the essential features and concepts of the present invention. Accordingly, it should be clearly understood that the embodiments of the present invention described herein are only to exemplify the invention and not to limit the scope of the present invention in accordance with that defined in the appended claims.

Claims (1)

1. CLAIMS A hydrophobic polyester resin that can be dispersed in water having the formula: In ~ - m where I is an ionic group; n = l-3 is the number of ionic groups; P is a polyester structure; A is a fatty aliphatic group; m = 3-8 is the number of fatty aliphatic groups and where I is present in an amount of about 1% to 20% by weight; the polyester structure is present in an amount of about 30% to 80% by weight and the fatty aliphatic group is present in an amount of about 10% to 60% "by weight, said polyester resins having a high characteristic of Water repellency as shown through an initial contact angle of at least 98 when a drop of water is applied on the surface of a cellulosic substrate coated with said resin. The hydrophobic polyester resin and which can be dispersed in water of the claim 1, wherein I is present in an amount which is within a range of 5% to 10% by weight The hydrophobic and water-dispersible polyester resin of claim 1, wherein the structure of polyester P is present in an amount that is within a range of 50% to 60% by weight The "hydrophobic and water dispersible polyester resin of claim l," where the group A of fatty acid is present in an amount that is within a range of 20% to 40% by weight. The hydrophobic and water dispersible polyester resin of claim 1, wherein I is derived from polycarboxylic acid or anhydrides selected from the group consisting of trimellitic anhydride, trimellitic acid and maleic anhydride, and hydrophobic polyester resin that can be dispersed. in water of claim 1, wherein the polyester structure P is a polyalkylene terephthalate selected from the group consisting of polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate. The hydrophobic polyester resin can be dispersed in The water of claim 1, wherein the fatty acid group A is selected from the group consisting of stearic acid, behenic acid, palmitic acid, lauric acid, oleic acid and linoleic acid, a polyester resin that is hydrophobic and can be dispersed water, which comprises a reaction product of 30-70% by weight of a polymer of terephthalate, 5-40% by weight of a hydroxy functional compound having at least two hydroxyl groups; 1-20% by weight of a carboxy functional compound having at least two carboxyl groups and 10-60% by weight of a hydrophobic compound selected from the group consisting of a straight or branched chain C6-C24 fatty acid or well triglycerides thereof; said resin is further characterized in that the "functional hydroxy compound" is present at 1-3 times the equivalents of a hydrophobic portion The hydrophobic and dispersible polyester resin of claim 8, which comprises the product of the reaction of residual terephthalate of the unitary formula where R is - the residue of an aliphatic or cycloaliphatic glycol of 2 to 10 carbon atoms or of oxygenated glycol of the formula H O (C? H2? O) nC? H 8? O H (2) where x is an integer from 2 to 4 and n is from 1 to 10. The water-dispersible hydrophobic polyester resin of claim 8, wherein the residual terephthalate polymer is polyethylene terephthalate, polyl terephthalate, 2- propylene, polyethyl terephthalate, 3-propylene, polybutylene terephthalate (poly (cyclohexanedimethanol terephthalate) or else a mixture thereof) The hydrophobic and water-dispersible polyester resin of claim 8, wherein said hydroxy functional compound having at least two hydroxyl groups are selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, Propylene glycol, 1, 2-propylene glycol, 1, 3-propanediol, 1, 2-butylene, 1, 3-butanediol, 1,4-butanediol, neopentyl glycol, 1, 5-pentanediol, 1, 6-hesandiol, glycerol, trimethylolpropane , trimethylolethane, pentaerythritol, erythritol or a monosaccharide. Resin hydrophobic polyester or that can be dispersed in water of claim 8, wherein said hydroxy functional compound having at least two hydroxyl groups is selected from the group consisting of derivatives of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol, or either an oxyalkylated monosaccharide with 5-30 moles of ethylene oxide, propylene oxide or a mixture thereof, by hydroxyl of the hydroxy functional compound. Resin hydrophobic polyester _Que can be dispersed in water of claim 8, wherein said hydroxy functional compound having at menso two carboxyl groups is selected from the group consisting of trimellitic acid, trimellitic anhydride, maleic acid, maleic anhydride, fumaric acid , and isophthalic acid. 14. The polyether resin hydrophobic and can be dispersed in water of claim 8 wherein said hydrophobic compound is selected from the group consisting of stearic acid, oleic acid, linoleic acid, behenic acid, lauric acid, palmitic acid, bait res, lard, corn oil, and soybean oil. The hydrophobic and water dispersible polyester resin of claim 8, which comprises the reaction product of 40-60% by weight of polyethylene terephthalate polymer; from 1 to 10% by weight of neopentyl glycol; from 5 to 10% pentaerythritol; from 3 to 15% by weight of trimellitic acid or trimellitic anhydride; and from 10 to 45% by weight of stearic acid. The hydrophobic and water dispersible polyester resin of claim 8, comprising a reaction product prepared in the presence of monobutyl ethanoic acid or a tetraalkyl titanate, or cradle mixture thereof. "" 17. The hydrophobic polyester resin that can be dispersed in water of claim 8, dispersed in water with an ammonium or alkali metal hydroxide or carbonate. 18. The hydrophobic or water dispersible polyester resin of claim 15, dispersed in water with an alkali metal ammonium carbonate or hydroxide. 19. A fabrication article comprising a substrate coated with a hydrophobic polyester coating composition and dispersible in water, comprising a reaction product of 30-70% by weight of a terephthalate polymer; from 5 to 40% by weight of a hydroxy functional compound having at least two hydroxyl groups; from 1 to 20% by weight of a carboxy functional compound having at least two carboxyl groups and from 10 to 60% by weight of a hydrophobic compound selected from the group consisting of a straight or branched chain C6-C24 fatty acid or triglycerides thereof. 20. The article of manufacture of claim 19, wherein said substrate is a fibrous substrate. 21. The article of manufacture of claim 19, wherein said substrate is a paper substrate. 22. The article of manufacture of claim 19, wherein said substrate is a textile substrate. 23. The article of manufacture of claim 19, wherein said substrate is a package for food. 24. The article of manufacture of claim 19, wherein said substrate is a release paper. 25. The article of manufacture of claim 19, wherein said substrate is concrete. 26. The coated article of claim 19, wherein said terephthalate polymer is a residual terephthalate of the unitary formula OROOC i- (D where R is the residue of an aliphatic or cycloaliphatic glycol of 2 to 10 carbon atoms or oxygenated glycol of the formula HO (C? H2X0) nC xH2? OH (2) where x is an integer from 2 to 4 and n is l0 27. The coated article of manufacture of claim 26, wherein the residual terephthalate polymer is polyethylene terephthalate, polyl terephthalate, 2-propylene, polyl terephthalate, 3-propylene, polybutylene terephthalate, poly (cyclohexanedimethanol terephthalate) or a mixture thereof. 28. The coated article of claim 19, wherein said hydroxy functional group having at least two hydroxyl groups is selected from the group consisting of ethylene glycol, diethylene glycol, triethylene glycol, cyclohexanedimethanol, propylene glycol, 1,2-propylene glycol, 1, 3- propanediol, 1,2-butylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol or a monosaccharide. 29. The coated article of claim 19, wherein said hydroxy functional compound having at least two hydroxyl groups is selected from the group consisting of derivatives of glycerol, trimethylolpropane, trimethylolethane, pentaerythritol, erythritol or an oxyalkylated monosaccharide with 5-hydroxy-5-methoxycarbonates. 30 moles of ethylene oxide, propylene oxide, or a mixture thereof, by hydroxyl of the hydroxy functional compound. 30. The coated article of claim 19, wherein said carboxy functional compound having at least two carboxyl groups is selected from the group consisting of trimellitic acid, trimellitic anhydride, maleic acid, maleic anhydride, fumaric acid, and isophthalic acid. 31. The coated article of manufacture of claim 19, wherein said hydrophobic compound is selected from the group consisting of stearic acid, oleic acid, linoleic acid, behenic acid, lauric acid, palmitic acid, beef bait, lard, oil corn, and soybean oil. 32. An article of manufacture comprising a substrate coated with a hydrophobic polyester coating composition that can be dispersed in water, comprising a reaction product of 40-60% by weight of a polyethylene terephthalate polymer; 1-10% by weight of neopentyl glycol; 5-10% pentaerythritol; from 3 to 15% by weight of trimellitic acid or trimellitic anhydride; and from 10 to 45% by weight of stearic acid. 33. The article of manufacture of claim 32, wherein said substrate is a fibrous substrate. 34. The article of manufacture of claim 32, wherein said substrate is a paper substrate. 35. The article of manufacture of claim 32, wherein said substrate is a textile substrate. 36. The article of manufacture of claim 32, wherein said substrate is packaged for food. "The article of manufacture of claim 32, wherein said substrate is release paper," the article of manufacture of claim 32, wherein said substrate is concrete. A water repellent polyester coating composition, comprising a reaction product of 30-70% by weight of a terephthalate polymer; from 5 to 40% by weight of a hydroxy functional compound having at least two hydroxyl groups; from 1 to 20% by weight of a carboxy functional compound having at least two carboxyl groups and from 10 to 60% by weight of a hydrophobic compound selected from the group consisting of straight or branched chain C6-C24 fatty acid or well triglycerides thereof. A water repellent polyester coating composition, comprising a reaction product of 40-60% by weight of polyethylene terephthalate polymer; 1-10% by weight of neopentyl glycol; from 5 to 10% pentaerythritol; 3 to 15% by weight of trimellitic acid or trimellitic anhydride, and 10 to 45% by weight of stearic acid One method to provide a water repellency characteristic to selected substrates within the group consisting of fibrous substrates and leather, comprising the application to such substrates of a composition comprising the reaction product of 30-70% by weight of a terephthalate polymer, 3 to 40% by weight of a hydroxy functional compound having at least two hydroxyl groups, from 1 to 20% by weight of a carboxy functional compound having at least two carboxyl groups and from 10 to 60% by weight of a hydrophobic compound selected from the group consisting of straight chain C6-C24 fatty acid or branched or triglycerides thereof.