MXPA98001655A - Dispersible adhesive compositions in a - Google Patents

Abstract

An essentially odorless, water-dispersible or dispersible adhesive composition is described which is useful for forming paper articles and other products that can be recycled by repulping in neutral and alkaline media. The water dispersible adhesive composition is preferably a hot-melt adhesive which is a low molecular weight branched copolyester containing a sulfonomer. The copolyester adhesive composition can be used alone or in formulation and has broad compatibility with a variety of adhesive additives, including non-polar adhesives

Description

DISPERSIBLE ADHESIVE COMPOSITIONS IN WATER DESCRIPTION OF THE INVENTION The present invention relates to water dispersible adhesive compositions. More particularly, the present invention is directed to an essentially odorless hot melt adhesive composition which, due to its dispersibility in water, allows paper products, non-woven assemblies and other disposable products to be recycled more effectively. The present invention is also directed to aqueous adhesive compositions and emulsions containing polyester and hot melt compositions containing polyester, glues and oils that are dispersible in water while maintaining excellent adhesive properties. Many adhesives including hot melt adhesives are useful for adhering multiple substrates together such as wood, paper, plastic, non-woven assemblies and textiles as well as other materials. One use for which they are very suitable is the manufacture of corrugated cardboard. The hot melt adhesives, useful to produce corrugated cardboard, must have a high adhesive strength under shock, tension, high humidity and extremes of temperature that occur during transport and storage. In addition, the melting point, wetting time, initial adhesion, settling time, life in the vessel, and general handling qualities in automatic corrugated cardboard machinery are essential considerations. It is now very desirable to recycle paper, paper products and other disposable products to conserve natural resources and avoid large areas of waste accumulation. It is therefore a general practice in the paper industry to recover at least a portion of the corrugated material used and discarded and to re-form pulp of the material for use in the preparation of other materials such as cardboard. The use of polyolefin hot melt adhesives for closing or sealing boxes made of corrugated material has presented problems in relation to the pulp reformation of the boxes used (see US patents 4,070,316, 4,127,619, 4,146,521, 4,460,728, 4,471,086 and 4,886,853). . In fact all existing hot melt and pressure sensitive adhesives are largely insoluble in water and very difficult to disperse during the repulping process. This fact makes certain paper products in which adhesives are used by necessity, are unattractive since the inability to disperse the insoluble adhesives results in a low quality recycled paper having variable composition and lack of uniformity, and thus a lower value of the product. An attempt to avoid the presence of insoluble adhesives in recycled paper products is the use of adhesives whose density is different to the density of water and pulp in water, allowing separation by gravitation. However, this requires separation steps that can increase the recycling costs of paper products that contain adhesives. The present "soluble" or water-dispersible "natural" adhesives such as dextrins, cellulose gum, and animal glues derived from animal horns and bones have little strength, do not adhere well to paper and have strong coatings or applications of ink, and sometimes require special treatment and handling due to its high viscosity. Therefore, the use of these adhesives, which can be easily recycled, is very low due to the low adhesive characteristics. Attempts to produce water-dispersible hot melt synthetic adhesive compositions have been unsuccessful due to low adhesive properties such as thermal stability, low strength, low viscosity and low cold flow resistance. Additionally, the costs and manufacturing facility have prevented its use (see US Patents 3,919,176 and 5,098,962). In addition to paper and paper products there are many disposable products such as diapers, tampons and sanitary napkins, in which hot melts and other types of adhesives are used. The use of current hot melt adhesives in these products complicates attempts to recycle the products and separate insoluble sticky hotmelt adhesives.

The co-pending application SN 08 / 283,011 filed on July 29, 1994 solves these problems and describes water-dispersible or hot-melt aqueous adhesives that maintain the desirable properties of currently existing hot melt adhesives. However, the specific adhesives described in this copending application 08 / 283,011 are not compatible in high concentrations with non-polar additives such as hydrocarbon adhesive resins and naphthenic / paraffinic oils. Additionally, it would be highly desirable to produce an adhesive composition that is essentially odorless. A water-dispersible adhesive composition according to the present invention consists of a copolyester composition dispersible in branched water made from radicals or units of reaction products: (I) 1,4-cyclohexanedicarboxylic acid; (II) 2 to 40 mole percent, based on the total equivalence of all acids, of at least one difunctional sulfonomizer containing at least one sulfonate group linked to an aromatic ring in which the functional groups are their carboxyl or esters; (III) at least one diol or a mixture of diols consisting of: (A) 0.1 to 85 molar percent, based on the total molar percentage of the diol units having the formula H (-0CH2CH2-) n0H wherein n is 2 to 20, with the proviso that the molar percentage of these units is inversely proportional to the value of n; (B) 0.1 to 15 molar percent, based on the total molar percentage of the diol units of a poly (ethylene glycol) having the formula H (- 0CH2CH2-) n0H wherein n is 2 to 500, with the proviso that that the molar percentage of these units is inversely proportional to the value of n; and (C) 0. to 99 mole percent of the diol component selected from the group consisting of glycols containing two groups -C (R1) 2-0H in which R1 in the reagent is a hydrogen atom, an alkyl with 1 to 5 carbon atoms, or an aryl group with 6 to 10 carbon atoms; (IV) or at 40 molar percent of a hydrocarboxylic acid having a -C (R-) 2-0H group, in which R in the reagent is hydrogen or an alkyl group with 1 to 6 carbon atoms; and (V) 0.5 to 40 molar percent of a "multifunctional" or "branching inducer" reagent containing at least three functional groups selected from hydroxyl, carboxyl and mixtures thereof; the copolyester having substantially equal molar proportions of acid equivalents (100 mole percent) and diol in which the inherent viscosity is at least 0.1 dL / g measured in a solution in 60/40 parts by weight of phenol / tetrachloroethane at 25 ° C and with a concentration of 0.25 g of copolyester in 100 ml of solvent, the crystalline transcision temperature T is not higher than 20 ° C, and the ring and ball softening points are at least 70 ° C. The present invention further comprises the above copolyester in an adhesive formulation consisting of a mixture of: (a) 20 to 80 weight percent of the above copolyester, consisting of the above amounts of units I, II, III, IV and V; (b) 2 to 60 weight percent of an adhesive selected from the group consisting of terpene resins, aromatic resins, aliphatic hydrocarbon resins, rosins and functionalized polymers; (c) 0 to 30 weight percent of an extender oil selected from the group consisting of paraffinic oils, naphthenic oils, liquid polyesters, liquid hydrocarbon resins, liquid rosins, polyethylene glycols of low molecular weight, dibenzoates, isobutyrates, phthalate oils, animal oils, vegetable oils and mineral oils; and (d) 0.1 to 2 weight percent of a stabilizer. Applicants have unexpectedly discovered an improved adhesive that not only has excellent properties of hot melt adhesive and is fully dispersible but also essentially odorless and highly compatible with adhesive resins including non-polar adhesive resins even at higher concentrations. The present adhesive composition can be applied as a liquid dispersion (aqueous or solvent) on substrates as well as hot melt applications. The present adhesive composition is completely dispersible and can be removed from the paper fibers or wood pulp used in the disposable products. The hot melt adhesive according to the present invention allows the recycling of the disposable products with significantly reduced processing costs without affecting the physical properties of the adhesive and the resulting article. The water dispersible polyester composition of the present invention has an inherent viscosity of at least 0.1, preferably 0.2 dL / g, more preferably 0.28 a 0. 65 dL / g, and more preferably 0.28 to 0.65 dL / g, and more preferably 0.4 to 0.6 dL / g measured in a solution of 60/40 parts by weight of phenol / tetrachloroethane at 25 ° C and a concentration of 0.25 g of polymer in 100 ml of solvent. In the water-dispersible adhesive composition of the present invention, (I) 1,4-cyclohexanedicarboxylic acid is preferably at a concentration equal to 100 mole percent of the acid component in combination with 1 sulfonomer of dicarboxylic acid. However, component (I) may also contain up to 10 molar percent, based on a total of 100 molar percent of acid of difunctional dicarboxylic acids other than 1,4-cyclohexanedicarboxylic acid selected from the group consisting of aliphatic dicarboxylic acids, dicarboxylic acids alicyclics, aromatic dicarboxylic acids, and mixtures of two or more of these acids. Examples of preferred suitable dicarboxylic acids include succinic; glutaric; adipic, azelaic; sebacic smoking maleic itaconic; 1-3-cyclohexanedicarboxylic; 1,3-diclohexanedicarboxylyl; phthalic terephtalic; and isophtalic. The 1,4-cyclohexanedicarboxylic acid of (I) is preferably at a concentration of 0 to 95 molar percent based on total acid equivalents, more preferably 60 to 90 molar percent, with a molar percentage of 70 to 90 being most preferred. The difunctional sulfonomer component of (II) is preferably a dicarboxylic acid or an ester thereof containing a metal sulfonate group. The cation of the sulfonate salt is preferably monovalent and may be NH 4 +, or the Li +, Na +, K + metal ions and the like. The radical or reagent (II) in the polyester of the present invention is a difunctional monomer containing an -SO3M group attached to an aromatic nucleus, wherein M is hydrogen, NH4 +, or a metal ion. The cation of the sulfonate salt group can be NH + or the metal ions Li +, Na +, K + and the like. The -S03M group is attached to an aromatic nucleus examples of which include benzene, naphthalene, anthracene, diphenyl, oxydiphenyl, sulfonyl diphenyl and methylene diphenyl. The cationic portion of a non-metallic sulfonate group optionally present in reagent (II) is a nitrogen-based cation derived from nitrogen-containing bases which may be aliphatic, cycloaliphatic or aromatic compounds having ionization constants in water at 25 ° C. from 10 ~ 2 to 10_1 °, preferably from 10"5 to 10" 8. Especially preferred nitrogen-containing bases are ammonia, dimethylethanolamine, diethanolamine, triethanolaine, pyridine, morpholine and peperidine, due to availability, cost and utility. Such as bases containing nitrogen and cations derived therefrom described in the US patent. do not. 4,304,901. The amount of reagent (II) is present in a concentration of 2 to 40 molar percent. The amount of reagent or unit (II) is preferably 4 to 25 molar percent, with the molar percentage of 6 to 20 being most preferred based on the total acid equivalents. In quantities below 2 and in some chaos below 4 molar percent, polyester is less repulpable while quantities above 40 and in some cases above 20 polyester is more sensitive to water. Example of preferred diols of (III) (A) due to availability include diethylene glycol, triethylene glycol and mixtures thereof. The preferred concentration of (III) (A) is from 10 to 80 molar percent; however when those are the diols referred to in (III) (A) the concentration is 10 to 80 molar percent. With amounts outside this range the polyesters have lower softening points or Tg which is generally the most preferred. Examples of suitable poly (ethylene glycols) of (III) (B) include low molecular weight polyethylene glycols, some of which are commercially available under the name "Carbowax", a product of Union Carbide. Poly (ethylene glycols) having molecular weights of from 500 to 5000 are especially suitable. The units of (B), if they are used they are preferably in a concentration of 1 to 5 molar percent, particularly when m is 1 to 30 due to the preferably higher softening points. The remaining portion of the glycol (III) component (C) may be in a concentration of 0 to 99 molar percent, more preferably 10 to 60 molar percent. This glycol component can generally be selected from the group consisting of aliphatic, alicyclic and aralkyl glycols. Examples of those glycols include ethylene glycol; propylene glycol; 1,3-propanediol; 2,4-dimethyl-2-ethylhexane-1,3-diol; 2, 2-dimethyl-1,3-propanediol; 2-ethyl-2-butyl-1,3-propanediol; 2-ethyl-2-isobutyl-l, 3-propanediol; 1,3-butanediol; 1,4-butanediol; 1,5-pentanediol; 1,6-hexanediol; 2,24-trimethyl-1,6-hexanediol; 1,2-cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-cyclohexanediemethanol; 2,2,4,4-tetraethyl-1,3-cyclobitanodiol; and p-xylylenediol. The copolymers can be prepared from two or more of the above glycols. Preferred glycols, due to availability, cost and utility, include ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol and cyclohexanedimethanol with 1,4-cyclohexanediethanol and ethylene glycol being most preferred. The units of (IV) are less preferred, because of their cost and co-behavior, but they may be present. The concentration of those units is preferably below 20 molar percent, more preferably below 10 molar percent, including zero. The amount of this branching agent (V) is preferably below 20 molar percent, more preferably 1 to 10 molar percent with a concentration of 2 to 6 molar percent being most preferred. In very high amounts of branching agents the polyester tends to gelation while with low amounts, such as less than 0.5 mole percent, the polyester exhibits poorer behavior and properties. The polyester adhesive raw material compositions preferably have a molecular weight of from 7,000 to 20,000, more preferably 7,000 to 15,000. Although it is desirable to have as high a molecular weight as possible to achieve maximum physical properties, such as tensile strength and strength Upon detachment, the viscosity of the melt also increases as the molecular weight increases. Therefore, with very high molecular weights the melt viscosity is too high for many useful applications. The preferred Tg of the polyester adhesive raw material composition according to the present invention is below 20"c and more preferably ranges from -20 to 20 ° C, with a Tg of -5 to 5 ° C being most preferred. The T9 (crystalline transition temperature) of the adhesive compositions of the present invention are preferably as low as possible, thus Tg below 5 ° C and still preferred below 0 ° C. Tg greater than 0 ° C have generally ring and ball softening points (RBSP) greater and resistance to heating but not so flexible.A low Tg means that the adhesive compositions will not be brittle, so the boards adhered to each other with the adhesive compositions of the present invention when impact, even under extremely low temperatures will not release and thus maintain adhesion, however, extremely low Tg are not easily obtained or at least not easily obtained without affecting greatly some other property, such as the decrease of the ring and ball softening point. The composition of the polyester adhesive raw material according to the present invention preferably has a viscosity of 1500 to 90000 centipoise at 177 ° C, more preferably 10000 to 60000 cP at 177 ° Q due to the ease of application. The ring and ball softening point (RBSP) of the polyester adhesive raw material composition of the present invention is generally at least 70 ° C, preferably at least 80 ° C, more preferably 80-120 ° C. of RBSP are better since this means at higher storage temperatures no delamination will occur (High RBSP provides resistance to delamination.) The polyester adhesive raw material compositions according to the present invention are particularly useful due to their good combination of properties and are suitable for use as adhesives for many substrates, particularly when mixed with conventional adhesives and additives.These substrates include non-woven assemblies (such as non-woven polypropylene) paper products (such as paper and cardboard), and wood pulp and are easily recyclable and repulpable. The hot melt adhesives according to the present invention are recyclable / repulpable and better on existing hot melt adhesive compositions in which fixing time, temperature sensitivity, compatibility, storage stability, tear resistance, tensile strength, viscosity and strength to the cold flow are improved. The adhesive composition according to the present invention, either pure or formulated with other components, is applied to a substrate by placing a second substrate on the top of the adhesive forming an article having the adhesive laminated between two substrates. The adhesive composition according to the present invention can be applied in liquid form in solvent or in an aqueous solution at a concentration of 10 to 70 percent by weight, preferably 20 to 50, with the remainder being solvent or water or its mixtures. Surfactants and other additives may also be present to assist in the dispersibility of the adhesive composition. When applied as a solution, the adhesive compositions are generally applied by means of conventional processes, such as extrusion coating, spray coating, roller coating, brush coating, dipping, etc. The adhesive raw material composition is already rushed or mixed with other components it can also be applied as a base in the liquid form to substrates such as cardboard which will then be coated with polyolefin films. This dispersion will generally have 20 to 60 percent solids, preferably 40 percent solids before being applied to the substrate. The extrusion of the molten polyolefin film activates the adhesive properties of the polyester composition which allows the polyolefins to be extrusion coated on the substrates at lower temperatures, thus saving energy. In this application the adhesive composition contains the copolyester component having IV greater than at least 0.4 dl / g. With IV below 0.4 substrates already base when stored tend to block and are not easy to separate for subsequent extrusion coating. This aqueous dispersion containing the copolyester adhesive composition of the present invention may contain other conventional adhesive additives such as polymer emulsions, polyethylene emulsions and resin emulsions to attack the adhesion and strength properties. Suitable examples of polyethylenes used in polyethylene emulsions include low molecular weight polyethylene waxes such as Epolene E-20 from Eastman Chemical Company. The adhesive raw material composition can also be applied in coating formulations to a substrate such as printing and ink formulations. Particularly useful in these applications are the top copolyester IV compositions. , even in water-based formulations. The adhesive composition according to the present invention is preferably formulated with other standard adhesive compounds and used as a hot-melt adhesive. The hot melt adhesive composition is preferably applied fused at a temperature of 150 to 200 ° C to a surface of a substrate and while it remains fused and stackable, apply a second surface of a substrate to the water dispersible hot melt adhesive composition forming a manufacturing article that it comprises the water-dispersible hot-melt adhesive composition laminated between two substrates or two surfaces of a substrate (such as a folded article forming a container) The adhesive compositions of the present invention are preferably not crosslinked as it would impair their dispersibility in water and their However, they could be reticulated to a certain degree with diisocyanates to improve strength and thermal resistance although this is less preferred.

The adhesive composition according to the present invention may also contain standard additives including stabilizers. Suitable stabilizers include the antioxidant type and generally consist of sterically hindered phenols, or phenols substituted with sulfur or phosphorus. Representative hindered phenols include: 1, 3,5-trimeti-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy-benzyl) benzene; pentaerythritol t is-3- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate; N-octadecyl 3,5-di-tert-butyl-4-hydroxyphenyl) propionate; 4,4'-methylenebis (2,6-di-tert-butylphenol); 4,4'-thiobis (6-tert-butyl-o-cresol); 2,6-di-tert-butylphenol; 60 (4-hydroxyphenoxy) -2,4-bis (n-octylthio) -1,3,5-triazine; di-n-octadecyl-3,5-di-tert-butyl-4-hydroxy-benzylphosphonate; 2- (n-octylthio) -ethyl 3,5-di-tert-butyl-4-hydroxybenzoate; and hex [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate] sorbitol. If the stabilizer is used, it is present in levels of 0.1 to 3 weight percent, preferably 0.1 to 2 weight percent, with more than 0.1 to 0.5 being preferred. An especially useful antioxidant is Irganox 1010 (from Ciba Geigy, Hawthorne, NY) which is a pentaerythritol tkis-3 (3,5-di-butyl tertiary-4-hydroxyphenyl) propionate. Additional additives can be added to increase and disingest Tg and RBSP. These include, for example, elastomers, extender oils, low molecular weight polyolefins and adhesives (for example adhesive resins). Although elastomers can be added to the polyester composition, the presence of those elastomers can impair certain desired properties of the composition. Therefore, it is preferable that the composition of the present invention contains substantially no elastomer. Additionally, plasticizers such as COP DOTP, isobutyrates, phenols, glycols, phthalate esters and the like that can be added can subtract the thermal resistance of the final composition, reducing the rbsp. Other additives such as UV light absorbers, nucleating agents, colorants, pigments, solvents, solvents and fillers may be present in small amounts which are required and known in the adhesive art. The glues are added to the copolyester composition to prevent cold flow and increase the softening point. The glues are typically selected from at least one of the groups consisting of aliphatic hydrocarbon resins, aromatic resins, synthetic polyterpenes or terpene resins, functionalized polymers and rosins. These adhesive resins preferably have softening points of at least 100 * C and more preferably at least 120 ° C. These adhesive resins can be used alone or in combination and can be used in amounts of 2 to 60 percent by weight, preferably 10 to 55 percent by weight of the adhesive composition, more preferably 25 to 50 percent by weight. In some cases where greater thermal stability is desired, minor amounts of glues are desired, such as less than 40 percent by weight. Aliphatic hydrocarbon resins are described in U.S. Pat. do not. 3,850,858 and 3,701,760. They are generally polymerized low molecular weight pleum hydrocarbons. Functionalized polymers are well known in the art and include copolymers such as styrene-co-maleic anhydride and carboxylated polyolefins such as amorphous polypropylenes. Aromatic resins are generally modified aromatic hydrocarbons, such as NEVEX 100 from Neville Chemical Company. The terpene resins are generally polymeric resinous materials including the dimers as well as the higher polymers obtained by polymerization and / or copolymerization of terpene hydrocarbons such as alicyclic, monocyclic and bicyclic monoterpenes and mixtures thereof including alloxiraine, carene, isomerized pinene , pinene, dipentene, tepinene, terpinolene, limonene, turpentine, and a fraction cut of terpene and other different terpenes. Commercially available terpene-type adhesive resins include the ZONAREZ terpene B series and the 7000 series from Arizona Chemical. Also included are rosin esters with acid numbers above 5 such as Arizona Chemical's ZONATAC resins. Particularly useful materials are mixtures of terpene containing a mixture of sulphate terpene, and at least 20% of at least one other terpene selected from the group consisting of pinene, liraonene or dipentene. The rosins include rubber rosins, wood rosins, bait oil rosins (for example FORAL AX from Hercules Incorporated) and hydrogenated rosins (for example PERMOLYN glues also from Hercules incorporated). Depending on the final application and particularly for uses requiring pressure sensitive properties, various compatible plasticizers or extender oils may be present in the composition to soften and plasticize the composition. Amounts of these oils are preferably 1 to 30 percent by weight, based on the total weight of the adhesive formulation, more preferably 5 to 15 percent by weight, 10 percent by weight being more preferred. Preferred compatible oils include naphthenic oils; paraffinic oils (such as SHELL FLEX 371 from Shell Chemical Company, a paraffinic mixture); phthalate oils such as dioctyl phthalate; liquid polyesters such as DYNACOL 720 from Huís; dibenzoates such as dipropylene glycol dibenzoate (for example BENZOFLEX 9-88 commercially available from Velsicol); isobutyrates (for example TXIB distributed by Eastman Chemical Company); low weight poly (ethylene glycols) and their derivatives such as poly (ethylene glycol) phenyl ester (for example PYCAL 95 distributed by ICI); liquid rosin derivatives having ring and ball melting points less than 60 ° C such as methyl esters of hydrogenated rosin (for example HERCOLYN D from Hercules) liquid hydrocarbon resin such as WINGTAC from Goodyear Chemical Company; mineral oils such as the TUFFLO series from Arco Chemical, as well as glyceryl esters of fatty acids and their polymerization products. Other applications that conventionally employ adhesives based on such polylactide polymers may require the use of wax diluents to reduce the melt viscosity or cohesive characteristics of the hot melt adhesive compositions without noticeably diminishing their adhesive bonding characteristics. These waxes are often used in adhesives that do not have pressure sensitive properties. Suitable waxes include 12-hydroxysteahedral wax, hydrogenated castor oil, oxidized synthetic waxes, poly (ethylene oxide) having an average molecular weight above 1000, and functionalized synthetic waxes such as ECOMER H101 containing Exxon carbonyl. Some adhesive formulations described herein may contain wax and extender oil components in such a way that the presence of one or the other is not mutually exclusive. These adhesive compositions can be modified to increase the RBSP and reduce cold flow by including additives such as precipitated calcium carbonates and silicas such as fumed silica. A silica of that type is obtained from Cabot Corp as CABOSIL. The present copolyester composition can be modified with random or alternating styrenic copolymers useful in the compositions of this invention and can be prepared by any of the various existing methods for their synthesis. For example, copolymers can be obtained by means of solution copolymerization directly from the respective monomers by means of incremental additions of the more reactive monomer as shown in U.S. Pat. do not. 2,971,939 or by means of continuous recycle polymerization described in U.S. Pat. us. 2,769,804 and 2,989,517. Commercial random or alternating copolymers include the styrene / maleic anhydride copolymers DYLARK. Suitable block copolymers, for example from Shell Chemical, include linear block copolymers is ethylene-1-butenestyrene styrene KRATON FG-1901X or KRATON FG-1921X. In formulating adhesives or sealants used herein, the block copolymers should be used at 5-20 percent, preferably 7-12 percent. The copolyester adhesive raw material composition of this invention can be prepared by adding one or more of the above modifiers to the branched copolyester, by mixing with the copolyester at the melting temperatures of 177-200 ° C and mixing until a mixture is obtained homogeneous, An agitator provides effective mixing for these preparations. The present water dispersible adhesive compositions is an improvement over the water dispersible adhesive composition described in copending application 08 / 283,011 filed July 29, 1994 and WO 95/18191. Disclosed in this publication and patent are water-dispersible adhesive compositions consisting of a single component made of a copolyester and a mixture of linear and branched copolyesters. The one component water dispersible adhesive composition as a raw material consists of a branched water dispersible polyester composition made from the reaction product units which are; a difunctional dicarboxylic acid that is not a sulfonator that contains at least one sulfonate group linked to an aromatic ring; at least one diol or mixture of diols of the formula H (-0CH2CH2-) n0H where n 2 to 20 and then an additional diol where n can be from 2 to 500 in combination with 0 to 99 molar percent of a possible third diol or glycol having two groups C- (R1) 2-0H when R1 is as defined above; a hydroxycarboxylic acid; and 0.1 to 40 molar percent of a multifunctional reagent containing three functional groups. The mixture of this co-pending application SN 08 / 283,011 and publication of two different polyesters contains: 20 to 80 weight percent of a water dispersible polyester. This linear polyester is made of a difunctional dicarboxylic acid that is not a sulfonomer; at least one difunctional sulfonator containing a sulfonate group bound to an aromatic ring, a diol or mixture of indoles containing 15 mole percent of the diol of formula H (-0CH2CH2-) n0H where n 2 to 20 and 0. 50 molar percent of a polyethylene glycol being n 2 to 500; and an optional hydroxycarboxylic acid. The branched component of the mixture is 20 to 890 percent which is made up of units of a difunctional carboxylic acid which is not a sulfonomizer; a difunctional sulfonomer containing at least one sulfonate group bound to an aromatic ring; a difunctional reagent which is a glycol, an optional hydrocarboxylic acid; and a multifunctional reagent containing at least three functional groups. As is the case with the copolyester adhesive raw material composition of the present invention, the copolyester compositions defined in the co-pending application SN 08 / 283,011 can also be mixed and formulated with other additives and used as described herein. However, the present invention is significantly improved over the compositions described in the co-pending application SN 08 / 283,011 in which the present polyester is essentially odorless and is more compatible at higher concentrations with more additives such as glues. The present copolyester is also very compatible with non-polar additives. Although the raw materials of copolyester adhesives described in the application SN OB / 283,011 can be mixed with glues in concentrations of 10 to 50 weight percent, the lower copolyester IV of 0.2 dL / g are the only ones that are fully compatible and dispersible in water at higher concentrations of glue.The copolyester compositions of the present invention can be mixed with hydrocarbon glues at concentrations much higher than those which are possible with the above compositions and are more compatible even when the copolyester composition has a higher IV as 0.4 dL / g. When the higher IV copolyester composition is used the resulting adhesive compositions are more suitable adhesives with excellent strength and are completely dispersible in water. Please see the examples. The following examples are intended to illustrate the present invention but are not intended to limit its reasonable scope. EXAMPLES Example 1 - Preparation of Water Dispersible Branched Polyester A 1000 ml round flask equipped with a glass head, agitator shaft, nitrogen inlet and a side arm was charged with 158.2 grams (0.2 mole) of 1,4-dichloxanedicarboxylic acid , 23.7 grams (0.08 moles) of dimethyl-5-sodiosulfoisophthalate, 95.4 grams (0.90 mole) of diethylene glycol, 43.2 grams (0.30 mole) of 1,4-dichloanedimethanol, 6.70 grams (0.05 mole) trimethylol propane and 1.17 ml of a solution at 1.46% (w / v) of titanium isopropoxide in n-butanol. The flask was flushed with nitrogen and immersed in a Belmont metal bath at 200 ° C for 90 minutes and 220 ° C for a further 90 minutes with a nitrogen sweep with sufficient agitation. After raising the temperature to 250 ° C, a vacuum less than 0.5 mm was installed for 15 minutes to perform the polycondensation. The vacuum was then displaced with a nitrogen atmosphere and the polymer allowed to cool after removing the flask from the bath. An inherent viscosity of 0.41 dL / g was determined for the polymer recovered in accordance with ASTM D3835-79 and the crystalline transition temperature of 0 ° C was obtained from the thermal analysis by means of DSC. The polymer was odorless, transparent and almost colorless. Example 2 - Preparation of branched polyester dispersible in water This polyester was prepared as in example 1 except that the vacuum was maintained for 5 minutes. The resulting polymer was also odorless, clear and almost colorless. The inherent viscosity was 0.2 dL / g, and the crystalline transition temperature was -10 ° C. Example 3 - Preparation of a water-dispersible hot melt adhesive A branched copolyester prepared as in example 1 was mixed with an adhesive and oil and stirred at 177 ° C for 2 hours to produce the adhesive composition The composition presented a Tg of - 7 ° C at 1 ° C and a vicosity of 400 cP at 20,000 centipoise at 177 ° C) determined on a Brookfield HV: II viscosimeter The formulation was odorless at mixing temperatures of 177 ° C. The formulation presented good adhesion to films polyethylene and polypropylene [ASTM D1876 T-release) and good tensile strength (Test Method ASTM 412) The adhesive components and results are reported in Table I. IN 100 ml of hot water (65-80 ° C) a a pH of 7.8, 0.5 grams of adhesive chips were mixed in. Within 15 minutes under gentle agitation the adhesive was completely dispersed in water to form a milky mixture.The following tables (Table I, Table II and Table III) compare n the properties of the water-dispersible hot melt adhesives according to this invention with typical hot melt adhesive formulations currently used and one according to SN 98 / 283,011. Tables and physical test data, particularly T-release adhesion, indicate that the polyester-based adhesives demonstrate greater adhesion to olefin and aluminum film. Example 4 - Preparation of Water-dispersible Hot Melt Adhesive The copolyester of Example 2 was mixed as in Example 3 with the amount of components shown in Table I. The comparisons are given in the following tables. Example 5 (Comparative) - Preparation of Water Dispersible Branched Polyester A 1000 ml round flask equipped with a glass head, agitator shaft, nitrogen inlet and a side arm was charged with 186.0 grams (0.92 mol) of dimethyl-1 , 4-cyclohexanedicarboxylate, 23.7 grams (0.08 mole) of dimethyl-5-sodiosulfoisophthalate, 95.4 grams (0.90 mole) of diethylene glycol, 43.2 grams (0.30 mole) of 1,4-diclohenedimethanol, 6.70 grams (0.05 mole) trimethylol propane and 1.17 mi of a 1.46% (w / v) solution of titanium isopropoxide in n-butanol. The flask was flushed with nitrogen and immersed in a Belraont metal bath at 200 ° C for 90 minutes and 220 ° C for a further 90 minutes with a nitrogen sweep with sufficient agitation. After raising the temperature to 240 ° C, a vacuum less than 0.5 rom was installed for 5 minutes to perform the polycondensation. The vacuum was then moved with a nitrogen atmosphere and the polymer was allowed to cool after removing the flask from the bath. An inherent viscosity of 0.2 dL / g was determined for the polymer recovered according to ASTM D3835-79 and the crystalline transition temperature of + 4 ° C was obtained from the thermal analysis by means of DSC. The polymer had a smell that was transparent and yellow in color. Example 6 (Comparative) - Preparation of a water-dispersible hot-melt adhesive The copolyester prepared as in example 5 was mixed as in example 3. The components and amounts are shown in Table II. The formulation had a predominant odor at a mixing temperature of 177 ° C. The comparisons given in the following tables. Table I Polyester-based adhesive formulations Percent by weight 0.2 polyester IB example 3 40 0.4 polyester IB example 1 40 Pentaeritrol ester (non-polar) 50 50 glue Dipropylene glycol Dibenzoate 10 10 plastific. Antioxidant 0.3 0.3 Tetra-bis-methylene-3 (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate methane Brookfield Thermosel 177 ° C 1650 18400 centipoise Viscosity ASTM D3236 190 ° C 910 5,380 Ring and ball softening point ASTM E-28 71 97 Crystal transition DSC ° C -8 Tensile strength mpa 0.02 0. 14 ASTM D412 Release adhesion T ASTM DI876 Aluminum g / mm 3.8 52 Polypropylene g / mm 4.4 11 PET g / mm 10.3 19 Dispersion of water Dispersed in Dispersed in 1 gm in 100 ml of water RT .n «ennoo» s .2 hhoorraa * s aenos de a horas TABLE II INITIAL POINT FORMULATIONS Tßr * ofusible on the basis of polyester Terßofualblß a base dß EVA and SIS COMERCIAL% in weight t in weight Poliestßr 0.2 IV Ejeaplo 5 SO Elvax 220 30% - Bßnioflßx 9-ßß 10 Kraton 1107 SIS 20% Poral AX 39.7 EaStotaC H-100R 45 SO Irganox 1010 0.10 Parafllnt Hl wax 25 - Cyanox 1212 0.20 Shellflex 371 20 Irganox 1010 0.1 0.1 Viscosity at 77'C ASI D3236 »B4 cp» ft60 cps 2230 cps RBSP "C ASTM E-29 ß6'C 10" "C 87'C ELVAX 220 - Polymer of ethylene vinyl acetate from DuPont KRATON 1107 - Shell styrene block copolymer Chemical FORAL AX - wood rosin acid # of 140-160 of Hercules BENZOFLEX 9-88 - Plasticizer of dipropylene glycol dibenzoate of Velsiol Chemical IRGANOX 1010 - Antioxidant of Ciba Geigy CYANOX 1212 - Antioxidant of American Cyanamid EASTOTAC H-100R - Glue of Eastman Chemical Company PARAFLINT Hl Wax - Moore and Munger SHELLFLEX 371 - Paraffinic / Naphthenic Oil of Shell Chemical Adhesion detachment T ASTM D1876 g / mm g / mm g / mm PET 7.3 6.5 2.3 PE 11.9 10.7 5.6 PP 14.8 NA 7.1 Water dispersion 100% dispersion 1 g in 100 ml of drinking water, pH 7.8 at RT (24 hours).

Example 7 (comparative) An attempt was made to mix the polyester 0.2 IV of Example 5 with 30 weight percent of the non-polar pentaerythritol glue used in Table I. The mixture was incompatible and the phase was separated in the molten state. Example 8 (comparative) An attempt was also made to form an adhesive such as the previous one of Example 6 with the same formulation and additives shown in Table II. The copolyester is carried out as in example 5 but with IV of 0.4 dL / g (kept under vacuum for a longer period of time). The mixed phase was separated in the molten state. EXAMPLE 9 Aqueous Dispersion The following results are from a 40 percent aqueous dispersion of the copolyester of Example 2 with an IV of 0.2 and another dispersion of the copolyester of Example 1 having an IV of 0.4. The dispersions were coated with a dry film thickness of 2 mil. Adhesion of detachment R was performed on each substrate. Table III Test results: 0.2 IV 0.4 IV Polyethylene 9.0 g / mm 6.3 g / mm Polypropylene 93.5 g / mm 7.3 g / mm PET 110.9 g / mm 64.7 g / mm Example 10 Construction of a diaper The above 0.4 polyester dispersion of the Example 9 was coated on a polyethylene film and adhered to wood pulp of a diaper "Huggies" registered trademark of Kimberly Clark The assembly was left to dry overnight.

Five grams of this assembly was placed in an ionic solution 0. 2 molar (simulated body fluid). The assembly remained together. The adhesive did not disperse. The dispersibility in drinking water and the non-dispersibility of an ionic solution is a unique advantage in non-woven articles. * Test method AATCC 15-1985 Alkaline solution 10 g NaCl 4 g ammonia carbonate 1 g disodium hydrophosphate 0.25 g histidine hydrochloride up to 1 liter.

Claims (26)

1. CLAIMS 1.- A water-dispersible adhesive composition consisting of a copolyester composition dispersible in branched water made from radicals or units of reaction products: (I) 1,4-cyclohexanedicarboxylic acid; (II) 2 to 40 mole percent, based on the total equivalence of all acids, of at least one difunctional sulfonomizer containing at least one sulfonate group linked to an aromatic ring in which the functional groups are their carboxyl or esters; (III) at least one diol or a mixture of diols consisting of: (A) 0.1 to 85 molar percent, based on the total molar percentage of the diol units having the formula H (-0CH2CH2-) n0H wherein n is 2 to 20, with the proviso that the molar percentage of these units is inversely proportional to the value of n; (B) 0.1 to 15 molar percent, based on the total molar percentage of the diol units of a poly (ethylene glycol) having the formula H (- 0CH2CH2-) n0H wherein n is 2 to 500, with the proviso that that the molar percentage of these units is inversely proportional to the value of n; and (C) 0. to 99 mole percent of the diol component selected from the group consisting of glycols containing two groups -C (R1) 2-0H in which R1 in the reagent is a hydrogen atom, an alkyl with 1 to 5 carbon atoms, or an aryl group with 6 to 10 carbon atoms; (IV) or at 40 molar percent of a hydrocarboxylic acid having a -C (R-) 2-0H group, in which R in the reagent is hydrogen or an alkyl group with 1 to 6 carbon atoms; and (V) 0.5 to 40 molar percent of a "multifunctional" or "branching inducer" reagent containing at least three functional groups selected from hydroxyl, carboxyl and mixtures thereof; the copolyester containing substantially equal molar proportions of acid equivalents (100 mole percent) and diol in which the inherent viscosity is at least 0.1 dL / g measured in a solution in 60/40 parts by weight of phenol / tetrachloroethane at 25 ° C and with a concentration of 0.25 g of copolyester in 100 ml of solvent, the crystalline transference temperature Tg is not higher than 20 ° C, and the ring and ball softening points are at least 70 ° C.
2. 2. The composition according to claim 1, wherein the 1,4-dicyclohexanedicarboxylic acid of (I) is in a concentration of 50 to 95 molar percent based on the total acid equivalents.
3. 3. The composition according to claim 2 wherein an amount of up to 10 mole percent of the 1,4-cyclohexanedicarboxylic acid is substituted with an additional acid selected from the group consisting of aliphatic, alicyclic and aromatic dicarboxylic acids.
4. 4. The composition according to claim 2, wherein the 1,4-cyclohexanedicarboxylic acid of (I) is in a concentration of 60 to 90 molar percent in bas-e to the total equivalent of acid.
5. 5. The composition according to claim 4 wherein the 1,4-cyclohexanedicarboxylic acid of (I) is in a concentration of 60 to 90 mole percent based on the total acid equivalent.
6. 6. The composition according to claim 1 in which the difunctional sulfonomer of (II) is in a concentration of 4 to 25 molar percent.
7. 7. The composition according to claim 1 wherein the units of (A) in the diol are in a concentration of 20 to 80 molar percent and the units of (A) are selected from the group consisting of diethylene glycol, triethylene glycol and its mixtures.
8. 8. The composition according to claim 1 in the lime component (A) and (B) of (III) are different units and the units of (A) are selected from the group consisting of diethylene glycol, triethylene glycol and their mixtures and the units of (B) are in a concentration of 0.1 to 5 molar percent and are selected from poly (ethylene glycols), being n 5 to 50.
9. 9. The composition according to claim 8 wherein the units of (B) are present in a concentration of 1 to 5 molar percent and n is 10 to 30.
10. 10. The composition according to claim 1 wherein the units of component (C) are present in a concentration of 30 to 70 molar percent and are selected from the group consisting of ethylene glycol, 1,3-propane diol, 1,4-butane diol, 1,6-hexane diol and cyclohexane dimethanol.
11. 11. The composition according to claim 1 in which the units of (V) are present in a concentration of 0.5 to 20 molar percent.
12. 12. The composition according to claim 11 in which the units of (V) are present in a concentration of 2 to 6 molar percent.
13. 13. The composition according to claim 1, wherein the inherent viscosity is at least 0.28 dL / g.
14. 14. - The composition according to claim 1 wherein the Tg is between -20 to 20 ° C.
15. 15. The composition according to claim 1 wherein the ring and ball softening point of the composition is from 80 to 120 ° C.
16. 16. A water-dispersible adhesive composition comprising: (a) 20 to 80 percent by weight of the copolyester of claim 1; (b) 2 to 60 weight percent of an adhesive selected from the group consisting of terpene resins, aromatic resins, aliphatic hydrocarbon resins, rosins and functionalized polymers; (c) 0 to 30 weight percent of an extender oil selected from the group consisting of paraffinic oils, naphthenic oils, liquid polyesters, liquid hydrocarbon resins, liquid rosins, polyethylene glycols of low molecular weight, dibenzoates, isobutyrates, phthalate oils, animal oils, vegetable oils and mineral oils; and (d) 0.1 to 2 weight percent of a stabilizer.
17. 17. The composition according to claim 16 wherein the glue is present in a concentration of 10 to 50 percent by weight and has a ring and ball softening point of at least 120 ° C.
18. 18. The composition according to claim 17, wherein the glue is selected from the group of glues consisting of aliphatic hydrocarbon resins, rosin and terpene resins.
19. 19. The composition according to claim 16 wherein the extender oil is in a concentration of 1 to 30 percent by weight and is selected from the group consisting of naphthenic oils, paraffinic oils, isobutyrates, phthalate oils, dibenzoates and their mixtures
20. 20. The composition according to claim 16 wherein the stabilizer is in a concentration of 0.1 to 0.5 percent by weight and is selected from the group consisting of hindered phenols, phosphates.
21. 21. An article of manufacture comprising the adhesive composition according to claim 16 laminated between two substrates.
22. 22. The article of manufacture according to claim 21 in which at least one of the substrates is selected from the group consisting of paper, cardboard and wood pulp.
23. 23. A process that consists in applying in liquid form to a surface of a substrate the water-dispersible adhesive composition according to claim 16 and while it remains in liquid form, applying a second surface of a substrate to the adhesive composition dispersible in water. water thus forming a laminate.
24. 24. The process according to claim 23 in which the liquid form is in the melt and the adhesive composition is a hot-melt adhesive composition that is applied at a temperature of 150 to 200 ° C.
25. 25. The process according to claim 23 in which the liquid form is in an aqueous solution at a concentration of 10 to 70 percent by weight of solids.
26. 26. The process according to claim 23 further comprising pulping with the resulting laminate, in an aqueous pulp solution separating the water-dispersible adhesive composition from the surface, the composition of at least one substrate being a fibrous material.