MXPA97002166A - Paper products containing a chemical softening composition based on vegetable oil, biodegrated - Google Patents

Abstract

The present invention relates to a soft paper product, characterized in that it comprises: a) fibers making cellulose paper, and b) from about 0.005% to about 5.0% by weight of said fibers to make cellulose paper of a softening compound with biodegradable, quaternary ammonium ester functionality having the formula: wherein, each Y is -0- (0) -C, or -C (0) -0-; m = 1 to 3, preferably, m = 2; each n = 1 to 4, preferably n = 2, each R is a C1-C6 alkyl group, a hydroxyalkyl group, a hydrocarbyl group, a substituted hydrocarbyl group, a benzyl group or mixtures thereof, preferably each R is a C1-C3 alkyl group, more preferably each R is a methyl group, each R2 is a C11-C23 hydrocarbyl or a substituted hydrocarbyl substituent and the counter ion, X, is any anion compatible with the softener, where the R2 part of the softening compound is derived from C12-C24 fatty acyl groups, preferably most of R2 is derived of fatty acyl groups containing at least 90% of a chain length of C18-C24, most preferably fatty acyl groups containing at least 90% of C18 or C22, said groups of fatty acyl having an Iodine Value of from more from 5 to less than 100, preferably 10 to

Description

OUE PAPER PRODUCTS CONTAIN A CHEMICAL SOFTENING COMPOSITION BASED ON VEGETABLE OIL. BIODEGRADABLE FIELD OF THE INVENTION This invention relates to tissue paper webs. More particularly, it refers to absorbent, soft tissue paper webs, which can be used in paper towels, diapers, facial tissues, and toilet tissue products.

BACKGROUND OF THE INVENTION Bands or sheets of paper, sometimes called bands or sheets of tissue or tissue paper, find extensive use in modern society. Such articles, such as paper towels, diapers, and toilet tissues are articles of short commercial fibers. It has long been recognized that the three physical attributes of these products are their smoothness; its absorbency, particularly its absorbency for aqueous systems; and its resistance, particularly its resistance when wet. Research and development efforts have been directed towards the improvement of each of these three attributes, without seriously affecting the others, as well as the improvement of two or three attributes simultaneously. The softness is the tactile sensation perceived by the consumer at the moment that sustains a particular product, rubs it on his skin, or wrinkles it with his hands. This tactile sensation is a combination of several physical properties. One of the most important physical properties, related to the softness, is generally considered by those skilled in the art and it is the rigidity of the paper web, from which the product is made. The stiffness, in turn, is usually considered to depend directly on the dry tension strength of the web and the rigidity of the fibers forming the web. Resistance is the ability of the product, and its constituent bands, to maintain physical integrity and resist rupture, bursting and crumbling under conditions of use, particularly when wet. Absorbency is the measure of the ability of a product, and its constituent bands, to absorb quantities of liquid, particularly aqueous, solutions or dispersions. The total absorbency, as perceived by the human consumer, is generally considered as a combination of the total amount of a liquid that a given mass of tissue paper will absorb in saturation, as well as the speed at which the mass absorbs the liquid.

The use of moisture resistant resins to improve the strength of a paper web is widely known. For example, Westfelt described a number of such materials and discussed their chemistry in Cellulose Chemistry and Technology, Vol. 13, pages 813-825 (1979). Freimark et al., In U.S. Patent No. 3,755,220, issued August 28, 1973, mentioned that certain chemical additives known as debonding agents interfere with the natural fiber-to-fiber binding, which occurs during formation. of the sheet in processes for making paper. This reduction in the joint leads to a softer, or less rough, sheet of paper. Freimark et al. Taught the use of moisture resistant resins to improve the moisture resistance of the sheet together with the use of debonding agents to balance the undesirable effects of the moisture resistant resin. These debonding agents reduce the resistance to dry stress, but generally there is also a reduction in wet tensile strength. Shaw, in U.S. Patent No. 3,821,068, issued June 28, 1974, also teaches that chemical debonders can be used to reduce stiffness, and thus improve the smoothness of a tissue paper web. Chemical debonding agents have been described in several references, such as U.S. Patent No. 3,554,862, issued to Hervey et al. On January 12, 1971. These materials include quaternary ammonium salts, such as trimethylcocoammonium chloride, trimethylolethyl ammonium chloride, tallow di (hydrogenated) dimethyl ammonium chloride and trimethylstearylammonium chloride. Emanuelsson et al., In U.S. Patent No. 4,144,122, issued March 13, 1979, teach the use of complex quaternary ammonium compounds, such as bis (alkoxy (2-hydroxy) propylene) quaternary ammonium chlorides, to soften bands. These authors also attempted to overcome any reduction in absorbency, caused by the debonding agents through the use of surfactants, such as adducts of ethylene oxide and propylene oxide of fatty alcohols. Armak Company, of Chicago, Illinois, in its newsletter 76-17 (1977) discloses that the use of di (hydrogenated) dimethylammonium tallow chloride in combination with fatty acid esters of polyoxyethylene glycols can impart both softness and absorbency to tissue paper webs. An illustrative result of research directed to improved paper webs is described in U.S. Patent No. 3,303,746, issued to Sanford and Sisson, on January 31, 1967. Despite the high quality of the paper webs made by the procedure described in this patent, and despite the commercial success of the products formed from these bands, the search efforts directed to find improved products have continued. For example, Becker et al., U.S. Patent No. 4,158,594, issued January 19, 1979, describe a method that will form a strong, soft fibrous sheet. More specifically, they teach that the strength of a web of tissue paper (which has been softened by the addition of chemical debonding agents) can be improved by adhering, during processing, a web surface to a curled surface in an arrangement of fine pattern by a binding material (such as an acrylic latex rubber emulsion, a water soluble resin, or an elastomeric bonding material), which has been adhered to a surface of the web and to the curled surface in the fine pattern arrangement, and corrugation of the curled surface band to form a sheet material. Conventional quaternary ammonium compounds, such as the well-known dialkyldimethylammonium salts (eg, disodium dimethyl ammonium chloride, disodium dimethyl ammonium sulfate, tallow di (hydrogenated) dimethylammonium chloride, etc.) are effective chemical softening agents. The variations of mono-ester and diester of these quaternary ammonium salts have been proven to be benevolent to the environment and also function effectively as chemical softening agents to increase the softness of cellulose fiber materials. Unfortunately, these quaternary ammonium compounds can be subjected to odor problems and can also be difficult to disperse.

Applicants have discovered that the monoester and diester of quaternary ammonium salts based on vegetable oil also effectively function as chemical softening agents to improve the softness of fibrous cellulose materials. The tissue paper made with quaternary softeners lt. of monoester and diester based on vegetable oil exhibited good softness and absorbency with improved odor compared to silk paper made with quaternary monoester softeners and animal based diesters. In addition, due to good fluidity (low melting points) of the Quaternary softeners of monoester and diester based on vegetable oil, a good dispersion can be obtained with minimal use or no use of diluent. It is an object of this invention to provide soft, absorbent tissue paper products. It is an object of this invention to provide soft, absorbent facial tissue products. It is an object of this invention to provide soft, absorbent paper towel products. It is a further object of this invention to provide a method for making soft, absorbent tissue paper and towel products (i.e., facial and / or toilet tissue). These and other objects are obtained using the present invention, as will be readily apparent from reading the following description.

BRIEF DESCRIPTION OF THE INVENTION The present invention provides soft, absorbent paper products. In summary, soft paper products comprise: a) fibers that make cellulose paper; and b) from about 0.005% to about 5.0% by weight of said fibers to make cellulose paper of a quaternary ammonium softening compound with ester functionality, biodegradable, having the formula: (R) 4-m - + - [(CH2) n - Y - R2] m X- where, each Y is -0- (0) C-, or -C (0) -0-; is from 1 to 3; n is from 1 to 4; each R is an alkyl group of C 1 -C 6, a hydroxyalkyl group, a hydrocarbyl group, a substituted hydrocarbyl group, a benzoyl group, or mixtures thereof; each R2 is a hydrocarbyl of C ^ -C ^ or a substituted hydrocarbyl substituent; and X "is any anion compatible with the softener, wherein the R2 portion of the softening compound is derived from C12-C24 fatty acyl groups having an Iodine Value from greater than about 5 to less than about 100. preferably, most of the fatty acyl groups are derived from vegetable oil sources.

Preferably, the biodegradable, ester-functional quaternary ammonium compound is diluted with a liquid vehicle at a concentration of 0.01% to about 25.0% by weight, before being added to the fibrous cellulose material. Preferably, the liquid vehicle temperature ranges from about 30 ° C to about 60 ° C, and the pH is less than about 4. Preferably, at least 20% of the biodegradable ester-functional quaternary ammonium compounds, added to fibrous cellulose, are retained. Examples of preferred quaternized amine-ester compounds suitable for use in the present invention include compounds having the formulas: (CH3) 2 N + - (CH2CH2- f0-C-C17H33) 2 X " (CH3) 2-IT - (CH2CH2-0-C-C21H41) 2 X "These compounds can be considered as variations of monoester and diester of the diester chloride of dileyl dimethyl ammonium (i.e., di (octadec-z-9) chloride. -enyloxyethyl) dimethylammonium) (DEDODMAC) and dieryldimethylammonium diester chloride (ie di (docos-z-13-methyloxyethyl) dimethylammonium chloride) (DEDEDMAC), respectively. It should be understood that although the oleyl and fatty acyl groups of erucyl are derive from naturally occurring vegetable oils (for example, olive oil, rapeseed oil, etc.), minor amounts of other fatty acyl groups may also be present. For a discussion of the variable compositions of naturally occurring vegetable oils, see Bailey's Industrial Oil and Fat Products, 3rd. edition, John Wiley and Sons (New York 1964), incorporated here by reference. Depending on the characteristic requirements of the product, the saturation level of the fatty acyl groups of the vegetable oils can be designed. Briefly, the process for making the silk webs of the present invention comprises the steps of forming raw materials for making paper from the aforementioned components, the deposition of the raw materials for making paper on a foraminous surface, such as a wire of Fourdrinier, and the removal of water from the raw materials deposited. All percentages, ratios and proportions herein are by weight, unless otherwise specified. r DETAILED DESCRIPTION OF THE INVENTION Since this specification concludes with claims that particularly point out and indifferently claim the main subject in relation to the invention, it is believed that the invention can be better understood from the following detailed description and from the appended examples. As used herein, the terms "tissue paper web", "paper web", "web", "paper sheet", and "paper product" all refer to paper web made by a process comprising the formation of aqueous raw materials for making paper, the deposition of these raw materials on a foraminous surface, such as a Fourdrinier wire, and the removal of water from raw materials by gravity or vacuum-assisted drainage, with or without compression, and by evaporation. As used herein, the aqueous raw materials for making paper are aqueous sludge from papermaking fibers and the chemicals described below. The first step in the process of this invention, is the formation of aqueous raw materials to make paper. Raw materials comprise papermaking fibers (hereinafter sometimes referred to as wood pulp), and at least one quaternized ester-amine compound based on vegetable oil, all of which will be described below. It is anticipated that wood pulp in all its varieties will normally comprise the paper fibers used in this invention. However, other fibrous cellulose pulps can be used, such as cotton liners, bagasse, rayon, etc., and none of these is recognized. Wood pulps useful herein include chemical pulps such as Kraft, sulphite and sulfate pulps, as well as mechanical pulps including, for example, ground wood, thermomechanical pulps and chemically modified thermomechanical pulp (CTMP). Pulps derived from both deciduous and coniferous trees can be used. Also applicable in the present invention are fibers derived from recirculated paper, which may contain any or all of the above categories, as well as other non-fibrous materials such as fillers and adhesives used to facilitate the manufacture of original paper. Preferably, the papermaking fibers used in this invention comprise Kraft pulp derived from soft northern woods.

(A) Quaternary ammonium ester compound, biodegradable The present invention contains as an essential component from about 0.005% to about 5.0%, most preferably from 0.03% to 0.5%, by weight, on a dry fiber basis, of a compound with quaternary ammonium ester functionality, biodegradable, having the formula: (R) 4-m N * - [(CH, R] Jmm X " wherein, each Y is -0- (0) C-, or -C (0) -0-; m = 1 to 3; preferably, m = 2; each n = 1 to 4; preferably, n = 2; lacquered substituent R is a short chain alkyl group of C 1 -C 6, preferably C 1 -C 3, for example, methyl (most preferred), ethyl, propyl, and the like, a hydroxyalkyl group, a hydrocarbyl group, a group Substituted hydrocarbyl, a benzyl group or mixtures thereof; wherein each R 2 is a long chain, at least partially unsaturated C 4 -C 4 hydrocarbyl (IV greater than about 5 to less than about 100, preferably from about 10 to 85), or a substituted hydrocarbyl substituent and the counterion, X ", can be any anion compatible with the softener, for example, acetate, chloride, bromide, methyl sulfate, formate, sulfate, nitrate, and the like Preferably, most of R2 comprises fatty acyl containing at least 90% of a chain length of C18-C24, most preferably, most of R2 is selected from the group consisting of fatty acyl containing at least 90% C18, C22, and mixtures thereof. The biodegradable, quaternary ammonium ester-functional compound, prepared with fully saturated acyl groups, is rapidly biodegradable and excellent softeners. However, it has now been discovered that compounds prepared with at least partially unsaturated acyl groups (i.e., IV greater than about 5 and less than about 100, preferably less than about 85, most preferably about 10 to 85) derivatives of vegetable oil sources present many advantages (such as better fluidity) and are highly acceptable for consumer products when certain conditions are met. The variables that must be adjusted to obtain the benefits to use the unsaturated acyl groups include the Iodine (IV) value of the fatty acyl groups; the weight ratios of the cis / trans isomer in the fatty acyl groups. Any reference to the IV values hereinafter refers to the IV (Iodine Value) of fatty acyl groups and not to the resultant, biodegradable quaternary ammonium ester compound. Preferably, these biodegradable, quaternary ammonium ester-functional compounds are made from fatty acyl groups having an IV of from about 5 to about 25, preferably from about 10 to 25, most preferably from about 15 to about 20, and a weight ratio of the cis / trans isomer of greater than about 30/70, preferably greater than about 50/50, most preferably greater than about 70/30, are stable at low temperature. The weight ratios of the cis / trans isomer provide an optimal concentration capacity at these IV scales. On the scale of IV above about 25, the ratio of cis to trans isomers is less important, unless higher concentrations are needed. The relationship between the IV and the ability to concentrate is described below. Generally, the hydrogenation of acid grades to reduce the polyunsaturation and to reduce the IV to ensure a good color, leads to a high degree of trans configuration in the molecule. Therefore, compounds with quaternary ammonium ester functionality, biodegradable, derivatives of fatty acyl groups that have low IV values, can be made by mixing a fully hydrogenated fatty acid with a touch of hydrogenated fatty acid in a ratio that provides an IV of about 5 to about 25. The poly-unsaturation content of the toughened fatty acid should be less than about 30%, preferably less than about 10%, and most preferably less than 5%. As used herein, these percentages of polyunsaturation refer to the number of fatty acid (or fatty acyl) groups that are polyunsaturated per 100 groups. During touch hardening, the weight ratios of the cis / trans isomer are controlled by methods known in the art, such as optimal mixing, using specific catalysts, providing high H2 availability, etc. It has also been found that for the good hydrolytic stability of the biodegradable, quaternary ammonium ester compound compound, during storage in the molten state, the moisture level in the raw material must be controlled and minimized, preferably to less than about 1% and more preferably less than about 0.05% water. Storage temperatures should be kept as low as possible, and still maintain a material in a fluid state, ideally in the range of from about 49 ° C to about 66 ° C. The optimum storage temperature for stability and fluidity depends on the specific IV of the fatty acid used to make the compounds with quaternary ammonium ester, biodegradable, and the selected level / type of solvent. It is important to provide good storage stability in the molten state to provide a commercially viable raw material that will not degrade significantly during normal transportation / storage / handling of material in manufacturing operations.

Synthesis of a compound with quaternary ammonium ester functionality, biodegradable. The synthesis of a preferred, biodegradable, quaternary ammonium ester compound compound used herein, can be accomplished by the following two step procedure: Step A. Synthesis of Amine Et3N RC (0) OCH2CH2 CH3-N- (CH2CH2? H) 2 * 2 RC (0) CI N-CH3 / CH2CI2 RC (0) OCH2CH2 RC (0) = Derivative of oleic acids or erucic acids.

Amin N-methyl diamine (440.9 g, 3.69 mol) and triethylamine (561.2 g, 5.54 mol) were dissolved in CH2C12 (12 L) in a 22-liter three-necked flask, equipped with an addition funnel, thermometer, mechanical stirrer , condenser and an argon sweeper. The vegetable oil-based fatty acid chloride (2.13 kg, 7.39 moles) was dissolved in two liters of CH2C12 and added slowly to the amine solution. The amine solution was then heated to 35 ° C to maintain the fatty acyl chloride in solution as it was added. The addition of the acid chloride increased the reaction temperature to reflux (40 ° C). The addition of acid chloride is slow enough to maintain reflux, but not so fast as to lose methylene chloride out of the top of the condenser. The addition should take 1.5 hours. The solution was heated to reflux for an additional 3 hours. The heat was removed and the reaction was stirred for two hours to cool to room temperature. CHC13 (12 L) was added. This solution was washed with 3.78 liters of saturated NaCl and 3.78 liters of Ca (0H) 2. The organic layer was allowed to settle overnight at room temperature. It was then extracted three times with 50% K2C03 (7.56 liters each). This was followed by two washes with saturated NaCl (7.56 liters each). Any emulsion that formed during these extractions was resolved by the addition of CHC13 and / or saturated salt and heated on a steam bath. The organic layer was then dried with MgSO 4, filtered and concentrated. The yield is 2,266 kg of the olefin precursor amine or erucyl. TLC of silica (75% Et20 / 25% hexane one spot at Rf 0.69).

Step B. Quaternization CH3CN Amine with ester functionality + CH3Cl-- > (CH) 2N + (CH2CH20 (0) CR) 2C1" The oleyl / erucyl precursor amine (2.166 kg, 3.47 moles) was heated on a steam bath with CH3CN (3.78 liters) until it became fluid. The mixture was then poured into a stirred, glass-lined Pfaudler reactor of 37.8 liters, containing CH3CN (15.12 liters). CH3C1 (11.35 kg, liquid) was added via a tube, and the reaction was heated at 80 ° C for 6 hours. The CH3CN / amine solution was removed from the reactor, filtered, and the solid allowed to dry at room temperature over the weekend. The filtrate was roto-evaporated, allowed to dry overnight and combined with another solid. Yield: 2,125 kg of white powder. The compounds with quaternary ammonium ester functionality, biodegradable, can also be synthesized by other procedures: (C2H5) 3N (CH3) - N- (CH2CH2OH) 2 + 2 C1C (0) C21H41 > (CHj) - N- [CH2CH2OC (0) C21H41] 2 0.6 moles of diethylamine amine was placed in a three-necked three-necked flask equipped with a reflux condenser, an argon (or nitrogen) inlet and two addition funnels. 0.4 mole of triethylamine was placed in an addition funnel and 1.2 mole of erucyl chloride was placed in a 1: 1 solution with methylene chloride in the second addition funnel. Methylene chloride (750 ml) was added to the reaction flask containing the amine, and heated to 35 ° C (water bath). The triethylamine was added dropwise, and the temperature was increased to 40-45 ° C while stirring for half an hour. The erucyl chloride / methylene chloride solution was added dropwise and allowed to warm to 40-45 ° C, under an inert atmosphere, overnight (12-16 hours). The reaction mixture was cooled to room temperature and diluted with chloroform (1500 ml). The chloroform solution of the product was placed in a separatory funnel (4 L) and washed with saturated NaCl, was diluted with Ca (0H) 2, 50% K2C03 (three times) *, and finally, saturated NaCl. The organic layer was collected and dried over MgSO4, filtered and the solvents were removed by rotary evaporation. The final drying was carried out under high vacuum (0.25 mm Hg). * Note: The 50% layer of K2C03 will be below the chloroform layer.

Step B. Quaternization CH3C1 (CH3) -N- [CH2CH2OC (0) C21H4l] 2 > (CH3) -N * - [CH2CH2OC (O) C21H41] 2 Cl " 0.5 moles of the methyldiethanol eruciate amine from Step A was placed in an autoclave sleeve together with 200-300 ml of acetonitrile (anhydrous). The sample was then inserted into the autoclave and purged three times with N2 (16275 mm Hg / 21.4 ATM) and once with CH2C1. The reaction was heated to 80 ° C under a pressure of 3604 mm Hg / 4.7 ATM in CH3C1 for 24 hours. The magrit of the autoclave was removed after the reaction mixture. The mixture was dissolved in chloroform and the solvent was removed by rotary evaporation, followed by drying under high vacuum (0.25 mm Hg). Another method by which the preferred biodegradable, quaternary ammonium ester-functional compounds are commercially available is the reaction of fatty acids (eg, oleic acids, eric acids, etc.) with methyldiethanolamine. Well-known reaction methods are used to form the ester precursor with ester functionality. The quaternary ester functionality is then formed by the reaction with methyl chloride as previously discussed. The above reaction procedures are generally known in the art for the production of quaternary ammonium ester softening compounds. To achieve the IV, the cis / trans ratios, and the percentage of unsaturation, underlined above, additional modifications to these procedures should generally be made. Various types of vegetable oils (for example, olive, rapeseed, safflower, sunflower, soybean, meadow foam, etc.) can be used as sources of fatty acids to synthesize the compound with quaternary ammonium ester functionality, biodegradable . Preferably, olive oils, meadowfoam oil, safflower oil with a high oleic content, and / or rapeseed oils with a high erucic content are used to synthesize the compound with quaternary ammonium ester functionality, biodegradable. Most preferably, the higher erucic acids derived from rapeseed oils are used to synthesize the compound with quaternary ammonium ester functionality, biodegradable. It should be understood that although fatty acyl groups are derived from naturally occurring vegetable oils (e.g., olive oil, rapeseed oil, etc.), minor amounts of other fatty acyl groups may also be present. For a discussion of the variable compositions of naturally occurring vegetable oils see Bailey's Industrial Oil and Fat Products, 3rd. edition, John Wiley and Sons (New York 1964), incorporated here by reference. Importantly, it has been discovered that the biodegradable, quaternary ammonium ester based quaternary ester functionality compounds of the present invention can be dispersed without the use of dispersion aids such as wetting agents. Without being bound by theory, it is believed that its superior dispersion properties are due to the good fluidity (low melting points) of vegetable oils. This is in contrast to conventional quaternary ammonium compounds, based on animal fat (eg, tallow) which require a dispersion aid due to their relatively high operating points. Vegetable oils also provide improved oxidant and hydrolytic stability. In addition, tissue paper made with vegetable oil based softeners exhibit good softness and absorbency with improved odor characteristics, compared to silk paper made with animal fat softeners. The present invention is generally applied to tissue paper, including, but not limited to, tissue paper conventionally of compressed felt; densified patterned tissue paper as illustrated in the United States Patent, of Sanford-Sisson, and progeny, mentioned above, and non-compacted, high-volume tissue paper such as that illustrated by the United States patent No. 3,812,000, Salvucci, Jr., issued May 21, 1974. The tissue paper may be of a homogeneous or multi-layer construction.; the tissue paper products made therefrom can be of a single fold or multiple pleat construction. Silk structures formed from layered paper webs are described in U.S. Patent 3,994,771, Morgan, Jr., et al., Issued November 30, 1976, and incorporated herein by reference. In general, a structure of absorbent, mixed, air-laid, soft, bulky paper is prepared from two or more layers of raw materials, which are preferably composed of different types of fiber. The layers are preferably formed from the deposition of separate streams of diluted fiber sludge, the fibers typically having relatively short softwood fibers and relatively short hardwood fibers, as used in the manufacture of tissue paper, on one or more endless foraminous sieves. The layers are subsequently combined to form a mixed band in layers. The layered web subsequently conforms to the surface of an open-screen drying / embossing fabric, by applying a fluid to force the web and then thermally pre-drying onto said web as part of a process for making low density paper. The layered web can be layered with respect to the type of fiber or the fiber content of the respective layers which can be essentially the same. The tissue paper preferably has a basis weight of between 10 g / m2 and approximately 65 g / m2, and a density of about 0.60 g / cm3 or less. Preferably, the basis weight will be below about 35 g / m2 or less; and the density will be about 0.30 g / cm3 or less. Most preferably, the density will be between 0.04 gr / cm3 and about 0.20 g / cm3. Conventionally compressed tissue paper and methods for making such paper are known in the art. Typically, said paper is made by depositing raw materials to make paper on a foraminous forming wire. This forming wire is usually referred to in the art as a Fourdrinier wire. Once the raw materials are deposited on the forming wire, this is called a band. The band is drained, compressing the band and drying at elevated temperature. The particular techniques and typical equipment for making the bands according to the procedure just described are well known to those skilled in the art, in a typical procedure, raw materials of low consistency pulp are provided in a pressurized headbox. The head box has an opening for supplying a thin deposit of pulp raw materials on the Fourdrinier wire to form a wet band. The web is then typically drained to a fiber consistency of between about 7% and about 25% (basis in total weight of the web) by vacuum draining and further dried by compression operations, wherein the web is subjected to developed pressure. by means of opposed mechanical members, for example, cylindrical rollers.

The dewatered web is then compressed and further dried by a current drum apparatus, known in the art as a Yankee dryer. The pressure in the Yankee dryer can be developed through mechanical means such as an opposing cylindrical drum compressing against the band. Vacuum can also be applied to the band as it is compressed against the Yankee surface. Multiple Yankee dryer drums can be employed, whereby additional compression is optionally incurred between the drums. The tissue paper structures, which are formed, are referred to hereafter as tissue paper structures, compressed, conventional. Said sheets are considered to be compacted since the web is subjected to substantial, total mechanical compression forces, while the fibers are wet and then dried (and optionally crimped) while in a compressed state. The pattern densified tissue paper is characterized by having a field with a relatively high volume of relatively low fiber density, and an array of densified zones with a relatively high fiber density. The highly voluminous field is alternatively characterized as a field of support regions. The densified zones are alternatively referred to as knotty regions. The densified zones may be discretely separated within the highly voluminous field, or they may be interconnected, either totally or partially, within the highly bulky field. Preferred methods for making pattern densified silk webs are described in U.S. Patent No. 3,301,746, issued to Sanford and Sisson, January 31, 1967, U.S. Patent No. 3,974,025, issued to Peter G. Ayers, on August 10, 1976, and United States Patent No. 4,191,609, issued to Paul D. Trokhan, March 4, 1980, and United States Patent 4,637,859, issued to Paul D. Trokhan, January 20, 1987; all of these are incorporated here by reference. In general, densified pattern webs are preferably prepared by depositing raw materials for making paper onto a foraminous forming wire, such as a Fourdrinier wire to form a wet web and then juxtaposing the web against a support arrangement. The band is compressed against the arrangement of supports, thus presenting densified zones in the band at the sites corresponding geographically to the points of contact between the arrangement of supports and the wet band. The rest of the uncompressed band, during this operation, is referred to as the highly bulky field. This highly bulky field may be further densified by the application of fluid pressure, such as with a vacuum type device or a blow dryer, or by mechanically compressing the web against the support arrangement. The web is drained, and optionally pre-dried, in such a manner so as to substantially avoid compression of the highly bulky field. This is preferably achieved by fluid pressure, such as with a vacuum type device or blow dryer, or alternatively by compressing, mechanically, the web against a support arrangement, wherein the highly bulky field is not compressed. The operations of drainage, optional pre-drying and formation of the densified zones can - * - be integrated or partially integrated to reduce the total number of processing steps carried out. Subsequent to the formation of the densified zones, drainage and optional predrying, the band is dried until finished, preferably still avoiding mechanical compression. Preferably, from about 8% to about 55% of the tissue paper surface comprises densified knots having a relative density of at least 125% of the density of the highly bulky field. The arrangement of supports is preferably a stamping vehicle fabric having a displacement of pattern knots, which operate as the arrangement of supports that facilitates the formation of densified areas under the application of pressure. The knot pattern constitutes the previously named support arrangement. Patterned vehicle fabrics are described in U.S. Patent No. 3,301,746, Sanford and Sisson, issued January 31, 1967, U.S. Patent No. 3,821,068, Salvucci, Jr., et al., Issued at May 21, 1974, U.S. Patent No. 3,974,025, Ayers, issued August 10, 1976, U.S. Patent No. 3,573,164, Friedberg 5 et al., Issued March 30, 1971, patent of the United States No. 3,473,576, Amneus, issued October 21, 1969, United States Patent No. 4,239,065, Trokhan, issued December 16, 1980, and United States Patent No. 4,528,239, Trokhan, issued September 9, July 1985, lu >; - all of these are incorporated here by reference. Preferably, the raw materials are first formed to a wet web on a foraminous forming vehicle. Such as a Fourdrinier wire. The band is drained and transferred to a patterned fabric. Subjects bonuses can alternatively be deposited at the beginning on a foraminous support vehicle, which also operates as a stamping cloth. Once formed, the wet web is dewatered and, preferably, thermally predried to a selected fiber consistency of between about 40% and approximately 80%. The drain can be made with suction boxes or other vacuum devices or with blow dryers. The print of the knot of the embossing fabric is printed on the band as discussed above, before the band is completely dried. One method to achieve this is to through the application of mechanical pressure. This can be done, for example, by compressing a pressure roller, which holds the embossing fabric against the face of a dryer drum, such as a Yankee dryer, where the band is disposed between the pressure roller and the dryer drum. Also, preferably, the band is molded against the embossing fabric before the end of drying, by applying fluid pressure with a vacuum device such as a suction box, or with a blow dryer. The fluid pressure can be applied to induce the printing of densified zones during the initial drain, in a subsequent, separate process step, or a combination thereof. The non-compacted, densified, unpatterned tissue paper structures are described in U.S. Patent No. 3,812,000, issued to Joseph L. Salvucci, Jr., and Peter N. Yiannos, on May 21, 1974, and U.S. Patent No. 4,208,459, issued to Henry E. Becker, Albert L. McConnell, and Richard Schutte, June 17, 1980, both incorporated herein by reference. In general, non-compacted, densified, unpatterned tissue paper structures are prepared by depositing raw materials to make paper on a foraminous forming wire such as a Fourdrinier wire, to form a wet band, draining the band and removing the additional water without mechanical compression until the band has a fiber consistency of at least 80%, and curling the band. The water is removed from the band by vacuum draining and thermal drying. The resulting structure is a soft but weak highly bulky sheet of relatively uncompacted fibers. The bonding material is preferably applied to portions of the band before crimping. Compacted, densified, unpatterned silk structures are commonly known in the art as conventional silk structures. In general, densified, densified, unconfined tissue paper structures are prepared by depositing raw materials to make paper on a foraminous wire such as a Fourdrinier wire to form a wet band, draining the web and removing the additional water with the help of compaction. uniform mechanics (compression) until the web has a consistency of 25-50%, transferring the web to a term dryer, such as a Yankee dryer and curling the web. Finally, the water is removed from the belt through vacuum, mechanical pressure and thermal means. The resulting structure is strong and generally of singular density, but very low in volume, absorbency and softness. The tissue paper web of this invention can be used in any application where absorbent, soft tissue paper webs are required. Particularly advantageous uses of the tissue paper web of this invention are in paper towels, toilet tissue and facial products. For example, two webs of tissue paper of this invention can be embossed and adhesively secured together, in a face-to-face relationship, as taught in U.S. Patent No. 3,414,459, issued to Wells on December 3. of 1968, and which is incorporated herein by reference, to form two-fold paper towels.

ANALYTICAL AND TEST PROCEDURES By any method accepted in the applicable art, analyzes may be made of the amount of treatment chemicals used herein or retained in tissue paper webs.

A. Quantitative Analysis for the Compound with Ester Functionality of Quaternary Ammonium For example, the level of compounds with quaternary ammonium ester functionality, such as dioleldimethylammonium diester chloride (DEDODMAC), dieryldimethylammonium diester chloride (DEDEDMAC) retained by the tissue paper, can be determined by solvent extraction of DODMAC / DEDMAC by an organic solvent, followed by an anionic / cationic titration using Dimidium bromide as an indicator. These methods are illustrative, and are not intended to exclude other methods that may be useful in determining the levels of particular components retained by the tissue paper.

B. Hydrophilicity (Absorbency) The hydrophilicity of tissue paper refers, in general, to the predisposition of the tissue paper to be moistened with water. The hydrophilicity of the tissue paper can be a little quantified by determining the period required to dry the tissue paper to moisten completely with water. This period is referred to as the "wetting period." In order to provide a consistent and repeatable test for the wetting period, the following procedure can be used for moistening period determinations: first, a conditioned sample unit sheet (The environmental conditions for the test of paper samples are 23 + 1 ° C and 50 + 2% R.H., as specified in the method TAPPI T402), a tissue paper structure of approximately 11.1 cm x 12 cm is provided; secondly, the sheet is bent into four juxtaposed rooms, and then wrinkled to a ball with a diameter of about 1.9 cm to about 2.5 cm; thirdly, the ball-shaped sheet is placed on the surface of a body of distilled water at 23 + 1 ° C and a time controller is operated simultaneously; Fourth, the time controller is stopped 3.3 and read when the wetting of the ball-shaped sheet is completed. A complete wetting is observed visually. Of course, the hydrophilicity characteristics of the tissue paper embodiments of the present invention can be determined immediately after manufacture. However, substantial increases in hydrophobicity can occur during the first two weeks after the tissue paper has been made; that is, after the paper has completed two weeks after its manufacture. In this way, the wetting times are preferably measured at the end of said two week period. Therefore, the wetting times measured at the end of a period of two weeks at room temperature are referred to as "wetting periods of two weeks".

C. Density The density of the tissue paper, as the term used in the present, is the average density calculated as the basis weight of that paper divided by the caliber, with the appropriate unit conversions incorporated in it. The caliper of the tissue paper, as used herein, is the thickness of the paper when it is subjected to a compression load of 15.5 g / cm2.

OPTIONAL INGREDIENTS Other chemicals commonly used in papermaking may be added to the chemical softening composition described herein, or to the raw materials for making paper, as long as they do not significantly and adversely affect the softness, absorbency of the fibrous material, and the softness enhancing actions of the biodegradable, quaternary ammonium ester softening compounds of the present invention.

A. Wetting Agents The present invention may contain as an optional ingredient from about 0.005% to about 3.0%, most preferably from 0.03% to about 1.0%, by weight, on a dry fiber base of a wetting agent. (1) Polyhydroxyl Compounds Examples of water soluble polyhydroxy compounds that can be used as wetting agents in the present invention, include glycerol, polyglycerols having a weight average molecular weight of about 150 to about 800, and polyoxyethylene glycols and polyoxypropylene glycols, which have a weight average molecular weight of from about 200 to about 4000, preferably from about 200 to about 1000 , most preferably from 200 to 600, approximately. Especially preferred are polyoxyethylene glycols having a weight average molecular weight of about 200 to about 600. Mixtures of the polyhydroxy compounds described above can also be used. A particularly preferred polyhydroxy compound is polyoxyethylene glycol having a weight average molecular weight of about 400. This material is commercially available from the Union Caerbide Company of Danbury, Connecticut under the tradename "PEG-400". (2) Non-ionic Surfactant (Alkoxylated Materials) Suitable nonionic surfactants can be used as wetting agents in the present invention, and include addition products of ethylene oxide and, optionally, propylene oxide, with fatty alleles, fatty acids , fatty amines, etc. As the nonionic surfactant, any of the alkoxylated materials of the particular type described hereinbefore can be used. Suitable compounds are substantially water-soluble surfactants of the general formula: R2 - Y - (C2H40) z - C2H4OH wherein R2, for both solid and liquid compositions, is selected from the group consisting of primary and secondary branched alkyl and / or acyl hydrocarbyl groups; secondary alkenyl hydrocarbyl and branched chain groups; and branched chain primary, secondary alkyl and alkenyl-substituted phenolic hydrocarbyl groups; said hydrocarbyl groups having a hydrocarbyl chain length of from about 8 to about 20, preferably from about 10 to about 18, carbon atoms. Most preferably, the length of the hydrocarbyl chain for liquid compositions is from about 16 to about 18 carbon atoms, and for solid compositions from about 10 to about 14 carbon atoms. In the general formula for the ethoxylated nonionic surfactants herein, Y is typically -0-, -C (0) 0-, -C (0) N (R) -, or -C (0) N (R ) R-, wherein R2, and R, when present, have the meanings presented above, and / or R can be hydrogen, and z is at least about 8, preferably at least about 10-11. The yield and, usually, the stability of the softening composition is reduced when few ethoxylate groups are present. The surfactants herein are characterized by a HLB (hydrophilic-lipophilic balance) of from about 7 to about 20, preferably from about 8 to about 15. Of course, by defining R2 and the number of ethoxylate groups, the agent's HLB Surfactant is, in general, determined. However, it should be noted that the ethoxylated nonionic surfactants useful herein, for concentrated liquid compositions, contain relatively long chain R2 groups and are relatively and highly ethoxylated. Since shorter alkyl chain surfactants having short ethoxylated groups may possess the HLB requirement, they are not very effective here. Below are examples of nonionic surfactants. The nonionic surfactants of this invention are not limited to these examples. In the examples, the integer defines the number of ethoxy groups (EO) in the molecule.

ALCOXYLATED LINEAR ALCOHOLS to. Primary Linear Alcohol Alcoxylates The deca-, undeca-, dodeca-, tetradeca-, and pentadeca-ethoxylates of n-hexadecanol and n-octadecanol having an HLB within the scale set forth herein, are useful wetting agents in the context of this invention. The illustrative alkoxylated primary alcohols useful in the present invention as the viscosity / dispersibility modifiers of the compositions are n-C18EO (10); and n-C10EO (11). Also useful herein are natural or synthetic mixed alcohol ethoxylates in the "oleic" chain length scale. Specific examples of such materials include alcohol -EO (11) oleic, Alcohol -EO (18) oleic, and alcohol-EO (25) oleic. b. Alcoxlates of Linear Alcohol. Secondary The deca-, undeca-, dodeca-, tetradeca-, pentadeca-, octadeca-, and nonadeca- ethoxylates of 3-hexadecanol, 2-octadecanol, 4-eicosanol, and 5-eicosanol, which have a HLB within the above-mentioned scale herein, they can be used as wetting agents in the present invention. Illustrative ethoxylated secondary alcohols can be used as wetting agents, in the present invention, and are: 2-C16EO (ll); 2-C20EO (ll); and 2-C16E0 (14).

ALCOHOLS LINEALES ALQÜILFENOXILADOS As in the case of the alkoxylates and alcohol, the hexa- to the octadeca- ethoxylates of alkylated phenols, particularly monohydric alkylphenols, having an HLB within the scale mentioned herein, are useful as the viscosity / dispersibility improvers of the compositions of the present. The hexa- to the octadeca- ethoxylates of p-tridecylphenol, m-pentadecylphenol, and the like, are useful herein. Illustrative ethoxylated alkylphenols useful as the wetting agents of the mixtures herein are: p-tridecylphenol E0 (11) and p-pentadecylphenol E0 (18). As used herein, and as generally recognized in the art, a phenylene group in the nonionic formula is the equivalent of an alkylene group containing from 2 to 4 carbon atoms. For purposes of the present, it is considered that nonionics having a phenylene group contain an equivalent number of carbon atoms calculated as the sum of the carbon atoms in the alkyl group plus about 3.3 carbon atoms for each phenylene group.

OLEFINIC ALCOXYLATES The alkenyl alcohols, both primary and secondary, and the alkenylphenols corresponding to those described above, can be ethoxylated to a HLB within the scale mentioned herein, can be used as wetting agents in the present invention.

BRANCHED CHAIN ALCOXYLATES Branched chain primary and secondary alcohols, which are available from the well known "0X0" process, can be ethoxylated and used as wetting agents in the present invention. The above ethoxylated nonionic surfactants are useful in the compositions herein alone or in combination, and the term "nonionic surfactant" encompasses mixed nonionic surfactants. The level of surfactant if used, preferably is from about 0.01% to about 2.0% by weight, based on the weight of the dry fiber of the tissue paper. The surfactants preferably have alkyl chains with 8 or more carbon atoms. Illustrative anionic surfactants are linear alkylsulfonates and alkylbenzene sulphonates. Illustrative nonionic surfactants are alkyl glycosides, including alkyl glycoside esters such as Crodesta SL-40, available from Croda, Inc. (New York, NY); alkyl glycoside ethers as described in U.S. Patent No. 4,011,389, issued to W.K. Langdon et al., March 8, 1977; and alkyl polyethoxylated esters such as Pegorperse 200 ML available from Glyco Chemicals, Inc. (Greenwich, CT) and IGEPAL RC-520 available from Rhone Poulenc Corporation (Cranbury, N.J.).

B. Resistance Additives Other types of chemicals can be added, which include strength additives to increase the dry tensile strength and the wet burst of the silk bands. The present invention may contain as an optional component from about 0.01% to about 3.0%, preferably from about 0.3% to about 1.5% by weight, on a dry weight basis of fiber, of an additive strength resin, soluble in water . (a) Dry Strength Additives Examples of the dry strength additives include carboxymethylcellulose, and cationic polymers of the ACCO chemical family such as ACCO 711 and ACCO 514, with the ACCO chemical family being preferred. These materials are commercially available from American Cyanamid Company of Wayne, New Hersey. (b) Moisture Permanent Resistance Additives Resistance wet permanent resins can be of various types. Generally, those resins that have previously found and will now find utility in the papermaking art are useful herein. Numerous examples are known from the aforementioned Westfelt document, incorporated herein by reference. In the usual case, wet strength resins are cationic materials, soluble in water. That is, the resins are soluble in water at the time they are added to the raw materials to make paper. It is quite possible, and it is still expected, that subsequent cases, such as entanglement, will render the resins insoluble in water. In addition, some resins are soluble only under specific conditions, such as over a limited variety of pH. Generally, it is believed that wet strength resins undergo interlacing or other curing reactions after they have been deposited on, in, or between the papermaking fibers. Entanglement and healing do not occur normally as long as substantial amounts of water are present. Of particular utility are the various polyamide-epichlorohydrin resins. These materials are low molecular weight polymers provided with reactive functional groups such as amino, epoxy and azetidinium groups. The patent literature is full of descriptions of procedures for making such materials. U.S. Patent No. 3,700,623, issued to Keim, October 24, 1972 and U.S. Patent No. 3,772,076, issued to Keim, November 13, 1973, are examples of such patents, and both they are incorporated here by reference. Polyamide-epichlorohydrin resins sold under the tradenames of Kymene 557H and Kymene 2064 by Hercules Incorporated of Wilmington, Delaware, are particularly useful in this invention. These resins are generally described in the aforementioned Keim patents. The activated base polyamide-epichlorohydrin resins useful in the present invention are sold under the trademark of Santo Res, such as Santo Res 31, by Monsanto Company of St. Louis, Missouri. These types of materials are generally described in the patents of the United States Nos. 3,855,158 issued to Petrovich on 17 _ .. December 1974; 3,899,388 issued to Petrovich on August 21, 1975; 4,129,528 issued to Petrovich on December 12, 1978; 4,147,586 issued to Petrocivh on April 3, 1979; and 4,222,921 issued to Van Eenam on September 16, 1980, all incorporated herein by reference. Other water-soluble cationic resins useful in the present are polyacrylamide resins, such as those sold under the trade name Parez, such as Parez 631NC, by American Cyanamid Company of Stanford, Connecticut. These materials are generally described in U.S. Patent Nos. 3,556,932 issued to Coscia 0 and others on January 19, 1971; and 3,556,933 issued to Williams et al. on January 19, 1971, all incorporated herein by reference. Other types of water soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latexes. Numerous examples of these types of resins are provided in U.S. Patent No. 3,844,880, Meisel, Jr., et al., Issued October 29, 1974, incorporated herein by reference. Still other water-soluble cationic resins which find utility in this invention are the urea-formaldehyde and melamine-formaldehyde resins. These polyfunctional, reactive polymers have molecular weights in the order of a few thousand. The most common functional groups include nitrogen containing groups such as amino groups and methylol groups attached to nitrogen. Although less preferred, polyethylene imine type resins find utility in the present invention. More complete descriptions of the aforementioned water soluble resins, including their manufacture, can be found in TAPPI Monograph Series No. 29, Wet Strength in Paper and Paperboard, Technical Association of the Pulp and Paper Industry (New York, 1965), incorporated here for reference. As used herein, the term "permanent wet strength resin" refers to a resin which allows the paper sheet, when placed in an aqueous medium, to maintain most of its initial wet strength during a period greater than at least two minutes. (c) Moist Temporary Resistance Additives The above-mentioned wet strength additives typically result in paper products with temporary wet strength, ie, the paper when placed in an aqueous medium retains a substantial portion of its initial strength. wet during a period. However, permanent wet strength in some types of paper products can be an unnecessary and unwanted property. Paper products such as head scarves, etc., are generally discarded after short periods of use in septic systems and the like. The clogging of these systems can result if the paper product permanently retains its resistance properties, resistant to hydrolysis. More recently, manufacturers have added temporary wet strength additives to paper products for which the wet strength is sufficient for the intended use, but which is reduced by submerging in water. The reduction of the wet strength facilitates the flow of the paper product through septic systems. Examples of suitable temporary wet strength resins include modified starch wet strength agents, such as National Starch 78-0080, sold by National Starch and Chemical Corporation (New York, New York). This type of wet strength agent can be made by reacting dimethoxyethyl-N-methyl-chloroacetamide with cationic starch polymers. Wet modified starch temporary strength agents are also described in U.S. Pat. No. 4, 675,394, Solarek et al., Issued June 23, 1987, and incorporated herein by reference. Preferred resins of temporary wet strength include those described in U.S. Patent No. 4,981,557, Bjorkquist, issued lo. January 1991, and incorporated herein by reference. With respect to the classes and specific examples of wet strength resins both permanent and For the purposes of the foregoing, it should be understood that the above mentioned resins are illustrative in nature and are not intended to limit the scope of this invention. In the practice of this invention, mixtures of compatible resins of wet strength can also be used. The above lists of optional chemical additives are intended to be merely illustrative in nature, and are not intended to limit the scope of the invention.

EXAMPLE 1 The purpose of this example is to illustrate a method that can be used to be an aqueous dispersion of the quaternary ammonium ester compound based on biodegradable vegetable oil, (for example dioleyl dimethyl ammonium diester chloride (DEDODMAC) or diester chloride of dierucyl dimethylammonium (DEDEDEDMAC)). A 2% dispersion of DEDODMAC was prepared according to the following procedure: 1. A known charge of DEDODMAC was measured; 2. The DEDODMAC was heated to approximately 50 ° C. 3. The dilution water was preconditioned at a pH of about 3 to about 50 ° C; 4. Adequate mixing was provided to form an aqueous submicron dispersion of the DEDODMAC softening composition; 5. The particle size of the vesicle dispersion was determined using an optical microscope technique. The particle size scale is about 0.1 to 1.0 microns. A 2% dispersion of DEDEDMAC was prepared according to the following procedure: 1. A known charge of DEDEDMAC was measured; 2. The DEDEDMAC was heated to approximately 50 ° C. 3. The dilution water was preconditioned at a pH of about 3 to about 50 ° C; 4. Adequate mixing was provided to form an aqueous submicron dispersion of the DEDEDMAC softening composition; 5. The particle size of the vesicle dispersion was determined using an optical microscope technique. The particle size scale is about 0.1 to 1.0 microns.

EXAMPLE 2 The purpose of this example is to illustrate a method using a technique for making paper by blow-drying to make absorbent and soft paper towel sheets, treated with a chemical softening composition of quaternary diester softeners based on vegetable oil. (DEDODMAC) and a permanent wet strength resin. In the practice of the present invention, a machine for making pilot scale Fourdrinier paper was used. First, a 1% solution of the biodegradable chemical softener was prepared according to the procedure of Example 1. Secondly, an aqueous slurry of 3% by weight of NSK was made in a conventional repulper. The NSK slurry was moderately refined and a 2% solution of a permanent wet strength resin (ie, Kymene 557H sold by Hercules Incorporated of Wilmington, DE) was added to the NSK supply pipe at a rate of 1 % by weight of the dry fibers. The adsorption of Kymene 557H to NSK was improved by an in-line mixer. A 1% solution of carboxymethylcellulose (CMC) was then added to the in-line mixer at a rate of 0.2% by weight of the dry fibers to improve the dry strength of the fibrous substrate. The Adsorption of CMC to NSK can be improved by an in-line mixer. Next, a 1% solution of the chemical softener (DEDODMAC) was added to the NSK sludge at a rate of 0.1% by weight of the dry fibers. The adsorption of the chemical softening mixture to NSK can also be improved by an in-line mixer. The NSK sludge was diluted to 0.2% through the ventilation pump. Third, a 3% by weight CTMP aqueous slurry was made in a conventional repulper. A nonionic surfactant (Pegosperse) was added to the repulper at a rate of 0.2% by weight of dry fibers. A 1% solution of the chemical softening mixture was added to the CTMP supply line before the pump was supplied at a rate of 0.1% by weight of the dry fibers. The adsorption of the chemical softening mixture to CTMP can be improved by an in-line mixer. The CTMP sludge was diluted to 0.2% by the ventilation pump. The mixture of raw materials treated (NSK / CTMP) was combined in the head box and deposited on a Fourdrinier wire to form an embryonic band. The drain was presented through the Fourdrinier wire and was helped by a baffle and vacuum boxes. The Fourdrinier wire is of a satin drawing configuration of 5 shed, having 84 monofilaments in the machine direction and 76 monofilaments in the machine transverse direction by 2.54 cm, respectively. The embryonic wet band was transferred from the Fourdrinier wire, at a fiber consistency of about 22% at the transfer point, to a photopolymer fabric having 240 Idaho linear cells per 6.45 cm2, 34% knotted areas and 355.6 microns deep. photopolymer An additional drainage was achieved by vacuum assisted drainage, until the band has a fiber consistency of approximately 28%. The patterned web was pre-dried by blowing air to a fiber consistency of approximately 65% by weight. Thereafter, the web was adhered to the surface of a Yankee dryer with a sprayed, curled adhesive comprising 0.25% of an aqueous solution of polyvinyl alcohol (PVA). The consistency of the fiber was increased to an estimated 96%, before curling the band dry with a blade. The blade has a bevel angle of approximately 25 ° and is positioned with respect to the Yankee dryer to provide an impact angle of approximately 81 °. The Yankee dryer is operated at approximately 244 meters per minute. The dry band was formed on a roller at a speed of 214 meters per minute. Two web folds were formed into paper towel products by taping and laminating them together using a PVA adhesive. The paper towel had a basis weight of approximately 26 # / 3M .0929 m2, containing approximately 0.2% of the chemical softener (DEDODMAC) and approximately 1.0% of the permanent wet strength resin. The resulting paper towel is soft, absorbent, and very strong when moistened.

EXAMPLE 3 The purpose of this example is to illustrate a method using a blow-drying paper technique to make absorbent and soft paper towel sheets, treated with a biodegradable softening chemical composition of oil-based quaternary diester softeners. plant (DEDEDMAC) and a temporary wet strength resin. In the practice of the present invention, a machine for making pilot scale Fourdrinier paper was used. First, a 1% solution of the biodegradable chemical softener was prepared according to the procedure of Example 1. Secondly, an aqueous slurry of 3% by weight of NSK was made in a conventional repulper. The NSK slurry was moderately refined and a 2% solution of a permanent wet strength resin (ie, National Starch 78-0080 sold by National Starch Chemical Corporation of New York, NY) was added to the supply pipeline. NSK at a rate of 0.75% by weight of the dry fibers. The adsorption of the temporary wet strength resin on NSK fibers was improved by an in-line mixer. The NSK slurry was diluted to a consistency of approximately 0.2% in the ventilation pump. Third, a 3% by weight slurry of Eucalyptus fibers was made in a conventional repulper. A 1% solution of the chemical softening mixture was added to the Eucalyptus supply line before the pump was supplied at a rate of 0.2% by weight of the dry fibers. Adsorption of the chemical softening mixture for Eucalyptus fibers can be improved by an in-line mixer. The Eucalyptus sludge was diluted to a consistency of approximately 0.2% in the ventilation pump. The mixture of treated raw materials (30% NSK / 70% Eucalyptus) was combined in the headbox and deposited on a Fourdrinier wire to form an embryonic band. The drain was presented through the Fourdrinier wire and was helped by a baffle and vacuum boxes. The Fourdrinier wire is of a satin drawing configuration of 5 puffs, which has 84 monofilaments in the machine direction and 76 monofilaments in the machine's transverse direction by 2.54 cm, respectively. The embryonic wet band was transferred from the photopolymer wire, to a fiber consistency of about 15% at the transfer point, to a photopolymer fabric having 562 Idaho linear cells by 6.45 cm2, 40% knotted areas and 228.6 microns deep of photopolymer. An additional drainage was achieved by vacuum assisted drainage, until the band has a fiber consistency of approximately 28%. The patterned web was pre-dried by blowing air to a fiber consistency of approximately 65% by weight. Thereafter, the web was adhered to the surface of a Yankee dryer with a sprayed, curled adhesive comprising 0.25% of an aqueous solution of polyvinyl alcohol (PVA). The consistency of the fiber was increased to an estimated 96%, before curling the band dry with a blade. The blade has a bevel angle of approximately 25 ° and is positioned with respect to the Yankee dryer to provide an impact angle of approximately 81 °. The Yankee dryer is operated at approximately 244 meters per minute. The dry band was formed on a roller at a speed of 214 meters per minute. The band became a single-fold tissue paper product. The tissue paper has a weight of approximately 18 # / 3M of .0929 m2, contains approximately 0.1% of the biodegradable chemical resurfacer (DEDEDMAC) and approximately 0.2% of the temporary wet strength resin. Importantly, the resulting tissue paper is soft, absorbent and is suitable for use as facial and / or toilet tissue.

EXAMPLE 4 The purpose of this Example is to illustrate a method using techniques for making paper in layers and drying through blowing to make soft and absorbent toilet roll paper, treated with a quaternary diester softener based on vegetable oil, biodegradable, ( DEDEDMAC) and an additive dry strength resin.

In the practice of the present invention, a machine for making pilot scale Fourdrinier paper was used. First, a 1% solution of the biodegradable chemical softener was prepared according to the procedure of Example 1. Secondly, an aqueous slurry of 3% by weight of NSK was made in a conventional repulper. The NSK slurry was moderately refined and a 2% solution of a dry strength resin (i.e., Acco 711 sold by American Cyanamid Company of Fairfield, OH) was added to the NSK supply pipe at a rate of 0.2. % by weight of the dry fibers. The adsorption of the dry strength resin on NSK fibers was improved by an in-line mixer. The NSK slurry was diluted to a consistency of approximately 0.2% in the ventilation pump. Third, a 3% by weight slurry of Eucalyptus fibers was made in a conventional repulper. A 1% solution of the chemical softening mixture was added to the Eucalyptus supply line before the pump was supplied at a rate of 0.2% by weight of the dry fibers. The adsorption of the biodegradable chemical softening mixture for Eucalyptus fibers can be improved by an in-line mixer. The Eucalyptus sludge was diluted to a consistency of approximately 0.2% in the ventilation pump. The mixture of treated raw materials (30% NSK / 70% Eucalyptus) was combined in the headbox and deposited on a Fourdrinier wire to form an embryonic band. The drain was presented through the Fourdrinier wire and was helped by a baffle and vacuum boxes. The Fourdrinier wire is of a satin drawing configuration of 5 shed, having 84 monofilaments in the machine direction and 76 monofilaments in the machine transverse direction by 2.54 cm, respectively. The embryonic wet band was transferred from the photopolymer wire, to a fiber consistency of about 15% at the transfer point, to a photopolymer fabric having 562 Idaho linear cells by 6.45 cm2, 40% knotted areas and 228.6 microns deep of photopolymer. An additional drainage was achieved by vacuum assisted drainage, until the band has a fiber consistency of approximately 28%. The patterned web was pre-dried by blowing air to a fiber consistency of approximately 65% by weight. Thereafter, the web was adhered to the surface of a Yankee dryer with a sprayed, curled adhesive comprising 0.25% of an aqueous solution of polyvinyl alcohol (PVA). The consistency of the fiber was increased to an estimated 96%, before curling the band dry with a blade. The blade has a bevel angle of approximately 25 ° and is positioned with respect to the Yankee dryer to provide an impact angle of approximately 81 °. The Yankee dryer is operated at approximately 244 meters per minute. The dry band was formed on a roller at a speed of 214 meters per minute. Two folds of the web were formed into tissue paper products by laminating them together using a fold joining technique. The tissue paper had a basis weight of approximately 23 # / 3M .0929 m2, containing approximately 0.1% of the biodegradable chemical softener (DEDEDMAC) and approximately 0.1% of the dry strength resin. Importantly, the resulting tissue paper is soft, absorbent and is suitable for use as facial and / or toilet tissue.

EXAMPLE 5 The purpose of this example is to illustrate a method for using a conventional papermaking, drying technique, to make soft, absorbent tissue paper, treated with a biodegradable vegetable oil based quaternary diester softener (DEDEDMAC) and an additive dry strength resin. In the practice of the present invention, a machine for making pilot scale Fourdrinier paper was used. First, a 1% solution of the biodegradable chemical softener was prepared according to the procedure of Example 3. Secondly, an aqueous slurry of 3% by weight of NSK was made in a conventional repulper. The NSK sludge was moderately refined and a 2% solution of a dry strength resin (i.e., Acco 514, Acco 711 sold by American Cyanamid Company of Wayne, New Jersey) was added to the NSK supply pipe to a regimen of 0.2% by weight of the dry fibers. The adsorption of the dry strength resin on NSK fibers was improved by an in-line mixer. The NSK slurry was diluted to a consistency of approximately 0.2% in the ventilation pump. Third, a 3% by weight slurry of Eucalyptus fibers was made in a conventional repulper. A 1% solution of the chemical softening mixture was added to the Eucalyptus supply line before the pump was supplied at a rate of 0.2% by weight of the dry fibers. The adsorption of the chemical softening mixture for Eucalyptus fibers can be improved by an in-line mixer. The Eucalyptus sludge was diluted to a consistency of approximately 0.2% in the ventilation pump. The mixture of treated raw materials (30% NSK / 70% Eucalyptus) was combined in the headbox and deposited on a Fourdrinier wire to form an embryonic band. The drain was presented through the Fourdrinier wire and was helped by a baffle and vacuum boxes. The Fourdrinier wire is of a satin drawing configuration of 5 shed, having 84 monofilaments in the machine direction and 76 monofilaments in the machine transverse direction by 2.54 cm, respectively. The embryonic wet band was transferred from the Fourdrinier wire, at a fiber consistency of about 15% at the transfer point, to a conventional felt. An additional drainage was achieved by vacuum assisted drainage, until the band has a fiber consistency of approximately 35%. Then, the band adhered to the surface of a Yankee dryer. The consistency of the fiber was increased to an estimated 96%, before curling the band dry with a blade. The blade has a bevel angle of about 25 ° and is positioned with respect to the Yankee dryer to provide an impact angle of about 81 °; The Yankee dryer is operated at approximately 244 meters per minute. The dry band was formed on a roller at a speed of 214 meters per minute. Two folds of the web were formed into tissue paper products by laminating them together using a fold joining technique. The tissue paper had a basis weight of approximately 23 # / 3M .0929 m2, containing approximately 0.1% of the biodegradable chemical softener (DEDEDMAC) and approximately 0.1% of the dry strength resin. Importantly, the resulting tissue paper is soft, absorbent and is suitable for use as facial and / or toilet tissue.

Claims (10)

1. - A soft paper product, characterized in that it comprises: a) fibers that make cellulose paper; and b) from about 0.005% to about 5.0% by weight of said fibers to make cellulose paper of a softening compound with quaternary ammonium ester functionality, biodegradable, having the formula: (R), m - N + - [(CH., - Y - R2) m X " wherein, each Y is -0- (0) C-, or -C (0) -0-; m = 1 to 3; preferably, m = 2; each n = 1 to 4; preferably, n = 2; each R is a C1-C6 alkyl group, a hydroxyalkyl group, a hydrocarbyl group, a substituted hydrocarbyl group, a benzyl group or mixtures thereof; preferably each R is an alkyl group of C., - C3, more preferably each R is a methyl group; each R2 is a C-C23 hydrocarbyl or a substituted hydrocarbyl substituent and the counterion, X ", is any anion compatible with the softener, wherein the R2 part of the softening compound is derived from C12-C24 fatty acyl groups, preferably the most of R2 is derived from fatty acyl groups containing at least 90% of a chain length of C18-C24, most preferably fatty acyl groups containing at least 90% of C18 or C22, said fatty acyl groups having a value Iodine from more than 5 to less than 100, preferably from 10 to 85.

2. The paper product according to claim 1, further characterized in that most of the fatty acyl groups are derived from oil sources Vegetable

3. The paper product according to claim 1 or 2, further characterized in that the fatty acyl groups have a weight ratio of cis / trans isomer greater than about 50/50. l according to any of claims 1 to 3, further characterized in that it comprises from about 0.005% to about 3.0% of a wetting agent. 5. The paper product according to claim 4, further characterized in that said wetting agent is a water-soluble polyhydroxy compound, linear alkoxylated alcohols, linear alkylphenoxylated alcohols, and mixtures thereof. 6. - The paper product according to any of claims 1 to 5, further characterized in that the level of polyunsaturated fatty acyl groups is less than about 30%, preferably less than 10%. 7. The paper product according to any of claims 1 to 6, further characterized in that X "is selected from the group consisting of chloride, acetate, methyl sulfate, and mixtures thereof. paper according to claims 2 to 7, further characterized in that most of said fatty acyl groups based on vegetable oil are derived from vegetable oil sources selected from olive oil, rapeseed oil, oleic oil from safflower; meadowfoam oil, and mixtures thereof 9. - The paper product according to any of claims 1 to 8, further characterized in that said paper product is a paper towel 10. - The paper product of according to claims 8, further characterized in that said paper product is a facial tissue or a tissue for a toilet.