KR100310142B1 - Paper products and biodegradable chemical softener compositions containing biodegradable chemical softener compositions - Google Patents

Abstract

The present invention relates to fibrous cellulose materials useful for the production of soft, absorbent paper products such as paper towels, high-quality tissues, and toilet tissues. The paper product contains a biodegradable chemical softener composition comprising a mixture of a biodegradable quaternized ester-amine compound and a polyhydroxy compound. Preferred biodegradable quaternized ester-amine compounds are diester dialkyldimethylammoniums such as diester ditallow dimethyl ammonium chloride, di (slightly hydrogenated) tallow dimethyl ammonium chloride and di (hydrogenated) tallow dimethyl ammonium chloride Salts. Preferred polyhydroxy compounds are those selected from glycerol and polyethylene glycols and polypropylene glycols having a weight average molecular weight of about 200 to about 4000. The biodegradable chemical emollient composition first mixes the biodegradable quaternized ester-amine compound with the polyhydroxy compound in a specific temperature range where the polyhydroxy compound is miscible with the biodegradable quaternized ester-amine compound, The mixture is prepared by diluting the mixture with water in the pH range to form an aqueous vesicle dispersion suitable for treating fibrous cellulose materials.

Description

[Name of invention]

Paper products and biodegradable chemical softener compositions containing biodegradable chemical softener compositions

Detailed description of the invention

[Field of Invention]

The present invention relates to a tissue paper web. More specifically, the present invention relates to soft absorbent tissue paper webs that can be used in towel, napkin, facial tissue and toilet tissue products.

[Background of invention]

Paper webs or sheets, sometimes called tissue or paper tissue webs or sheets, are widely used in modern society. Items such as paper towels, napkins, fine tissues and toilet tissues are commercially important items. Two important physical properties of these products are their softness; Their absorbency, in particular their absorption into an aqueous system; And their strength, especially when wet. Research and development efforts have been made not only to improve the properties of each of them without severely affecting other properties but also to improve two or three properties at the same time.

Softness is the feeling the consumer feels when he grabs a particular product, rubs it on his skin or crumbles it in his hand. This touch is a mixture of several physical properties. One of the more important properties associated with bloat is generally recognized by those skilled in the art as the stiffness of the paper web constituting the product. Stiffness is again generally recognized as directly dependent on the dry tensile strength of the web and the stiffness of the fibers making up the web.

Strength is the ability of a product and its component web to maintain physical bonds and resist tearing, rupture and fragmentation under conditions of use, especially when wet.

Absorbency is a measure of the ability of a product and its component web to absorb large amounts of liquid, especially aqueous solutions or dispersions. It is generally recognized that a consumer's perceived overall absorption capacity combines the rate of absorption of liquid as well as the total amount of liquid absorbed by a given amount of tissue paper in saturation.

It is well known to use wet strength resins to enhance the strength of paper webs. For example, Westfelt describes many of these materials in Cellulose Chemistry and Technology, Volume 13, p 813-825 (1979) and discusses their chemical properties. Freimark et al., In US Pat. No. 3,755,220, issued August 28, 1973, mention that certain chemical additives known as separation agents interfere with the natural fiber-to-fiber bonds that occur during sheet formation in the papermaking process. This reduction in bond yields softer or less coarse paper sheets. Freimark et al. Continue to teach that we use wet strength resins to improve the wet strength of the sheet and use separators to counteract the undesirable effects of the wet strength resins. Such separators reduce dry tensile strength but also generally reduce wet tensile strength.

Shaw teaches in US Pat. No. 3,821,068, issued June 28, 1974, that chemical separation agents can be used to reduce stiffness and improve softness of tissue paper webs.

Chemical separators are described in various documents such as US Patent No. 3,554,862, issued to Hervey et al. On January 12, 1971. Such materials include quaternary ammonium salts such as trimethyl cocoammonium chloride, trimethyl oleylammonium chloride, di (hydrogenated) tallow dimethylammonium chloride and trimethylstearyl ammonium chloride.

Emanuelsson et al., US Pat. No. 4,144,122, issued March 13, 1979, disclose complex quaternary ammonium compounds such as bis (alkoxy (2-hydroxy) propylene) quaternary ammonium chloride for softening the web. Teaches use. Emanuelson et al also attempted to address the reduction in absorption capacity caused by the separating agent through the use of nonionic surfactants such as ethylene oxide and propylene oxide additives of fatty alcohols.

Armark Company of Chicago, Illinois (76-1977) used dimethyl di (hydrogenated) tallow ammonium chloride with fatty acid esters of polyoxyethylene glycol to soften and absorb It also states that it may provide.

One example of a study seeking to improve the paper web is described in US Pat. No. 3,301,746, issued January 31, 1967 to Sanford and Sisson. Despite the high quality of paper webs produced by the methods described in this patent and the commercial success of such web-made products, research efforts to improve the products continue.

For example, Becker et al., In US Pat. No. 4,158,594, issued Jan. 19, 1979, describe their intended method for producing strong, soft fibrous sheets. More specifically, the strength of the tissue web (which may be softened by the addition of a chemical separating agent) is a bonding material (e.g. acrylic latex) that adheres to one surface and the creping surface of the web in a fine pattern arrangement during the process. Rubber emulsions, water soluble resins or elastomeric binder materials) to one surface of the web to a crepe surface in a fine patterned arrangement, and the web can be enhanced by creping from the creping surface to form a sheet material. Teach

Conventional quaternary ammonium compounds, such as known dialkyl dimethyl ammonium salts (e.g., ditallow dimethyl ammonium chloride, ditallow dimethyl ammonium methyl sulfate, di (hydrogenated) tallow dimethyl ammonium chloride, etc.) are effective It is a chemical separator. Unfortunately the quaternary ammonium compound is not biodegradable. Applicants have found that the biodegradable mono- and di-ester variants of the quaternary ammonium salts also act effectively as chemical separators and enhance the softness of the fibrous cellulose material.

It is an object of the present invention to provide a soft absorbent toilet tissue product.

It is an object of the present invention to provide a soft absorbent high quality tissue paper product.

It is an object of the present invention to provide a soft absorbent towel paper product.

It is another object of the present invention to provide a method for producing soft absorbent tissue paper and towel paper products.

These and other objects are achieved using the present invention as is apparent from the following description.

[Overview of invention]

The present invention provides a soft absorbent paper product. In summary, the paper product comprises about 0.005 to about 5 weight percent of a biodegradable chemical softener composition comprising a sheet of cellulose material and a mixture of (a) and (b), based on the weight of the fibrous cellulose material. .: a polyhydroxy compound selected from the group consisting of (a) a quaternary ester-amine compound having the general formula and (b) glycerol, and polyethylene glycol and polypropylene glycol having a weight average molecular weight of about 200 to 4000 ( At this time, the weight ratio of the quaternary ester-amine compound to the polyhydroxy compound is about 1: 0.1 to 0.1: 1, and the polyhydroxy compound is miscible with the quaternary ester-amine compound at a temperature of 50 ° C. or more).

Wherein each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, or a mixture thereof;

Each substituent is a C ₁₄ -C ₂₂ hydrocarbyl group, or a mixture thereof;

Each R 3 substituent is a C ₁₂ -C ₂₀ hydrocarbyl group, or a mixture thereof;

X- is a compatible anion.

Preferably the mixture of quaternary ester-amine and polyhydroxy compound is diluted with a liquid carrier to a concentration of from about 0.01 to about 25.0% by weight based on the weight of the chemical softener composition prior to addition to the fibrous cellulose material. Preferably, the liquid carrier has a temperature of about 40 to about 80 ° C. and a ph of less than about 4. Preferably, at least 20% of the polyhydroxy compound and quaternary ester-amine compound added to the fibrous cellulose are retained.

Examples of preferred quaternary ester-amine compounds that are suitable for use in the present invention include compounds having the following general formula;

And

The compounds are mono and diester variants of known dialkyldimethylammonium salts, for example diester dielow dimethyl ammonium chloride, monoester dielow dimethyl ammonium chloride, diester di (hydrogenated) tallow dimethyl ammonium methylsulfate, di Ester di (hydrogenated) tallow dimethyl ammonium chloride, di (hydrogenated) tallow dimethyl ammonium chloride and preferred is di (nonhydrogenated) tallow dimethyl ammonium chloride, di (slightly hydrogenated) tallow dimethyl Ammonium chloride and di (hydrogenated) tallow dimethyl ammonium chloride. Depending on the required characteristics of the product, the saturation of the detalow may be slightly, partially or fully hydrogenated (cured) from non-hydrogenated (softened).

Without wishing to be bound by theory, it is believed that the ester moiety (s) provide biodegradability to the compound. Importantly, the quaternary ester-amine compounds used herein biodegrade faster than conventional dialkyl dimethylammonium chemical emollients.

Examples of polyhydroxy compounds useful in the present invention include glycerol and polyethylene glycols having a weight average molecular weight of about 200 to about 4000 and preferred are polyethylene glycols having a weight average molecular weight of about 200 to about 600.

Particularly preferred tissue paper embodiments of the present invention comprise from about 0.03 to about 0.5 weight percent of a mixture of a quaternary ester-amine compound and a polyidoxy compound.

In summary, the method of making a tissue web of the present invention prepares a paper feed from the above-mentioned components, attaches the paper feed on a porous surface, such as a Fourdrinier wire, and attaches the attached feed. Removing water from the water.

All percentages, ratios, and amounts herein are by weight unless otherwise indicated.

[Brief Description of Drawings]

While this specification includes the specifically claimed claims and expressly claims the invention, the invention will be better understood from the following description in conjunction with the accompanying drawings:

1 is a phase diagram of DODMAMS and DHTDMAMS.

2 is a phase diagram of the DODMAMS PEG-400 system.

3 is a phase diagram of a PEG-400 / methyl octanoate system.

4 is a phase diagram of the DEDTDMAC and PEG-400 systems.

5 is a phase diagram of the DEDHTDMAC and PEG-400 systems.

FIG. 6 is a low-temperature transmission micrograph of magnified vesicle dispersion having a weight ratio of diester dielow dimethyl ammonium chloride and PEG-400 system at a magnification of 63,000.

FIG. 7 is a low-temperature transmission micrograph showing an enlarged vesicle dispersion having a weight ratio of diester dielow dimethyl ammonium chloride and glycerol system 1: 1 at a magnification of 63,000.

FIG. 8 is a cold transmission micrograph at magnification of 66,000 magnification of a vesicle dispersion having a weight ratio of diester di (hydrogenated) tallow dimethyl ammonium chloride to PEG-400 system in a 1: 1 ratio.

The invention is described in more detail below.

Detailed description of the invention

While this specification expressly claims the subject matter which is considered to be the invention, including the specifically pointed out claims, the invention can be better understood from the following detailed description and the accompanying drawings.

As used herein, the term tissue paper web, paper web, web, paper sheet and paper product all include the steps of preparing a modified paper feed, adhering the paper feed on a porous surface, such as a forward linear wire, And removing the water from the feed by gravity or vacuum-assisted dehydration and evaporation with or without compaction.

As used herein, an aqueous paper feed is an aqueous slurry of papermaking fibers and the chemicals mentioned hereinafter.

The first step in the process of the present invention is to prepare an aqueous paper feed. The feed includes papermaking fibers (hereinafter sometimes referred to as wood pulp), and mixtures of one or more quaternary ester-amine compounds and one or more polyhydroxy compounds (all mentioned later).

Wood pulp is expected to generally include the papermaking fiber used in the present invention as a variant thereof. However, other cellulose fibrous pulp may be used, such as cotton liners, bagasse, rayon, and the like, none of which are rejected. Wood pulp useful herein includes chemical pulp, such as kraft, sulfite and sulfate pulp, as well as mechanical pulp including, for example, pulverized wood, thermomechanical pulp and chemically modified thermomechanical pulp (CTMP). do. Pulps derived from both hardwoods and conifers can be used. Pulps that may also be applied to the present invention are fibers derived from recycled paper, which may contain some or all of the above classes as well as other non-fibrous materials, for example fillers and adhesives used to facilitate the original papermaking process. . Preferably, the papermaking fibers used herein comprise kraft pulp derived from northern softwood.

[Biodegradable Chemical Softener Composition]

The present invention contains as an essential component a mixture of a quaternary ester-amine compound and a polyhydroxy compound of about 0.005 to about 5% by weight, more preferably about 0.03 to about 0.5% by weight of the dry fiber. The ratio of quaternary ester-amine compound to polyhydroxy compound is about 1: 0.1 to 0.1: 1, preferably about 1: 0.3 to 0.3: 1, more preferably about 1: 0.7 to 0.7: 1, The ratio will depend on the molecular weight of the particular polyhydroxy compound and / or quaternary ester-amine compound used. Examples of compounds of this type will be mentioned in detail below.

[A. Quaternary ester-amine compounds]

The chemical emollient composition contains, as essential components, quaternary ester-amine compounds having the general formula:

or

In the abovementioned general formula, each R ₁ is a C ₁₄ -C ₂₂ hydrocarbyl group, preferably tallow C ₁₆ -C ₁₈ alkyl, and R 2 is a C ₁ -C ₆ alkyl or hydroxyalkyl group, preferably C _1- C ₃ alkyl, X- is a compatible anion, for example a halide (e.g. crolide or bromide) or methyl sulfate. As mentioned in Swern, Bailey's Industrial Oil and Fat Products, Third Edition, John Wiley and Sons (New York 1964), tallow is a natural material with a variety of compositions. In the aforementioned references published by Swarn, Table 6.13 typically indicates that at least 78% of tallow fatty acids contain 16 or 18 carbon atoms. Typically, half of the fatty acids present in the tallow are unsaturated mainly in the form of oleic acid.

Synthetic and natural "tallows" fall within the scope of the present invention. It is also known that depending on the required characteristics of the product, the saturation of the detalow can be slightly, partially or fully hydrogenated (cured) from non-hydrogenated (softened).

Substituents R ₁ , R ₂ and R ₃ may optionally be substituted with various groups such as alkoxyl, hydroxyl, or branched, although such materials are not contemplated herein. Preferably, each R ₁ is C ₁₆ -C ₁₈ alkyl, most preferably each R 1 is straight chain C ₁₈ alkyl. Preferably each R ₂ is methyl. R ₃ is C ₁₄ -C ₁₆ alkyl, most preferably R ₃ is straight chain C ₁₆ alkyl, and X- is chloride or methyl sulfate.

Specific examples of quaternary ester-amine compounds with the groups mentioned above and suitable for use herein are known diester dialkyl dimethyl ammonium salts, for example diester ditallow dimethyl ammonium chloride, monoester dallow dimethyl ammonium Chloride, diester dielow dimethyl ammonium methyl sulfate, diester di (hydrogenated) tallow dimethyl ammonium methyl sulfate, diester di (hydrogenated) tallow dimethyl ammonium chloride. Especially preferred are diester ditallowdimethyl ammonium chloride and diester di (hydrogenated) tallow dimethyl ammonium chloride. This particular material is manufactured under the tradename "ADOGEN DDMC" from Serex Chemical Company Inc., Dublin, Ohio. Available for purchase.

Di-quaternized variants of quaternary ester-amine compounds may also be used, meaning that they are within the scope of the present invention. Such compounds have the following general formula.

Wherein each R ₂ is a C ₁ -C ₆ alkyl or hydrocarbyl group, R ₃ is a C ₁₂ -C ₂₀ hydrocarbyl group and X- is a compatible anion such as a halide (e.g. chloride or bromide ) Or methyl sulfate. Preferably, each R ₃ is C ₁₄ -C ₁₆ alkyl, most preferably each R ₃ is straight C ₁₆ alkyl and R ₂ is methyl.

[B. Polyhydroxy compound]

The chemical emollient composition contains a polyhydroxy compound as an essential component.

Examples of polyhydroxy compounds useful in the present invention include glycerol and polyethylene glycols and polypropylene glycols having a weight average molecular weight of about 200 to about 4000, preferably about 200 to about 1000, most preferably about 200 to about 600. It includes. Particular preference is given to polyethylene glycols having a weight average molecular weight of about 200 to about 600.

Particularly preferred polyhydroxy compounds are polyethylene glycols having a weight average molecular weight of about 400. This compound is commercially available from Union Carbide Company, Danbury, Connecticut, under the trade name "PEG-400".

Aqueous softener composition as described above, i.e., a mixture of quaternary ester-amine compound and polyhydroxy compound, at the wet end of the papermaking machine at any suitable point in front of the forward linear wire or at the sheet forming stage Preference is given to adding to the slurry or feed. However, applying the chemical softener composition described above after the wet tissue web has been formed and before the web is completely dried will also provide significant softness, absorbency and wet strength benefits, which are clearly within the scope of the present invention.

It has been found that chemical emollient compositions are more effective when the quaternary ester-amine compound and the polyhydroxy compound are premixed together prior to addition to the paper feed. Preferred methods, such as those described in more detail in Example 1 below, heat the polyhydroxy compound to a temperature of about 66 ° C. (150F) and then add the quaternary ester-amine compound to the hot polyhydroxy compound to provide fluidity. Melt ". The weight ratio of quaternary ester-amine compound to polyhydroxy compound is about 1: 0,1 to 0.1: 1, preferably about 1: 0.3 to 0.3: 1, more preferably about 1: 0.7 to 0.7: 1 This ratio will depend on the molecular weight of the particular polyhydroxy compound and / or quaternary ester-amine compound used. The quaternary ester-amine compound and polyhydroxy compound melt are then diluted to the desired concentration and an aqueous solution containing the vesicle dispersion of the mixed quaternary ester-amine compound / polyhydroxy compound mixture is formed, which is then fed to papermaking. Add to water Preferably, the mixture of quaternary ester-amine compound and polyidoxy compound is diluted with a liquid carrier such as water prior to addition to the papermaking feed such that the concentration of the softener composition is from about 0.01% to about 25% by weight. It is preferable that ph of a liquid carrier is 2-4. The temperature of the liquid carrier is preferably about 40 to about 80 ° C. The mixture of quaternary ester-amine compound and polyhydroxy compound is present as particles dispersed in the liquid carrier. The average particle diameter is preferably in the range of about 0.01 to 1.0 micron, most preferably about 0.1 to about 10 micron. As shown in Figures 6-8, the dispersed particles are in the form of vesicle particles.

The quaternary ester-amine compound and the polyhydroxy compound are mixed at an elevated temperature of at least 50 ° C, more preferably from about 50 ° C to about 100 ° C.

Without wishing to be bound by theory, the diester detallow dimethyl ammonium chloride (DEDTDMAC) and the diester di (hydrogenated) tallow dimethyl ammonium chloride (DEDHTDMAC) are liquid and are miscible with polyhydroxy compounds. The physical state of di (hydrogenated) tallow dimethyl ammonium methyl sulfate (DHTDMAMS) will be described in more detail below.

Paper feed can be readily formed or produced by mixing techniques and apparatus known to those skilled in the art of papermaking.

It was unexpectedly found that when the polyhydroxy compound was premixed with a quaternary ester-amine compound prior to addition to the paper, the adsorption of the polyhydroxy compound onto the paper was significantly increased. In fact, at least 20% of the polyhydroxy compounds and quaternary ester-amine compounds added to the fibrous cellulose are retained, and preferably the retention levels of the quaternary ester-amine compounds and polyhydroxy compounds are the weight of the dried fibers. From about 50% to about 90%.

It is important that the adsorption takes place at the actual concentration and time range used during the papermaking process. In order to better understand the surprisingly high retention of the polyhydroxy compounds onto the paper, the physical properties of the melted and aqueous dispersions of di (hydrogenated) tallow dimethyl ammonium methyl sulfate and polyethylene glycol 400 were studied.

Without being bound by theory or limiting the invention in other ways, the following discussion will explain how quaternary ammonium compounds promote the adsorption of polyhydroxy compounds onto paper.

DHTDMAMS di (hydrogenated) tallow dimethyl ammonium methyl sulfate, (C ₁₇ H ₃₅ ) ₂ N + (CH ₃ ) ₂ N ⁺ (CH ₃ ) ₂ CH ₃ OSO ₃ ⁻ ; DODMAMS (dioctadecyl dimethyl ammonium methyl sulfate) _{, (C 18 H 37) 2} N + (CH 3) 2 · CH 3 OSO 3 -; DEDTDMAC ( diester dital low-dimethyl ammonium _{chloride), (CH 3) 2 N} + (CH 2 CH 2 OCOC 16 H 33) ₂ · C1 ^- and the information on the physical state of the DEDHTDMAC (diester di (hydrogenated) tallow dimethyl ammonium chloride) is obtained by the X- ray data and NMR data on the commercial mixture. DODMAMS is the main component of DHTDMAMS and is used as a model compound of commercially available mixtures.

It is useful to consider a simpler DODMAMS system and then to consider a more complex commercial DHTDMAMS mixture.

Depending on the temperature, DODMAMS can exist in one of four phase states (FIG. 1), two homogeneous crystals (X ^β and X ^α ), lamellar liquid crystal, or liquid phase). X ^β crystals are present at temperatures between less than room temperature and 47 ° C. The X ^β crystal is transformed into a homogeneous X ^α crystal at this temperature and transformed into a lamellar liquid crystal phase at 72 ° C. In other words, the phase transforms into a 150 ° C. isotropic liquid. The Lamellar liquid crystal phase is also present in both DEDTDMAC and DEDHTDMAC compounds. DEDTDMAC is predicated to be similar in physical properties except that the phase transition temperature is lower and wider than DEDHTDMAC. For example, the transition from X ^β crystals to X ^α crystals occurs at 27 ° C. in DHTDMAMS and at 47 ° C. in DODMAMS. In addition, calorimetric data indicates that some transition from crystal to lamellar phase occurs in DHTDMAMS rather than in DOMAMS. The highest onset temperature of these transitions was 56 ° C, with X-ray data

Although consistent, the calorimetric results show two peaks, 59 ° C and 63 ° C.

DODMAC (Dioctadecyl Dimethyl Ammonium Chloride) exhibits quantitative properties different from DODMAMS, in which there is no lamellar liquid crystal phase in this compound. Such differences are believed to be insignificant to the use of the compound (or its commercially available analog DHTDMAC) in treating paper (Laughlin et al., Journal of Physical Chemistry, Physical, incorporated herein by reference). Science of the Dioctadecyldimethylammonium Chloride-Water System.1.Equillibrium Phase Behavior, 1990, volume 94, pages 2546-2552].

[Mixture of DHTDMAMS and PEG 400]

Mixtures of 1: 1 weight ratios of these two materials are studied and a good model for phase homology of the system is presented in FIG. In this diagram, DODMAMS and PEG cannot be mixed at high temperatures, indicating that they coexist as two liquid phases. As the mixture of the two liquids in the zone cools, the lamella phase separates from the mixture. As a result, the two materials that cannot be mixed at high temperatures become compatible with the lamellar liquid crystal phase at low temperatures. It is expected that at lower temperatures the crystalline phase will separate from the lamellar phase and the compounds do not mix again.

The results therefore suggest that in order to form good dispersions of DHTDMAMS and PEG-400 in water, the preliminary mixture diluted in water must be maintained at an intermediate temperature at which the two compounds can be miscible.

[Mixture of DHTDMAC and PEG-400]

Phase studies of these two materials using stepwise dilution showed that their physical properties were significantly different from those of DHTDMAMS. The liquid crystal phase is not found. These compounds are miscible over a wide temperature range, which indicates that dispersions can be prepared from these compounds at significant temperature ranges. There is no upper temperature limit for miscibility.

[Mixture of DEDTDMAC and PEG-400]

Phase studies of these two materials using stepwise dilution (FIG. 4) showed that their physical properties were similar to those of DHTDMAC. These compounds are miscible over a wide temperature range (> 50 ° C.), indicating that dispersions can be prepared from these mixtures over a fairly wide temperature range. There is no upper temperature limit for miscibility.

[Mixed mixture of DEDHTMAC and PEG-400]

Phase studies of these two materials using stepwise dilution (FIG. 5) showed that their physical properties were similar to those of DHTDMAC. They are miscible over a wide temperature range (> 67 ° C.), indicating that dispersions can be prepared from these mixtures over a fairly wide temperature range. There is no upper temperature limit for miscibility.

[Production of Dispersion]

Dispersions of any of these materials can be prepared by diluting the mixture, keeping the polyhydroxy compound and the quaternary ammonium salt at a temperature miscible with water. It is not of great importance whether they are miscible in the liquid crystal phase (as in the case of DHTDMAMS) or in the liquid phase (as in the case of DHTDMAC). Since both DHTDMAMS and DHTDMAC are water insoluble, dilution of the anhydrous phase with water will precipitate the quaternary ammonium compound as small particles. Regardless of whether the anhydrous solution is liquid or liquid crystal, all quaternary ammonium compounds will precipitate as liquid crystal phases at elevated temperatures in dilute aqueous solutions. Polyhydroxy compounds are dissolved in water at all ratios and therefore do not precipitate.

Analysis by low temperature electron microscopy revealed that the particles present had a size of about 0.1 to 1.0 microns and a wide variety of structures. Some are half-sheets with a sheet (flex or flat) structure, others are closed parcels. The membrane of these particles has a bilayer molecular structure in which the head group is exposed to water and the tail groups are gathered together. It is believed that PEG binds to these particles. Application of the dispersion prepared as described above to paper causes quaternary ammonium ions to adhere to the paper, greatly promoting the adsorption of the polyhydroxy compound onto the paper and preferably improving the softness and water retention.

[State of dispersion]

Cooling the dispersion described above may result in partial crystallization of the material in the colloidal particles. However, since it will take a long time (approximately several months) to reach equilibrium, the disordered particles in which the film is either liquid crystal or disordered crystalline phases will interact with the paper. The chemical softener compositions described herein are preferably used before reaching equilibrium.

Vesicles containing DHTDAMAMS and PEG are thought to break when drying the fibrous, cellulosic material. Once the vesicles are broken down, most PEG components penetrate into the cellulosic fibers, increasing the flexibility of the fibers. In particular, some PEG remains on the surface of the fibers to increase the absorption of cellulose fibers. Due to the ionic interaction, the cationic portion of the DHTDMAMS component stays on the surface of the cellulose fibers to increase the surface feel and softness of the paper product.

The second step of the present invention is to attach the papermaking feed using the above described chemical softener composition as an additive on the porous surface, and the third step is to remove water from the attached feed. Techniques and apparatus that can be used to accomplish these two processing steps will be readily apparent to those skilled in the art of papermaking. Preferred tissue paper embodiments of the present invention contain from about 0.005 to about 5.0 weight percent, more preferably from about 0.03 to 0.5 weight percent of the chemical emollient composition described herein, based on dry fibers.

The present invention generally relates to felt-compressed tissue paper; pattern dense tissue paper as exemplified in the United States patent document issued to Sanford-Sieson et al .; And thick, unpressurized tissue paper as exemplified in US Pat. No. 3,812,000 to Salvucci, Jr., issued May 21, 1974. The tissue paper may have a uniform or multi-layered structure, and the tissue paper produced therefrom may have a uniform or multi-layered structure, and the tissue paper product produced therefrom may be a single or multi-layered structure. Tissue structures formed from layered paper webs are described in US Pat. No. 3.994.771, issued to Morgan.jr et al. On November 30, 1976, which is incorporated herein by reference. In general, the soft and thick absorbent paper structures of wet laminated composites are made from two or more feeds which are preferably composed of different fiber types. The layers are preferably formed by adhering individual streams of thin slurries of relatively long soft wood fibers and relatively short hard wood fibers used in tissue paper onto one or more endless porous screens. The layers are then combined to form a layered composite web. Subsequently, in order to conform the web layer to the surface of the dry / imprinteng fabric of the open net, the web is subjected to a force by fluid and then pre-dried by applying heat to the fabric as part of a low density papermaking process. The layered web may be matured depending on the fiber type, or the fiber content of each layer may be essentially the same. The tissue paper preferably has a basis weight of 10 g / m 2 to about 65 g / m 2 and a density of about 0.60 g / cc or less. It is preferred that the basis weight is about 35 g / m 2 or less and the density is about 0.30 g / cc or less. Most preferably, the density is from 0.04 g / cc to about 0.20 g / cc.

Typically pressurized tissue paper and methods of making the same are known in the art. The paper is typically made by attaching a paper feed on a porous forming wire. Such shaped wires are often referred to in the art as FOOD linear wires. When the feed is attached to the forming wire, it is referred to as a web. The web is turbid by pressurizing the web and drying at elevated temperature. Certain techniques and typical devices for making webs according to the methods described above are known to those skilled in the art. In a typical process, low consistency pulp feed is provided in a pressurized headbox. The headbox has an opening for moving a thin deposit of pulp feed onto the fore linear wire to form a wet web. The web is then dewatered to have a fiber consistency of about 7% to about 25% (based on the total web weight), typically by vacuum dewatering, and the pressure exerted by the butting machine member such as a cylindrical roll It is further dried by a pressurizing process to receive a.

The dewatered web is further pressurized and dried by a stream drum apparatus known in the art as a Yankee dryer. Pressure in the Yankee dryer may be applied by mechanical means such as opposing cylindrical drums that pressurize the web. As the web is pressed by the Yankee surface, a vacuum may be applied to the web. Multiple Yankee dryer drums may be used to create additional pressurization between the drums. The tissue paper structure formed is hereinafter referred to as conventional pressurized tissue paper structure. The sheet is believed to be pressurized because the web is subjected to substantially the entire mechanical pressing force, while the fibers are wettable and then dried (or optionally creped) under pressure.

Pattern dense tissue paper is characterized by having a relatively thick field of relatively low fiber density and an array of dense bands of relatively high fiber density. The thick field is otherwise characterized as a pillow area field. The dense band is otherwise referred to as the knuckle region. The dense bands may be discontinuously spaced within the thick field, or may be completely or partially interconnected within the thick field. Preferred methods for making pattern-dense tissue webs are described in U.S. Patent No. 3.301,746, issued to Peter G. Ayers on August 10, 1967, and U.S. Patent No. 4,191,609. (Paul D. Trokhan, issued March 4, 1980), US Pat. No. 4,637,859, issued to Trocan on January 20, 1987.

In general, pattern dense webs are preferably prepared by attaching a paper feed on a porous molded wire, such as a forward linear wire, to form a wettable web, which is then elevated alongside the rows of supports. Pressing the web against a column of supports creates a dense zone in the web at a location geometrically corresponding to the point of contact between the column of columns and the wettable web. The remainder of the web that is not pressurized during the process is referred to as thick field. The thick field can further reduce densification by applying fluid pressure, for example using a vacuum device or blow-through dryer, or by mechanically pressing the web against the heat of the support. The web is dewatered and optionally pre-dried in a manner that avoids compressing substantially thick fields. This is accomplished, for example, by applying a fluid pressure using a vacuum device or a blow dryer or by mechanically pressing the web against the support column so that the thick field is not compressed. The processes of dehydration, optional predrying and dense band forming can be integrated or partially integrated to reduce the total number of processing steps performed. Following dense zone formation, dehydration and optional predrying, the web is allowed to dry completely, but still it is desirable to avoid mechanical pressurization. Preferably about 8 to about 55% of the tissue paper surface comprises dense knuckles having a relative density of at least 125% relative to the density of the thick field.

The support row is preferably a blade conveying fabric having a pattern potential of knuckles that acts as a support row, which facilitates the formation of dense zones upon pressing. The pattern of knuckles constitutes the row of supports mentioned previously. The stamped conveying fabrics are U.S. Patent No. 3,301,746, issued to Sanford and Sison on January 31, 1967, and United States Patent No. 3,821,068, issued to Salbutch et al. On May 21, 1974. U.S. Patent No. 3,974,025 to Ayers on August 10, 1976; U.S. Patent 3,573,164 to Friedberg et al. On March 30, 1971; U.S. Patent No. 3,473,567 (1969) To Amneus as of October 21) US Pat. No. 4,239,065 (to Trocan as of December 16, 1980) to US Pat. No. 4,528,239 (to Trocan to July 9, 1985). Is disclosed.

It is preferred that the feed is first molded into a wettable web on a porous forming carrier, such as a forward linear wire. The web is dewatered and transferred to a stamped fabric. Alternatively, the feed may initially be attached onto a porous support carrier which also acts as a stamp fabric. Once molded, the wettable web is dewatered and preferably pre-dried to heat to have a selected fiber consistency of about 40 to about 80%. Dewatering can be carried out using a reduced pressure box or other vacuum apparatus or blow dryer. The knuckle seal of the stamp fabric is stamped onto the web as described above before the web is completely dried. One way to perform the stamping is to apply mechanical pressure. This can be done, for example, by pressing a nip roll supporting the fabric, which is a blade opposite to a drying drum surface, such as a Yankee dryer, wherein the web is disposed between the nip roll and the drying drum. It is also desirable to mold the web to the stamped fabric by applying a fluid pressure using a vacuum apparatus such as a vacuum box or a blow dryer before the web is completely dried. During the initial dehydration. Fluid pressure may be applied to induce stamping in a compact zone in a subsequent subsequent processing step or in a combined step thereof.

Unpressurized, unpatterned, dense tissue constructs are disclosed in US Pat. No. 3,812,000, issued to May 21, 1974 to Cell N. Yiannos, and US Pat. No. 4,208,459. (Henry E. Becker, Albert L. McConnell and Richard Schutte, issued June 17, 1980). In general, unpressurized, unpatterned tissue paper structures adhere to a paper feed on a porous molded wire, such as a forward linear wire, to form a wet web and without mechanical press until the web has a fiber consistency of at least 80%. Dehydrate the saw, remove additional water and creep the web.

Water is removed from the web by vacuum dehydration and heat drying. The resulting structure is a thick sheet of relatively unpressurized fiber that is soft but weak in strength. It is desirable to apply the binder to a portion of the web before creping.

Pressed, unpatterned tissue structures are known in the art as conventional tissue structures. In general, pressurized, unpatterned tissue paper structures, such as woven linear wires, attach a paper feed on a porous wire to form a wet web and uniform mechanical compression until the web has a 25-50% consistency. It is manufactured by dewatering the web with (pressurization) to remove additional water, moving it to a heat dryer such as a Yankee dryer, and creping the web. In total, water is removed from the web by vacuum, mechanical pressurization and heating means. The resulting structure is high in strength and generally has a uniform density, but very little volume, absorbency and softness.

The tissue paper web of the present invention can be used in any case where a soft, absorbent tissue paper web is required. Particularly advantageous applications of the tissue paper webs of the present invention are paper towels, toilet tissues and high-quality tissue products.

For example, the two tissue paper webs of the present invention are embossed and glued together with cotton (as taught in US Pat. No. 3,414,459, issued to Wells on Dec. 3, 1968, incorporated herein by reference). As can be seen, two-ply paper towels can be formed.

[Molecular Weight Measurement]

[A.Overview]

An essential distinguishing property of polymeric materials is that they are molecular size

The properties that make the polymers versatile are mostly due to their macromolecular properties. In order to fully characterize these materials, it is essential that there must be some means of defining and measuring their molecular weight and molecular weight distribution. Although the term relative molecular mass is more accurate than molecular weight, molecular weight is more commonly used in the polymer art. Measuring the molecular weight distribution is not always practiced. However, the measurement of molecular weight distribution is becoming more common by using a chromatography technique. The molecular size is also expressed in terms of average molecular weight.

[B. Average Molecular Weight]

When considering a simple molecular weight distribution representing the weight fraction wi of a molecule having a relative molecular mass (Mi), several useful averages can be defined. The average calculated on the basis of the number Ni of molecules of a specific size Mi yields the number average molecular weight.

An important result of the above definition is the number average molecular weight expressed in grams (g), which contains as many molecules as Avogadro. The definition of molecular weight is consistent with the molecular weight of monodisperse molecular species, ie molecules with the same molecular weight. It is more important to know that Mn can be easily measured if the number of molecules in a given mass of the polydisperse polymer can be measured in any way. This is the basis of overall quality measurement.

Averaging based on the weight fraction wi of a molecule of a given mass Mi gives a definition of the weight average molecular weight.

Mw is a more useful means of expressing polymer molecular weight than Mn, since Mw more accurately reflects properties such as the melt viscosity and the mechanical properties of the polymer, and therefore Mw is used in the present invention.

[Analysis and test method]

As used herein, the analysis of the amount of biodegradable treatment chemical and the amount retained by the tissue paper web can be performed by any method that is acceptable in the art.

[Quantitative Analysis of A. Quaternary Ester-amines and Polyhydroxy Compounds]

For example, diester di (hydrogenated) tallowdimethyl ammonium chloride (DEDHTDMAC) retained in tissue paper (ie ADOGEN DDMC) Levels of quaternary ester-amine compounds such as) can be measured by solvent extraction of DEDHTDMAC with an organic solvent followed by anionic / cationic titration using dimdium bromide as an indicator; Levels of polyhydroxy compounds such as PEG-400 can be measured by extraction in an aqueous solvent such as water and then subjected to gas chromatography or calorimetry to determine PEG-400 levels in the extract. These methods are exemplary and do not imply that they do not include other methods that may be useful for determining the level of a particular compound held by tissue paper.

[B. Hydrophilicity (absorption capacity)]

The hydrophilicity of tissue paper generally relates to the nature of the tissue being wetted with water. The hydrophilicity of tissue paper can be measured to some extent quantitatively by measuring the time it takes for the dry tissue paper to fully wet with water. This time is referred to as "wet time". In order to provide a consistent and repeatable test for the wetting time, the following procedure can be used to determine the wetting time: First, a conditioned sample unit site (ambient conditions for testing paper samples are 23 + 1 ° C. and 50 + 2% Relative Humidity, which is as described in TAPPI Method T 402), providing a tissue tissue structure of about 4-3 / 8 inches x 4-3 / 4 inches (about 11.1 cm x 12 cm); Second, folding the sheet into four quarter portions in parallel, then rolling it into a ball shape having a diameter of about 0.75 inches (about 1.9 cm) to about 1 inch (about 2.5 cm); Thirdly, the ball-shaped sheet was placed on the surface of distilled water at 23 ± 1 ° C. and simultaneously timed; Fourth, when the ball-shaped sheet is completely wet, the timer is stopped to read the time. Complete wetting is observed with the naked eye.

The hydrophilicity of the tissue paper embodiments of the invention can of course be measured immediately after preparation. However, during the first two weeks after the manufacture of the tissue paper, ie after the paper has been aged for two weeks, the hydrophilicity may increase substantially. Therefore, the wet time is preferably measured after such a two week period. Thus, the wet time measured after two weeks at room temperature is referred to as "two week wet time".

[C. density]

As used herein, the density of tissue paper is the average density calculated by dividing the basis weight of the paper by a caliper and by appropriately converting the units involved in the process. The caliper of the tissue paper used herein is the thickness of the paper when a pressurized load of 95 g / in 2 (15.5 g / cm 2) was applied.

[Optional ingredients]

Other chemicals commonly used in the papermaking process may be added to the biodegradable chemical softener composition or paper feed described herein, as long as they have little influence on the softness, absorbency, and improvement of the chemical softener composition of the fibrous material and have no adverse effects. Can be.

For example, surfactants can be used to treat the tissue paper web of the present invention. When used, the amount of surfactant is preferably from about 0.01% to about 2.0% by weight based on the dry fiber weight of the tissue paper. Preferably, the surfactant has an alkyl chain having at least 8 carbon atoms. Exemplary anionic surfactants are linear alkyl sulfonates and alkyl benzene sulfonates. Exemplary nonionic surfactants include alkylglycoside esters such as Crodesta SL-40, available from Croda, Inc., New York, NY; March 8, 1977. Alkylglycoside ethers described in US Pat. No. 4,011,389 to WK Langdon; And 200 ml Pegosperse and Rhone Poulenc Corporation (Kran, NJ, available from Glyco Chemicals, Inc., Greenwich, Connecticut, USA). Alkylglycosides including alkylpolyethoxylated esters such as IGEPAL RC-520 available from Berry.

Other types of chemicals that may be added include dry strength additives to increase the tensile strength of the tissue web. Examples of dry strength additives include carboxymethyl cellulose and cationic polymers of the ACCO chemical group, such as ACCO 711 and ACCO 514, with the ACCO chemical group being preferred. These materials are commercially available from American Cyanamid Company, Wayne, NJ. When used, the amount of dry strength additive is preferably from about 0.01% to about 1.0% by weight based on the dry fiber weight of the tissue paper.

Other types of chemicals that may be added include wet strength additives to increase the wet burstability of the tissue web. The present invention may contain, as an optional component, from about 0.01% to about 3.0%, more preferably from about 0.3% to about 1.5% by weight of a water soluble permanent wet strength resin, based on the dry fiber weight.

The permanent wet strength resins useful herein can be in several forms. In general, these resins that are already utilized in the papermaking sector or will be utilized later are useful herein. Various examples are shown in the aforementioned documents by Westfeldt, which is incorporated herein by reference.

In conventional cases, the wet strength resin is a water soluble, cationic material. That is, the resin is water soluble when the resin is added to the paper feed. It is quite possible and expected that a series of reactions, such as crosslinking, may render the resin insoluble in the crystals. In addition, some resins are limited and soluble under only certain conditions, such as over a pH range.

Wet strength resins are believed to generally undergo crosslinking or other purifying reactions after they have been attached to, in, or in papermaking fibers. Crosslinking or curing does not usually occur as long as a significant amount of water is present.

Various polyamide-epichlorohydrin resins are particularly useful. These materials are low molecular weight polymers provided with reactive functional groups such as amino, epoxy and azetidinium groups. Some patent documents fully describe the preparation of such materials. United States Patent No. 3,772,076, issued to Keim on October 24, 1972, is an example of that patent, all of which are incorporated herein by reference.

Polyamide-epichlorohydrin resins sold under the trade names Kymene 557H and Kymen 2064 by Hercules Incorporated, Wilmington, Delaware, USA are particularly useful in the present invention. . These resins are generally described in the patents mentioned in the above mentioned patents.

Base-activated polyamide-epichlorohydrin resins useful in the present invention are sold by the Monsanto Company, St. Louis, Missouri, USA, under the Santores brand name, such as Santores 31. have. Materials of this type are generally described in US Pat. No. 3,855,158 issued to Petrorovich, dated December 17, 1974; 3,899,388 to Petrovic, issued August 12, 1975; 3,129,528 to Petrovic, issued December 12, 1978; 4,222,921, issued to Petrobeach on 3 April 1979, all of which are incorporated herein by reference.

Other water soluble cationic resins useful herein are polyacrylamide resins sold under the name of Parez, such as Parez 631NC, by American Cyanamide Campani, Stanford, Connecticut, USA. These materials are generally described in U.S. Patent Nos. 3,556,932 to Coscia et al. On January 19, 1971; And 3,556,933 to Williams et al., January 19, 1971, all of which are incorporated herein by reference.

Other forms of water soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latelles. Various examples of these resin forms are provided in US Pat. No. 3,844,880, issued May 29, 1974 to Meisel jr. Et al., Which is incorporated herein by reference.

Other water soluble cationic resins useful in the present invention are also urea formaldehyde and melamine formaldehyde resins. These multifunctional reactive polymers have a molecular weight of thousands. More common functional groups include amino groups and groups containing nitrogen such as methyl bound groups to nitrogen. Although less preferred, polyethyleneimine type resins are useful in the present invention.

A more complete description of the aforementioned water soluble resins, including methods for their preparation, is given in TAPPI Monograph Series No. 29, Wet Strength In Paper and Paperboard, Technical Association of the Pulp and Paper Industry (New York; 1965), which is incorporated herein by reference. As used herein, the term "permanent wet strength resin" refers to a resin in which the paper sheet maintains most of its initial wet strength for a time longer than two minutes when present in an aqueous medium.

The above mentioned wet strength additives typically give paper products a permanent wet strength. In other words, when present in an aqueous medium, the paper retains most of its initial wet strength for a long time. However, in some types of paper products, permanent wet strength is unnecessary and may be undesirable. Paper products, such as toilet tissues, are usually disposed of in decaying and similar systems after a short period of use. If the paper product maintains its hydrolysis-resistant strength properties permanently, it can be an obstacle in these systems. More recently, manufacturers have added temporary wet strength additives to paper products such that they are sufficient for their intended use but have a reduced wet strength when submerged in water. The reduction in wet strength facilitates the flow of paper products through the decay system.

Examples of suitable temporary wet strength resins are modified starch temporary wet strength formulations such as National Starch 78-0080 sold by National Starch and Chemical Corporation (New York, NY, USA). Wet strength formulations of this type can be prepared by reacting dimethoxyethyl-N-methyl-chloroacetamide with cationic starch polymers The modified starch temporary wet strength formulations are also dated June 23, 1987. US Patent No. 4,675,394, issued to Solarek et al., Incorporated herein by reference, Preferred temporary wet strength resins are US patents issued to Bjorkquist on January 1, 1991. 4,981,557, the resins of which are incorporated herein by reference.

In view of the classes and specific examples of both the above-mentioned permanent and temporary wet strength resins, it should be understood that the resins mentioned are, of course, illustrative and not intended to limit the scope of the invention.

Mixtures of compatible wet strength resins can also be used when carrying out the invention.

The optional chemical additives mentioned above are, of course, merely exemplary and are not intended to limit the scope of the invention.

The following examples illustrate the performance of the invention, but are not intended to limit the invention.

Example 1

The purpose of this example is to illustrate a method that can be used to prepare a biodegradable chemical softener composition comprising a mixture of diester detallow ammonium chloride (DEDTDMAC) and polyethylene glycol 400 (PEG-400).

A 1% solution of biodegradable chemical softener is prepared according to the following procedure: 1. Weigh 1 equivalent of DEDTDMAC and PEG-400, respectively. 2. Heat PEG to about 66 ° C. (150F); 3. DEDTDMAC was dissolved in PEG to form a molten solution at 66 ° C. (150F); 4. Apply shear stress to form a homogeneous mixture of DEDTDMAC in PEG; Adjust the pH of the dilution water to about 3 by adding a solution of HC1 at a concentration of 5.0.1%; 6. Heat the dilution water to about 66 ° C. (150F); 7. Dilute the melt mixture of DEDTDMAC and PEG to 1% solution; 8 shear stress is applied to form an aqueous solution containing the vesicle dispersion or suspension of the DEDTDMAC and PEG mixture; 9. Scale the particle size of the vesicle dispersion using scientific microscopy techniques. The particle size is about 0.1 to 1.0 micron.

Figure 6 illustrates a cold-transmission micrograph of 63,000 times the vesicle dispersion in a DEDTDMAC and PEG-400 system 1: 1 weight ratio. Figure 6 illustrates particles having a layer of one or two layers thick, the shape of the particles ranging from closed / opened vesicles to disk-shaped structures and sheets.

Example 2

The purpose of this example is to illustrate a method that can be used to prepare a biodegradable chemical softener composition comprising a mixture of diester dielow dimethyl ammonium chloride (DEDTDMAC) and glycerol.

A 1% solution of biodegradable chemical softener is prepared according to the following procedure: 1. Weigh 1 equivalent of DEDTDMAC and 1 equivalent of glycerol; 2. Heat glycerol to about 66 ° C. (150F); 3. DEDTDMAC was dissolved in glycerol to form a molten solution at 66 ° C. (150F); 4. Apply shear stress to form a homogeneous mixture of DEDTDMAC in glycerol; 5. Adjust the pH of the dilution water to about 2 by adding a solution of 0.1% concentration of HC1; 6. Heat the dilution water to about 66 ° C. (150F); 7. Dilute the melt mixture to 1% solution; And 8. shear stress to form an aqueous solution containing a vesicle dispersion or suspension of the DEDTDMAC and glycerol mixture; 9. Measure the particle size of the vesicle dispersion using scientific microscopy techniques. The particle size is about 0.1 to 1.0 micron. FIG. 7 illustrates a cold-permeation micrograph of 63,000 times the vesicle dispersion in a 1: 1 weight ratio of DEDTDMAC and glycerol system.

Figure 7 illustrates a particle having a film of one or two layers thick, the shape of which ranges from a closed vesicle to a disk-like structure.

Example 3

The purpose of this example is a biodegradation comprising a mixture of diester di (hydrogenated) tallow dimethylammonium crawlide (DEDHTDMAC) (ie ADOGEN DDMC from Serex Company) and polyethylene glycol 400 (PEG-400). Illustrates methods that can be used to prepare the sex softener composition. A 1% solution of biodegradable chemical softener is prepared according to the following procedure: 1. Weigh 1 equivalent of DEDHTDMAC and PEG-400, respectively; 2. Heat PEG to about 90 ° C. (194F); 3. Dissolve DEDHTDMAC in PEG to form a molten solution at 90 ° C. (194F); 4. Apply shear stress to form a homogeneous mixture of DEDHTDMAC in PEG; Adjust the pH of the dilution water to about 3 by adding a solution of HC1 at a concentration of .0.1%; 6. Heat the dilution water to about 70 ° C. (158F); 7. Dilute the melt mixture to 1% solution; 8. Apply shear stress to form an aqueous solution containing the vesicle dispersion or suspension of the DEDHTDMAC and PEG mixture; 9. Determine the particle size of the vesicle dispersion of DEDHT-DMAC and PEG using optical microscopy techniques. The particle size is about 0.1 to 1.0 micron.

Figure 8 illustrates a cold-permeation micrograph of 66,000 times the vesicle dispersion in a 1: 1 weight ratio of DEDHTDMAC and PEG-400 systems.

FIG. 8 illustrates particles having a layer of one or two layers thick, wherein the shape of the particles ranges from closed vesicles to disk-like structures.

Example 4

The purpose of this example was to prepare a soft, absorbent paper towel sheet treated with a biodegradable chemical softener composition comprising a mixture of diester titanol dimethyl ammonium chloride (DEDTDMAC), polyethylene glycol 400 (PEG-400) and permanent wet strength resin. It is to illustrate how to use blow gonzo papermaking techniques.

An experimental forward linear wire paper machine is used in the practice of the present invention.

First, a 1% solution of biodegradable chemical softener is prepared according to the procedure of Example 1. Secondly, 3% by weight of an aqueous slurry of NSK is prepared in conventional re-pulper. The NSK slurry was gently refined and a 2% solution of permanent wet strength resin (i.e., Kymen 557H, available from Hercules Incorporated, Wilmington, USA) at a rate of 1% by weight of the dry fibers. The adsorption of Kymene 557H on NSK is enhanced by an in-line mixer. After treatment with an in-line mixer, a 1% solution of carboxymethyl cellulose (CMC) at a rate of 0.2% by weight of the dry fibers improves the dry strength of the additive fiber substrate. The adsorption rate of CMC to NSK can be improved by an in-line mixer. A 1% solution of the chemical softener mixture (DEDTDMAC / PEG) is then added to the NSK slurry at a rate of 0.1% based on the weight of the dry fibers. Adsorption of the chemical softener mixture to the NSK can also be enhanced through an in-line mixer. NSK slurry is diluted to 0.2% consistency by a fan pump. Third, an aqueous slurry of CTMP is prepared with 3% by weight conventional re-pulper. Nonionic ?? modifiers (Pegosespurs) are added to the re-pulper at a rate of 0.2% based on the weight of the dry fibers.

A 1% solution of the chemical softener mixture is added to the CTMP feed pipe in front of the feed pump at a rate of 0.1% by weight of the dry fibers. Adsorption of the chemical softener mixture to CTMP may be enhanced by an in-line mixer. The CTMP slurry is diluted to 0.2% by a fan pump. The treated feed mixture (NSK / CTMP) is blended in the head box and adhered to the forward linear wire to form an embryonic web. Dewatering takes place through the forward linear wires and is assisted by deflectors and vacuum boxes. The forelinear wire is a five-shed satin woven structure with 84 machine and 76 cross-machine direction monofilaments per inch, respectively. The initial web is a photo-polymer fabric with a knuckle area of 34% and 14 mils of photo-polymer thickness of 240 linear Idaho cells per square inch from the forward linear wire, moving at about 22% fiber consistency. do. In addition, the web is dewatered by vacuum assisted dehydration until the web has a fiber consistency of about 28%. The patterned web is predried by air blowing to a fiber consistency of about 65% by weight. The web is then adhered to the surface of the Yankee dryer with a sprayed creping adhesive comprising 0.25% stock solution of polyvinyl alcohol (PVA). Fiber consistency increases to approximately 96% before dry creping the web by the doctor blade. The doctor blade has an inclination angle of about 25 degrees and is positioned towards the Yankee dryer to provide an impact angle of about 81 degrees; The Yankee dryer operates at about 800 fpm (about 244 meters / minute). The dry web is formed into a roll at a speed of 700 fpm (214 meters / minute).

The two-ply web is embossed and laminated together using PVA adhesive to form a paper towel product. The paper towel has a basis weight of about 26 # / 3M Sq Ft and contains about 0.2% of a biodegradable chemical softener mixture and about 1.0% of permanent wet strength resin. The resulting paper towels are soft, absorbent and very strong when wet.

Table 1 below summarizes the retention and average particle size of the DEDTDMAC / PEG-400 vesicle dispersion compared to adding only PEG-400 to the feed slurry.

TABLE 1

Example 5

The purpose of this example is to prepare a soft, absorbent toilet paper that has been treated with a biodegradable chemical softener composition comprising a mixture of diester die-low dimethyl ammonium chloride (DEDTDMAC) and polyethylene glycol 400 (PEG-400) and a temporary wet strength resin. A blow drying technique and a layered papermaking technique are illustrated.

An experimental forward linear wire paper machine is used in the practice of the present invention. First, a 1% solution of biodegradable chemical softener is prepared according to the procedure of Example 1. Secondly, 3% by weight of an aqueous slurry of NSK is made of conventional re-pulper. The NSK slurry was gently refined and a 2% solution of temporary wet strength resin (ie, National Starch 78-0080 sold by National Starch & Chemical Corporation, New York, NY, USA) was 0.75% by weight of dry fiber. It is added to the NSK raw pipe in proportion. Adsorption of the temporary wet strength resin to the NSK is enhanced by an in-line mixer. NSK slurry is diluted in a fan pump to approximately 0.2% consistency. Third, 3% by weight of an aqueous slurry of Eucalyptus fibers is made from conventional re-pulper. A 1% solution of the chemical softener mixture is added to the eucalyptus feed pipe before the feed pump at a rate of 0.2% based on the weight of the dry fibers. Adsorption of the biodegradable chemical softener mixture to the eucalyptus fibers can be enhanced by an in-line mixer. Eucalyptus slurry is diluted to 0.2% consistency in a fan pump.

The treated feed mixture (NSK 30% / eucalyptus 70%) is blended in the head box and adhered to the forward linear wire to form the initial web. Dewatering occurs through the forward linear wires and is assisted by deflectors and vacuum boxes. The forelinear wire is a five-seat satin woven structure with 84 machine and 76 cross-machine direction monofilaments per inch, respectively. The initial wet web was moved from the photo-polymer wire to a photo-polymer fabric with 562 linear Idaho cells per square inch, 40% knuckle area, and 9 mil photo-polymer thickness at about 15% fiber consistency. In addition, the web is dewatered by vacuum assisted dehydration until the web has a fiber consistency of about 28%. The patterned web is predried by air blowing to a fiber consistency of about 65% by weight. The web is then adhered to the surface of the Yankee Dryer with a spray creping adhesive comprising 0.25% aqueous solution of polyvinyl alcohol (PVA). Fiber consistency increases to approximately 96% prior to dry creping the ube with the doctor blade. The doctor blade has an inclination angle of about 25 degrees and is positioned towards the Yankee dryer to provide an impact angle of about 81 degrees; The Yankee dryer operates at about 800 fpm (about 244 meters / minute). The dry web is formed into a roll at a speed of 700 fpm (214 meters / minute).

Turn the web into a single layer of tissue paper product. The tissue paper has a basis weight of about 18 # 3M Sq Ft and contains about 0.1% of the biodegradable chemical softener mixture and about 0.2% of the temporary wet strength resin. Importantly, the prepared tissue paper is soft, absorbent and suitable for use as a high quality and / or toilet tissue.

Table 2 below summarizes the retention and average particle size of the DEDTDMAC / PEG vesicle dispersion compared to adding only PEG-400 to the feed slurry.

TABLE 2

Example 6

The purpose of this example is to provide a soft, absorbent toilet paper that has been treated with a biodegradable chemical softener composition comprising a mixture of diester die-low dimethyl ammonium chloride (DEDTDMAC), periethylene glycol 400 (PEG-400) and a dry strength additive resin Illustrates a method of using blow dry papermaking techniques for manufacturing.

An experimental forward linear wire paper machine is used in the practice of the present invention. First, a 1% solution of biodegradable chemical softener is prepared according to the procedure of Example 1. Secondly, 3% by weight of an aqueous slurry of NSK is made of conventional re-pulper. The NSK slurry is gently refined and a 2% solution of dry strength resin (i.e., Acco 514, Acco 711 sold by American Cyanamide Campanisa, Fairfield, Ohio, USA) is 0.2% by weight of dry fiber. Is added to the NSK raw pipe at a ratio of. Adsorption of dry strength resin to NSK fibers is enhanced by an in-line mixer. NSK slurry is diluted in a fan pump to about 0.2% consistency. Third, 3% by weight of an aqueous slurry of eucalyptus fibers is made from conventional re-pulper. A 1% solution of the chemical softener mixture is added to the eucalyptus feed pipe in front of the feed pump at a rate of 0.2% by weight of the dry fibers. Adsorption of the biodegradable chemical softener mixture to the eucalyptus fibers can be enhanced by an in-line mixer. Eucalyptus slurry is diluted to 0.2% consistency in a fan pump.

The treated feed mixture (NSK 30% / eucalyptus 70%) is blended in the headbox and adhered to the forward linear wire to form the initial web. Dewatering takes place through the forward linear wires and is assisted by deflectors and vacuum boxes. The forelinear wire is a five-seat satin woven structure with 84 machine and 76 cross-machine direction monofilaments per inch, respectively. The initial wet web was moved from the photo-polymer wire to a photo-polymer fabric with 562 linear adiaho cells per square inch, 40% knuckle area, and 9 mil photo-polymer thickness at about 15% fiber consistency. In addition, the web is dewatered by vacuum assisted dehydration until the web has a fiber consistency of about 28%. The patterned web is predried by air blowing to a fiber consistency of about 65% by weight. The web is then adhered to the surface of the Yankee Dryer with a spray creping adhesive comprising 0.25% aqueous solution of polyvinyl alcohol (PVA). Fiber consistency increases to approximately 96% before dry creping the web with the doctor blade. The doctor blade has an inclination angle of about 25 degrees and is positioned towards the Yankee dryer to provide an impact angle of about 81 degrees; The Yankee dryer operates at about 800 fpm (feet / minute) (about 244 meters / minute). The dry web is formed into a roll at a speed of 700 fpm (214 meters / minute).

Two layers of web are formed into a tissue paper product and all laminated using layer bonding techniques. The tissue paper has a basis weight of about 23 # / 3M Sq Ft and contains about 0.1% of a biodegradable chemical softener mixture and about 0.1% of dry strength resin. Importantly, the resulting tissue paper is soft, absorbent, and suitable for use as a high quality and / or toilet tissue.

Table 3 below summarizes the retention and average particle size of the DEDTDMAC / PEG vesicle dispersion compared to the addition of only PEG-400 to the feed slurry.

TABLE 3

Example 7

The purpose of this example is a soft and absorbent process treated with a biodegradable chemical softener composition comprising a mixture of diester di (hydrogenated) tallow dimethyl ammonium chloride (DEDHTDMAC), polyethylene glycol 400 (PEG-400) and a dry strength additive resin. A method of using conventional dry paper making techniques for making toilet tissue is illustrated.

An experimental forward linear wire paper machine is used to carry out the present invention. First, a 1% solution of biodegradable chemical softener is prepared according to the procedure of Example 3. Secondly, 3% by weight of an aqueous slurry of NSK is made of conventional re-pulper. The NSK slurry was gently refined and a 2% solution of dry strength resin (i.e., Acco 514, Acco 711 sold by American Cyanamide Campani, Fairfield, Ohio) was 0.2% by weight of the dry fiber. Is added to the NSK feed pipe at the rate of. Adsorption of dry strength resin to NSK fibers is enhanced by an in-line mixer. NSK slurry is diluted in a fan pump at 0.2% consistency. Third, 3% by weight of an aqueous slurry of eucalyptus fibers is made from conventional re-pulper. A 1% solution of the chemical softener mixture is added to the eucalyptus feed pipe in front of the feed pump at a rate of 0.2% by weight of the dry fibers. Adsorption of the biodegradable chemical softener mixture to the eucalyptus fibers can be enhanced by an in-line mixer. Eucalyptus slurry is diluted to 0.2% consistency in a fan pump.

The treated feed mixture (NSK 30% / eucalyptus 70%) is blended in the head box and attached onto the forward linear wire to form the initial web. Dewatering takes place through the forward linear wires and is assisted by deflectors and vacuum boxes. The forelinear wire is a five-seat satin woven structure with 84 machine and 76 cross-machine direction monofilaments per inch, respectively. The initial wet web is moved from the woven linear wire to conventional felt, at about 15% fiber consistency. The web is also dewatered by vacuum assisted dehydration until the web has a fiber consistency of about 35%. The web is then bonded to the surface of a Yankee dryer. Fiber consistency increases to approximately 96% before dry creping the web with the doctor blade. The doctor blade has an inclination angle of about 25 degrees and is facing towards the Yankee dryer to provide an impact angle of about 81 degrees; The Yankee dryer operates at about 800 fpm (feet / minute) (about 244 meters / minute). The dry web is formed into a roll at a speed of 700 fpm (214 meters / minute).

Two layers of web are formed into a tissue paper product and all laminated using layer bonding techniques. The tissue paper has a basis weight of about 23 # / 3M Sq Ft and contains about 0.1% of a biodegradable chemical softener mixture and about 0.1% of dry strength resin. Importantly, the resulting tissue paper is soft, absorbent, and suitable for use as a high quality and / or toilet tissue.

Table 4 below summarizes the retention and average particle size of DEDHTDMAC and PEG-400 vesicle dispersions compared to adding only PEG-400 to the feed slurry.

TABLE 4

Claims (71)

Sheets of fibrous cellulose material; And based on the weight of the fibrous cellulose material, (a) a quaternary ester-amine compound having the general formula (b) about 0.005% to about 5.0% by weight of a biodegradable chemical softener composition comprising a mixture of glycerol and a polyhydroxy compound selected from the group consisting of polyethylene glycol and polypropylene glycol having a weight average molecular weight of about 200 to 4000 Wherein the weight ratio of the quaternary ester-amine compound to the polyhydroxy compound is mixed with the quaternary ester-ami compound at elevated temperatures such that the weight ratio of the quaternary ester-amine compound is miscible with the quaternary ester-amine compound; or Wherein each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, or a mixture thereof: each R ₁ substituent is a C ₁₄ -C ₂₂ hydrocarbyl group, or a mixture thereof: R ₃ substituents are C ₁₂ -C ₂₀ hydrocarbyl groups, or mixtures thereof: X- is a compatible anion. The paper product of claim 1, wherein each R ₂ is selected from C ₁ -C ₃ alkyl, each R ₁ is selected from C ₁₆ -C ₁₈ alkyl, and each R 3 is selected from C 14 -C ₁₆ alkyl. The paper product of claim 2, wherein each R ₂ is methyl. The paper product of claim 1 wherein X- is chloride or methyl sulfate. The paper product of claim 4 wherein the quaternary ester-amine compound is diester di (nonhydrogenated) tallow dimethyl ammonium chloride. The paper product of claim 4 wherein the quaternary ester-amine compound is a diester di (slightly hydrogenated) tallow dimethyl ammonium chloride. 8. The paper product according to claim 7, wherein the quaternary ester-amine compound is diester di (partially hydrogenated) tallow dimethyl ammonium chloride. The paper product of claim 4 wherein the quaternary ester-amine compound is a diester di (hydrogenated) tallow dimethyl ammonium chloride. 5. The paper product of claim 4, wherein the quaternary ester-amine compound is diester dielow dimethyl ammonium methyl sulfate. 5. The paper product of claim 4, wherein the quaternary ester-amine compound is diester di (hydrogenated) tallowdimethyl ammonium methyl sulfate. 6. The paper product of claim 5, wherein the polyhydroxy compound is miscible with diester di (nonhydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 7. The paper product of claim 6, wherein the polyhydroxy compound is miscible with diester di (slightly hydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 8. The paper product of claim 7, wherein the polyhydroxy compound is miscible with diester di (partially hydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 9. A paper product according to claim 8, wherein the polyhydroxy compound is miscible with diester di (hydrogenated) tallow dimethyl ammonium chloride in the liquid phase. The paper product of claim 1, wherein the polyhydroxy compound is polyethylene glycol having a weight average molecular weight of about 200 to about 1000. 10. The polyhardy glycol compound according to claim 1 is a polypropylene glycol having a weight average molecular weight of about 200 to about 1000. The paper product of claim 1 wherein the polyhydroxy compound is glycerol. The paper product of claim 1 wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 3.0 to 0.3: 1. 19. The paper product of claim 18 wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1 The paper product according to claim 1, wherein the quaternary ester-amine compound is mixed with the polyahydroxy compound at an elevated temperature of 50 ° C or higher. 21. The paper product of claim 20, wherein the quaternary ester-amine compound is mixed with the polyhydroxy compound at a temperature of about 50 ° C to 100 ° C. The paper product of claim 1, wherein the mixture of the quaternary ester-amine compound and the polyhydroxy compound is diluted with the liquid carrier at a concentration of about 0.01% to about 25.0% by weight based on the chemical emollient composition. 23. The paper product of claim 22, wherein the mixture of the quaternary ester-amine compound and the polyhydroxy compound is present as particles dispersed in a liquid carrier. 23. The paper product of claim 22, wherein the liquid carrier has a temperature of about 40 ° C to 80 ° C. 23. The paper product of claim 22, wherein the pH of the liquid carrier is less than about 4. 24. The paper product of claim 23, wherein the quaternary ester-amine compound and the polyhydroxy compound have an average particle diameter of about 0.01 to 10 microns. 27. The paper product of claim 26, wherein the average particle diameter of the quaternary ester-amine compound and the polyhydroxy compound is about 0.1 to 1.0 micron. The paper product of claim 15 wherein the polyhydroxy compound is polyethylene glycol having a molecular weight of about 200 to about 600. 17. The paper product of claim 16, wherein the polyhydroxy compound is a polypropylene glycol having a molecular weight of about 200 to about 600. 29. The paper product of claim 28, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1 30. The paper product of claim 29, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1. 18. The paper product of claim 17, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is about 1: 0.7. 24. The paper product of claim 23 wherein the dispersed particles are vesicle particles. The paper product of claim 1 wherein the quaternary ester-amine compound is in a liquid state when mixed with a polyhydroxy compound. The paper product of claim 1 which is a towel. The paper product according to claim 1, which is a toilet tissue or a high quality tissue tissue. The toilet tissue according to claim 1, which contains a dry strength additive. a mixture of (a) a quaternary ester-amine compound having the general formula and (b) glycerol, and a polyhydroxy compound selected from the group consisting of polyethylene glycol and polypropylene glycol having a weight average molecular weight of about 200 to 4000 Wherein the weight ratio of the quaternary ester-amine compound to the polyhydroxy compound is about 1: 0.1 to 0.1: 1, and the quaternary ester at an elevated temperature at which the polyhydroxy compound is miscible with the quaternary ester-amine compound Biodegradable Chemical Softener Compositions Mixed with Amine Compounds or Wherein each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, or a mixture thereof; Each R ₁ substituent is a C ₁₄ -C ₂₂ hydrocarbyl group, or a mixture thereof; Each R ₃ substituent is a C ₁₂ -C ₂₀ hydrocarbyl group, or a mixture thereof; X- is a compatible anion. The biodegradation of claim 38, wherein each R ₂ is selected from C ₁ -C ₃ alkyl, each R ₁ is selected from C ₁₆ -C ₁₈ alkyl, and each R ₃ is selected from C ₁₄ -C ₁₆ alkyl Sex chemical softener composition. 40. The biodegradable chemical softener composition of claim 39, wherein each R ₂ is methyl. 39. The compound of claim 38 wherein X- is chloride or methyl sulfate Biodegradable Chemical Softener Composition. 42. The biodegradable chemical softener composition of claim 41, wherein the quaternary ester-amine compound is diester di (nonhydrogenated) tallow dimethyl ammonium chloride. 42. The biodegradable chemical softener composition of claim 41, wherein the quaternary ester-amine compound is diester di (slightly hydrogenated) tallow dimethyl ammonium chloride. 42. The biodegradable chemical softener composition of claim 41, wherein the quaternary ester-amine compound is diester di (partially hydrogenated) tallow dimethyl ammonium chloride. 42. The biodegradable chemical softener composition of claim 41 wherein the quaternary ester-amine compound is diester di (hydrogenated) tallow dimethyl ammonium chloride. 42. The biodegradable chemical softener composition of claim 41, wherein the quaternary ester-amine compound is diester dielow dimethyl ammonium methyl sulfate. 42. The biodegradable chemical softener composition of claim 41, wherein the quaternary ester-amine compound is diester di (hydrogenated) tallow dimethyl ammonium methyl sulfate. 42. The biodegradable chemosoftener composition of claim 41, wherein the polyhydroxy compound is miscible with diester di (nonhydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 44. The biodegradable chemical softener composition of claim 43, wherein the polyhydroxy compound is miscible with diester di (slightly hydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 45. The biodegradable chemical softener composition of claim 44, wherein the polyhydroxy compound is miscible with diester di (partially hydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 46. The biodegradable chemical softener composition of claim 45, wherein the polyhydroxy compound is miscible with diester di (hydrogenated) tallow dimethyl ammonium chloride in the liquid phase. 39. The biodegradable chemical softener composition of claim 38, wherein the polyhydroxy compound is polyethylene glycol having a weight average molecular weight of about 200 to about 1000. 39. The biodegradable chemical softener composition of claim 38, wherein the polyhydroxy compound is polypropylene glycol having a weight average molecular weight of about 200 to about 1000. 39. The biodegradable chemolytic agent composition of claim 38, wherein the polyhydroxy compound is glycerol. 39. The biodegradable chemical softener composition of claim 38, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.3 to 0.3: 1. 56. The biodegradable chemical softener composition of claim 55, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1. The biodegradable chemical softener composition of claim 38, wherein the quaternary ester-amine compound is mixed with the polyhydroxy compound at an elevated temperature of at least 50 ° C. 59. The biodegradable chemical softener composition of claim 57, wherein the quaternary ester-amine compound is mixed with the polyhydroxy compound at a temperature of about 50 ° C to 100 ° C. 39. The biodegradable chemical softener composition of claim 38, wherein the mixture of the quaternary ester-amine compound and the polyhydroxy compound is diluted with the liquid carrier at a concentration of about 0.01% to about 25.0% by weight based on the chemical softener composition. 60. The biodegradable chemical softener composition of claim 59, wherein the mixture of the quaternary ester-amine compound and the polyhydroxy compound is present as particles dispersed in a liquid carrier. 60. The biodegradable chemical softener composition of claim 59, wherein the liquid carrier has a temperature of about 40 ° C to 80 ° C. 60. The biodegradable chemical softener composition of claim 59, wherein the liquid carrier has a pH of less than about 4. 61. The biodegradable chemical softener composition of claim 60, wherein the average particle diameter of the quaternary ester-amine compound and the polyhydroxy compound is about 0.01 to 10 microns. 64. The biodegradable chemical softener composition of claim 63, wherein the quaternary ester-amine compound and the polyhydroxy compound have an average particle diameter of about 0.1 to 0.1 microns. 53. The biodegradable chemical softener composition of claim 52, wherein the polyhydroxy compound is polyethylene glycol having a molecular weight of about 200 to 600. 54. The biodegradable chemical softener composition of claim 53, wherein the polyhydroxy compound is polyethylene glycol having a molecular weight of about 200 to 600. 66. The biodegradable chemical softener composition of claim 65, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1. 67. The biodegradable chemical softener composition of claim 66, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1. 55. The biodegradable chemical softener composition of claim 54, wherein the weight ratio of quaternary ester-amine compound to polyhydroxy compound is from about 1: 0.7 to 0.7: 1. 61. The biodegradable chemical softener composition of claim 60, wherein the dispersed particles are antifoam particles. 39. The biodegradable chemical softener composition of claim 38 which is in the liquid state when mixed with a quaternary ester-amine compound and a polyhydroxy compound.