KR100333211B1 - Multi-layer tissue paper web comprising biodegradable chemical softener composition and binder, and articles comprising the same - Google Patents

Abstract

Multi-layered tissue paper webs comprising biodegradable chemical softener compositions and binder materials are disclosed. The multi-layered tissue webs are useful in the manufacture of soft, absorbent paper products such as facial tissues and/or toilet tissues. The multi-layered tissue paper products contain a biodegradable chemical softening composition, preferably comprising a mixture of an ester-functional quaternary ammonium compound and a polyhydroxy compound. Preferred ester-functional quaternary ammonium compounds include diester dialkyl dimethyl ammonium salts such as diester di(touch hardened)tallow dimethyl ammonium chloride, diester di(hydrogenated)tallow dimethyl ammonium chloride. Preferred polyhydroxy compounds are selected from the group consisting of glycerol, sorbitols, polyglycerols having a weight average molecular weight of from about 150 to about 800, polyoxyethylene glycols and polyoxypropylene glycols having a weight average molecular weight from about 200 to 4,000. The multi-layered tissue paper webs also contain an effective amount of binder materials to control linting and/or to offset the loss in tensile strength, if any, resulting from the use of the chemical softening compositions. The binder materials are selected from the various wet and dry strength additives, and retention aids used in the paper making art. Preferably, the majority of the biodegradable chemical softening compositions will be disposed on the outer layers of the multi-layered tissue paper products where they are most effective. The binder materials are typically dispersed throughout the multi-layered product to control linting. In other words, the chemical softening compositions and the binder materials can be selectively distributed within the multi-layered tissue paper web to enhance the softness, absorbency, and/or lint resistance of a particular layer or ply.

Description

Multi-layer tissue paper web comprising biodegradable chemical softener composition and binder, and articles comprising same

Paper webs or sheets, often referred to as tissue or paper tissue webs or sheets, are widely used in modern society. Items such as fine tissues and toilet tissues are commercially important items. It has long been recognized that the four important physical properties of these products are their strength, ductility, absorbency, especially for aqueous systems, and lint resistance, especially when wet. There has been research and development to improve the above properties without adversely affecting each other as well as to improve the two or three properties at the same time.

Strength is the ability of the product and its constituent webs to maintain physical bonds and prevent them from tearing, breaking or chipping during use, especially when wet.

Softness is the user's sense of touch when a user grabs a particular product and rubs it on his skin or rolls it in his hand. This texture is provided by combining several physical properties. One of the most important physical properties associated with ductility is generally recognized by those skilled in the art as the stiffness of the paper web constituting the product. Stiffness is also generally recognized as directly dependent on the dry tensile strength of the web and the stiffness of the fibers making up the web.

Absorbency is a measure of the amount by which a product and its constituent web absorb liquids, especially aqueous solutions or dispersions. It is recognized that the total absorption capacity perceived by the user is generally a combination of the total amount of liquid absorbed in a saturated state by a multilayer tissue paper of a certain size and the rate at which the liquid absorbs the liquid.

Lint resistance is the ability of a fibrous product and its constituent web to bind together during use, especially when wet. In other words, the higher the lint resistance, the lower the propensity of the web to lint.

It is well known to use wet strength resins to improve the strength of paper webs. For example, Westfelt describes a number of such materials and is described in Cellulose Chemistry and Technology, Volume 13, pp. 813-825 (1979). United States Patent No. 3,755,220, issued to Freimark et al. On August 28, 1973, discloses that certain chemical additives, known as debonding agents, inhibit the natural fiber-to-fiber binding that occurs during sheet manufacturing in the papermaking process. It is described as. Reduced bonding results in sheets of softer or less coarse paper. Freymark et al. Teach the use of wet strength resins when using solution solutions to counteract the undesirable effects of solution solutions. This solution reduces both dry and wet tensile strengths.

US Pat. No. 3,821,068, issued to Shaw on June 28, 1974, teaches that chemical solution mixtures can be used to reduce the stiffness of the tissue paper web and improve ductility.

Chemical solutions are described in various documents, such as in US Pat. No. 3,554,862, issued to Hervey et al. On January 12, 1971. Such materials include quaternary ammonium salts, such as cocotrimethylammonium chloride, oleyltrimethylammonium chloride, di (hydrogenated) tallow dimethyl ammonium chloride and stearyltrimethyl ammonium chloride.

United States Patent No. 4,144,122, issued to Emanuelsson et al. On March 13, 1979, uses quaternary ammonium complexes such as bis (alkoxy (2-hydroxy) propylene) quaternary ammonium chloride to soften the web. Initiate. Emmanuelson also sought to overcome the decrease in absorption due to the solution by using nonionic surfactants such as ethylene oxide and propylene oxide adducts of fatty alcohols.

Amak Company (76-17 (1977)) of Armak Company, Chicago, Ill., Reported that dimethyl di (hydrogenated) tungsten ammonium chloride was added to polyoxyethylene to impart both ductile and absorbent capacity to tissue paper webs. It is described for use with fatty acid esters of glycols.

One of the findings to improve the paper web is described in US Pat. No. 3,301,746, issued January 31, 1967 to Sanford and Sisson. Despite the excellent quality of paper webs produced by the process described in this patent and the commercial success of products made from such webs, research efforts to improve products continue.

For example, US Pat. No. 4,158,594, issued to Becker et al. On January 19, 1979, describes that the method they claim to produce a strong, soft fibrous sheet. More particularly, they are binding agents (eg It can be improved by attaching to the creping surface in a precise patterned arrangement with an acrylic latex rubber emulsifier, water soluble resin, or elastomeric binder) and creping the web from the creping surface to produce a sheet material.

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 chemical solutions. However, such quaternary ammonium compounds are hydrophobic, biodegradable, and can adversely affect the absorbency of the treated paper web. Applicants have found that mixing a biodegradable quaternary ammonium compound with a polyhydroxy compound (eg glycerol, sorbitol, polyglycerol or polyoxyethylene glycol) improves both the ductility and the absorption rate of the fibrous cellulose material. .

Unfortunately, the use of biodegradable chemical softener compositions comprising biodegradable quaternary ammonium compounds and polyhydroxy compounds can reduce lint resistance of the treated paper web. Applicants have found that lint resistance can be improved by using suitable binders such as wet and dry strength resins and by using retention aid resins known in the papermaking art.

The present invention is generally applicable to tissue paper, but in particular in multi-layer tissue paper products, as described in US Pat. No. 3,994,771, incorporated herein by reference and issued to Morgan et al. On November 30, 1976. Applicable

It is an object of the present invention to provide a multilayer tissue paper product that is soft, absorbent and lint resistant.

It is another object of the present invention to provide a method of making a multilayer tissue paper product that is soft, absorbent and lint resistant.

These and other objects are obtained using the present invention as will be readily apparent from the following description.

Summary of the Invention

The present invention provides a soft, absorbent, lint resistant multilayer tissue paper product comprising papermaking fibers, a biodegradable chemical softener composition and a binder. Briefly, the biodegradable chemical softener composition comprises a mixture of the following compounds.

(a) about 0.01 to about 3.0% of a biodegradable quaternary ammonium compound, preferably having the general formula: And

(b) preferably selected from the group consisting of glycerol, sorbitol, polyglycerol having a weight average molecular weight of about 150 to about 800, and polyoxyethylene glycol and polyoxypropylene glycol having a weight average molecular weight of about 200 to 4000 0.01 to about 3.0% of a mixture of polyhydroxy compounds;

In the above formula,

Each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, benzyl group or mixtures thereof;

Each R ₁ substituent is a C ₁₂ -C ₂₂ hydrocarbyl group, or a substituted hydrocarbyl group or mixtures thereof;

Each R ₃ substituent is a C ₁₁ -C ₂₁ hydrocarbyl group, or a substituted hydrocarbyl or mixture thereof;

Y is —O— (O) —, —C (O) —O—, —NH—C (O) —, —C (O) —NH—, and mixtures thereof;

n is 1 to 4;

X ⁻ is a suitable anion such as chloride, bromide, methylsulfate, ethylsulfate, nitrate and the like.

Preferred increase ratios of the biodegradable quaternary ammonium compound to the polyhydroxy compound are about 1.0: 0.1 to 0.1: 1.0. Biodegradable chemical emollient compositions have been found to be more effective when the polyhydroxy compound is mixed with the biodegradable quaternary ammonium compound at the temperature at which the biodegradable quaternary ammonium compound and the polyhydroxy compound are mixed.

Examples of suitable ester-functional quaternary ammonium compounds for use in the present invention include compounds having the following general formula:

In the above formula,

Each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, benzyl group or mixtures thereof;

Each R ₁ substituent is a C ₁₂ -C ₂₂ hydrocarbyl group, or a substituted hydrocarbyl group or mixtures thereof;

Each R ₃ substituent is a C ₁₁ -C ₂₁ hydrocarbyl group, or substituted hydrocarbyl or mixture thereof.

The compounds are mono or diester variants of known dialkyldimethylammonium salts, for example diester dietal dimethyl ammonium chloride, diester diesteryl dimethyl ammonium chloride, monoester dielow dimethyl ammonium chloride, diester di (hydrogenation) Tallow dimethyl ammonium methylsulfate, diester di (hydrogenated) tallow dimethyl ammonium chloride, diester variant of monoester di (hydrogenated) tallow dimethyl ammonium chloride, and combinations thereof, preferred is di (nonhydrogenated) Tallow dimethyl ammonium chloride, di (contact hydrogenation) tallow dimethyl ammonium chloride (DEDTHDMAC) and di (hydrogenated) tallow dimethyl ammonium chloride (DEDHTDMAC) diester variants, and combinations thereof. Depending on the characteristic requirements of the product, the saturation of the detalow can vary from non-hydrogenated (soft) to contact, partial or fully hydrogenated (hard).

Without wishing to be bound by theory, it is believed that the ester residue (s) confer biodegradability on such compounds. Importantly, the ester-functional quaternary ammonium compounds used herein biodegrade more rapidly than conventional dialkyl dimethyl ammonium chemical softeners.

Examples of polyhydroxy compounds useful in the present invention include glycerol, sorbitol, polyglycerols having a weight average molecular weight of about 150 to about 800 and polyoxyethylene glycols having a weight average molecular weight of about 200 to about 4000, preferably Polyoxyethylene glycol having a weight average molecular weight of about 200 to about 600.

The term binder refers to various wet and dry strength additives and retention aids known in the art. These materials not only improve the lint resistance of the tissue paper webs of the present invention but also counteract the decrease in tensile strength caused by the biodegradable chemical softener composition. Examples of suitable binders are permanent wet strength resin (ie, Delaware Will Kymene (kymene), available from Herr particulate Les, Inc., mington ^material? 557H), temporary wet strength resin (ie, the New York National Star of New York, National star takes to take on the market and Chemical Co., 78-0080), (ekko (Acoo available from American and Asian mid Campanile of your words, Wayne, NJ material), dry strength ^resins? 514, ^aekko? 711) and holds a secondary resin (ie, stand peokol Virginia ^(Percol)? 175, available from Allied colloid of Polk material) it includes.

In summary, the method of making a multilayer tissue paper web of the present invention forms a multilayer papermaking composition from the aforementioned components, deposits the multilayer papermaking composition on a porous surface, such as a foodliner wire, and removes water from the deposited composition. Steps.

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

Brief description of the drawings

While the specification includes claims that specifically point out and explicitly claim the invention, it is contemplated that the invention may be better understood from the following description with reference to the accompanying drawings;

1 is a schematic cross-sectional view of a single layer of toilet tissue in three layers according to the present invention.

2 is a schematic cross-sectional view of a two-ply advanced tissue of two layers in accordance with the present invention.

The invention is described in more detail below.

The invention relates to a multilayer tissue paper web. More specifically, the present invention relates to a multilayer tissue paper web comprising a biodegradable chemical softener composition and a binder. The tissue web treated as described above can be used to make soft, absorbent and lint resistant paper products, such as advanced tissues, and toilet tissue products.

While the specification includes claims that specifically point out and explicitly claim patent subject matter regarded as the invention, it is contemplated that the invention may be better understood from the following detailed description and the accompanying drawings.

As used herein, the term "lint resistant" refers to the ability of a fibrous product and its constituent web to bind together in use, especially when wet. In other words, the higher the lint resistance, the lower the propensity for lint of the web.

As used herein, the term "binder" refers to various wet and dry strength resins and retention aid resins known in the art of papermaking.

The term "water soluble" as used herein denotes that the material is dissolved in water at least 3% at 25 ° C.

As used herein, the term “tissue paper web, paper web, web, paper sheet and paper product” all form an aqueous papermaking composition, which is deposited on a pore surface, such as a foodliner wire, and pressed or Refers to a sheet of paper produced by a process comprising removing water by gravity or vacuum-assisted drainage without compression and by evaporation.

As used herein, “aqueous papermaking composition” is an aqueous slurry of papermaking fibers and chemicals, described later.

As used herein, the terms "multilayer tissue paper web, multilayer paper web, multilayer web, multilayer paper sheet, and multilayer paper product" are all papers, preferably made from two or more layers of aqueous papermaking composition, of different fiber types. Refers to a sheet of, which is typically a relatively long softwood and a relatively short hardwood fiber as used in tissue paper making. The layers are preferably formed by depositing separate streams of thin fiber slurry on one or more infinite pore screens. When the individual layers are initially formed on separate wires, the layers are subsequently mixed when wet to form a layered composite web.

The first step in the process of the present invention is to form an aqueous papermaking composition. The composition comprises papermaking fibers (hereinafter sometimes referred to as wood pulp), and a mixture of one or more biodegradable quaternary ammonium compounds, polyhydroxy compounds, and binders described hereinafter.

Wood pulp is expected to include the papermaking fibers usually used in the present invention in all its variants. However, other cellulose fibrous pulp such as cotton linter, vargas, rayon and the like can be used, all of which are claimed. Wood pulp useful for the reduction includes chemical pulp, such as kraft, sulfite and sulfate pulp, as well as mechanical pulp including groundwood pulp, thermodynamically treated pulp and chemical-thermodynamically treated pulp (CTMP). Pulps derived from both deciduous and coniferous trees can also be used.

Both hardwood pulp and softwood pulp and blends of both may be used. The term hardwood pulp as used herein refers to fibrous pulp derived from the wood of deciduous trees (pizza plants); The term conifer pulp is fibrous pulp derived from the wood of conifers (naja plants). Hardwood pulp, such as eucalyptus, is particularly suitable for the outer layer of the multilayered tissue web described later, while northern softwood kraft pulp is preferred for the inner layer (s) or ply (s). Also applicable to the present invention are fibers derived from recycled paper, which may contain any or all of the above classes, and other non-fibrous materials such as fillers and additives originally used to facilitate papermaking. .

Biodegradable Chemical Softener Composition

The present invention contains, as an essential component, a mixture of biodegradable quaternary ammonium compounds and polyhydroxy compounds. The ratio of biodegradable quaternary ammonium compound to polyhydroxy compound is about 1.0: 0.1 to 0.1: 1.0, preferably about 1.0: 0.3 to 0.3: 1.0, more preferably about 1.0: 0.7 to 0.7: 1.0, but such The ratio will vary depending on the molecular weight of the particular polyhydroxy compound and / or biodegradable quaternary ammonium compound used.

Each of these types of compounds will be described in detail below.

A. Biodegradable Quaternary Ammonium Compounds

The biodegradable chemical emollient composition comprises from about 0.01 to about 3.00% by weight, preferably from about 0.01 to about 1.00% by weight of biodegradable quaternary ammonium compounds, preferably biodegradable quaternary ammonium compounds having the general formula Contains;

In the above formula,

Each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, benzyl group or mixtures thereof;

Each R ₁ substituent is a C ₁₂ -C ₂₂ hydrocarbyl group, or a substituted hydrocarbyl group or mixtures thereof;

Each R ₃ substituent is a C ₁₁ -C ₂₁ hydrocarbyl group, or a substituted hydrocarbyl or mixture thereof;

Y is —O—C (O) —, —C (O) —O—, —NH—C (O) —, —C (O) —NH—, and mixtures thereof;

n is 1 to 4;

X- is a suitable anion such as chloride, bromide, methylsulfate, ethylsulfate, nitrate and the like.

As mentioned in Swern, Bailey's Industrial Oil and Fat Products, Third Edition, John Wiley and Sons (New York 1964), tallow is a natural substance with various compositions. Table 6.13 in Swarn's literature typically shows that at least 78% of the fatty acids in the tallow 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. In addition, depending on the characteristic requirements of the product, the saturation of the tallow can vary from non-hydrogenated (soft) to contact, partial or fully hydrogenated (hard). All of the above mentioned saturation degrees are expressed as being within the scope of the present invention.

Substituents R ₁ , R ₂ and R ₃ may be optionally substituted with various groups such as alkoxyl, hydroxyl, or branched, although such materials are not preferred herein. Preferably, each R ₁ is C ₁₂ -C ₁₈ alkyl and / or alkenyl, most preferably each R ₁ is straight chain C ₁₆ -C ₁₈ alkyl and / or alkenyl. Preferably, each R ₂ is methyl or hydroxyethyl. Preferably, R ₃ is C ₁₃ -C ₁₇ alkyl and / or alkenyl, most preferably R ₃ is straight chain C ₁₅ -C ₁₇ alkyl and / or alkenyl, and X- is chloride or methyl sulfate. Moreover, ester-functional quaternary ammonium compounds are small amounts of up to about 10% of mono (long chain alkyl) derivatives, for example (R ₂ ) ₂ -N ⁺ -((CH ₂ ) ₂ OH) ((CH ₂ ) may optionally contain ₂ OC (O) R ₃ ) X-. These minor components act as emulsifiers and are useful in the present invention.

Specific examples of ester-functional quaternary ammonium compounds having the above-mentioned structure and suitable for use in the present invention are known diester dialkyl dimethyl ammonium salts, for example diester dietalow dimethyl ammonium chloride, monoester dielow dimethyl Ammonium chloride, diester dielow dimethyl ammonium methyl sulfate, diester di (hydrogenated) tallow dimethyl ammonium methyl sulfate, diester di (hydrogenated) tallow dimethyl ammonium chloride, and mixtures thereof. Especially preferred are diester ditallow dimethyl ammonium chloride and diester di (hydrogenated) tallow dimethyl ammonium chloride. This particular material is commercially available under the trade name "ADOGEN DDMC ^? " From Serex Chemical Company, Dublin, Ohio.

Di-quaternary variants of ester-functional quaternary ammonium compounds may also be used, meaning that they are within the scope of the present invention. These compounds have the following general formula:

In the above-mentioned structure, each R ₂ is a C ₁ -C ₆ alkyl or hydroxyalkyl group, R ₃ is a C ₁₁ -C ₂₁ hydrocarbyl group, n is 2 to 4, X- is a suitable anion, For example halides (eg chloride or bromide) or methyl sulfate. Preferably, each R ₃ is C ₁₃ -C ₁₇ alkyl and / or alkenyl, most preferably each R ₃ is straight C ₁₅ -C ₁₇ alkyl and / or alkenyl, and R ₂ is methyl .

B. Polyhydroxy Compounds

The biodegradable chemical softener composition contains from about 0.01 to about 3.00% by weight, preferably from about 0.01 to about 1.00% by weight of a polyhydroxy compound as an essential component.

Examples of polyhydroxy compounds useful in the present invention are glycerol, sorbitol, polyglycerols having a weight average molecular weight of about 150 to about 800 and about 200 to about 4000, preferably 200 to about 1000, most preferably about 200 to Polyoxypropylene glycol having a weight average molecular weight of about 600. Particular preference is given to polyoxyethylene glycols having a weight average molecular weight of about 200 to about 600. Mixtures of the aforementioned polyhydroxy compounds may also be used. For example, mixtures of glycerol and polyoxyethylene glycols having a weight average molecular weight of about 200 to 1000, more preferably about 200 to 600, are useful in the present invention. Preferably, the weight ratio of glycerol to polyoxyethylene glycol is about 10: 1 to 1:10.

Particularly preferred polyhydroxy compounds are polyoxyethylene glycols having a weight average molecular weight of about 400. This material is commercially available under the trade name "PEG-400" from Union Carbide Co., Denver, Connecticut.

The biodegradable chemical softener compositions referred to herein, ie mixtures of biodegradable quaternary ammonium compounds and polyhydroxy compounds, are diluted to the desired consistency to form sheet or at the wet end of the paper machine at a suitable point in front of the foodliner wire. It is preferred to form dispersions of quaternary and polyhydroxy compounds prior to addition to the aqueous slurry or composition of papermaking fibers in the step. However, applying the aforementioned biodegradable chemical softener compositions immediately following the formation of the wet tissue web and prior to terminating the drying of the web also provides significant softness, absorbency and wet strength benefits and falls within the scope of the present invention. Is represented.

Biodegradable chemical emollient compositions have been found to be more effective when the biodegradable quaternary ammonium compound and the polyhydroxy compound are first mixed together first before being added to the papermaking composition. As described in more detail in Example 1 hereinafter, a preferred method is to first heat the polyhydroxy compound to a temperature of about 66 ° C. (150 ° F.) and then add the biodegradable quaternary ammonium compound to the hot polyhydroxy compound Consists of forming a homogeneous fluid. The weight ratio of quaternary ammonium compound to polyhydroxy compound is about 1.0: 0.1 to 0.1: 1.0, preferably the weight ratio of biodegradable quaternary ammonium compound to polyhydroxy compound is about 1.0: 0.3 to 0.3: 1.0, and more Preferably the weight ratio of biodegradable quaternary ammonium compound to polyhydroxy compound is about 1.0: 0.7 to 0.7: 1.0, but this ratio will vary depending on the molecular weight of the polyhydroxy compound and / or biodegradable quaternary ammonium compound used. will be.

It was unexpectedly found that the process of adsorbing a polyhydroxy compound on paper was significantly improved when the polyhydroxy compound was mixed with a biodegradable quaternary ammonium compound and added to the paper by the process mentioned above. In fact, at least 20% of the polyhydroxy compound and the biodegradable quaternary ammonium compound added to the fibrous cellulose are retained, and preferably the retention of the biodegradable quaternary ammonium compound and the polyhydroxy compound is from about 50 to about 90 %to be.

Importantly, the adsorption takes place at the consistency and combustion time performed during the papermaking process. In order to better understand that polyhydroxy compounds are retained on paper at high rates, melt and aqueous dispersions of diester di (contact curing) tallow dimethyl ammonium chloride (DEDTHTDMAC), and the properties of polyoxyethylene glycol 400 Studied.

Without wishing to be bound by theory or otherwise limiting the invention, the following description is presented to explain how ester-functional quaternary ammonium compounds promote the paper-based adsorption of polyhydroxy compounds.

DEDTHTDMAC (Diesder di (contact curing) tallow dimethyl ammonium chloride) is present in equilibrium as a mixture of liquid crystals and crystalline phases. X-ray data indicate a liquid crystalline phase that does not prove that commercial DEDTHTDMAC is in fact crystalline.

Mixture of DEDTHTDMAC and PEG-400

Study of the phases of these two materials using stepwise dilution indicates that their physical properties are similar to those of di (hydrogenated) tallow dimethyl ammonium chloride. These compounds are miscible at a wide range of temperatures (above 50 ° C.), indicating that dispersions may be prepared from these mixtures at comparable ranges of temperatures. There is no upper limit temperature of miscibility. X-ray data show that the mixture of crystal and liquid phase is in fact present as a DEDTHTDMAC / PEG-400 mixture.

Mixture of DEDTHTDMAC and Glycerol

A mixture of DEDTHTDMAC and glycerol in a 1: 1 weight ratio appears to be liquid (from direct observation and X-ray data); glycerol can form liquid crystals with other surfactants, but with these compositions it is not so in these systems. It doesn't seem to be.

Mixture of DEDHTDMAC and PEG-400

Studying the phases of the two materials using a stepwise dilution shows that their physical properties are similar to those of DEDTHTDMAC. The compounds are miscible at a wide range of temperatures (above 67 ° C.), indicating that dispersions may be prepared from these mixtures at comparable ranges of temperatures. There is no upper limit temperature of miscibility.

Physical Properties of Quaternary / Polyhydroxy Compounds / Water Mixtures

Dispersions of any of these materials may also be prepared by dilution with water of a mixture in which the polyhydroxy compound and ester-functional quaternary ammonium salt are maintained at a temperature compatible with each other. Since neither DEDTHTDMAC nor DEDHTDMC is soluble in water, dilution of the dry phase with water precipitates the ester-functional quaternary ammonium compound as small particles. Polyhydroxy compounds dissolve in water in all ratios and do not precipitate.

A mixture of approximately equal amounts of DEDTHTDMAC and a polyhydroxy compound (eg, glycerol, PEG-400, etc.) is added to water to form a mixture containing about 1% DEDTHTDMAC and DEDTHTDMAC will precipitate. In most cases, the DEDTHTDMAC phase is lamellar liquid crystals near room temperature.

Colloidal Structure of Dispersion

Liquid crystals in the diluted mixture exist mostly as hermetic and spherical vesicles. The formation of such dispersions results from large osmotic pressure gradients present instantaneously in the process. The origin of this pressure purchase is the spatial gradient in the composition (and thermodynamic activity) of the resulting water. Since the liquid phase of the DEDTHTDMAC / glycerol mixture may exist at a wide range of temperatures, it may produce dispersions at a wide range of temperatures.

Observation by low temperature electron microscopy shows that the particle size is about 0.1 to 1.0 micrometers, and the structure is very diverse. Some are sheets (curved or planar) while others are closed vesicles. All the membranes of the particles are molecular bilayers with the head exposed to water and the tail facing each other. PEG is thought to associate with these particles. Application of the dispersion prepared in this manner to paper strongly promotes adsorption of the polyhydroxy compound onto the paper by attaching the ester functional quaternary ammonium ions to the paper, and is modified to retain soft and moisture.

State of dispersion

Cooling the aforementioned dispersions may partially crystallize the material in the colloidal particles. However, equilibrium will require a long time (perhaps months) for the disordered particles to interact with the paper, where the film is in liquid or disordered crystalline phase. Preferably, the biodegradable chemical softener composition described herein above is used before equilibrium is achieved.

Drying the fibrous cellulose material decomposes the biodegradable quaternary compounds and polyhydroxy compounds (ie, glycerol, PEG-400, etc.). When the vesicles break down, most of the PEG component penetrates into the cellulose fibers, thereby enhancing the fiber's visibility. What is abundant is that some PEG remains on the fiber surface and acts to improve the rate of absorption of cellulose fibers. Because of the ionic interaction, the cationic portion of the biodegradable quaternary compound component stays on the cellulose fibers, thereby improving the surface feel and ductility of the paper product.

Binder material

The present invention provides, as an essential component, a binder selected from the group consisting of permanent wet strength resin, temporary wet strength resin, dry strength resin, retention aid resin, and mixtures thereof, as an essential component, from about 0.01% to about 3.0% by weight, preferably about 0.01% by weight. % To about 1% by weight. The binder controls the lining and, if any, offsets the tensile strength loss due to the biodegradable chemical softener composition.

If permanent wet strength is required, the binder is selected from the group consisting of polyamide-epichlorohydrin, polyacrylamide, styrene-butadiene latex, insoluble polyvinyl alcohol, urea formaldehyde, polyethyleneimine, chitosan polymer and mixtures thereof. You can choose. Polyamide-epichlorohydrin resins are cationic wet strength resins that are known to be particularly useful. Suitable forms of such resins are described in US Pat. No. 3,700,623, issued Oct. 24, 1972, and US Pat. No. 3,772,076, issued Nov. 13, 1973, both of which are patents of Keim, Cited by reference. Commercial sources of useful polyamide-epichlorohydrin resins are available from the trade name Kymeme ^? 557H, Hercules, Inc., Wilmington, Delaware.

Polyacrylamide resins have also been found to be useful as wet strength resins or retention aid resins. The resins are described in U.S. Patent No. 3,556,932 to Coscia et al. 19 January 1971 and U.S. Patent No. 3,556,933 to Williams et al. 19 January 1971, both of which are described above. All patents are incorporated herein by reference.

One commercial source of polyacrylamides is that the resin may be traded under the trade name Parez ^? American Cyanamid Co. of Stanford, Connecticut, sold at 631 NC. Another commercial source of cationic polyacrylamide resins is the trade name Percol ^? (Percol) 175 and Retten ^? Allen Colloids from Sulfork, Virginia, 1232, and Hercules Inc. of Wilmington, Delaware.

Other water soluble cationic resins known to be useful in the present invention are urea formaldehyde and melamine formaldehyde resins. More common functional groups of such multifunctional resins are nitrogen containing groups such as amino groups and methylol groups bonded to nitrogen. Polyethylenimine type resins are also known to be useful in the present invention.

If temporary wet strength is required, the binder may be a starch-based temporary wet strength resin, a cationic dialdehyde starch-based resin (e.g. Caldas from Japan Carlet or Cobond from National Starch). Cobond) 1000), dialdehyde starch and / or resins described in US Pat. No. 4,981,557, issued January 1, 1991 to Bjorkquist, which is incorporated herein by reference.

If dry strength is required, the binder may be polyacrylamide (e.g. Cypro 514 and Accostrength 711 from American Cyanamide, Wayne, NJ), starch (e.g. corn starch or potato starch), Polyvinyl alcohols (e.g. Airvol 540 from Air Products, Allentown, Pennsylvania), guar gum or low-cursor soy gum, polyacrylate lactes and / or carboxymethyl cellulose (e.g. Delaware Aqualon CMC-T manufactured by Aqualon Co., Wilmington). In general, starches suitable for practicing the present invention are characterized by water solubility and hydrophilicity. Examples of starch materials include, but are not limited to, corn starch, potato starch and waxy corn starch (in the industry known and particularly preferred amicoa starch). Amioca starch differs from ordinary corn starch containing both amylopectin and amylose in that the whole is amylopectin. The various and unique properties of Amioka starch are described in "Amioca- The Starch from Waxy Corn", H. H. Schopmeyer, food Industries, December 1945, pp. 106-108 (Vol. Pp. 1476-1478). Starch is preferably in granulated or dispersed form but in granules. Starch preferably induces swelling of the granules when heated sufficiently. More preferably, as it is heated, the starch granules swell until just before dispersion of the starch granules. Such highly swollen starch granules are referred to as "fully heated". In general, the dispersion conditions may vary depending on the size of the starch granules, the crystallinity of the granules and the amylose content. For example, fully heated Amioca starch is prepared by heating a liquid slurry of starch granules having a consistency of about 4 × for about 30 minutes to about 40 minutes at about 190 ° F. (about 88 ° C.). Examples of other starch materials that can be used are modified cationic starches (North Starch and Chemical Company, Bridgewater, NJ, modified to have nitrogen-containing groups such as amino groups and methyl groups bonded to nitrogen). Company). The modified starch material is mainly used as a pulp composition additive for increasing the wet and / or dry emphasis strength. Given that the modified starch is more expensive than unmodified starch, unmodified starch is more preferred.

The application method, like the method of applying other chemical additives, is preferably a wet end addition method and a spray method and is less preferably by stamping. The binder may be applied to the paper web alone or before and after addition of softener, absorbent and / or cosmetic additives. In order to obtain an increase in strength at the same time as inhibiting lining against drying compared to the same sheet not treated with the binder, an effective amount of binder, preferably starch, is preferably applied to the sheet. Preferably, from about 0.01% to about 3.0%, more preferably from about 0.1% to about 1.0% of the binder, preferably starch, as calculated on the basis of dry fiber weight, is maintained on a dry sheet.

The second step of the present invention is to add the aforementioned chemical softener composition and binder to the porous surface to deposit the multilayered tissue paper composition, and the third step is to remove water from the deposited composition as above. Methods and apparatus that can be used to perform these two process steps are well known to those skilled in the art of papermaking. Preferred multilayer tissue paper embodiments of the present invention are from about 0.01% to about 3.0% by weight, preferably from about 0.1% to about 1.0% by weight, based on the dry fibers of the biodegradable chemical softener composition and binder described herein. It contains.

The present invention is applicable to multilayer tissue paper, which typically includes, but is not limited to, felt-compressed multilayer tissue paper, high bulk pattern tight multilayer tissue paper, and high bulk uncompressed multilayer tissue paper. The multi-layered tissue paper product prepared from the above may be of a single ply or multiply structure. Tissue structures made from layered paper webs are described in US Pat. No. 3,994,771 to Morgan Jr. et al., November 30, 1976, which is incorporated herein by reference. Generally the soft and bulky absorbent paper structures of the composition in which the web is present are preferably made from two or more layers of finish support material composed of different kinds of fibers. The layer is preferably prepared from the deposition of a separate stream of thin fiber slurry, which is typically a softwood fiber and a relatively short hardwood fiber used for the production of multilayered tissue paper on one or more endless pore membranes. If individual layers are formed on already separated wires, the layers combine when wet so as to form a layered composite web. The layered web is shaped into an open mesh drying / imprinting fabric surface by applying flow force to the web, and then thermally pre-dried onto the fabric as part of a low density papermaking process. The layered webs are classified according to the type of fiber and the fiber content of each layer is essentially the same. The basis weight of the multilayer tissue paper is preferably from 10 g / m 2 to about 65 g / m 2 and a density of about 0.60 g / m 3 or less. Preferably the basis weight is about 35 g / m 2 or less and the density is about 0.30 g / m 3 or less. Most preferably the density is from 0.04 g / m 3 to 0.20 g / m 3.

The multi-layered tissue paper web of the present invention consists of a second or more overlapped layer consisting of a first pack and one or more second packs that are continuously overlapped with the first layer. Preferably, the multi-layer tissue paper consists of three overlapping layers, which consists of an inner layer or a center layer and two outer layers, wherein the inner layer is located between the two outer layers. The two outer layers preferably comprise at least 60% by weight of relatively short papermaking fibers having an average fiber of about 0.2 to about 1.5 mm. The short papermaking fibers are typically hardwood fibers, preferably eucalyptus fibers. On the other hand, inexpensive sources of short fibers, such as sulfite fibers, thermodynamically treated pulp fibers, chemically-thermodynamically treated pulp fibers, fibers separated from recycled fibers and mixtures thereof, may be provided in one of the outer layers or It can be used for both and can be incorporated in an inner layer as needed. The inner layer includes fibers having an average fiber length of at least about 2.0 mm and at least about 60% of primary filament components based on the weight of the relatively long papermaking fibers. The long papermaking fibers are typically coniferous fibers and are preferably northern coniferous kraft fibers. 1 is a cross-sectional view of a three-layered toilet paper for toilets according to the present invention. In FIG. 1, a three layered single layer web 10 comprises three overlapping layers, an inner layer 12 and two outer layers 11. The outer layer 11 consists mainly of short papermaking fibers 16, and the inner layer 12 mainly consists of long papermaking fibers 17.

In another preferred embodiment of the invention, the multiply tissue paper product is formed by placing two or more multilayer tissue paper webs in parallel. For example, a two-ply tissue paper product is made to include in parallel a first two layer tissue paper web and a second two layer tissue paper web. In this example, each ply is a two layer tissue sheet comprising a first layer and a second layer. The first layer preferably comprises short hardwood fibers and the second layer preferably comprises long coniferous fibers. The two plies are joined with the conifer short fibers on each ply surface facing outwards and the layer containing the conifer long fibers facing inward. 2 is a cross-sectional view of a two layer double surface tissue in accordance with the present invention. In FIG. 2, the two-ply two-ply web 20 consists of two plies 15 positioned in parallel. Each ply 15 consists of an inner layer 19 and an outer layer 18. The outer layer 18 consists mainly of short papermaking fibers 16, and the inner layer 19 consists mainly of long papermaking fibers 17. Similarly, three-ply tissue paper products can be made by placing three multilayer tissue paper webs in parallel.

In the above statement, the present invention is not limited to three layers (one or two layers) and two layers of tissue paper products. Tissue products consisting of three or more plies combined with each ply of one or more layers are also within the scope of the present invention.

Preferably, most biodegradable quaternary ammonium compounds and pulleyhydroxy compounds are contained in one or more outer layers of the multilayer tissue paper web of the present invention. More preferably, most biodegradable quaternary ammonium compounds and polyhydroxy compounds are contained in both outer layers. Biodegradable chemical softener compositions have been found to be most effective when added to the outer layer or ply of tissue paper products. Wherein the mixture of biodegradable quaternary compounds and polyhydroxy compounds serves to improve both the absorbency and the ductility of the multilayer tissue product of the present invention. In Figures 1 and 2, the biodegradable chemical softener composition comprising a mixture of biodegradable quaternary ammonium compounds and polyhydroxy compounds is represented by dark colored circles (14). In Figures 1 and 2 it can be seen that most of the biodegradable chemical softener composition 14 is contained in the outer layers 11 and 18, respectively.

However, lint resistance of multilayer tissue paper products is reduced with the introduction of biodegradable quaternary ammonium compounds and polyhydroxy compounds. Therefore, the binder is used to suppress lining and increase the tensile strength. Preferably, the binder is contained in the inner layer and at least one outer layer of the multilayer tissue paper web of the present invention. More preferably, the binder is contained throughout the multilayer article, ie in the inner and outer layers. In Figures 1 and 2, the binder is represented by a white circle (13). In Figures 1 and 2 it can be seen that many binders 13 are contained in the inner layers 12 and 19, respectively. In another preferred embodiment (not shown), most binders are contained in at least one outer layer, more preferably both outer layers of the multilayer article.

Combining biodegradable chemical emollient compositions containing biodegradable quaternary ammonium compounds and polyhydroxy compounds with a binder yields tissue paper products with excellent ductility, absorbency and lint resistance. Most biodegradable chemical softener compositions can be added to the outer layer or outer pleats of tissue paper to enhance their efficiency. Typically the binder is dispersed throughout the tissue sheet to inhibit lining. However, as with biodegradable chemical softener compositions, a binder may optionally be added to the most necessary portion.

Conventionally compressed multilayer tissue papers and methods for their preparation are known in the art. The paper is typically made by placing the papermaking composition on the hole-forming wire. The hole-forming wire is often referred to as a foodliner wire in the art. Once the composition is placed on the pore forming wire, it is called a web. The web is transferred to a dewatering felt to compress and dehydrate the web by drying at elevated temperature. Certain papermaking methods and apparatuses described in connection with the present process are well known to those skilled in the art. In a typical process, a low consistency pulp composition is placed in a compressed headbox. The head box has an opening for delivering a thin deposit of pulp finish support material onto the foodliner wire to form a wet web. The web is typically dewatered by vacuum dewatering to become a fiber having a consistency of about 7% to about 25% based on the weight of the total web and further to the pressure created by applying the web to a mechanical element, such as a cylindrical roll. It is dehydrated by applying an operation to apply.

The dewatered web is further compressed during delivery and dried by a steam drum apparatus known in the art as a Yankee dryer. Pressure may be generated in the Yankee dryer by mechanical methods such as bulk cylindrical drums that compress back against the web. Vacuum may also be applied while compressing the web against the Yankee vacuum surface. Multiple Yankee dryer drums may be used and additional pressure may optionally be applied between the drums by the apparatus. The multilayer tissue paper structure produced is referred to herein as a conventional compressed multilayer tissue paper structure. It is believed that the sheet became dense because the web was subjected to substantially mechanical pressure, while the fibers were wet and then dried in a compressed state.

The dense pattern of multilayer tissue paper is characterized by having a high bulk area of relatively low fiber density and an arrangement of dense zones of relatively high fiber density. The high volume region, on the one hand, is characterized by a pillow region. The dense zone is also called the knuckle zone on the one hand. Dense zones may be interspersed in high volume areas or partially or wholly connected to one another. A preferred process for dense patterned tissue webs is US Pat. No. 3,301,746, issued January 31, 1967 to Sanford and Sisson, and Peter G., August 10, 1976. United States Patent No. 3,974,025 to Peter G. Ayers, Paul D., March 4, 1980. United States Patent No. 4,191,609 to Paul D. Trokhan and Paul D., January 20, 1987. US Patent No. 4,637,859 to Trocan, which is incorporated herein by reference in its entirety.

In general, the dense pattern web preferably places the papermaking composition on a pore forming wire such as a foodliner wire to form a wet web and the web in parallel with the support arrangement. The web is compressed against the arrangement of the support, resulting in a dense zone in the web at a location that is geographically corresponding to the point of contact of the support arrangement and the wet web. The remaining uncompressed web during this operation is called a high bulk area. The high bulk region can be further dedensified by applying flow pressure, for example using a vacuum device or a blow dryer. The web is dewatered and further pre-dried to substantially avoid compression of the high bulk area. This is preferably done by applying a flow pressure using a vacuum apparatus or a blow dryer, or alternatively by a method of mechanically compressing the web against the support arrangement and not compressing the high bulk region. Dehydration, selective predrying, and the formation of dense zones are carried out together or partially together to reduce the total number of steps to be performed. As a result of the formation of dense zones, dehydration and selective predehydration, the web is completely dry and preferably still mechanical compression is avoided. Preferably from about 8% to about 55% of the multilayer tissue paper surface comprises a dense knuckle with a relative density of at least 125% of the bulk area.

The support array is preferably a print carrier fabric with a patterned array of knuckles that acts as a support array and promotes tight band formation upon application of pressure. The pattern of knuckles forming the support array has already been mentioned. Printed carrier structures are described in US Pat. No. 3,301,746 to Sanford and Sisson, Jan. 31, 1967, and US Pat. No. 3,821,068 to Salvucci, Jr., et al., May 21, 1974. US Pat. No. 3,974,025 to Ayers, August 10, 1976, US Pat. No. 3,573,164 to Friedberg, et al., March 30, 1971, Cancer, October 21, 1969 In U.S. Patent No. 3,473,576 to Nemes, U.S. Patent No. 4,239,065 to Trokhan, December 16, 1980, and U.S. Patent No. 4,528,239 to Trocan, July 9, 1985 And all of the above patents are incorporated herein by reference.

Preferably, the finish support material is first formed in a wet web on a pore forming carrier such as a foodliner wire. Dewater the web and transfer to a print fabric. Alternatively, the finish support fee may first be deposited on a porous support carrier that acts as a print fabric. Once formed, the wet web is dewatered and preferably pre-dried to achieve a selected fiber consistency of about 40% to about 80%. Dewatering is carried out using suction boxes or other vacuum devices or blow dryers. Knuckle printing of the print fabric prints on the web described above before the web is completely dried. One way of performing printing is by applying mechanical pressure. For example, a printing fabric, such as a Yankee dryer, may be performed by compressing a nip roll that supports a drying drum, wherein the web is disposed between the nip roll and the dry dream. Further, preferably, the web is molded to the printing fabric before the printing fabric is completely dried by flow pressure using a vacuum apparatus such as a suction box or a blow dryer. During the initial dewatering process, aside from this, flow pressure can be applied during the subsequent step or during the mixing step to induce compaction of the compact zone.

The uncompressed unpatterned-dense multi-layer tissue paper structure was produced by Joseph L. May 21, 1974. Salbutchi, J. R. And Peter Yen. United States Patent No. 3,812,000 to Ianos and Henry E. Becker, Albert L., June 17, 1980. US Pat. No. 4,208,459 to McConnell and Richard Schwet, which is incorporated herein by reference. In general, uncompressed, non-pattern-dense multi-layer tissue paper structures deposit paper finishes onto pore forming wires, such as foodliner wires, to form wet webs, dewater the webs, and the webs to at least 80% fiber. The excess water is removed and the web is creped without using mechanical compression until the consistency is achieved. The water is removed from the web by vacuum dehydration or thermal drying. The resulting structure is a high bulk sheet of soft but weak relatively uncompressed fibers. Preferably the binder is added to the web portion prior to creping.

The multilayer tissue paper web of the present invention can be used for all applications where a soft absorbing multilayer tissue paper web is desired. Particularly suitable for use of the multi-layer tissue paper web of the present invention are toilet tissue and high quality tissue products. For example, two multi-layer tissue paper webs of the present invention can be joined to produce two layers of high quality tissue or toilet tissue products.

Molecular Weight Measurement

A. Overview

An essential distinguishing property of polymeric materials is their molecular size. The properties that enable polymers to be used in various applications almost all stem from their macro-molecular properties. In order to fully characterize these materials it is essential to define and measure their molecular weight and molecular weight distribution. It is more correct to use the term relative molecular mass rather than molecular weight, but the former is more commonly used in the polymer field. It is not always practical to measure the molecular weight distribution. However, it is even more necessary when using chromatographic techniques. Rather, it is reliable to express the molecular size in terms of average molecular weight.

B. Average Molecular Weight

Considering the relative molecular mass (M _i) a simple molecular weight distribution that represents the weight fraction (w _i) of molecules with, it is possible to define several useful average values. By calculating the average value based on the number of molecules (N _i ) of a specific size (M _i ), the number of average molecular weights can be obtained.

An important result of the above definition is that the number average molecular weight (g) contains molecules of avogadro's number. The definition of molecular weight is consistent with the definition of monodisperse molecular species, ie molecules having the same molecular weight. More importantly, it was found that M _n can be easily calculated by measuring the number of molecules in a constant weight of polydisperse polymer. This is based on a comprehensive measure.

The median mean molecular weight, when averaged based on the weight fraction (W _i ) of the molecule having an arbitrary mass (M _i) ), is defined as follows:

Is more accurate in reflecting the polymer's properties such as melt viscosity and physical properties. Even more useful means and used in the present invention for this purpose.

Assays and Test Methods

Assays of the amount of biodegradable treatment chemicals used herein or retained in tissue paper webs are performed by any method permitted in the application.

A. Quantitative Assay of Ester-functional Quaternary Ammonium and Polyhydroxy Compounds

For example, ester-functional quaternary ammonium compounds retained in tissue paper, such as diester di (hydrogenated) tallow dimethyl ammonium chloride (DEDHTDMAC) (i.e., ADOGEN DDMC), are solvent extracted from DEDHTDMAC with an organic solvent. After determination, it can be determined by conducting a cation / anion titration using dimidium bromide as an indicator. The amount of polyhydroxy compound, such as PEG-400, may be extracted in an aqueous solvent such as water and then gas chromatography or calorimetry to determine the amount of PEG-400 in the extract. The method is illustrative and is not intended to exclude other methods useful for determining the amount of a particular component retained in tissue paper.

B. Hydrophilicity

The hydrophilicity of multilayer tissue paper generally refers to the tendency of the multilayer tissue paper to be wetted by water. The hydrophilicity of the multilayer tissue paper is quantitatively determined by determining the period of time required for the dry multilayer tissue paper to fully wet with water. This period is called "wetting time". The following wet time determination method can be used to consistently and repeatedly test the wet time. First, a conditioned unit sample sheet (environmental conditions for testing paper specimens are 23 + 1 ° C. and 5 + 2% RH as described in TAPPI method T 402.) about 4-3 / 8 in × Provide 4-3 / 4 inch (about 11.1 cm × 12 cm) multilayer tissue paper structures. Secondly, the sheets are folded in equal quarters and agglomerated into balls of diameters of about 0.75 in (about 1.9 cm) to about 1 in (about 2.5 cm). Third, the ball-shaped sheets are placed on the surface of distilled water at 23 ± 1 ° C. and the timer is started at the same time. Fourth, stop the timer when the ball sheet is completely wet. Complete wetting is visually observed.

Of course, the hydrophilic nature of the multilayer tissue paper embodiments of the present invention can be determined immediately after preparation. However, a substantial increase in hydrophobicity may occur during the first two weeks after making the multilayer tissue paper, that is, two weeks after the paper is made. Therefore, the wet time is preferably measured at the end of the two weeks. In addition, the wet time measured at the end of two weeks at room temperature is referred to as "two week wet time".

C. Biodegradability

Self-emulsifiable biodegradable chemical softener compositions without water suitable for use in the present invention are biodegradable. As used herein, the term "biodegradable" refers to the complete decomposition of the substrate by microorganisms into carbon dioxide, water, organisms and inorganic materials. Biodegradability potential is assessed by measuring the rate of carbon dioxide generation and the rate at which dissolved organic carbon is removed from a medium containing dilute bacterial inoculum obtained from a supernatant of a simple carbon and energy source and homogenized activated sludge as test substance. See Larson, "Estimation of Biodegradation Potential of Xenobiotic Oraganic Chemicals," Applied and Environmental Microbiology, Volume 38 (1979), pages 1153-61, which describes suitable biodegradability assays. The substrate is readily biodegradable if the substrate is used to generate 70% carbon dioxide and at least 90% dissolved organic carbon has been removed in 28 days using the method. Softeners used in the present invention satisfy the above biodegradability conditions.

D. Density

As used herein, the density of multi-layer tissue paper is the average density calculated as the basis weight of the paper divided into calipers using a suitable conversion method. The caliper of the multilayer tissue paper used herein is the thickness of the paper when a compressive force of 95 g / in ² (15.5 g / cm ² is applied.

E. lint

Dry lint

Dry lint can be measured using a Sutherland Rub Tester, a piece of black felt, a four pound weight and a Hunter Color meter. Sutherland testers are motor-powered devices that allow the weight to be hit back and forth across the suspended sample. Hang a 4 pound weight on a piece of black felt. The tester rubs or moves the weighted felt over a stationary sample every five hits. The Hunter Color L value of the black felt is determined before and after rubbing. The difference between the two hunter color values constitutes the measurement of the dry lint. Other dry lint measurement methods known in the art can also be used.

Wet lint

Suitable methods for measuring the wet lint properties of tissue samples are described in US Pat. No. 4,950,545 to Walter et al., August 21, 1990, incorporated herein by reference. The method essentially involves passing the tissue sample through two steel rolls, one of which is partially submerged in the water bath. The lint obtained from the tissue sample is transferred to a steel roll moistened in a water bath. The steel roll is continuously rotated to deposit the lint in the water bath. The lint is recovered and counted. See column 5, line 45 to line 6, line 27 of Walter et al. Other wet lint measurement methods known in the art can be used.

Random ingredient

Other chemicals conventionally used in papermaking may be added to the biodegradable chemical softener compositions described herein or added to the papermaking composition unless they have a significant adverse effect on the softness and absorption of the fibrous material. Can improve the action.

For example, surfactants can be used to treat the multilayer tissue paper web of the present invention. If necessary, the amount of surfactant is preferably from about 0.01% to 2.0% by weight based on the dry fiber weight of the multi-ply tissue paper. The surfactant preferably has an alkyl chain having 8 or more carbon atoms. Examples of anionic surfactants are linear alkyl sulfonates and alkylbenzene sulfonates. Examples of anionic surfactants include alkylglycoside esters such as Crodesta SL-40 from Croda, Inc., New York, NY; March 8, 1977 W.K. Alkylglycoside ethers described in US Pat. No. 4,011,389 to W.K.Langdon et al .; And alkylpolyethoxylated esters such as Glyco Chemicals Inc., Greenwich, Connecticut, Pegosperse 200ML, and IGEPAL RC-520, Long Franc Corporation, Cranbury, NJ. Alkylglycosides.

The above enumeration of any chemical additives is for illustrative purposes only and is not intended to limit the scope of the present invention.

The following examples are intended to illustrate the practice of the invention and not to limit it.

Example 1

The purpose of this example is a substantially moisture-free self-emulsifiable biodegradable chemistry comprising a mixture of diester di (contact curing) tallow dimethyl ammonium chloride (DEDTHTDMAC) and polyoxyethylene glycol 400 (PEG-400) To illustrate a method that can be used to prepare the emollient composition.

A water-free self-emulsifiable biodegradable chemical softener composition is prepared according to the following procedure: 1. Weigh the equivalents of DEDTHTDMAC and PEG-400 separately; 2. Heat PEG to 66 ° C. (150 ° F.); 3. Dissolve DEDTHTDMAC in PEG to produce a melt solution at 66 ° C. (150 ° F.); 4. mixing appropriately to produce a homogeneous mixture of DEDTHTDMAC in PEG; 5. Cool the homogeneous mixture of (4) to room temperature to form a solid.

Substantially moisture-free self-emulsifiable biodegradable chemical softener composition (5) is premixed in a chemical feeder (e.g., Sherex Company, Dublin, Ohio) (steps 1 to 5 above), followed by a biodegradable chemical softener After being economically shipped to the end user of the composition, it can be diluted to the desired consistency.

Example 2

The purpose of this example is to prepare a substantially moisture-free self-emulsifiable biodegradable chemical softener composition comprising a mixture of diester di (contact curing) tallow dimethyl ammonium chloride (DEDTHTDMAC) and a mixture of glycerol and PEG-400 To illustrate a method that can be used.

A substantially moisture free self-emulsifying biodegradable chemical softener composition is prepared according to the following procedure: 1. Blend a mixture of glycerol and PEG-400 at 75:25 (weight ratio); 2. separately weigh the equivalent of DEDTHTDMAC and mixture (1); 3. heat the mixture of (1) to 66 ° C. (150 ° F.); 4. Dissolve DEDTHTDMAC in (3) to produce a melt solution at 66 ° C. (150 ° F.); 5. Mixing appropriately to produce a homogeneous mixture of DEDTHTDMAC in (3); 6. Cool the homogeneous mixture of (5) to room temperature to form a solid.

Substantially moisture-free self-emulsifying biodegradable chemical softener composition (6) is premixed in a chemical feeder (e.g., Sherex Company, Dublin, Ohio) (steps 1 to 6 above), and then biodegradable chemical softener After being economically shipped to the end user of the composition, it can be diluted to the desired consistency.

Example 3

The purpose of this example is a soft, absorbent lint treated with a chemical softener composition comprising diester di (contact curing) tallow dimethyl ammonium chloride (DEDTHTDMAC) and polyoxyethylene glycol 400 (PEG-400) and a temporary wet strength resin. It illustrates a method of using a dry blowing method and a lamination papermaking technique for producing a resistant toilet paper of a plurality of tissues.

Test scale foodliner paper making machines are used in the practice of the present invention. First, a chemical softener composition is prepared according to the procedure of Example 1, wherein a homogeneous premix of DEDTHTDMAC and polyhydroxy compound in solid state is redissolved at 66 ° C. (150 ° F.). The melt mixture is then dispersed in a controlled water tank (pH = 3, temperature = 66 ° C.) to produce a fine blister dispersion. The particle diameter of the blister dispersion is measured using an optical microscope technique. The particle size range is 0.1-1.0 micrometer.

Second, 3 wt% of an aqueous slurry of NSK is prepared in a conventional re-pulp maker. Slowly purify the NSK slurry and add 2% solution of transient wet strength resin (ie, National Starch 78-0080, marketed by National Starch & Chemical Corporation, New York, NY) to 0.75% (weight of dry fiber) At a rate of; Adsorption of the temporary wet strength resin to the NSK fibers by an in-line mixer. NSK slurry is diluted to a consistency of 0.2% in a fan pump.

Third, 3% by weight of an aqueous slurry of eucalyptus fibers is prepared in a conventional re-pulp maker. A 2% solution of the temporary wet strength resin (ie, National Starch 78-0080, marketed by National Starch & Chemical Corporation, New York, NY) was placed in a eucalyptus feed tube prior to the feed pump by 0.1% (based on the weight of the dry fiber). Adding at a rate of; A 1% solution of the biodegradable chemical softener mixture is added to the eucalyptus feed tube before the in-line mixer at a rate of 0.2% (based on the weight of the dry fibers). Eucalyptus slurry is diluted to a consistency of 0.2% in a fan pump.

The treated surfacing mixture (NSK 30% / eucalyptus 70%) is blended in a head box and deposited on a wire in a foodliner to produce a raw web. Dehydration takes place through the foodliner wire, which is assisted by a deflector and a vacuum box. The foodliner wire is of a five-shed satin woven structure with 84 machine directions and 76 cross machine direction monofilaments each per inch. The unprocessed wet web has a photoresist fabric (15 linear fiber Idaho cells per 1 in ² ) from the photoresist wire (fiber consistency at delivery), 40% knuckle area and 9 mils of photosensitive polymer depth). Further dehydration is achieved by draining by vacuum until the fiber consistency of the web is 28%. The patterned web is pre-dried by air blowing to bring the fiber consistency to 65% by weight. The web is then adhered to the surface of a Yankee dryer with a spray creping adhesive comprising 0.25% polyvinyl alcohol (PVA) aqueous solution. After increasing the fiber consistency to 96%, the web is dry creped with a doctor blade. The doctor blade is positioned with a bevel angle of 25 ° and a contact angle of 81 ° relative to the Yankee dryer; The Yankee Dryer is run at 800 fpm (ft / min) (244 m / min). The dry web is molded into a roll at a speed of 700 fpm (214 m / min).

The web is converted to a single layer of multilayer tissue paper product. The multilayer tissue paper has a basis weight of 18 # / 3M ft ² and contains 0.2% biodegradable chemical softener mixture and 0.3% temporary wet strength resin. Importantly, the resulting multi-layer tissue paper is soft and absorbent, has good lint resistance, and is suitable for use as high-quality tissue and / or toilet tissue.

Example 4

The purpose of this example is a soft treated with a chemical softener composition comprising a diester di (contact curing) tallow dimethyl ammonium chloride (DEDTHTDMAC) and a mixture of a polyhydroxy compound (glycerol / PEG-400) and a dry strength additive resin. It is to illustrate a method of using a blow-by-drying method and a lamination paper making method for producing a multi-layer tissue paper for an absorbent lint resistant toilet.

Test scale foodliner paper making machines are used in the practice of the present invention. First, a chemical softener composition is prepared according to the procedure of Example 2, wherein the homogeneous premix of DEDTHTDMAC and polyhydroxy compound in solid state is redissolved at 66 ° C. (150 ° F.). The melt mixture is then dispersed in a controlled water tank (pH = 3, temperature = 66 ° C.) to produce a fine blister dispersion. The particle diameter of the blister dispersion is measured using an optical microscope technique. The particle size range is 0.1-1.0 micrometer.

second; 3 wt% of the aqueous slurry of NSK is prepared in a conventional re-pulp maker. Purification of the NSK slurry slowly and the dry strength resin (i.e., akko commercially available by American cyanamide Co. you Ohio Fairfield ^material? (Acco) 514, ^akko? 711) 2% solution of a 0.2% (dry on NSK material tube Based on the weight of the fibers). The in-line mixer promotes adsorption of dry strength resin to NSK fibers. NSK slurry is diluted to a consistency of 0.2% in a fan pump.

Third, 3% by weight of an aqueous slurry of eucalyptus fibers is prepared in a conventional re-pulp maker. Dry strength resin of a 2% solution of (i.e., akko commercially available by American cyanamide Co. you Ohio Fairfield ^material? 514, ^akko? 711), based on the weight of 0.1% (dry fiber to the eucalyptus raw material pipe before the raw material pump Adding at a rate of; A 1% solution of the biodegradable chemical softener mixture is added to the eucalyptus feed tube before the in-line mixer at a rate of 0.2% (based on the weight of the dry fibers). Eucalyptus slurry is diluted to a consistency of 0.2% in a fan pump.

The treated surfacing mixture (NSK 30% / eucalyptus 70%) is blended in the headbox and deposited on a wire in a foodliner to produce a raw web. Dehydration takes place through the foodliner wire, which is assisted by a deflector and a vacuum box. The foodliner wire is of a 5-shed satin woven structure with 84 machine directions and 76 cross machine direction monofilaments each in. The raw, wet web was fabricated from the photosensitive polymer wire (fiber consistency of 15% on delivery) with a photosensitive polymer fabric (562 linear Idaho cells per 1 in ² , 40% junction area and 9 mil photosensitive polymer depth). To pass). Further dehydration is achieved by draining by vacuum until the fiber consistency of the web is 28%. The patterned web is pre-dried by air blowing to bring the fiber consistency to 65% by weight. The web is then adhered to the surface of the Yankee dryer with a spray creping adhesive comprising 0.25% polyvinyl alcohol (PVA) aqueous solution. After increasing fiber consistency to 96%, the web is dry creped with a doctor blade. The doctor blade is positioned with a bevel angle of 25 ° and a contact angle of 81 ° relative to the Yankee dryer; The Yankee Dryer is run at 800 fpm (ft / min) (244 m / min). The dry web is molded into a roller at a speed of 700 fpm (214 m / min).

Two ply webs are molded into a multilayer tissue paper product and laminated together using a ply bonded technique. The multilayer tissue paper has a basis weight of 23 # / 3M ft ² and contains 0.1% biodegradable chemical softener mixture and 0.2% dry strength resin. Importantly, the resulting multi-layer tissue paper is soft and absorbent, has good lint resistance, and is suitable for use as high-quality tissue and / or toilet tissue.

Example 5

The objectives of this example are diester di (contact curing) tallow dimethyl ammonium chloride (DEDTHTDMAC) and polyoxyethylene glycol 400 (PEG-400), cationic polyacrylamide additive resins (Percol ^? (Percol) 175) to illustrate a method using dry blowing and laminated papermaking techniques to produce soft, absorbent lint resistant multi-layer tissue paper treated with a chemical softener composition comprising (175).

Test scale foodliner paper making machines are used in the practice of the present invention. First, a chemical softener composition is prepared according to the procedure of Example 1, wherein a homogeneous premix of DEDTHTDMAC and polyhydroxy compound in solid state is redissolved at 66 ° C. (150 ° F.). The melt mixture is then dispersed in a controlled water tank (pH = 3, temperature = 66 ° C.) to produce a fine blister dispersion. The particle diameter of the blister dispersion is measured using an optical microscope technique. The particle size range is 0.1-1.0 micrometer.

Second, 3 wt% of the aqueous slurry of NSK is prepared in a conventional re-pulp maker. Purification of the NSK slurry slowly and the dry strength resin (i.e., akko are camphor you are commercially available American cyanamide, Ohio Fairfield ^material? 514, ^akko? 711) 2% of the weight of 0.2% (dry fiber to the NSK material tube a solution of As a reference). The in-line mixer promotes adsorption of dry strength resin to NSK fibers. NSK slurry is diluted to a consistency of 0.2% in a fan pump.

Third, 3% by weight of an aqueous slurry of eucalyptus fibers is prepared in a conventional re-pulp maker. 1% solution of the biodegradable chemical softener mixture is added to the eucalyptus feed tube prior to the feed pump at a rate of 0.2% (based on the weight of the dry fibers); Percol ^? A 0.05% solution of 175 is added to the eucalyptus layer before the fan pump at a rate of 0.05% (based on the weight of the dry fibers). In-line mixers promote the adsorption of the biodegradable chemical softener composition to eucalyptus fibers. Eucalyptus slurry is diluted to a consistency of 0.2% in a fan pump.

Treated surfacing mixtures (NSK 30% / eucalyptus 70%) are blended in the headbox and deposited on wire in a foodliner to produce a raw web. Dehydration takes place through the foodliner wire, which is assisted by a deflector and a vacuum box. The foodliner wire is of a 5-shed satin woven structure with 84 machine directions and 76 cross machine direction monofilaments each in. The unprocessed wet web is transferred from the foodliner wire (fiber consistency at delivery to 15%) to the usual felt. Further dehydration is achieved by draining by vacuum until the fiber consistency of the web is 35%. The web is then bonded to the surface of the Yankee Dryer. After increasing fiber consistency to 96%, the web is dry creped with a doctor blade. The doctor blade is positioned with a bevel angle of 25 ° and a contact angle of 81 ° relative to the Yankee dryer; The Yankee Dryer is run at 800 fpm (ft / min) (244 m / min). The dry web is molded into a roller at a speed of 700 fpm (214 m / min).

Two ply webs are molded into a multilayer tissue paper product and laminated together using a fold-bonding technique. The multilayer tissue paper has a basis weight of 23 # / 3M ft ² and contains 0.1% biodegradable chemical softener mixture, 0.1% dry strength resin and 0.05% retention aid resin. Importantly, the resulting multi-layer tissue paper is soft and absorbent, has good lint resistance, and is suitable for use as high-quality tissue and / or toilet tissue.

Example 6

This embodiment purpose, diester di (touch hardened) tallow dimethyl ammonium chloride (DEDTHTDMAC) and Polyoxyethylene Glycol 400 (PEG-400), a permanent wet strength resin and a retention aid chemical softening agent comprising a ^(peokol? 175) To illustrate a method using dry blowing and laminated papermaking techniques for producing soft absorbent lint resistant multilayer tissue paper for treatment with a composition.

Test scale foodliner paper making machines are used in the practice of the present invention. First, a chemical softener composition is prepared according to the procedure of Example 1, wherein a homogeneous premix of DEDTHTDMAC and polyhydroxy compound in solid state is redissolved at 66 ° C. (150 ° F.). The melt mixture is then dispersed in a controlled water tank (pH = 3, temperature = 66 ° C.) to produce a fine blister dispersion. The particle diameter of the blister dispersion is measured using an optical microscope technique. The particle size range is 0.1-1.0 micrometer.

Second, 3 wt% of the aqueous slurry of NSK is prepared in a conventional re-pulp maker. NSK gradually refining the slurry and permanent wet strength resin (i.e., Delaware Will Kymene commercially available by Herr particulates less, Inc. of mington ^material? (Kymene) 557H) 2% solution of a 1% (dry on NSK material tube Based on the weight of the fibers). The in-line mixer promotes the adsorption of the temporary wet strength resin to the NSK fibers. NSK slurry is diluted to a consistency of 0.2% in a fan pump.

Third, 3% by weight of an aqueous slurry of eucalyptus fibers is prepared in a conventional re-pulp maker. 1% solution of the biodegradable chemical softener mixture is added to the eucalyptus feed tube before the in-line mixer at a rate of 0.2% (based on the weight of the dry fibers); Percol ^? A 0.5% solution of 175 is added to the eucalyptus layer before the fan pump at a rate of 0.05% (based on the weight of the dry fibers). Eucalyptus slurry is diluted to a consistency of 0.2% in a fan pump.

Treated surfacing mixtures (NSK 50% / eucalintus 50%) are blended in the headbox and deposited on wire in a foodliner to produce a raw web. Dehydration takes place through the foodliner wire, which is assisted by a deflector and a vacuum box. The foodliner wire is of a five-shed satin woven structure with 84 machine directions and 76 cross machine direction short filaments each per inch. The unprocessed wet web was fabricated from the photosensitive polymer wire (fiber consistency at delivery 15%) with a photopolymer fabric (711 new Idaho cells per ² in, with a bonding area of 40% and a photosensitive polymer depth of 9 mils). To pass. Further dehydration is achieved by draining by vacuum until the fiber consistency of the web is 28%. The patterned web is pre-dried by air blowing to bring the fiber consistency to 65% by weight. The web is then adhered to the surface of the Yankee dryer with a spray creping adhesive comprising 0.25% polyvinyl alcohol (PVA) aqueous solution. After increasing fiber consistency to 96%, the web is dry creped with a doctor blade. The doctor blade is positioned with a bevel angle of 25 ° and a contact angle of 81 ° relative to the Yankee dryer; The Yankee Dryer is run at 800 fpm (ft / min) (244 m / min). The dry web is molded into a roller at a speed of 700 fpm (214 m / min).

Two ply webs are molded into a multilayer tissue paper product and laminated together using a fold-bonding technique. The multilayer tissue paper has a basis weight of 23 # / 3M ft ² and contains 1% permanent wet strength resin, 0.2% biodegradable chemical softener mixture and 0.05% retention aid resin. Importantly, the resulting multi-layer tissue paper is soft and absorbent, has good lint resistance, and is suitable for use as high-quality tissue and / or toilet tissue.

Claims (35)

(a) papermaking fibers; (b) 0.01 to 3.0% by weight of a biodegradable quaternary ammonium compound selected from the group consisting of compounds having the following structural formulae and mixtures thereof: (Wherein Each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; Each R ₃ substituent is a C ₁₁ -C ₂₁ hydrocarbyl group, or a substituted hydrocarbyl or mixture thereof; Y is —O—C (O) —, —C (O) —O—, —NH—C (O) —, —C (O) —NH, or a mixture of dies; n is 1 to 4; x ^- is a suitable anion.) (c) 0.01 to 3.0 weight percent of a water soluble biodegradable polyhydroxy compound; And (d) 0.01% to 30% by weight of the binder material; Three overlapping layers consisting of one inner layer and two outer layers, wherein the inner layer is located between the two outer layers; Most biodegradable quaternary ammonium compounds, polyhydroxy compounds and binders are contained in one or more outer layers Multilayer tissue paper web. The method of claim 1, The binder is contained in the inner layer Multilayer tissue paper web. The method of claim 1, Most biodegradable quaternary ammonium compounds and polyhydroxy compounds are contained in two outer layers Multilayer tissue paper web. The method of claim 1, The inner layer comprises relatively long papermaking fibers having an average length of at least 2.0 mm and the two outer layers each comprise relatively short papermaking fibers having an average length of 0.2 to 1.5 mm Multilayer tissue paper web. The method of claim 4, wherein The inner insect comprises softwood fibers and the two outer layers each comprise hardwood fibers Multilayer tissue paper web. The method of claim 5, Coniferous fiber is northern Kraft coniferous fiber and hardwood fiber is eucalyptus fiber Multilayer tissue paper web. The method of claim 4, wherein The inner layer comprises coniferous fibers or a mixture of coniferous fibers and inexpensive fibers and the at least one outer layer comprises low cost fibers or a mixture of hardwood fibers and inexpensive fibers Multilayer tissue paper web. The method of claim 7, wherein The low cost fibers are selected from the group consisting of sulfite fibers, thermodynamically treated pulp fibers, chemical-thermodynamically treated pulp fibers, recycled fibers and mixtures thereof Multilayer tissue paper web. The method of claim 4, wherein The web comprises at least a single ply with three layers Multilayer tissue paper web. The method of claim 1, The binder material is selected from the group consisting of permanent wet strength resins, temporary wet strength resins, dry strength resins, retention aid resins, and mixtures thereof. Multilayer tissue paper web. The method of claim 10, The binder material is a permanent wet strength resin selected from the group consisting of polyamide-epichlorohydrin resins, polyacrylamide resins and mixtures thereof Multilayer tissue paper web. The method of claim 10, The binder material is a starch-based transient wet strength resin Multilayer tissue paper web. The method of claim 1, Biodegradable quaternary ammonium compounds are compounds of the general formula Multilayer tissue paper web. In the above formula, Each R ₂ substituent is a C ₁ -C ₆ alkyl or hydroxyalkyl group, benzyl group or mixtures thereof; Each R ₃ substituent is a C ₁₁ -C ₂₁ hydrocarbyl group, or a substituted hydrocarbyl or mixture thereof; Y is —O—C (O) —, —C (O) —O—, —NH—C (O) —, —C (O) —NH—, or a mixture thereof; n is 1 to 4; X ⁻ is a suitable anion. The method of claim 13, R ₂ is methyl and R ₃ is C ₁₅ -C ₁₇ alkyl or alkenyl Multilayer tissue paper web. The method of claim 13, Y is -O-C (O)-or -C (O) -O- Multilayer tissue paper web. The method of claim 13, X ^- is chloride or methylsulfate Multilayer tissue paper web. The method of claim 1, A multilayer tissue paper web wherein the biodegradable quaternary ammonium compound is a compound of the general formula: In the above formula, Each R ₂ is a C ₁ -C ₄ alkyl or hydroxyalkyl group, benzyl group or a mixture thereof; Each R ₃ is a C ₁₁ -C ₂₁ hydrocarbyl group, or a substituted hydrocarbyl or mixtures thereof; Y is —O—C (O) —, —C (O) —O—, —NH—C (O) —, —C (O) —NH—, or a mixture thereof; X ⁻ is a suitable anion. The method of claim 17, R ₂ is methyl and R ₃ is C ₁₅ -C ₁₇ alkyl or alkenyl Multilayer tissue paper web. The method of claim 17, Y is -O-C (O)-or -C (O) -O- Multilayer tissue paper web. The method of claim 17, X ^- is chloride or methylsulfate Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is selected from the group consisting of glycerol, sorbitol, polyglycerol having a weight average molecular weight of 150 to 800, polyoxyethylene glycol and polyoxypropylene glycol having a weight average molecular weight of 200 to 4000, and mixtures thereof Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is selected from the group consisting of polyoxyethylene glycol and polyoxypropylene glycol having a weight average molecular weight of 200 to 1000 Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is glycerol Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is a polyglycerol having a weight average molecular weight of 150 to 800 Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is a mixture of polyoxyethylene glycol and glycerol having a weight average molecular weight of 200 to 1000 Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is a mixture of polyglycerol and glycerol having a weight average molecular weight of 150 to 800 Multilayer tissue paper web. The method of claim 1, The polyhydroxy compound is a mixture of polyglycerol having a weight average molecular weight of 150 to 800 and polyoxyethylene glycol having a weight average molecular weight of 200 to 1000 Multilayer tissue paper web. The method of claim 1, The biodegradable quaternary ammonium compound and the polyhydroxy compound have a weight ratio of 1.0: 0.3 to 0.3: 1.0 Multilayer tissue paper web. The method of claim 28, The weight ratio of the biodegradable quaternary ammonium compound and the polyhydroxy compound is 1.0: 0.7 to 0.7: 1.0 Multilayer tissue paper web. The method of claim 22, The polyhydroxy compound is a polyoxyethylene glycol having a weight average molecular weight of 200 to 600 Multilayer tissue paper web. The method of claim 9, The biodegradable quaternary ammonium compound is diester di (contact curing) tallow dimethyl ammonium chloride, the polyhydroxy compound is polyoxyethylene glycol having a weight average molecular weight of 200 to 600, and the binder material is starch-based transient wet strength resin Is; Most biodegradable quaternary ammonium compounds and polyhydroxy compounds are contained in at least one outer layer and most binder materials are located in the outer layer. Multilayer tissue paper web. A multi-plies tissue paper product comprising the multilayer tissue paper web according to claim 1 arranged in two or more parallel arrangements. The method of claim 32, A multi-layer tissue paper web consisting of two layers, each consisting of three layered layers; The biodegradable quaternary ammonium compound is diester di (contact curing) tallow dimethyl ammonium chloride, the polyhydroxy compound is polyoxyethylene glycol having a weight average molecular weight of 200 to 600, and the binder material is a permanent wet strength resin and a temporary Wet strength resin; Most biodegradable quaternary ammonium compounds and polyhydroxy compounds are contained in at least one outer layer and most binder materials are located in the inner layer. Multi-ply tissue paper products. The method of claim 31, wherein Tissue paper web is a toilet tissue Multilayer tissue paper web. The method of claim 33, wherein Tissue paper web is a high quality tissue Multilayer tissue paper web.