CZ180095A3 - Paper article and biologically degradable chemical softening mixture contained therein - Google Patents

Description

The paper product and the biodegradable chemical softening composition it contains

Technical field

The invention relates to a tissue paper web. In particular, it relates to soft absorbent bands of tissue paper (tissue paper ¹ ;, ----).

can be used to make napkins, diapers, facial tissue and toilet paper.

BACKGROUND OF THE INVENTION which

Paper strips or sheets, sometimes called tissue paper or strips or sheets of tissue paper, find widespread use in modern society. Products such as paper napkins, diapers, facial and toilet papers are a permanent business item.

It has long been recognized that the three properties of these products are in particular aqueous systems and the basic significant physical properties of their softness, absorbency and strength, especially in the wet state. Research and development focuses on improving each of these properties separately, without seriously affecting the other properties, as well as improving two or three of these properties simultaneously. Softness is a tactile perception that the user perceives when holding the product, wiping the skin with it, or squeezing the perception is a combination of several physical, more significant physical properties related to the softness of the hands. This tactile property. In one field, the stiffness of a paper web is usually considered to be straight tensile, and the stiffness of the fibers constituting those is generally considered by the workers from which the product is made. Stiffness dependent on belt strength of the belt.

Strength is the ability of the article and the belt of which it consists to maintain physical integrity and to resist rupture, cracking and disintegration into pieces when used particularly in a wet state.

Absorbability is a measure of the ability of the article and the belt of which it consists to absorb liquids, especially aqueous solutions or dispersions. The overall absorbability, as perceived by the human consumer, is usually considered to be the combination of the total amount of fluid the tissue tissue absorbs at saturation, as well as the rate at which the mass absorbs the fluid.

The use of wet strength resins to improve the strength of a paper web is generally known. For example, Westfelt described a number of such materials and their chemistry was discussed in Cellulose Chemistry and Technology, Vol. 13, pp. 813-825 (1979). In U.S. Patent 3,752,520 (August 28, 1973) Freimark et al. chemical additives known as disintegrating agents interfere with the natural fiber bond that occurs during the production of the sheet in papermaking processes. This reduction in binding results in a softer and less rough sheet of paper. Freimark et al. discloses the use of wet strength resins to improve sheet strength in connection with the use of disintegrating agents to reduce dry tensile strength, but is also generally a reduction in wet tensile strength.

Shaw in U.S. Pat. No. 3,810,168 (June 28, 1974) also discloses that chemical disintegrants can be used to reduce stiffness and hence to promote softness of the tissue paper web.

Chemical disintegrants are described in numerous patents (for example, U.S. Patent 3,548,662, Hervey et al., Jan. 12, 1971). These materials include quaternary ammonium salts such as trimethylcocmonium chloride, trimethyloleylammonium chloride, dimethylammonium chloride of hydrogenated tallow and trimethylstearylammonium chloride.

Emanuelsson et al. (U.S. Patent 4,144,1232, March 13, 1979) discloses the use of complex quaternary ammonium compounds such as bis (alkoxy (2-hydroxy) propylene) ammonium chlorides to soften the bands. These authors also seek to counter any decrease in absorbency caused by the disintegrants by the use of nonionic surfactants such as ethylene oxide and propylene oxide adducts of fatty alcohols.

In his bulletin 76-17 (1977), Armak Company, Chicago,. 7

Illinois, that the use of dihydroxy tallow hydrogenated tallow hydrogenated acid in combination with polyoxyethylene glycol fatty acid esters can confer both softness and absorbency to tissue paper webs.

One exemplary result of research to improve paper webs is described in U.S. Pat

301746 (Sanford and Sisso, Jan. 31, 1967). Despite the high quality of paper webs produced by the method described in this patent and the commercial success of products made from these webs, research efforts to find improved products continue.

For example, Becker et al. (U.S. Pat

158594, Jan. 9, 1979) discloses a method which it claims to form a solid, soft, fibrous sheet. In particular, it states that the strength of a paper web (which may have been softened by the addition of chemical disintegrants) can be improved by adhering, during the process, one surface of the web to the creping surface in a finely patterned configuration by binding material (such as a rubber emulsion of acrylic latex resin, or a laser binding material) that adhered to one surface of the web on the creping surface in a finely patterned configuration and creping the web from the creping surface to form the sheet material.

Conventional quaternary ammonium compounds, such as the well-known dialkyldimethylammonium salts (for example dimethylammonium chloride, dicycidyl-tallow, di-bh-yl) -ammonium-ethyl-ul-fate-alkyls with el-in-tallow, The hydrogenated diacid (di-methylammonium chloride of tallow) are effective chemical scenting agents. However, these quaternary ammonium compounds are not biodegradable. It has now surprisingly been found that the biodegradable monoester α-di-ester variants of these quaternary ammonium salts also function effectively as chemical disintegrants and improve the softness of the fibrous cellulosic materials.

SUMMARY OF THE INVENTION It is an object of the present invention to provide absorbent soft tissue paper products. It is also an object of the present invention to provide soft absorbent tissue paper products. It is also an object of the present invention to provide articles of soft absorbent wipe material. It is also an object of the present invention to provide a manufacturing process for the production of soft absorbent articles from tissue and tissue paper. Indeed, the invention solves these and other objects.

SUMMARY OF THE INVENTION

The paper product of the invention consists of a sheet of fibrous cellulosic material and from 0.005 to 5.0% by weight, based on the weight of the fibrous cellulosic material, a biodegradable chemical softener composition comprising (a) a quaternized esteramine compound of formula

xor

R 2 (CH 2) 2 -O-C-R 3

where x0

-. 5

R1 is in each case a hydrocarbyl group of 14 to 22 carbon atoms or a mixture thereof, preferably an alkyl group of 16 to 18 carbon atoms,

R2 is in each case an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms or a mixture thereof, preferably an alkyl group having 1 to 3 carbon atoms and in particular a methyl group,

R3 is in each case a hydrocarbon group having 12 to 20 carbon atoms or a mixture thereof, preferably an alkyl group having 14 to 16 carbon atoms,

X is a compatible anion, preferably a chloride or sulfate anion (b), a polyhydroxy compound selected from the group consisting of cerol and polyethylene glycols and polypropylene glycols having an average molecular weight of from 200 to 4000, preferably from 200 to 1000, and in particular from 200 to 600, wherein the weight ratio of the quaternized esteramine compound to the polyhydroxy compound is 1: 0.1 to 0.1: 1, preferably 1: 0.3 to 0.3: 1, especially 1: 0.7 to 0.7: 1, and wherein the polyhydroxy compound it is miscible with the quaternized esteramine compound at a temperature of at least 50 ° C.

Preferably, the mixture of the quaternized esteramine compound and the polyhydroxy compound is diluted with a liquid carrier to a concentration of about 0.01 to about 25% by weight of the chemical softening compound prior to addition to the fiber. irr-o-rullo from the atherial-lu-r

Preferably, the temperature of the liquid carrier is about 40 ° C to about 80 ° C and the pH is less than about 4. Preferably, at least 20% of the polyhydroxy compound and the quaternized esteramine compound are added to the fibrous cellulose. ·

Preferred quaternized esteramine compounds suitable for use in the present invention include compounds of the following formulas:

(CH3) 2-N ⁺ -CH 2 CH 2 -O- C-C 16 H 33 X C 1 and H 3 7 0 (CH 3) 2-N ⁺ - (CH 2 CH 2 O-C-C 16 H 33) 2 X

These compounds can be considered as monoester and diester variants of the known di-alkyldimethylammonium salts, such as tallow dimethylammonium chloride diester, tallow acid dimethylammonium chloride monoester, hydrogenated tallow hydrogenated diester dimethylammonium dihydrochloride, dihydroxylammonium hydrogen chloride diester, hydrogenated dihydrochloride dihydrochloride, diester variations of dimethylammonium methyl chloride, non-hydrogenated tallow diacids, dimethylammonium chloride tallow hydrogenated to the touch, with dimethyl ammonium chloride hydrogenated tallow hydrogenated acid being preferred. Depending on the desired product characteristics, the degree of saturation of tallow diacids may be adjusted from a non-hydrogenated (soft) hand to a partially or fully hydrogenated hard hand.

Without wishing to be bound by any theory, it is believed that the ester moieties of these compounds confer biodegradability. Significantly, the quaternized esteramine compounds used in the present invention break down biologically faster than conventional dialkyldimethylammonium chemical plasticizers.

Examples of polyhydroxyl compounds useful herein include glycepol and polyethylene glycols having a weight average molecular weight of about 200 to about 4000, with preferred polyethylene glycols having a weight average molecular weight of about 200 to about 600.

A particularly preferred tissue paper of the invention comprises from about 0.03 to about 0.5% by weight of a mixture of a quaternized esteramine compound and a polyhydroxy compound.

In principle, the method of making the silk webs of the present invention is based on preparing the papermaking material from said components and depositing the papermaking material on a perforated surface such as a Fourdrinier screen and removing the water from the papermaking deposited material.

All percentages, ratios and proportions are by weight unless otherwise indicated. While the description agrees with the claims defining the invention, it is believed that the following description, accompanied by the following figures, will contribute to a good understanding.

Brief description of the pictures.

On giant . 1 Yippee phase diagram DODMAMS and DHTDMAMS, on giant . 2 Yippee phase diagram system DODMAMS and PEG-400 on giant . 3 Yippee phase diagram system PEG-400 / methyloctanoate, on giant . 4 Yippee phase diagram system DEDTDMAC and PEG-400 on giant . 5 Yippee phase diagram system DEDHTDMAC and PEG-400 on giant . 6 Yippee cryotransmission micrograph of bubble dispersion system

Fig. 7 shows a cryotransmission micrograph of 1: 1 tallow-glycerol dimethylammonium chloride di-acid glycerol diester, at a magnification of 63000 times; is a cryotransmission micrograph of the bubble dispersion of the dimethylammonium chloride diester system hydrogenated by se-Lin-Lo-is and -P-EG-400 in mass ratio of 1: 1 at a magnification of 66,000-fold.

Although the description agrees with the claims emphasizing and clearly claiming the essence of the invention, it is believed that

It is to be understood that the following detailed description and examples are provided

All terms used herein such as: tissue paper web, paper web, web, paper sheet or paper product refer to sheets of paper produced by a process consisting of preparing a paper forming material, applying the paper forming material to a perforated surface such as a Fourdrinier screen, and removing water from the deposited paper-forming material either by gravity or by vacuum suction with or without compression and from evaporation of the liquid.

The aqueous papermaking material is an aqueous suspension of paper fibers and the chemicals described below.

A first operation of the process of the invention is to prepare an aqueous paper forming material. This paper extrusion material consists of paper fibers (sometimes referred to as wood pulp) and a mixture of at least one quaternized esteramine compound and at least one polyhydroxy compound to be copied.

It is believed that wood pulp in all its variations generally consists of the papermaking fibers used according to the invention. However, other cellulosic fibrous pulps such as cotton lint, bagasse and viscose pulp may be used, with no cellulosic material being excluded. Suitable wood pulps are chemical pulps such as Kraft, sulphite, sulphate pulp, as well as mechanical pulps, including, for example, ground wood, thermomechanical pulps and chemically modified thermomechanical pulps (CTMP). Deciduous and coniferous pulps may be used. Recycled paper fibers may also be used according to the invention, which may comprise any or all of the above-mentioned types and other non-fibrous materials such as fillers and sizing agents used to promote the production of the original paper. Preferably, the paper fibers used according to the invention are Nordic deciduous Kraft pulp.

Composition of chemical softeners

As an essential component, the products of the invention comprise, by weight, about 0.005 to 5%, more preferably about 0.03 to 0.5%, based on dry fiber, mixtures of a quaternized esteramine compound and a polyhydroxy compound. The ratio of quaternized esteramine compound to polyhydroxy compound is about 1: 0.1 to 0.1: 1, preferably the weight ratio of quaternized esteramine compound to polyhydroxy compound is about 1: 0.3 to 0.3:

y

Even more preferably, the weight ratio of quaternized esteramine compound to polyhydroxy compound is about 1: 0.7 to 0.7:

1, although this ratio may vary depending on the molecular weight of the particular quaternized esteramine compound used and / or the hydroxyhydroxy compound used.

Each of the two types of compounds is described in detail below.

A. Quaternized ester-amine compound

The chemical softening agent comprises, as an essential component, a quaternized esteramine compound of the formula:

or

j • * · ^ · where means

R @ ^{1 is in} each case a hydrocarbyl group having 14 to 22 carbon atoms, preferably an alkyl group of tallow acids having from 16 to 18 carbon atoms;

R2 is in each case an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms,

R @ ^{3 is in} each case a hydrocarbyl group having from 12 to 20 carbon atoms, preferably an alkyl group having from 14 to 16 carbon atoms,.

X 'compatible anion, preferably a halide (chloride or bromide) or a methanesulfate.

According to a treatise in Swern's edition of Bailey's publication, Bailey's Industrial Oil and Fat Products, Third Edition, John Wiley and Sons (New York 1964), is a tallow naturally occurring fat having a different composition. Table 6 of the Swern publication states that, as a rule, 78 percent or more of tallow fatty acids contain 16 or 18 carbon atoms. Usually half of the tallow fatty acids are unsaturated acids mainly oleic acid. Synthetic and natural tallow fatty acids are within the scope of this invention. It is also known that, depending on the desired properties of the product, the degree of saturation of tallow diacids can be adjusted from a non-hydrogenated soft touch to a partial or fully hydrogenated state (hard touch).

It will be understood that R1, R2 and R3 may be optionally substituted by various groups such as alkoxy and hydroxyl, or may be branched, but such materials are not preferred herein. Preferably, each R 1 is a C 16 -C 18 alkyl group, most preferably each R 1 is a straight chain C 18 alkyl group. Preferably, each R 2 group is a methyl group. Preferably R 3 is C 14 -C 16 alkyl, most preferably C 16 -C 16 straight chain alkyl and X is chloride or methylsulfate.

Specific examples of quaternized esteramine compounds of the above formulas and suitable for use herein include the well-known di-dialkyldimethyl dimmonium ammonium salts, such as tallow dimethyl ammonium diester, tallow dimethylammonium chloride monoester, dimethyl ammonium methyl sulfonate diester, dihydroxymethylsulfate diester, dihydroxymethylsulfonate dihydrochloride, dihydroxymethyl ester dihydrochloride, hydrogenated tallow hydrogen ammonium methyl sulphate, hydrogenated tallow hydrogenated diester. Particularly preferred are the tallow dimethylammonium chloride diester and the tallow hydrogenated dimethylammonium chloride diester. These materials are commercial products of Sherex Chemical Company Inc., Dublin, Ohio under the trade name ADOGEN DDMC ^R.

Disqualified variations of the quaternized esteramine compounds may also be used and are considered to be within the scope of the invention. These compounds have the general formula:

(R 2) 2 (R 2) 2 0

I I

R3-C-O- (CH2) 2-N ⁺ - (C2H) 2-N ⁺ - (C2H) 2-O-C- R3 2X ~ where

R2 is in each case an alkyl or hydroalkyl group having 1 to 6 carbon atoms,

R 3 is a C 12 -C 20 hydrocarbon group; and

X 'compatible anion such as halide (for example chloride or bromide) or methyl sulfate.

Preferably, the alkyl radical is from 14 to 16 carbon atoms, most preferably a straight chain alkyl group having 16 carbon atoms and R2 a methyl group.

1 B. After yhydroxy with LOUČEŇ on ^_ '

The chemically softening agent contains a polyhydroxy compound as an essential component.

Examples of polyhydroxy compounds useful in the present invention include glycerol and polyethyl and polypropylene 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. Particularly preferred are

- 12 ^ι · polyethylene glycols having a weight average molecular weight of about 200 to about 600th

A particularly preferred polyhydroxy compound is polyethylene glycol having a weight average molecular weight of about 400. It is a product of the Union Carbide Company of Danbury, Connecticut under the trade name PEG-400.

The chemical softening agent described above, i.e. a mixture of quaternized esteramine compounds and polyhydroxy compounds, is preferably added to an aqueous papermaking suspension or material to form paper on the wet side of the papermaking machine at a suitable point in front of the Fourdrinier screen or before · forming a sheet. However, the application of the described chemical softening agent: The reagents following formation of the wet paper web and before drying the web for finishing also provide significant softening, absorbability and the advantage of wet strength and are within the scope of the invention.

The chemical softening agent has been found to be more effective when the quaternized esteramine compound and the polyhydroxy compound are first mixed prior to addition to the papermaking material. A preferred method, described in more detail in Example 1, is preheating the polyhydroxy compound to about 66 ° C. then, adding an ester-quaternized novel compound to the warm polyhydroxy compound to form a fluidized melt. The weight ratio of the quaternized esteramine compound to the polyhydroxy compound is about 1: 0.1 to 0.1; 1, preferably the weight ratio of the quaternized esteramine compound to the polyhydroxy compound is about 1: 0.3 to 0.3: 1, even more preferably ς is the weight ratio of the quaternized esteramine compound to the hydroxy polyesters is about 1; 0.7 to 0.7 L, although this ratio may vary depending on the molecular weight of the particular quaternized esteramine compound used and / or the polyhydroxy compound used. The melt of the quaternized esteramine compound and the polyhydroxy compound is then diluted to the desired concentration and mixed to form an aqueous solution containing the foamed mixture of the i-quaternized foam. an esteramine compound and a polyhydroxy compound which is then added to the paper forming material.

Preferably, the mixture of the quaternized esteramine compound and the polyhydroxy compound is diluted with a liquid carrier which is water to a concentration of about 0.01 to about 25% by weight of the softening agent before it is added to the paper forming material. The pH of the liquid carrier is preferably 2 to 4. The temperature of the liquid carrier is preferably about 40 ° C to about 80 ° C. The mixture of the quaternized esteramine compound and the polyhydroxy compound is in the form of particles dispersed in a liquid carrier. The average particle size is preferably about 0.01 to 10 microns, most preferably about 0.1 to 1.0 microns. As can be seen from FIGS. 6 to 8, the dispersed particles are bubble-shaped.

The quaternized esteramine compound and the polyhydroxy compound are admixed at an elevated temperature of at least 50 ° C, more preferably about 50 to about 100 ° C. Without intending to be bound by any theory, it is believed that at the preferred temperature both the dimethylammonium tallow diester (DEDTDMAC) and the dimethylammonium chloride dihydrate of hydrated tallow (DEDHTDMAO) are in the liquid phase and are miscible with the polyhydroxy compound. The physical state of dimethyl ammonium methylsulfate hydrogenated tallow (DHTDMAMS) will be discussed in more detail below.

Those skilled in the art are well aware of the method and apparatus by which paper-forming material can be easily formed or mixed.

Surprisingly, it has been found that adsorption of the polyhydroxy compound to the β-p-urea is largely supported by the quaternized esteramine compound prior to addition to the polyhydroxy compound. of paper. Indeed, at least 20% of the added polyhydroxy compound and the quaternized esteramine compound are retained on the fibrous cellulose; and preferably the retention of the quaternized esteramine compound and polyhydroxy compound is about 50 to about 90% by weight based on the weight of the dry fibers.

Importantly, adsorption occurs at a concentration and within a time interval suitable for use in the manufacture of paper. In order to better understand the surprisingly high degree of polyhydroxy trapping on paper, the physical state of the melted solution and aqueous dispersion of dimethyl ammonium methylsulfate of hydrogenated tallow and polyethylene glycol 400 was studied. Without attempting to link the invention to any theory or wish to limit the invention in any way, an explanation of how the quaternary ammonium compound promotes adsorption of the polyhydroxy compound to the paper.

Information on the physical state of DHTDMAMS dimethylamoniummethy1sulfátu hydrogenated diacid tallow (C 7H35) 2N ⁺ (CH3) 2CH3OSO3 ~ DODMAMS (dioktadecyldimethylamoniummethylsulfátu, (Ci8H37) 2N ⁺ (CH3) 2CH3OSO3) DEDTDMAC (diester dimethylammonium diacids tallow (CH3) 2N ⁺ (CH2CH2OCOC And DEDHTDMAC (diester of dimethylammonium chloride of hydrogenated tallow hydrogenated acids) provide the X-ray and NMR data of the commercial mixture. DODMAMS is a major component of / * · DHTDMAMS and serves as a model compound for a commercial blend. It is advisable to deal first with the simpler DODMAMS system and then with the more complex DHTDMAMS business mix.

Depending on the temperature, DODMAMS may exist in one of the

And four phase states (Fig. 1): two polymorphic crystals (Xa and

X1), lamellar liquid crystal (Lam) or in liquid phase. Crystal X (3 exists in the range from room temperature to 47 ° C. At this temperature it transforms into crystal Xa, which at 72 ° C transforms into the liquid crystal phase Lam. This phase is then transformed at 150 ° C to isotropic Lamellar Liquid Crystal (Lam) also exists as a phase in both DEDTDMAC and DEDHTDMAC Systems, and its physical behavior is expected to resemble DHTDMAMS to DODMAMS, except that phase transition temperatures decrease and expand, for example, to convert X crystals. 3 to Xa crystals occurs in DHTDMAMS at 27 ° C instead of 47 ° C in DODMAMS Calorimetric data also suggest that the conversion of several crystals to the Lam-phase occurs in DHTDMAMS rather than in the case of DODMAMS. is 56 ° C,

This is in good agreement with X-ray data, but calorimetry shows two peaks with an initial temperature of 59 and 63 ° C.

DODMAC (dioctadecyl imethylammonium chloride) exhibits a qualitatively different behavior from DODMAMS in that the compound does not have a liquid crystal phase Lam. This difference

However, it is not considered significant for the use of this compound (or its commercial analogue DHTDMAC) in paper processing. (Laughlin et al., Journal of Physical Chemistry, Physical Science of the Dioctadecyldimethylammonium Chloride-Water System. 1. Equilibrium Phase Behavior, 1990, Vol. 94, pp. 2546-2552).

Mixtures of DHTDMAMS with PEG 400

A mixture of the two materials in a 1: 1 weight ratio is studied and an acceptable behavioral model of this system is proposed in FIG.

2. In this diagram, it is shown that DHTDMAMS with PEG are miscible at high temperatures where, when the mixture of the two cools, they coexist as two liquid phases. of liquids in this region, separated from the Lam phase mixture. Thus, this study shows that while the two materials are immiscible at high temperatures, they become miscible at lower temperatures in the liquid crystal phase Lam. At even lower temperatures are expected to be discharged from the crystalline phase ^of Lam phase, and the components are again immiscible.

Thus, these studies indicate that to produce a good dispersion of DHTDMAMS and PEG 400 in water, the premix, which is diluted with water, should be maintained at a medium temperature within the range where both components are miscible.

Mixtures of DHTDMAC with PEG 400

Study of equilibrium phases of these two materials way

Dilect or dilute 11 to A Z 11 1 í. The IP i i nb f is very different from the behavior of DHTDMAMS. There is no liquid crystal phase. These compounds are miscible over a wide temperature range. lot, which means that dispersions can be prepared from these mixtures in a comparable temperature range. There is no upper temperature limit of solubility.

Mixtures of DEDTDMAC with PEG 400

The equilibrium phase studies (Fig. 4) of these two materials by sequential dilution show that their physical behavior is similar to that of DHTDMAC. These compounds are miscible

- 16 over a wide temperature range (> 50 ° C), which means that dispersions can be prepared from these mixtures in a comparable temperature range. There is no upper temperature limit of solubility.

Mixtures of DEDHTDMAC with PEG 400

The equilibrium phase studies (Fig. 5) of these two materials by sequential dilution show that their physical behavior is similar to that of DHTDMAC. These compounds are miscible over a wide temperature range (> 67 ° C), which means that dispersions can be prepared from these mixtures over a comparable temperature range. There is no upper temperature limit of solubility.

Preparation of dispersions

Dispersions of any of these materials can be prepared by diluting with water a mixture which is maintained at a temperature at which the hydroxy compound is miscible with the quaternary ammonium salt. It does not matter 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). Neither DHTDMAMS nor DHTDMAC are soluble in water, so diluting any dry phase with water results in precipitation of the quaternary ammonium compound in the form of small particles. Quaternary ammonium compounds precipitate at elevated temperatures as well as liquid crystal phases in dilute aqueous solutions, regardless of whether the dry solution was liquid or liquid crystal. After hydroxyhydroxy treatment, it is soluble in water in any ratio so that it is not precipitated.

Cryoelectron microscopy shows that the particles present are approximately 0.1 to 1.0 microns in size and have a very different structure. Some have the shape of plates (curved or flat), others are closed drops. The membranes of all these particles are bilayered, of molecular size, where the head groups are exposed to water and the backs are common. PEG is believed to be associated with these particles. Applying the dispersion thus prepared to the paper leads to the capture of the quaternary ammonium ion on the paper, strongly enhances adsorption of the polyhydroxy compound to pa17, feathers, and creates the desired softness modification and maintain wettability

Dispersion status .....

If the dispersions described above are cooled, partial crystallization of the material within the collodial particles may occur. However, it is likely that achieving equilibrium will require a long time (perhaps months), so that there will be interaction of disordered particles whose membranes are either liquid crystals or dispersed crystalline phases interacting with the paper. Preferably, the chemical softening agents described herein are used prior to reaching equilibrium.

It is believed that the bubbles containing DHTDMAMS and PEG will disintegrate upon drying the fibrous cellulosic material. Once the bubble bursts, most of the PEG component penetrates into the interior of the cellulosic fibers, where it improves the flexibility of the fibers. Importantly, a portion of the PEG is retained on the surface of the fiber where it acts to promote the rate of absorption of the cellulosic fibers. Due to the interaction of ions, the cationic portion of the DHTDMAMS component remains on the surface of the cellulosic fiber, where it improves the surface feel and softness of the paper product.

The second step of the process of the invention is to apply the paper forming material using the softening agent described above as an additive to the perforated surface, and the third step is to remove water from the paper forming material deposited therewith. The method and the method for carrying out these are known to those skilled in the art. According to a preferred embodiment, the tissue paper according to the invention comprises about 0.005 to about 5.0% by weight, preferably about 0.03 to 0.5%, of the chemical softening agent of the invention relative to the dry fibers. ,

The present invention is applicable to tissue paper in general, including conventional felt pressed paper, the patterned compacted tissue paper described in the aforementioned U.S. Pat. No. 3 301746 (Sanford and Sisson) and the bulk tissue paper described in U.S. Pat. No. 3,812,000 (Salvucci Jr., May 21, 1974) may be a homogeneous or multilayer structure;

uncompacted American PatentsHuman silk products

- 18 of which may be single-layer or multi-layer structures. Structures formed from laminated paper webs are described in U.S. Patent No. 3,994,771 (Morgan Jr. et al., Nov. 30, 1976). Generally, the structure is prepared from a wet-laid composite, soft, bulk, and absorbent paper from two or more layers of paper-forming material, which preferably consists of fibers of different types. The layers are preferably formed by depositing separate layers of dilute fibrous suspensions, the fibers being preferably long softwood fibers or relatively short hardwood fibers used in paper making on one or more perforated continuous webs. The layers are then combined to form a layered composite strip. The laminated web is allowed to correspond to the product dried on a loose screen for drying / printing the product by applying liquid to the web and then thermally drying on said product as part of a low density papermaking process. The layered web may be reinforced with respect to the fiber type or the fiber content of the corresponding layers may be substantially the same. The tissue paper preferably has a basis weight of about 10 to about 65 g / m ² and a density of about 0.60 g / cm ³ or less. Preferably, the basis weight is below about 35 g / cm ³ or less; and the density is about 0.30 g / cm ³ or less. Most preferably, it is 0.04 to about 0.20 g / cm ³ .

Conventional pressed tissue paper and methods for its manufacture are well known in the art. Typically, such paper is produced by depositing paper forming material on a perforated forming screen. This screen is often referred to as a Fourdrinier screen. Once the paper making material is deposited on the forming wire screen, it is referred to as a web. The belt gets rid of elevated temperature. Those skilled in the art and typical devices for producing the belt as described. In a typical process, low consistency pulp material is provided in the press head to form paper. The press head has an aperture for discharging a thin layer of pulp to form paper onto a Fourdrinier screen to form a web. The web is then reliably dewatered to approximately 25% (relative to the total weight of the web by reindeer) and is further dried by a compression operation where the web is subjected to a pressure exerted against each other mechanical elements such as rollers.

The dewatered web is then pressed and dried by a steam drum apparatus known in the art as Yankee dryer. The pressure is induced here by mechanical means, such as counter-rotating drums pressing the belt. Vacuum can also be used when pressing in the Yankee. Multiple Yankee drums may also be used, preferably the pressure between the drums is increased. The tissue paper structures so produced are hereinafter referred to as conventional, pressed tissue paper structures. Such sheets are considered to be compact since the web is subjected to substantial overall mechanical compressive forces when the fibers are wet and then dried (and creping strongly) in the molded state.

The patterned compacted paper is characterized in that it has relatively large bulk areas of low fiber density and a lattice of relatively compacted zones of relatively small dense fiber. The high-volume region is alternatively referred to as the pad region. The compacted zones are alternatively referred to as nodal regions. The densified regions may be located separately throughout the high-volume region, or may be interconnected in the high-volume region, either "b" or "completely" or "completely." The pattern of the compacted belts is described in U.S. Patent 3,301,746 (Sanford and Sisson, January 31, 1967), U.S. Patent No. 3,940,225. (Peter G. Ayers, Aug. 10, 1976), U.S. Pat. No. 4,191,609 (Paul D. Trokhan, March 4, 1980), and U.S. Pat. No. 4,637,859 (Paul D. Trokhan, January 20, 1987). ).

Generally, the patterned compacted belts are preferably prepared by applying paper forming material to a perforated forming screen, such as a Fourdrinier screen to form a wet web, and then placing the web against an ordered backing. The web is pressed against the arranged backing, thereby forming densified zones in the web, locating the points of contact between the backing and the wet web. The remaining strip, which remains non-compacted in this operation, is called the high-volume region. This high-volume region can be further compacted by applying a liquid pressure, such as a vacuum device or a blow dryer, or by mechanically pushing the strip against an arranged support. The web is dewatered and optionally pre-dried to substantially eliminate compression of the high volume region. This is preferably achieved by liquid pressure, such as in a vacuum device or a blow dryer, or alternatively by mechanically pressing the strip against an arranged support, whereby the high-volume region remains uncompressed. The dewatering, possibly pre-drying, and compacting areas may be combined or partially combined to reduce the total number of operations performed. After formation of the compacted areas, dewatering and optionally pre-drying, the web is dried in a finishing manner, preferably without applying mechanical pressure. The compacted nodes with a relative density of at least 125% of the density of the bulk region preferably occupy about 8 to about 55% of the tissue surface.

The arranged pads are preferably a molded carrier product having a patterned node distribution that functions as an ordered pad that facilitates the formation of densified zones upon application of pressure. The node pattern forms the above-described arranged washer. Pressed carrier products are described in U.S. Patent 3,301,746 (Sanford and Sisson, January 31, 1967), U.S. Patent 3,810,104 (Salvucci Jr. et al., May 21, 1974), U.S. Patent 3 974025, Ayers, Aug. 10, 1976), U.S. Pat. No. 3,573,164 (Freid, March 30, 1971), U.S. Pat. No. October 1969, U.S. Pat. No. 2,390,665 (Trokhan, Dec. 16, 1980), and U.S. Pat. 4,528,339 (Trokhan, Jul. 9, 1985).

Preferably, the papermaking material is processed into a wet web of a perforated wire screen, for example a Fourdrinier screen. The strip is drained and transferred to the press fabric. Alternatively, the papermaking material may be first applied to perforated noberg et al., Lo 3 473576 (Amneus, 21 with a number pressing article against the surface of a dryer, where the strip is positioned between use also in a separate

Becker, Alert L. As a rule, the patent is McConnell sic, which also acts as a molding agent. Once formed, the love is dehydrated, preferably about 40% to about 80% pre-dried to the selected fiber stiffness. Drainage can be carried out in a vacuum cabinet or other vacuum equipment or in a blow dryer. In the manner described above, the molding product is pressed into the web before final drying. One way is to apply mechanical pressure. This can be done, for example, by pressing the squeezing roller that carries a drying drum, such as a Yankee squeezing roller and a drying drum. Also preferably, the web is applied to the press product by a vacuum device such as a suction box or a blow dryer. To compress the compacted areas, hydraulic pressure can be applied during the initial dewatering process or in a combination thereof.

Non-compact patterned non-compacted tissue paper structures are described in U.S. Patent 3,812,000 (Joseph L. Salvucci Jr. and Peter N. Yiannos, May 21, 1974) and U.S. Patent No. 4,208,459 (Henry E and Richard Schutte, June 17, 1980). ) handle non-compact patterned non-compacted tissue paper structures by depositing paper forming material on a perforated forming screen, such as a Fourdrinier screen to form a wet web, drying the web, and removing excess water without mechanical

If the strip has a constriction-not-less-80% -a. , kr ová η í m — Fri -.

su. Water is removed from the belt by vacuum dewatering and thermal drying. The resulting structure is a soft but high-volume sheet of relatively densified fibers. Preferably, a binder material is applied to a portion of the web prior to creping. _ _____

Compacted patterned non-compacted paper structures are generally known in the art as conventional paper structures. Typically, compacted patterned non-compacted tissue paper webs are obtained by applying paper forming material to a perforated forming screen, such as a Fourdrinier screen to form a wet web, drying the web and removing excess water by uniform mechanical compression (pressing) to achieve consistency.

-22- - Belt 25 to 50%, transferring the web to a heat dryer such as Yankee and creping in web. In total, water is removed from the web by vacuum dewatering, mechanical pressing, and thermal means. The resulting structure is solid and generally of significant density, but of very low volume, absorbability and softness.

The tissue paper web of the present invention can be used wherever a soft tissue paper web is desired. A particularly preferred application of the tissue paper web of the present invention is paper towels, toilet paper, and tissue paper products. For example, the two paper webs of the present invention can be embossed and adhesively bonded together as described in U.S. Patent 3,441,459 (Wells, Dec. 3, 1968) for the manufacture of two-ply paper towels.

Determination of molecular weight

A. Introduction

An essential distinguishing feature of polymeric materials is the size of their molecules. The properties that have allowed polymers to be used for various purposes are derived from their macromolecules! nature. In order to fully characterize these materials, it is necessary to have the means to define and determine their molecular weights and molecular weight distributions. It is more accurate to use the term relative molecular weight than molecular weight, the term molecular weight being used more generally in polymer technology. It is not always easy to determine the molecular weight distribution. The use of chromatographic techniques has become more common. Rather, there are attempts to express the size of the molecules in average molecular weight.

B. Molecular weight averages

Considering the simple molecular weight distribution, which represents the mass fraction (Wi) of molecules having a relative molecular weight (Mi), several useful average quantities can be defined. Z. averaging_ based on the number of molecules (Ni) of a certain size (Mj) gives a number of the number average molecular weight 23 _ Ni Mi M _n = —-—

Σ Ni

An important consequence of this definition is that the number average molecular weight in grams contains the Avogadro number of the molecules. This definition of molecular weight is consistent with the molecular weight of monodisperse molecular species, i.e., molecules having the same molecular weight. Of greater importance is the finding that if the number of molecules in a given polydisperse polymer mass can be somehow defined, then M _n can be readily calculated. This is the basis for measuring the unifying properties. The averaging performed on the basis of the weight fractions (Wi) of the molecules of the given size (Mi) leads to the definition of the weight average molecular weight.

Σ Wi Ni Σ Ni Mi 2 Mw = = = Σ Wi Σ Ni Mi

Mw is a more useful way of expressing the molecular weights of polymers than M _n since it more accurately reflects properties such as melt viscosity and mechanical properties and is therefore used in this patent.

Analytical and test procedures

The analysis of the amount of biodegradable chemicals used according to the invention or entrapped on tissue paper strips can be performed by any method established in the art.

A. Quantitative analysis of quaternized esteramine compounds and polyhydroxy compounds.

For example, an amount of a quaternized esteramine compound such as dimethylammonium dichloride of hydrogenated diacids

24 tallow (DEDHTDMAC) (for example ADOGEN DDMC ^R ), captured on tissue paper, can be determined by solution extraction of DEDHTDMAC with an organic solvent followed by anionic / cationic titration with Dimidium bromide as an indicator; the amount of polyhydroxy compound, such as PEG-400, can be determined, for example, with water, followed by determining the amount by extraction with an aqueous solvent such as colorimetry or chromatography to PEG-400 in the extract. These methods are exemplified and do not in any way exclude other methods which may be used to determine the amount of the respective constituents contained in the tissue paper.

B. Hydrophilicity (absorption capacity)

The hydrophilicity of the tissue paper generally provides information about the wettability of the tissue paper. It can be defined to a certain extent by determining the time required to completely dry the tissue paper with water. This time period is called the wetting time. The following procedure may be used to ensure a consistent and reproducible wetting time test: first, a conditioned single sheet of paper is provided (external conditions for testing paper samples are 23 ± 1 ° C and 50 ± 2% relative humidity, as determined by TAPPI T 402) 11.1 x 12 cm, secondly, the sheet of paper is folded four times into opposing quarters and then crumpled into a ball of about 1.9 to about 2.5 cm in diameter, and thirdly, the crumpled sheet is placed on the surface of distilled water a temperature of 23 ± 1 ° C and the stopwatch is started simultaneously; after the fourth stopwatch it stops and the time is deducted when the moistening of the crumpled sheet is finished. Complete wetting is assessed visually.

However, the hydrophilicity characteristics of the tissue paper of the present invention can be determined immediately after manufacture. However, a substantial increase in the hydrophobicity of the paper can only occur in the first two weeks after the tissue paper has been produced; this is when the paper is aged for two weeks after its production. Therefore, the wetting times are preferably measured up to the end of this two-week period. Accordingly, the humidification supervision, measured at the end of the two-week aging at room temperature, is referred to as the two-week wetting times.

C. H u s t o t a _. .

By the density of tissue paper is meant here the average density, calculated on the basis of the weight of the paper divided by the caliper, with the respective unit conversion. By tissue caliper is meant here the thickness of the paper loaded with a pressure of 15.5 g / cm ² .

Possible ingredients

Other chemicals commonly used in papermaking can also be added to the biodegradable softeners of the present invention as long as they do not significantly or deleteriously affect the softening and absorbency of the fibrous material and promote the action of the softening chemical agent.

For example, surfactants may be used to process the tissue paper webs. If used, their amount is preferably from about 0.01 to about 2.0% by weight of the dry, fibrous tissue paper web. The surfactants preferably have alkyl chains of 8 or more carbon atoms. Exemplary anionic surfactants include linear alkylsulfonates α and alkylhenzenesulfonates. Exemplary nonionic surfactants are alkyl glycosides including alkyl glycoside esters such as Crodesta SL-40, a commercial product of Croda Inc., New

York, NY; the alkyigylic acid ethers described in U.S. Patent No. 4,011,389 (W. K. Langdon et al., Mar. 8, 1977); and polyethoxylated esters such as Pegosperse 200 ML, a commercial product of Glyco Chemicals Inc. (Greenwich, CT) and IGEPAL RC-520, a product of Rhone Poulenc Corporation (Cranbury,

N. J.).

Other chemicals that may be added include dry strengthening additives to increase the tensile strength of the paper webs. Examples of dry-strengthening additives include carbomethylamines and cationic polymers of the ACCO family of chemicals, such as ACCO 711 and ACCO 514. ACCO chemicals are preferred. These products are commercially available from American Cyanamid

Coman of Wayne, New Jersey. When amounts of dry-strengthening additives are used, the weight-benefit is about 0.01 to about 1.0% by weight of the tissue paper.

Another type of wet strength chemical additive, to the weight of the dry fiber web that may be added, is to increase the wet strength of the paper webs. The agent of the invention may contain, as an optional component, a water-soluble permanent wet strength resin in an amount by weight of about 0.01 to about 3.0%, more preferably about 0.3 to about 1.5%, based on the dry fiber weight.

Useful permanent wet strength resins may be of several types. In general, resins that are used previously and now commonly in papermaking are useful. Numerous examples are given in the above-mentioned Westfelt publication.

Typically, cationic products are water-soluble in wet strength resins. This means that the resins are soluble in water when added to the stock. It is quite possible and even expected that the following circumstances, such as crosslinking, will render the resins insoluble in water. In addition, some resins are water soluble only under specific conditions, such as within a certain pH range.

In general, it is believed that the wet strength resins undergo crosslinking or other curing reactions when applied to or between papermaking fibers. Crosslinking or curing normally does not occur until substantial amounts of water are present.

Various polyamide epichlorohydrin resins are particularly useful. These products are low molecular weight polymers with reactive functional groups such as amino, epoxy and azetidinium groups. The patent literature is overflowing with descriptions of the preparation of such products. See, for example, U.S. Patent 3,777,276 to Keim (November 13, 1973).

No. 3 700623 (Keim, Oct. 24, 1972), U.S. Pat

According to the invention, particularly useful are the depylorohydrin resins of the trade names Kymene 557H and Kymene 2064 from Hercules, Wilmington, Delaware. In these patents these resins are referred to as Keim.

The alkali-activated polyami-depichlorohydrin resins useful herein have the trade name Santo Res, such as Santo Res 31, of Monsanto Company St. Petersburg. St. Louis, Missouri. In general, these products are described in U.S. Pat. No. 3,855,158 (Petrovich, Dec. 17, 1974), U.S. Pat. No. 3,899,338 (Petrovich, Aug. 12, 1975, U.S. Pat. No. 4,129528, Petrovich, Dec. 12, 1978). ), U.S. Pat. No. 4,147,886 (Petrovich, Apr. 3, 1979) and U.S. Pat. No. 4,222,921 (Van Eenam, Sep. 16, 1980).

Other useful water-soluble cationic resins are polyacrylamide resins of the trade name Stump, such as Stump 63INC, from American Cyanamid Company Standford, Connecticut. These products are generally described in Coscia et al.

U.S. Pat. January 1971) and US Patent January 1971.

No. 3 556933 (Williams et al

Other water-soluble resins useful herein include acrylic emulsions and anionic styrene-butadiene latexes. Numerous examples of this feature of this phe-y-pu are post-ps-am-y in U.S. Pat. No. 3 844880 (Meisel Jr. and , Oct. 29, 1974).

Still other water-soluble resins suitable in accordance with the invention are urea-formaldehyde and melamine-formaldehyde resins. These polyfunctional reactive polymers have molecular weights of the order of several thousand. More known functional groups include nitrogen-containing groups such as amino groups and methylol groups attached to a nitrogen atom.

Although less suitable, polyethylene imine resins are also useful in the present invention.

A more complete description of these water-soluble resins, including methods of manufacture, is in TAPPI Monograph No. 29, Wet Strength in Paper and Paperboard, Technical Association of Pulp and Paper Industry (New York, 1965). As used herein, the term "permanent wet strength resin" refers to a resin that allows a sheet of paper, when placed in an aqueous environment, to retain most of its wet strength for more than two minutes.

Said wet strength delivery additives lead to paper products with permanent wet strength, i.e. paper which, when placed in an aqueous environment, retains a substantial part of its original wet strength over time. However, permanent wet strength may be an undesirable property in some paper products. Paper products, such as toilet paper, reach the septic system after a short period of use. If the paper product retains permanently its strength-resistant hydrolysis, such systems could become clogged. Recently, manufacturers have been providing temporary wet strength additives to paper products, where wet strength is sufficient for the intended use but disappears when soaked with water. Removal of wet strength facilitates the flow of paper product through the septic systems.

Examples of suitable temporary wet strength resins are modified starch wet strength agents such as National Starch 78-0080, a commercial product of National Starch and Chemical Corporation (New York, New York). This type of wet strength agent can be obtained by reacting dimethoxyethyl-N-methylchloroacetamide with cationic starch polymers. Modified starch wet strength agents are also described in U.S. Patent 4,675,394 (Solarek et al., June 23, 1987). Preferred wet strength resins include those described in U.S. Pat. No. 4,985,157 (Bjokquist, Jan. 1, 1991).

Classes and specific examples of resins that increase both permanently and temporarily wet strength are given by way of example only, without intending to limit the invention in any way.

Compatible wet strength resins can also be used in the process of the invention.

-. 29

All of the above mentioned optional ingredients are given by way of example only, without intending to limit the invention.

The following examples illustrate the invention and do not limit it in any way. Percentages are by weight unless otherwise indicated.

DETAILED DESCRIPTION OF THE INVENTION

Example 1

The purpose of this example is to illustrate a method that can be used to treat a biodegradable chemical softening agent consisting of a mixture of diester of dimethylammonium tallow diacid (DEDTDMAC) and polyethylene glycol 400 (PEG-400).

A 1% solution of a biodegradable chemical softening agent is prepared as follows:

1. separately weigh equivalent amounts of DEDTDMAC and PEG 400;

2. The PEG is heated to approximately 66 ° C;

3. DEDTDMAC is dissolved in PEG to form a molten solution at 66 ° C;

4. shear stress to form a homogeneous mixture of DEDTDMAC in PEG;

5. adjust the pH of the dilution water to 0.1 with 0.1% hydrochloric acid;

6. The dilution water is heated to a temperature of about 6 to 6 ° C. the melted mixture of utuumau and mercury is reacted to i »γοζϊοκ;

8. apply a shear stress to form an aqueous solution containing the bubble dispersion or suspension of the DEDTDMAC / PEG mixture;

9. The particle size of the bubble dispersion determined by optical microscopy is 0.1 to 1.0 micrometer.

Figure 6 is a 1: 1 ratio of the DEDTDMAC and PEG-400 bubble dispersion cryotransmission micrograph at a magnification of 63,000 times. Fig. 6 shows particles with 1 or 2-layer membranes whose geometry ranges from closed / open bubbles to discs, structures, and platelets.

Example 2

The purpose of this example is to illustrate a method that can be used to treat a biodegradable chemical softening agent consisting of a mixture of diester of dimethylammonium tallow diacid (DEDTDMAC) and glycerol.

A 1% solution of a biodegradable chemical softening agent is prepared as follows:

1. separately weigh equivalent amounts of DEDTDMAC and glycerol;

2. glycerol is heated to about 66 ° C;

3. DEDTDMAC is dissolved in glycerol to form a molten solution at 66 ° C;

4. a shear stress produces a homogeneous mixture of DEDTDMAC in glycerol;

5. adjust the pH of the dilution water to 0.1 with 0.1% hydrochloric acid;

6. heat the dilution water to about 66 ° C;

7. dilute the molten mixture of DEDTDMAC and glycerol to a 1% solution;

8. a shear stress is applied to form an aqueous solution containing the bubble dispersion or suspension of the DEDTDMAC / glycerol mixture;

9. The particle size of the bubble dispersion detected by the microscope is 0.1 to 1.0 microns.

Figure 7 is a cryo-transmission micrograph of a dispersion of DEDTDMAC and glycerol bubbles at a weight ratio of 1: 1 at a magnification of 63,000 times.

Figure 7 is a cryotransmission micrograph of DEDTDMAC and glycerol dispersion bubbles at a ratio of 1. Fig. 7 shows particles or 2 bilayers whose geometry ranges from closed / open bubbles to disc, structures and platelets.

using optical

1, at a magnification of 6300O-us membranes having a thickness of 1

Example 3

The purpose of this example is to illustrate a method that can be used to treat a biodegradable chemical softening agent consisting of a mixture of dimethylammonium chloride hydrogenated tallow diester (DEDHTDMAC), such as ADOGEN DDMC ^R from Sherex Company and polyethylene glycol 400 (PEG400).

Prepare a 1% solution of a biodegradable chemical softening agent as follows:

1. separately weigh equivalent amounts of DEDHTDMAC and PEG-400;

2. The PEG is heated to approximately 90 ° C;

3. DEDHTDMAC is dissolved in PEG to form a molten solution at 90 ° C;

a shear stress produces a homogeneous mixture of DEDHTDMAC in PEG; the pH of the dilution water is adjusted to 3 with 0.1% hydrochloric acid;

the dilution water is heated to a temperature of approximately 70 ° C; dilute the molten mixture of DEDTDMAC and PEG to a 1% solution; a shear stress is applied to form an aqueous solution containing a bubble dispersion or suspension of a mixture of DEDHTDMAC and PEG;

9. The particle size of the bubble dispersion determined by optical microscopy is 0.1 to 1.0 micrometer.

Figure 8 is a cryotransmission micrograph of DEDHTDMAC and PEG-400 bubble dispersions at a ratio of 1: 1, at a magnification of 63,000 times. Fig. 8 shows particles with membranes having a thickness of 1 or

Two layers whose geometry ranges from closed / open bubbles to disc-like structures and plates.

Example 4

The purpose of this example is to illustrate how, by means of a blow-drying papermaking technique, towel sheets can be prepared from soft absorbent paper treated with a biodegradable chemical softening agent consisting of a mixture of dimethylammonium tallow acid diester (DEDTDMAC), polyethylene glycol 400 (PEG-400) and permanent strength resin. wet.

Wilmington, DE)

In carrying out the process according to the invention, a pilot plant is used in a paper machine. For example, according to Example 1, a 1% solution of a biodegradable chemical softener is prepared. Second, a 3 wt% NSK suspension is formed in a conventional repulper. The NSK suspension is slightly refined and a 2% permanent wet strength resin solution (e.g., Kymene 557H by Hercules INC, at 1% by weight of dry fibers) is added to the NSK via the feed tube. A 0.2% carboxymethylcellulose (CMC) solution is added to the mixer in an amount of 0.2% by weight of the dry fibers to support the dry strength of the fibrous substrate, and CMC adsorption to the NSK can be promoted by the in-line mixer. % solution of chemical softener mixture (DEDTDMAC / PEG) in an amount of 0.1% with respect to the dry fiber weight Adsorption of chemical softener to NSK can also be supported by a line mixer. A 3% by weight aqueous suspension of CTMP is prepared in a conventional repulper. 0.2% by weight of dry fibers are added to the repulper and 1% of a chemical softener solution is added to the CTMP inlet pipe before the filling pump in an amount of 0.1% by weight of dry fibers. Adsorption of the mixture

The CTMP can be supported by a mixer that is diluted with a 2% vane pump of the chemical softener in the line. The CTMP suspension was

The treated pulp mixture (NSK / CTMP) is mixed in the head chamber and deposited on a Fourdrinier screen to form a seed band. Drainage takes place on a Fourdrinier screen using a deflector and suction boxes. The Fourdrinier screen is a five-finished, satin woven configuration having 33 monofibers per cm in the machine direction and 30 monofibers per cm in the transverse direction. The embryonic wet band is transferred from a Fourdrinier sieve at a consistency of approximately 22% at the time of transfer, to a photopolymer having 240 linear Idaho cells per 6.5 cm ² , 34 nodal areas and a photo-polymer depth of 0.3556 mm drainage occurs under drainage. with vacuum until it has a belt

To further consistency

-IN,.

approached 28%. By air purging, the patterned web is pre-dried to a fiber weight consistency of approximately 65%. The belt is then attached to a Yankee dryer with a sprayed sizing agent which is a 0.25% aqueous solution of 1 v inyl alcohol (PVA). The fiber consistency is estimated to increase to 96% prior to dry creping of the web with a craping scraper. The scraping rasp has a bevel angle of approximately 25 'and is positioned relative to the Yankee to provide an angle of incidence of approximately 81; the Yankee dryer has a speed of approximately 244 meters per minute. The dry belt is wound at 214 meters per minute.

A two-ply web is formed into a paper towel product by extrusion and harvesting with polyvinyl alcohol adhesive. The paper towel has a basis weight of approximately 26 µm per 0.093 m ² , contains approximately 0.2% of a biodegradable chemical softener composition and 1.0% resin to impart permanent wet strength. The resulting paper towel is soft, soaked and very firm when wetted.

In the following table, the retention values and average particle size of the DEDTDMAC / PEG-400 dispersion bubbles are compared to adding only PEG-400 to the pulp suspension.

Table I:

PEG into DEDTDMAC / PEG Bubble Dispersion

PEG retention in products (%) 5 80.0 DEDTDMAC retention in products (%) NA 85.0 Average particle size (nm) NA 0.4

Example 5

The purpose of this example is to illustrate how a soft and absorbent toilet paper treated with a biodegradable chemical softening agent consisting of a mixture of dimethylammonium-34 tallow diacid diester (DEDTDMAC), polyethylene glycol 400 (PEG400), and a temporary delivery resin can be prepared using a purge paper technique. wet strength.

In the process according to the invention, a pilot plant Fourdrinier paper machine is used. First, a 1% biodegradable solution or a chemical softener solution is prepared according to Example 1, by weight a 3% aqueous NSK suspension is prepared. The NSK suspension is slightly refined and a 2% resin solution is supplied to the NSK for temporary delivery (e.g. National Starch 780080;

New York, NY) in an amount of 0.75% by weight of the dry fibers. The in-line mixer supports the adsorption of the resin to impart temporary wet strength to the NSK fibers. The NSK suspension is diluted to approximately 0.2% consistency in the vane pump. Third, a 3% by weight suspension of eucalyptus fibers of the baffle is prepared. Second, in a conventional tube repulper, the wet strength of the company's product in the conventional repulper is added. Add gates to the germline pump through a deflector and with a 1% solution of the chemical softening feed pipe for the eucalyptus substance prior to the feed rate of 0.2% by weight with respect to dry fiber. The adsorption of the biodegradable plasticizer mixture to the eucalyptus fibers can be aided by the in-line mixer. The eucalyptus suspension is diluted to 0.2% with a vane pump.

The treated pulp mixture (30% NSK / 70% eucalyptus) is mixed in the head chamber and added to the Fourdrinier strainer to form the drainage on the Fourdrinier sieve cabinets. The Fourdrinier screen is a five-finished, satin woven configuration having 33 monofibers per cm in the machine direction and 30 monofibers per cm in the transverse direction. The embryonic wet band is transferred from a Fourdrinier sieve at a consistency of approximately 15% at the time of transfer, to a photopolymeric substance having 562 linear Idaho cells per 6.5 cm ² , 40 node regions and a photo-polymer depth of 0.2286 mm. Further drainage occurs by vacuum drainage until the belt has a consistency of approximately 28%. By air purging, the patterned web is pre-dried to a fiber weight consistency of approximately 65%. The belt is then attached to a Yankee dryer with a sprayed sizing agent which is a 0.25% aqueous solution of 35 lvinyl alcohol (PVA). The fiber consistency was increased to an estimated 96% prior to dry creping of the web with a crepe scraper. The scraping scraper has a bevel angle of approximately 25 'and is positioned relative to the Yankee dryer to provide an angle of incidence of approximately 81. The Yankee dryer has a speed of approximately 244 meters per minute. The dry belt is wound at 214 meters per minute.

The web is converted to a monolayer tissue paper product. The tissue paper has a basis weight of approximately 18 µm, 0.093 m ² , contains approximately 0.1% biodegradable chemical softener composition and 0.2% resin to impart temporary wet strength. Importantly, the resulting tissue paper is soft, absorbent, and suitable for use as facial and / or toilet paper.

In the following table, the retention values and average particle size of the DEDTDMAC / PEG-400 dispersion bubbles are compared to adding only PEG-400 to the pulp suspension.

Table II:

PEG into DEDTDMAC / PEG Bubble Dispersion

PEG retention in product (%) 5 75.0 DEDTDMAC retention in product (%) NA 85.0 Average particle size (μιη) NA 0.4

Example 6 - · ...... _. . ------.

The purpose of this example is to illustrate how a soft and absorbent toilet paper treated with a biodegradable chemical softening agent consisting of a mixture of diesters of dimethylammonium tallow diacid (DEDTDMAC), polyethylene glycol 400 (PEG400), and a dry strength resin can be prepared using a purge paper technique.

In the process according to the invention, a pilot plant Fourdrinier paper machine is used. First, a 1% solution of a biodegradable chemical plasticizer is added via a tube in a conventional repulper. Second, a 3% by weight aqueous NSK suspension is prepared by weight. The NSK suspension is slightly refined and a 2% dry strength resin feed to the NSK is supplied to dry strength (e.g., Acco 514, Acco 711, commercial products of American Cyanamid Company of Fairfield, OH). 2% by weight of the dry fibers. The in-line mixer supports the dry-resin absorption to the NSK fibers. The NSK suspension is diluted to approximately 0.2% consistency in the vane pump. Third, a 3% by weight suspension of eucalyptus fibers in a conventional repulper is prepared. A 1% solution of the chemical softener mixture is added to the inlet pipe for the eucalyptus substance upstream of the inlet pump in an amount of 0.2% by weight with respect to dry fiber. The adsorption of the biodegradable plasticizer mixture to the eucalyptus fibers can be aided by an in-line mixer. The eucalyptus suspension is diluted to 0.2% with a vane pump.

The treated pulp mixture (30% NSK / 70% eucalyptus) is mixed in the head chamber and added to the Fourdrinier strainer to form the drainage on the Fourdrinier sieve cabinets. The Fourdrinier screen is a five-finished, satin woven configuration having 33 monofibers per cm in the machine direction and 30 monofibers per cm in the transverse direction. The embryonic wet band is converted from a Fourdrinier sieve at a consistency of approximately 15% at the time of transfer, to a photopolymer fabric having 562 linear Idaho cells per 6.5 cm ² , 40 node regions and a photopolymer depth of 0.2286 mm. Further drainage occurs by vacuum drainage until the belt has a consistency of approximately 28%.

germ band by deflector and pre-weight to weight

By air purging, the patterned waist has a fiber consistency of approximately 65%. The belt is then attached to a Yankee dryer with a sprayed sizing agent which is a 0.25% aqueous solution of Polyol Poly (PVA). The fiber consistency is estimated to increase to 96% prior to dry creping of the web with a craping scraper. The creping rasp has a bevel angle of approximately 25 * and is positioned relative to the Yankee dryers to provide an angle of incidence of approximately 81; the Yankee dryer has a speed of approximately 244 meters per minute. The dry belt is wound at 214 meters per minute.

The two layers of the web are formed into a tissue paper product by a laminating technique. Tissue paper has a basis weight of about 2,3 M / 0.093 m ² , contains about 0.1% biodegradable chemical softener composition and about 0.1% resin to impart dry strength. Importantly, the resulting tissue paper is soft, absorbent, and suitable for use as facial and / or toilet paper.

In the following table, the retention values and average particle size of the DEDTDMAC / PEG-400 dispersion bubbles are compared to adding only PEG-400 to the pulp suspension.

Table III:

PEG into a dispersion of bubbles

DEDTDMAC / PEG

PEG retention in product (%) 5 75.0 DEDTDMAC retention in product (%) NA 80.0 Average particle size (μηι) NA 0.4

EXAMPLE 7 [0005] In this manner, it is possible to prepare a soft and absorbent toilet paper treated with a biodegradable chemical softening agent consisting of a mixture of dimethylammonium dihydrochloride diester by using conventional papermaking techniques. DEDHTDMAC), polyethylene glycol 400 (PEG-400) and dry strength resins.

In the process according to the invention, a pilot plant Fourdrinier paper machine is used. First, a solution of a biodegradable chemical softener is prepared according to Example 3. Second, a 3% by weight aqueous suspension of NSK is prepared in a conventional repulper. The NSK suspension is slightly refined, and a 2% dry strength resin solution is added to the NSK via a feed tube (e.g., Acco 514, Acco 711, commercial products of the American Cyanamid Company of Wayne, New Jersey) in an amount of 0.2% by weight based on mass of dry fibers. Adsorption of the resin to impart dry strength to the NSK fibers is supported by the in-line mixer. The NSK suspension is diluted to approximately 0.2% consistency in the vane pump. Third, a 3% by weight suspension of eucalyptus fibers in a conventional repulper is prepared. A 1% solution of the chemical softener mixture is added to the inlet pipe for the eucalyptus substance upstream of the inlet pump in an amount of 0.2% by weight with respect to dry fiber. The adsorption of the biodegradable plasticizer mixture to the eucalyptus fibers can be aided by an in-line mixer. The eucalyptus suspension is diluted to 0.2% with a vane pump.

The treated pulp mixture (30% NSK / 70% eucalyptus) is mixed in the head chamber and placed on a Fourdrinier screen to form a seed band. Drainage takes place on a Fourdrinier sieve using a deflector and suction boxes. The Fourdrinier screen is a five-finished, satin woven configuration having 33 monofibers per cm in the machine direction and 30 monofibers per cm in the transverse direction. The embryonic wet band is transferred from a Fourdrinier sieve at a consistency of approximately 15% at the time of transfer, to a conventional felt. Further drainage occurs by vacuum drainage until the web has a consistency of approximately 35%. The belt is then attached to a Yankee dryer. The fiber consistency is estimated to increase to 96% prior to dry creping of the web with a craping scraper. The creping rasp has a bevel angle of approximately 25 and is positioned relative to the Yankee to provide an angle of incidence of approximately 81 °; the Yankee dryer has a speed of approximately 244 meters per minute. The dry belt is wound at 214 meters per minute.

The two layers of the web are formed into a tissue paper product by a laminating technique. Tissue paper has a basis weight of about 2 3 # / 3 M 0.09 3 m 2, containing about 0.1% biodegradability and blends, and about 0.1% dry chemical softener resin to impart dry strength. Importantly, the resulting tissue paper is soft, absorbent, and suitable for use as facial and / or toilet paper.

In the following table, the retention values and average particle size of the DEDHTDMAC / PEG-400 dispersion bubbles are compared to the addition of mere PEG-400 to the pulp suspension.

Table IV

PEG into DEDTDMAC / PEG Bubble Dispersion

PEG retention in product (%) 5 70.0 DEDTDMAC retention in product (%) NA 75.0 Average particle size (μιη) NA 0.5

Industrial applicability

Absorbent paper product useful for making napkins, diapers, facial tissue and toilet paper.

Claims (10)

PATENT CLAIMS A paper product comprising a sheet of fibrous cellulosic material and 0.005 to 5.0% by weight of the fibrous cellulosic material, a biodegradable chemical softening composition comprising (a) a quaternized esteramine compound of the general formula Xor -R3 X -R3 where is R1 is in each case a hydrocarbyl group having 14 to 22 carbon atoms or a mixture thereof, preferably an alkyl group having 16 to 18 carbon atoms, <5 R2 is in each case an alkyl or hydroxyalkyl group having 1 to 6 carbon atoms or a mixture thereof, preferably an alkyl group having 1 to 3 carbon atoms and in particular a methyl group, R3 is in each case a hydrocarbon group having 12 to 20 carbon atoms or a mixture thereof, preferably an alkyl group having 14 to 16 carbon atoms, An X compatible anion, preferably a chloride or sulfate anion, and (b) a polyhydroxy compound selected from the group consisting of glycerol and polyethylene glycols and polypropylene glycols having an average molecular weight of 200 to 4000, preferably 200 to 1000, and particularly 200 to 600, wherein the weight ratio of quaternized esteramine compound the polyhydroxy compound is 1: 0.1 to 0.1: 1, preferably 1: 0.3 to 0.3: 1, especially 1: 0.7 to 0.7: 1, and wherein the polyhydroxy compound is miscible with the quaternized esteramine compound at elevated temperature. The paper product of claim 1, wherein the quaternized esteramine compound is selected from the group consisting of diester of dimethylammonium chloride of non-hydrogenated tallow, diester of dimethylammonium chloride of hydrogenated tallow hydrogenated, diester of dimethylammonium chloride of partially hydrogenated tallow dihydrochloride, diester of dimethylammonium dihydrochloride. tallow diacids. and tallow hydrogenated dimethylammonium methylsulfate diester. • · & The paper product of claim 1 or 2, wherein the polyhydroxy compound is miscible with the quaternized esteramine compound in the liquid phase. A paper product according to any one of claims 1 to 3, wherein the quaternized esteramine compound is miscible with the polyhydroxy compound at elevated temperature of at least 50 ° C. * more preferably at a temperature between 50 to 100 ° C. 5. A paper product according to claim 1, wherein the mixture of the quaternized esteramine compound and the polyhydroxy compound is diluted with a liquid carrier to a concentration of 0.01 to 25.0%, based on the weight of the chemical softening agent. Paper product according to claim 5, characterized in that the mixture of the quaternized esteramine compound with the polyhydroxy compound is present in the form of particles dispersed in a liquid carrier, the average particle size of the quaternized esteramine compound and the polyhydroxy compound being preferably 0.01 to 10 microns, most preferably 0.1 to 1.0 microns. Paper product according to claim 5 or 6, characterized in that the temperature of the liquid carrier is 40 to 80 ° C and the pH value of the liquid carrier is less than 4. 8. A paper product according to any one of claims 1 to 7, wherein the paper product is a towel, toilet paper or facial tissue. 9. A biodegradable chemical softening composition consisting of a composition comprising (a) a quaternized esteramine compound of formula (CH2) 2-O-C-R3 The composition of claim 9, wherein the quaternized esteramine compound is selected from the group consisting of dimethylammonium chloride diester, non-hydrogenated tallow diester, dimethylammonium chloride diester, hydrogenated tallow hydrogenated diester, dimethylammonium dihydrochloride diester dimethylammonium diester, hydrogenated diacids dimethylammonium methylsulfate. A biodegradable chemical softener composition according to claim 9 or 10, wherein the mixture of the quaternized esteramine compound and the polyhydroxy compound is diluted with a liquid carrier to a concentration of 0.01 to 25.0%, based on the weight of the chemical softener, The polyhydroxy compound compound is present in the form of particles dispersed in a liquid carrier and the average particle size of the quaternized esteramine compound and the polyhydroxy compound is preferably 0.01 to 10 microns, most preferably 01 to 1.0 microns.