HUT75855A

HUT75855A - Paper products containing a biodegradable chemical softening composition

Info

Publication number: HUT75855A
Application number: HU9502124A
Authority: HU
Inventors: Dean Van Phan; Paul Dennis Trokhan
Original assignee: Procter & Gamble
Priority date: 1993-01-14
Filing date: 1994-01-13
Publication date: 1997-05-28
Also published as: EP0679205A1; HU9502124D0; AU6029494A; NO952760D0; NZ261518A; FI953425A0; FI953425A; KR960700379A; CZ180095A3; NO952760L; MY111212A; KR100310142B1; AU683870B2; JPH08505663A; TW263544B

Description

The present invention relates to paper products comprising from 0.005 to 5.0% by weight of biodegradable chemical plasticizer composition per fibrous cellulosic material.

One component of the softening mixture is a quaternary ester amine of formula (I) or (11), wherein R 1, R 1 and R 1 are hydrocarbon groups and a compatible anion, preferably chloride or methyl sulfate ion. Another component of the softening mixture is a polyhydroxy compound such as glycerol, polyethylene or polypropylene glycol. The weight ratio of quaternary ester amine compound to polyhydroxy compound in the mixture is 1: 0.1 to 0.1: 1.

60.803 / BE • '· • · · · ««

Patent Office

Paper products containing a biodegradable chemical plasticizer

THE PROCTER & GAMBLE COMPANY, CINCINNATI, OH, US

inventors:

PHAN Dean Van, WEST CHESTER, Ohio, US

TROKHAN Paul Dennis, HAMILTON, Ohio, US

Date of announcement: 01.01.1994.

Priorities: 14/01/1993 (08 / 004,334) US

14/01/1993 (08 / 004,333) US

International Application Number: PCT / US94 / 00551

International Publication Number: WO 94/16143 * «

The invention relates to silk crepe paper. More particularly, the invention relates to soft, absorbent silk crepe papers which can be used as towel, napkin, face wiping and toilet paper products.

Paper rolls or spools, sometimes referred to as rolls of tissue / tissue / or silk crepe paper or rolls are often used only in papers /, are widely used in modern society. These articles, such as paper towels, napkins, face wipes and toilet paper, are permanent commodities of commerce. It has long been recognized that these products have three important physical characteristics, softness, ability to absorb, especially the ability to absorb water into the systems, and the strength, especially the wet strength. Research and development attempts have been made to improve all these qualities without adversely affecting the others, and to improve two or three properties at the same time.

Softness is the sensation of perception by a consumer when a man or woman wears a special product, wipes or collects his skin.

This sense of touch is a combination of several physical properties. One of the most important physical properties associated with softness is, according to experts, the rigidity of the paper from which the product is made. On the other hand, it is generally believed that rigidity is directly related to the dry tensile strength of the paper and the stiffness of the fibers from which the paper is made.

The strength of the products and papers they are made of is to maintain their physical integrity and to withstand tearing, tearing and shredding under the conditions of use, particularly in wet conditions.

Suction is the ability of products and papers to produce a degree of ability to absorb liquid, in particular aqueous solutions and dispersions. The overall absorbency, as perceived by a human consumer, is generally a combination of all the amount of fluid that a given weight of a silk crepe paper absorbs to saturation and the rate at which this mass absorbs fluid.

It is widely known to use wet strength resins to enhance the strength of the paper web. For example Westfeld has described a number of such materials and kémiájukat explained /.Cellulose Chemistry and Technology, mentioned 13, No. 813-825 / 1979/7 ^Ά 3,755,220 U.S. Patent discloses that certain chemical additives that debonders / debonding known as agents / acting on natural fiber-to-fiber bindings that are created during paper making in the papermaking processes. This reduction in bonding results in softer or less coarse paper. The above patent specification describes * · · · ·

- use of 4 wet strength resins to increase the wet strength of the paper, coupled with the use of loosening agents to eliminate undesirable properties of wet strength resins. Loosening agents reduce dry tensile strength, but generally also reduce wet tensile strength.

U.S. Patent No. 3,821,068 also discloses that chemical loosening agents can be used to reduce stiffness, and this increases the softness of the silk crepe paper roll.

Chemical relaxants are mentioned in numerous publications, such as U.S. Patent No. 3,554,862. These materials are quaternary ammonium salts such as trimethyl coconut alkyl ammonium chloride, trimethyl oleyl ammonium chloride, dihydrogenated tallowkyl dimethyl ammonium chloride and trimethyl stearyl ammonium chloride.

U.S. Patent No. 4,144,122 discloses the use of complex quaternary ammonium compounds such as bis-alkoxy-2-hydroxy-propylene-quaternary ammonium chlorides for softening paper webs. The authors also attempt to overcome the reduction in absorbency caused by the relaxants by using nonionic surfactants such as the ethylene oxide and propylene oxide adducts of aliphatic alcohols.

The Armak Company of Chicago, Illinois Company 1977.

describes the use of dimethyldihydrogenated tallowkyl ammonium chloride in its bulletin 76-17, in combination with polyoxyethylene glycol fatty acid esters which also provide softness and absorbency to silk crepe paper webs.

For example, the results of the research on producing improved paper rolls are described in U.S. Patent No. 3,301,746.

The excellent quality of the paper rolls produced by the process described herein and the commercial success of the products made from these rolls of paper continued to produce improved products.

For example, U.S. Patent No. 4,158,594 discloses a method which is claimed to provide strong, soft, fibrous ivy. More specifically, it is stated that the silk crepe paper web / which can be softened by the addition of chemical loosening agents may be enhanced by bonding one surface of the paper web to a crepe surface during finishing, with a binder such as an acrylic latex rubber emulsion, a water-soluble resin or an elastomeric binder / adhesive bonded to one side of the paper web and the creping surface in a finishing arrangement, and the paper web is creped with crepe paper creped from the creping surface.

• · · «

The conventional quaternary ammonium compounds, such as the well-known dialkyl dimethyl ammonium salts (for example, difaggyualkyldimethylammonium chloride, difaggyualkyldimethylammoniummethyl sulfate, dihydrogenated tallowalkyldimethylammonium chloride, etc.). / effective chemical relaxants. Unfortunately, these quaternary ammonium compounds are not biodegradable. The Applicant has found that the biodegradable mono and diester versions of these quaternary ammonium salts also function effectively as chemical relaxants and enhance the softness of the fibrous cellulosic materials.

It is an object of the invention to provide soft, absorbent toilet tissue paper products.

Another object of the invention is to provide soft, absorbent facial tissue paper products.

A third object of the invention is to provide soft, absorbent towel paper products.

Finally, it is an object of the present invention to provide a method for producing soft, absorbent silk-crepe and towel paper products.

The above and other objects are achieved by the use of the invention as will be apparent from the following description.

The present invention relates to soft, absorbent paper products. Briefly, paper products consist of a cellulosic sheet and comprise from about 0.005 to about 5% by weight of biodegradable chemical plasticizer mixture based on the following components:

• * · · «« • · «· ♦« ·

- a quaternary ester amine compound of the formula (1) or (11), wherein each substituent is (C 1 -C 6) alkyl or hydroxyalkyl or a mixture thereof; each substituent is a hydrocarbon group having from 14 to 22 carbon atoms or a mixture thereof; each R 1 substituent is a C 12-20 hydrocarbon group or a mixture thereof; and a compatible anion; and / b / a polyhydroxy compound such as glycerol or polyethylene glycols, or polypropylene glycols having a weighted average molecular weight of about 200-4000;

the weight ratio of the quaternary ester amine compound to the polyhydroxy compound in the mixture is from about 1: 0.1 to 0.1: 1; and the polyhydroxy compound is mixed with the quaternary ester amine compound at a temperature of at least 50 ° C.

The mixture of quaternary ester amine and polyhydroxy compound is diluted to a concentration of from about 0.01% to about 25.0% by weight of the chemical softening composition, preferably with a liquid carrier, before being added to the fibrous cellulosic material. The liquid carrier preferably has a temperature of from about 40 ° C to about 80 ° C and has a pH of less than about 4. Preferably at least 20% of the polyhydroxy compound added to the fibrous cellulose and the quaternary ester amine compound remain.

Preferred quaternary ester amine compounds useful in the present invention include compounds of formula III and IV.

These compounds are considered to be mono- and diester versions of the well-known dialkyl dimethylammonium salts, of which diester diphaggyualkyldimethylammonium chloride, monoester diphalglycyl dimethylammonium chloride, diester / hydrogenated are preferred. / -fluoroalkyldimethyl ammonium methyl sulfate, diester di / hydrogenated / naphthalyldimethylammonium chloride, monoester di / hydrogenated? agylkyl dimethylammonium chloride, di / non-hydrogenated / naphthyl dimethyl ammonium chloride diester variants, di / allyl hydrogenatedAfaggyualkyl dimethylammonium chloride and dihydrogenated tallowalkyldimethylammonium chloride. Depending on the desired properties of the product, the saturation level of the difaggyualkyl group can be controlled from non-hydrogenated / soft /, to barely, partially or completely hydrogenated / hard /.

Without theoretically limiting ourselves, it is believed that the ester group / groups / biodegradability of these compounds. Significantly, the quaternary ester amine compounds used according to the invention decompose much more biologically than conventional dialkyl dimethyl ammonium compounds are chemical plasticizers.

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

A particularly preferred silk crepe paper according to the invention comprises from about 0.03% to about 0.5% by weight of a quaternary ester amine compound and a mixture of polyhydroxy compound.

Briefly, the method for producing the silk crepe paper according to the invention includes making the papermaking pulp from the aforementioned components, layering the papermaking pulp on a perforated surface, such as a Fourdrinier sieve and removing the water from the stratified pulp.

Unless otherwise indicated, all percentages and ratios are given by weight.

Although the description and the appended claims describe the invention in detail and are clearly required, it is believed that the invention will become more readily understood by the accompanying drawings.

The meanings of the figures are as follows.

Figure 1 is a phase diagram of DODMAMS and DHTDMAMS.

Figure 2 shows the DODMAMS and PEG-AOO system phase diagrams and FIG.

Figure 3 is a phase diagram of the PEG-400 / methyl octanoate system;

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

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

Figure 6 is a diester difaggyualkyl dimethyl.

- Cryo-transmission microphotography of 10% ammonium chloride and 1: 1 vesicle dispersion of PEG-400 system / X 63,000 /.

Figure 7 is a cryo-transmission micrograph of a dispersion of a 1: 1 weight ratio of a diester diphaggyualkyl dimethyl ammonium chloride and a glycerol system / X 63,000 /.

Figure 8 is a cryo-transmission microphotography of a diisodium dihydrogenated tallowkyl dimethylammonium chloride and a 1: 1 weight ratio vesicle dispersion of the PEG-400 system / X 66,000 /.

The present invention will be described in more detail below.

Although the description is described in detail in the appended claims and is clearly required by the present invention, it will be understood that the invention will be more fully understood from the following detailed description and the appended examples.

As used herein, the terms "silk crepe paper / roll / paper web / roll / ribbon / roll / paper, paper and paper product" refer to paper sheets which are made by first making an papermaking pulp, the pulp on a perforated surface, e.g. layered on a Fourdrinier screen and removed from the pulp water by gravity or vacuum-assisted suction, with or without pressure, and evaporation.

* · * ··

- 11 In this specification, the aqueous ppair production pulp comprises an aqueous suspension of papermaking fibers and the chemical additives described below.

In the process of the present invention, the first step is to prepare an aqueous papermaking pulp. The pulp pulp comprises papermaking fibers (also referred to as cellulose pulp) and a mixture of at least one quaternary ester amine compound and at least one polyhydroxy compound, which will be described in detail below.

It is disclosed in advance that in all variations of the pulp, the papermaking fibers used in the process of the invention are generally included. However, they may be used and other cellulosic fibrous materials, such as cotton flakes, bagels, rayons, etc., may not be excluded. The celluloses used in the present invention are kraft, sulfite and sulfate celluloses, as well as mechanical celluloses such as wood pulp, thermomechanical celluloses and chemically modified thermomechanical celluloses / CTMP /. Wood pulp from both deciduous and coniferous trees can be used. The process according to the invention may also comprise recycled / recycled fibers, which may include all or some of the above categories, as well as other non-fibrous materials, such as fillers and binders, which have been used to promote the original paper production. In accordance with the present invention,

The papermaking fibers used in process 12 preferably consist of kraft cellulose from northern softwood.

Biodegradable chemical softening preparations

The softening composition of the present invention comprises as a basic component a mixture of quaternary ester amine compound and polyhydroxy compound of from about 0.005% to about 5% by weight, preferably from about 0.03% to about 0.5% by weight of dry fiber. The ratio of quaternary ester amine compound to polyhydroxy compound is about 1: 0.1 to 0.1: 1; the weight ratio of the quaternary ester amine compound to the polyhydroxy compound is preferably 1: 0.3 to 0.3: 1, more preferably the weight ratio of the quaternary ester amine compound to the polyhydroxy compound is 1: 0.7 to 0.7 : 1, but the ratio depends on the molecular weight of the particular polyhydroxy compound used and / or the quaternary ester amine compound.

All of the above types of compounds are described in detail below.

A. Quaternary ester amine compound

The chemical softening composition comprises as a basic component a quaternary ester amine compound of the formula (I) or (11): wherein R 1 is a C 14 -C 22 hydrocarbon group, preferably a C 16 -C 18 tallowkyl group; R 2 is C 1-6 alkyl or hydroxyalkyl, preferably C 1-3 alkyl; is a C 12-20 hydrocarbon group, preferably C 14 -C 16 alkyl

group; and a compatible anion such as a halide (e.g., chloride or bromide / or methyl sulfate).

As stated in the literature fSwern, Ed. In Bailey's Industrial Oil and Wood Products, Third Edition, John

Wiley and Sons, New York 1964, discloses tallow, a naturally occurring substance of variable composition.

Table 6.13 of the above publication shows that in general, 78% or more of tallow acids contain 16 or 18 carbon atoms. Generally, half of the fatty acids present in the sebum are unsaturated, especially in the form of an oil acid. Both synthetic and natural fat are included within the scope of the invention. It is also known that depending on the desired properties of the product, the level of saturation of the difaggyu may be non-hydrogenated / soft /, barely, partially and fully hydrogenated / hard.

It should be noted that, R ₂ and substituents may be optionally substituted with different groups such as alkoxy or hydroxy, or may be branched, but such materials are not preferred in this case. Preferably, the group is C 16-18 alkyl, most preferably R 18 is a straight chain C 18 alkyl group; R _{2 is} preferably methyl; R 1 is preferably C 14 -C 16 alkyl, most preferably R 16 is straight chain C 16 alkyl; and chloride or methyl sulfate ion.

Quaternary ester amine compounds of the above structure and suitable for use in the present invention are well-known diester dialkyl dimethylammonium salts such as diester diphaglycylkyl dimethyl ammonium chloride, monoester diphaglycyl dimethyl ammonium chloride. , diester difaggyualkyl dimethyl1-ammonium methyl sulfate, diester dihydrogenated tallowkyl dimethyl ammonium methyl sulfate and diester dihydrogenated tallowalkyldimethylammonium chloride. Particularly preferred are diester difaggyualkyl dimethylammonium chloride and diester dihydrogenated tallowalkyl dimethyl ammonium chloride. These special materials are commercially available from Sherex Chemical Company Inc. of Dublin, Ohio under the trade name ADOGEN DDMC®.

Di-quaternary variants of quaternary ester amine compounds may also be used and are within the scope of the invention. These are compounds of formula V, wherein each of C 1-6 alkyl or hydroxy is C 12-20 hydrocarbon; and Χθ a compatible anion such as a halide / chloride or bromide / methyl sulfate ion. Preferably, each of R 14 is C 14 to C 16 alkyl, most preferably each R 16 is a straight-chain C 16 alkyl group and R 2 is a methyl group.

B. Polyhydroxy compound

Chemical plasticizer compositions contain a polyhydroxy compound as a basic component.

Polyhydroxy compounds useful in the present invention, such as glycerol and polyethylene glycols and polypropylene glycols, having a weighted average molecular weight of from about 200 to about 4000, preferably from about 200 to about 1000, most preferably from about 200 to about 600. Particularly preferred are polyethylene glycols that are weighted an average molecular weight of about 200 to about 600.

A particularly preferred polyhydroxy compound is a polyethylene glycol having an average weighted molecular weight of about 400. This material is commercially available from Union Carbide Company of Danbury, Connecticut under the trade name PEG-400.

The above-mentioned chemical softening composition, i.e. a mixture of a quaternary ester amine compound and a polyhydroxy compound, is preferably added to the aqueous suspension or pulp of the papermaking fibers in the wet section of the papermaking machine at any appropriate location prior to the Fourdrinier screen or sheet forming phase. The use of the chemical softening compositions described above after the formation of the wet pellet tape and prior to the complete drying of the paper web provides significant advantages in softness, absorbency and wet strength, and this method is also within the scope of the invention.

It has been found that the chemical softening composition is more effective when the quaternary ester amine compound and the polyhydroxy compound are mixed before being added to the papermaking pulp. A preferred method as described in detail in Example 1 consists in first heating the polyhydroxy compound to about 66 ° C and then adding the quaternary ester amine compound to the hot polyhydroxy compound to form a fluidized melt. The weight ratio of the quaternary ester amine compound to the polyhydroxy compound is about 1: 0.1 to 0.1: 1, and the weight ratio of the quaternary ester amine compound to the polyhydroxy compound is preferably about 1: 0.3 to 0.3. 1: more preferably, the weight ratio of the quaternary ester amine compound to the polyhydroxy compound is from about 1: 0.7 to 0.7: 1, although this ratio is the specific poly hydroxy compound and / or quaternary ester amine compound. depending on its molecular weight. The melt of the quaternary ester amine compound and the polyhydroxy compound is then diluted to the desired concentration and mixed to form an aqueous solution containing the vesicle dispersion of the quaternary ester amine compound and the polyhydroxy compound, which is then added to the papermaking pulp. We are added. A mixture of the quaternary ester amine compound and the polyhydroxy compound with a liquid carrier such as water is diluted to about 0.01 to about 25% by weight of the softening composition before being added to the papermaking pulp. The pH of the liquid carrier is preferably 2-4. The temperature of the liquid carrier is from about 40 ° C to about 80 ° C. Quaternary ester amine compound and polyhydroxy compound «· ·

- 17 is present in the form of particles dispersed in the liquid carrier. The average particle size is preferably about 0.01 to 10 microns, most preferably about 0.1 to about 10 microns. As shown in FIGS. 1, the dispersed particles are present in the form of vesicle particles.

The quaternary ester amine compound and the polyhydroxy compound are mixed at a temperature of at least 50 ° C, more preferably at about 50 ° C to about 100 ° C. Without wishing to limit itself theoretically, it is believed that, in the preferred temperature range, both diester diphaglycanyldimethylammonium chloride / DEDTDMAC / and diester dihydrogenated tallowalkyldimethylammonium chloride / DEDHTDMAC / liquid is in phase and is miscible with the polyhydroxy compound. Dihydrogenated tallowkyl dimethyl ammonium methyl sulfate / DHTDMAMS / physical state will be discussed in more detail below.

The papermaking pulp can be easily formed or produced by mixing techniques and equipment well known to those skilled in the art of paper production.

Unexpectedly, it has been found that the adsorption of the polyhydroxy compound on paper is greatly enhanced by mixing this compound with the quaternary ester amine compound before being added to the paper. Polyhydroxy compound and quaternary ester amine added to fibrous cellulose · ··· · · V · · · · · ··· · «J

at least 20% of the compound remains; and preferably the retention amount of the quaternary ester amine compound and the polyhydroxy compound is from about 50 to about 90% by weight, based on the dry fibers.

It is important that the adsorption take place at a concentration and for a period of time that is practically useful during papermaking. In our attempt to better understand the surprisingly high retention rate of the polyhydroxy compound on paper, we studied the physics of a melt solution and aqueous dispersion of a dihydrogenated-phage-alkylkyl dimethyl ammonium methyl sulfate and polyethylene glycol-400.

Without wishing to be bound by theory or by any other limitation of the present invention, the following analysis is provided to explain that the quaternary ammonium compound promotes adsorption of the polyhydroxy compound on the paper.

Dihydrogenated naphthalene-1-dimethylammonium methyl sulfate / DHTDMAMS; / ^C 17 ^H _35/2 ^{+ N} / ^CH 3/2 ~ ^CH3 ~ ^ ^OS O ^3; dioctadecyl dimethyl ammonium methyl sulfate / DODMAMS; / ^ 18 ^ 37/2 ^{+ N} / CH 3 / CH ₃ OSO ₃ ₂ / '> ^the diester difaggyualkil dimethyl ammonium chloride / DEDTDMAC;

Obtained information / CH _{_3/2} N ⁺ / _CH2 _CH2 OCOC ^ gH _{_33/2} Cl 7 and of diester dihydrogenated tallow dimethyl ammonium chloride / DEDHTDMAC / physical condition of X-ray and NMR analysis of the commercial mixture. DODMAMS is the main component of DHTDMAMS and serves as a model for the commercial blend. It is advisable to consider the simpler DODMAMS system first and then the more complex commercial DHTDMAMS mixture.

Depending on the temperature, DODMAMS can be in any of four phases / 1. 2A, are two polymorphic crystals / X 1 and X 1, lamellar / lamella / liquid crystal phase or liquid phase. The crystal X ^ exists from room temperature below 47 ° C. At this temperature, the polymorph X ¹ * crystal is transformed into 72 ° C into the Lamam liquid crystal phase. This phase, however, converts at 150 ° C to an isotropic liquid. Lamellar / Lam / liquid crystal phase exists in both DEDTDMAC and DEDHTDMAC compounds. DHTDMAMS is expected to resemble DODMAMS in its physical behavior, with the exception that phase transition temperatures are lower and wider. For example, the transition from crystal to crystal Χ ° ály at DHTDMAMS takes place at 27 ° C, while at DODMAMS at 47 ° C. Calorimetric data also indicate that multiple crystals?? Lamam phase transition occurs more in DHTDMAMS than in DODMAMS. The highest of these transitions has an initial temperature of 56 ° C, in good agreement with the X-ray data, but the calorimetry has two peaks at initial temperatures of 59 and 63 ° C.

The dioctadecyldimethylammonium chloride / DODMAC / DODMAMS exhibits a qualitatively different behavior in that the Lamb liquid crystal phase in this compound does not exist. However, it is believed that this difference is not essential for the use of this compound / commercial analog in the treatment of DHTDMAC / paper in Laughlin et al., Journal of Physical Chemistry: Physical Science of the Dioctadecyldimethylammonium Chloride-Water System. 1. Equllibrium Phase Behavior, 94, 2546-2552 / 1990 / J.

Mixtures of DHTDMAMS and PEG-400

We have studied a mixture of these two materials in a 1: 1 weight ratio, and the probable phase behavior model of this system is illustrated in Figure 2. This diagram shows that DODMAMS and PEG are not mixed at high temperatures where two liquid phases are present. If the mixture of the two liquids in this region is cooled, a lamellar phase / Lam / is formed from the mixture. Thus, this study illustrates that these two materials are not miscible at higher temperatures, but are miscible at lower temperatures in the Lamam liquid crystal phase. Even at lower temperatures, it is expected that the crystal phases will be separated from the Lam phase and the compounds will again become non-miscible.

Thus, these studies show that to form good dispersions of DHTDMAMS and PEG-400 in water, the premix that is diluted with water should be kept at an intermediate temperature range where the two compounds are miscible.

··· <«· * * ·· ♦ * • · ·»? . · · * · · I ··· ··

- 21 Mixtures of DHTDMAC and PEG-400

Phase studies of these two materials, using the gradual dilution method, show that their physical behavior is quite different from DHTDMAMS. There is no liquid crystal phase here. These compounds are mixed in a wide range of temperatures, indicating that dispersions of these compounds can be made within similar temperature ranges. The mix has no upper temperature limit / 3. figure/.

Mixtures of DEDTDMAC and PEG-400

Phase studies of these two materials / 4. Fig. 3A, using a gradual dilution method, shows that their physical behavior is similar to that of DHTDMAC. These compounds are also in a wide temperature range of > 50 ° C, which indicates that dispersions of these mixtures can be made in similar temperature ranges.

There is no upper temperature limit for mixing.

Mixtures of DEDHTDMAC and PEG-400

Phases of these two materials / 5. Fig. 3A, using a gradual dilution method, shows that their physical behavior is similar to that of DHTDMAC. These compounds are in a wide temperature range / > 67 ° C, which indicates that dispersions of these compounds can be made in similar temperature ranges. There is no upper limit for blending.

·· · · · · ·

- 22 Preparation of dispersions

Dispersions can be prepared from any of the above materials by diluting a mixture at a temperature at which the polyhydroxy compound and the quaternary ammonium salt are mixed with water. The fact that the compounds in the liquid crystalline phase / as in DHTDMAMS / or in the liquid phase / as in DHTDMAC do not play a major role. Neither DHTDMAMS nor DHTDMAC is soluble in water, so dilution of any dry phase with water results in the quaternary ammonium compound being precipitated in the form of small particles. Both quaternary ammonium compounds exhibit higher temperatures than liquid crystalline phases from aqueous solutions, regardless of whether the dry solution was liquid or liquid crystalline. The polyhydroxy compound dissolves in water in all proportions so it does not.

Cryo-electron microscopy shows that the particles present are about 0.1 to 1.0 micrometers in size and have very variable structures. Some are flat / curved or flat, while others are closed vesicles. The membranes of each particle are two-layered in molecular dimensions where the head groups are directed towards the water, the back portions are together. Presumably, PEG is attached to these particles. Using the dispersions made in this way on paper, the result is that the quaternary ammonium ion is attached to the paper, strongly · ·· «· ··· ··

- 23 promotes the adsorption of the polyhydroxy compound on paper and ensures the desired modification of softness and retention of the wettability.

Status of the dispersions

When the above-mentioned dispersions are cooled, partial crystallization of the material in colloidal particles may occur. However, it is likely that the equilibrium state will take a long time / possibly months / months, so that the disintegrated particle, the membrane of which is a liquid crystal or a disordered crystal phase, interacts with the paper. The chemical softening compositions described are preferably used before reaching equilibrium.

It is likely that vesicles containing DHTDMAMS and PEG will be broken when the fibrous cellulosic material is dried. Once the vesicle is broken, most of the PEG component penetrates inside the cellulosic fibers, increasing the flexibility of the fiber. A significant part of the PEG is retained on the fiber surface, whereby the rate of absorption of the cellulosic fibers is improved. Due to ionic interactions, the cationic portion of the DHTDMAMS component remains on the surface of the cellulosic fiber, improving the surface feel and softness of the paper product.

In the process according to the invention, the second operation is the stratification of the papermaking pulp using the chemical softening composition described above as an additive on the perforated surface; and the third step is to remove water from the layered fiber pulp. The methods and apparatus that can be used to perform these two operations are well known to those skilled in the art of papermaking. Preferred silk crepe papers of the present invention comprise from about 0.005 to about 5.0% by weight of dry fiber, more preferably from about 0.03 to about 0.5% by weight of the above chemical softening composition.

The present invention is applicable to silk crepe papers in general, including, but not limited to, conventional felt-pressed silk papers; such as, for example, U.S. Patent No. 3,301,746, and the high specific volume, non-pressed silk crepe papers, such as U.S. Pat. No. 3,812,000. Silk crepe paper can be single or multilayered; and the paper products made from them may also have one or more layers. Silk crepe paper structures made of layered paper webs are disclosed in U.S. Patent No. 3,994,771. Wet layered, composite, high volume, and absorbent paper structures are made of two or more pulp layers, preferably composed of different types of fibers. The layers are preferably formed by depositing separate streams of diluted fiber suspensions with one or more endless perforated portions.

- 25 sieves, fibers are generally relatively long soft fibers used in papermaking and relatively short hardwood fibers. The layered composite web is then formed by combining the layers. The layered web is then fitted to the surface of a mesh-type dryer / printer screen, pressed onto a paper web using a liquid, and then the web is preheated on this substrate, part of a low density paper manufacturing process. The layered paper web may be layered with respect to the fibrous web or fiber / content of the respective layers, these layers being substantially the same. The silk crepe paper preferably has a basis weight of from 10 g / m to 65 g / m 2 and a density of about 0.60 g / ml or less. The weight per square meter 2 is preferably about 35 g / m or less; and a density of about 0.30 g / ml or less. Most preferably, the density is between 0.04 g / ml and about 0.20 g / ml.

Conventionally pressed silk crepe papers and methods for making such papers are known in the art. Such papers are generally made by laminating the papermaking fiber to a perforated screen.

This screen is often referred to as a Fourdrinier screen. Once the pulp is deposited on the sheet-forming screen, this is referred to as a paper web. The paper web is dewatered by pressing the paper web and drying at a higher temperature. Special methods and typical equipment suitable for producing paper webs according to the above method are well known to those skilled in the art. In a typical process, a low density cellulose fiber pulp is introduced into a high pressure rack. The runner has an opening through which the cellulose pulp passes through a thin layer to the Fourdrinier sieve and forms a wet paper web there. The paper web is then typically dewatered to a fiber density of from about 7% to about 25% by weight of the entire paper web / by vacuum dewatering and then further dried by compression operations when the paper web is subjected to pressure exerted by opposing mechanical members such as cylindrical rollers.

The dewatered paper web is then further pressed and blotted with a drum drying apparatus known in the art as a Yankee dryer. The Yankee dryer can be pressurized to mechanical pressure, thus pushing opposite cylindrical drums on the paper web. Vacuum can also be applied to the paper web when pressed against the Yankee dryer. Several Yankee dryers can be used, resulting in additional pressure between drums. The resulting silk-crepe paper structures, which are formed as conventional pressed silk crepe papers, are referred to. These cords are considered to be compressed because the paper web is subjected to significant general mechanical compression forces while the fibers are wet and then dried / optionally creped / compressed.

- 27 The patterned silk crepe papers are characterized by their relatively low fiber density, relatively high specific volume zone and a relatively high fiber density compacted zone pattern. The large volume field is also called a pillow / pillow / zone. The compacted zones are the knuckle / zones of the sieves. The compacted zones may be spaced apart from each other in the high specific volume field, or may be partially or fully bonded to each other in a high specific volume field. Preferred methods for the production of tissue-sealed silk crepe paper webs are described in U.S. Pat.

U.S. Patent Nos. 191,609 and 4,637,859.

Typically, the patterned paper webs are preferably made by depositing the papermaking pulp on a perforated sheet forming screen, such as a Fourdrinier screen, to form a wet paper web, and then placing the web alongside a patterned substrate.

The paper web is pressed against the patterned substrate so that the zones sealed in the paper web are formed on portions that correspond locally to the contact points between the patterned substrate and the wet paper web. The remainder of the paper web, which is not pressed during this operation, is the large volume volume field. This large volume area is further expanded by applying a hydrostatic pressure such as a vacuum type device or a pressurized dryer or a paper web pressed against the pattern carrier.

The paper web is then dewatered and optionally pre-dried so that the compression of the high specific volume field is substantially avoided. This is preferably done by hydrostatic pressure, such as by means of a vacuum-type device or a overflow dryer, or by mechanical pressing of the paper web against a sample carrier, so that the zone of high specific volume is not compressed. The operations of dewatering, possible pre-drying and forming of the compressed zones can be combined or partially combined to reduce the total number of process operations performed. After forming the compressed zones, dewatering and possibly pre-drying, the paper web is completely dried, preferably also avoiding mechanical compression. Preferably, about 8 to about 55% of the surface of the silk crepe paper comprises compacted mesh knots having a density of at least 125% of the density of a high specific volume field.

Preferably, the patterned substrate is a printer transfer sieve with a patterned position of the sieve nodes acting as a pattern carrier that facilitates the formation of compressed zones by pressure. The pattern of sieve nodes forms the said pattern of the carrier. Printer Transmission Screens \ t

821 068, 3 974 025, 3 573 164, 3 473 576, 4 239 065 and

U.S. Patent No. 528,239.

From the pulp, first, a wet paper web is formed on a perforated sheeting screen, such as a Fourdrinier screen. The paper web is dewatered and transferred to a printer screen, and it is also possible to layer the fiber pulp on a perforated substrate, which also acts as a printer screen. The resulting wet paper web is dewatered and preferably thermally dried to a fiber density of about 40% to about 80%. Dewatering can be done with suction cupboards or other vacuum devices or with overflow dryers. The print sieve imprint of the printer screen is pressed into the paper web as described above, before the paper web is completely dried. One method of doing this is using mechanical pressing. This can be done, for example, by pressing the tumbler roller with the screen of the printer in front of the dryer drum, so that the Yankee dryer surface is pressed, while the paper web is located between the punch roller and drum dryer. Preferably, the web is pressed against the printer screen before it is completely dried using a hydrostatic pressure, a vacuum device, such as a suction cup or overflow dryer. Hydrostatic pressure may be applied to induce compression of the compressed zones during initial dewatering, in a subsequent separate process operation, or by a combination thereof.

Non-pressed, non-patterned silk screen printing30

paper structures are disclosed in U.S. Patent Nos. 3,812,000 and 4,208,459.

Non-pressed, non-patterned, silk-crepe paper structures are generally made by laminating the papermaking pulp to a perforated sheet forming screen such as a Fourdrinier screen to form a wet paper web, extracting water from the web, and removing residual water without mechanical pressure, until the paper web has a fiber density of at least 80%, and then the paper web is creped. Water is removed from the paper web by vacuum dewatering and thermal drying. The structure thus obtained is a soft but weak, high volume volume iv consisting of relatively non-compressed fibers. Prior to creping, a binder is preferably added to the parts of the web.

Λ pressed, non-patterned silk-crepe paper structures are known in the art as conventional silk-paper paper structures. The pressed, non-patterned silk crepe paper structures are generally made by depositing the papermaking pulp on a perforated screen, such as a Fourdrinier screen, to form a wet paper web, dewatering the paper web, and removing the residual water by uniform mechanical pressure / compression / removal until the web is pressed. the fiber will be 25-50%, then the paper web is transferred to a heat dryer, such as a Yankee dryer, and then creped on the paper • ·

- 31 tapes. All water from the paper web is removed by vacuum, mechanical compression and heat. The structure thus obtained is strong ₍ and its density is generally excellent but with very low specific volume, low absorbency and not sufficiently soft.

The silk crepe paper web according to the invention can be used anywhere where soft, absorbent silk crepe paper rolls / rolls are required. The silk crepe paper webs / coils according to the invention are particularly preferably used as paper towels, toilet papers and facial tissue products. Two silk crepe paper webs according to the invention can be embossed / pressed / joined together and bonded to the face-to-face, as described in U.S. Patent No. 3,414,459 to two-layer paper towels.

Determination of molecular weight

A. Introduction

The basic distinctive feature of polymeric materials is their molecular size. The properties that enabled the polymers to be used in diverse applications are almost exclusively derived from their macromolecular nature. In order to fully characterize these materials, it is essential to have methods for defining and determining their molecular weight and molecular weight distribution. It is more appropriate to use the term relative molecular weight instead of molecular weight, although the latter is more commonly used in polymer technology. It is not always practical to determine the molecular weight distributions. However, the use of chromatographic methods is becoming increasingly important. The molecular size is expressed in terms of molecular weight averages.

B. Molecular Weight Averages

If we assume a simple molecular weight distribution that represents the mass fraction of molecules with relative molecular weight M 2, we can define some useful mean values. The averaging is based on the number of molecules of special mass M ^ / N ^ /, giving the average molecular weight:

An important consequence of this definition is that the average molecular weight in grams gives Avogadro number of molecules. This definition of molecular weight refers to monodisperse molecular species, i.e. molecules of the same molecular weight. It is more important to realize that if a number of molecules can be determined in a given mass of a polydisperse polymer, then M _n can be easily calculated. This is the basis for the measurement of colligativism.

Based on the mass fraction of the molecules of a given M ^ mass, this weighted molecule33 leads to the definition of mass averages.

£ W, N, £ NM

^ 11

it is more useful for expressing polymer molecular weights than M as it more accurately reflects certain properties such as melt viscosity and mechanical properties of polymers and is therefore used in the present invention.

Analytical and test procedures

Quantitative analysis of biodegradable chemicals used in the compositions of the present invention or retained on silk crepe paper webs can be carried out by any of the methods accepted in the art.

A. Quantitative analysis of quaternary ester amine and polyhydroxy compounds

For example, quaternary ester amine compound retained by silk crepe paper such as diester dihydrogenated tallowkyl dimethylammonium chloride / DEDHTDMAC, i.e. DDMeP / DOG, may be determined by extraction of DEDHTDMAC in an organic solvent followed by anion / cation. by titration using a dimidium bromide indicator. The amount of polyhydroxy compound, such as PEG-400, can be determined by extraction with an aqueous solvent such as water followed by the amount of PEG-400 in the extract.

34 is determined by gas chromatography or colorimetric methods. These methods are exemplary only and do not exclude the use of other methods for determining the amount of specific components retained by silk crepe paper.

B. Hydrophilicity / Absorption /

The hydrophilicity of the silk crepe paper generally refers to the tendency of the paper to wet with water. The hydrophilicity of the silk crepe paper can be quantified in terms of quantity when determining the time required to dry the dry paper perfectly with water. This duration is called the wetting time. In order to provide a suitable and repeatable test for the wetting time, the following procedure can be used to determine the wetting time: first, make a conditioned unit sample of about 11.1 x 12 cm in size from the silk crepe paper structure to test the paper samples 23 + 1 ° C and 50 + 2% relative humidity as described in TAPPI Method T 402; secondly, the fold is folded into four adjacent quarters, and then compressed into a dumpling of about 1.9 cm to about 2.5 cm in diameter; thirdly, placing the dripping water on the surface of a distilled water body at a temperature of 23 + 1 ° C and initiating a control clock simultaneously; fourth, the clock is stopped and read when the dripping of iv drip is complete. Total wetting is determined visually.

Of course, the hydrophilicity properties of the silk crepe paper according to the invention can be determined immediately after manufacture. However, in hydrophobicity, there may be a significant increase in the first two weeks after the production of the silk crepe paper, i.e. after the paper has aged two weeks after manufacture. Therefore, the wetting times are preferably measured at the end of the two-week period. At the end of the two-week aging period, the wetting times at room temperature are termed two-week wetting times.

C. Density

The density of the silk crepe paper, as used herein, is the average density, which is calculated by dividing the square mass of the paper by the thickness. Thickness of caliper paper / caliper / paper is the thickness obtained when 2 paper is subjected to a pressure of 15.5 g / cm.

Possible components

Other chemicals commonly used in papermaking may be added to the biodegradable, chemical softening composition or papermaking pulp described above, provided that they do not significantly and adversely affect the softness and absorbency of the fibrous material and enhance the effects of chemical softening compositions.

• ·

For example, surfactants can be used to treat the silk crepe paper webs of the present invention. When a surfactant is used, it is preferably present in an amount of from about 0.01 to about 2.0 weight percent, based on the dry weight of the paper. The surfactants preferably have eight or more carbon atoms. Suitable anionic surfactants include, for example, linear alkyl sulfonates and alkylbenzenesulfonates. Examples of nonionic surfactants include alkylglycosides, including alkylglycoside esters such as Crodesta SL-40, from Croda Inc. / New York, NY / company; alkylglycoside ethers described in U.S. Patent No. 4,011,389; and alkyl polyethoxylated esters such as Pegosperse 200 ML, Glyco Chemicals, Inc. / Greenwich, CT /; and IGEPAL RC-520, available at Rhone Poulenc Corporation / Cranbury, NJ /.

Other types of chemicals that can be added are dry strength enhancing additives that enhance the tensile strength of the silk crepe paper webs. Examples of dry strength enhancers include carboxymethylcellulose and cationic polymers from the ACCO chemical family such as ACCO 711 and ACCO 514; ACCO chemical family is preferred. These materials are commercially available from American Cyanamid Company of Wayne, New Jersey. If dry strength additives are used, they are preferably present in an amount of from about 0.01% to about 1.0% by weight,

- 37 based on the dry fiber weight of the silk crepe paper.

Other types of chemicals that can be administered are wet strength additives that promote wet disintegration of silk crepe papers. According to the invention, the paper may contain from about 0.01% to about 3.0%, more preferably from about 0.3% to about 1.5%, by weight of water-soluble, permanent wet strength resin as a component of the dry fiber.

Permanent wet strength resins useful in the present case may be of various types. Usually, resins that have already been used in papermaking can be used and then used. Many examples of these are described in Westfelt's prior art disclosure.

Typically, wet strength resins are water-soluble cationic materials. That is, the resins are water soluble at the time they are added to the papermaking pulp. However, it is possible, or even expected, that the events occurring, such as curing, will render the resin insoluble in water. Some resins also dissolve only under specific conditions such as a limited pH range.

In general, wet strength resins are likely to undergo crosslinking or other curing reactions after being placed on or between the papermaking fibers. Curing or curing usually does not take place until a significant amount

- 38 water is present.

Particularly useful are various polyamide epichlorohydrin resins. These materials are low molecular weight polymers with reactive functional groups such as amino, epoxy and azetidinium. The patent literature is full of methods for producing such materials. Examples include U.S. Patent Nos. 3,700,623 and 3,772,076.

The polyamide epichlorohydrin resins marketed by Hercules Incorporated of Wilmingtone, Delaware, under the trade names Kymene 557H and Kymene 2064, are particularly useful for the silk crepe papers of the present invention. These resins are generally described in the two patents above.

The base-activated polyamide-epichlorohydrin resins for use in the silk crepe paper of the present invention are marketed by the Monsanto Company of St. Louis, Santo Rés et al. Such types of materials are generally described in U.S. Patent Nos. 3,855,158, 3,899,388, 4,129,528, 4,147,586, and 4,222,921.

Other water-soluble cationic resins useful in the present case are polyacrylamide resins marketed under the trade name Parez, e.g., Parez 631NC, by Anerican Cyanamid Company of Stanford, Connecticut. These materials are generally described in U.S. Patent Nos. 3,556,932 and 3,556,933.

Water-soluble resins useful in the present invention include acrylic emulsions and anionic styrene-butadiene latexes. Examples of such type resins are disclosed in U.S. Patent No. 3,844,880.

Other water-soluble cationic resins useful in the present invention include urea-formaldehyde and melamine-formaldehyde resins. These polyfunctional reactive polymers have a molecular weight of some thousands. Typical functional groups include nitrogen-containing groups such as the amino group and the methylol group attached to the nitrogen atom.

Polyethyleneimine type resins, although less preferred, may also be used in the present case.

A more complete description of the above-mentioned water-soluble resins, including their preparation, can be found in the literature / TAPPI Monograph Series No. 29, Wet Strength In Paper and Paperboard, Technical Association of the Pulp and Paper Industry / New York; 1965/7. The term wet strength resin used herein refers to a resin that allows the majority of the paper to retain its initial wet strength for at least 2 minutes.

The above mentioned wet strength additives generally improve the permanent wet strength of the paper products, i.e., if the paper is placed on an aqueous medium, it retains a substantial portion of its initial wet strength for some time. However, permanent wet strength may be unnecessary and undesirable in some paper types. Certain paper products, such as toilet paper, etc. they are usually thrown into wastewater systems and the like after short usage periods. These systems can become clogged if the paper product permanently retains its hydrolysis resistance properties. Recently, manufacturers have added periodic / temporary / wet strength additives to paper products where wet strength is sufficient for the intended use, but it will fail as the paper is soaked with water. Damping the wet strength helps the paper product to pass through the wastewater systems.

Suitable intermittent wet strength resins include, for example, modified starch wet strength materials such as National Starch 78-0080, as described by National Starch and Chemical Corporation / New York, NY. Such type of wet strength agents can be prepared by reacting dimethoxyethyl-N-methyl chloroacetamide and cationic starch polymers. Transitional wet strength modified starches have also been described in U.S. Patent No. 4,675,394. Preferred periodic wet strength resins are disclosed in U.S. Patent No. 4,981,557.

Considering the above listed classes of permanent and periodic wet strength resins «·· · *

41 and specific examples, it should be noted that the listed resins are merely exemplary and do not limit the scope of the invention.

Mixtures of resilient wet strength resins may also be used in the practice of the invention.

The above list of optional chemical additives is also exemplary only, and is not limited by the invention.

The following examples illustrate the practice of the present invention without limiting the scope of the present invention.

l _r _ Example

The purpose of this example is to illustrate a process for preparing a biodegradable chemical softening composition comprising a mixture of diester diphaggyualkyl dimethylammonium chloride / DEDTDMAC / and polyethylene glycol 400 / PEG-400.

A 1% solution of the biodegradable chemical plasticizer is prepared as follows: 1. Weigh the equivalent weight of DEDTDMAC and PEG-400 separately; 2. heating the PEG to about 66 ° C; 3. DEDTDMAC is dissolved in PEG to form a melt solution at 66 ° C; 4. using a lymphatic force to form a homogeneous mixture of DEDTDMAC in the PEG; 5. adjust the pH of the dilution water to about 3 by adding 0.1% hydrochloric acid; 6. Dilute water to about 66 ° C * * «

- 42 is heated; 7. Dilute the DEDTDMAC and PEG melt mixture to a 1% solution; Applying Lithium 8 to form an aqueous solution comprising a vesicle dispersion or suspension of the DEDTDMAC and PEG mixture; 9. Determining the particle size of the vesicle dispersion using optical microscopy; the particle size is about 0.1 to 1.0 micron.

Figure 6 is a cryo-transmission microphotograph of a vesicle dispersion of a DEDTDMAC and PEG-400 1: 1 weight ratio system / X 63,000 /. Figure 6 shows that the membranes of the particles have a single or double layer thickness ranging from closed / open vesicles to disk-like structures and sheets.

Example 2 _x

The purpose of this example is to illustrate a process for preparing a biodegradable chemical softening composition comprising a mixture of diester diphaggyualkyl dimethyl ammonium chloride / DEDTDMAC / glycerol.

A 1% solution of the biodegradable chemical softener is prepared as follows: 1. the equivalent amount of DEDTDMAC and glycerol is measured separately;

2. heating the glycerol to about 66 ° C; 3. dissolving DEDTDMAC in glycerol to form a melt solution at 66 ° C; 4. using a shear force to form a homogeneous mixture of DEDTDMAC and glycerol; 5. the dilution water pH * * · · * • «• ♦ ·· ·· 43

is adjusted to about 3 by adding 0.1% hydrochloric acid; 6. heating the dilution water to about 66 ° C; 7. diluting the molten mixture to 1% solution; Forming an aqueous solution comprising a vesicle dispersion or suspension of a glycerol mixture of 87; 9. Determining the particle size of the vesicle dispersion using optical microscopy; the particle size ranges from about 0.1 to about 1.0 microns.

Figure 7 is a cryo-transmission micrograph of a vesicle dispersion of a DEDTDMAC and glycerol 1: 1 weight ratio system / X 63,000 /. Figure 7 shows that the membranes of the particles are of one or two layers and form their shape from closed vesicles to disk-like structures.

Example 3 -__

The purpose of this example is to illustrate a process for the preparation of a biodegradable chemical plasticizer composition comprising diester dihydrogenated tallowkyl dimethylammonium chloride / DEDHTDMAC or ADOGEN DDMC® from Sherex Company / and polyethylene glycol 400 / PEG-400 to use.

A 1% solution of the biodegradable chemical softening composition is prepared as follows: 1. The equivalent weight of DEDHTDMAC and PEG-400 is measured separately; 2. heating the PEG to about 90 ° C; 3. DEDHTDMAC is dissolved in the PEG so that it is melted at 90 ° C · «· ·

- Solution 44; 4) using a homogeneous blend of DEDHTDMAC and PEG; 5. adjust the pH of the dilution water to about 3 by adding 0.1% hydrochloric acid; 6. heating the dilution water to about 70 ° C; 7. diluting the melt mixture to a 1% solution; 8. Applying an aqueous solution to form a vesicle dispersion or suspension of the DEDHTDMAC and PEG mixture using lymphatic force; 9. determining the particle size of the DEDHTDMAC and PEG vesicle dispersion using optical microscopy; the particle size ranges from about 0.1 to about 1.0 microns.

Figure 8 is a cryo-transmission micrograph of a vesicle dispersion of a DEDHTDMAC and PEG-400 1: 1 weight ratio system / X 66,000 /. Figure 8 shows that the particles have membranes of one and two layer thicknesses and the shape of the particles ranges from the closed vesicle to the disk-like structures.

The purpose of this example is to illustrate a method of using a papermaking process employing over-drying to produce soft and absorbent paper towels which are diester diphaggyualkyl dimethyl ammonium chloride / DEDTDMAC / polyethylene glycol-400 / PEG-400 / and permanent. is treated with a biodegradable chemical softening composition comprising a mixture of wet strength resin.

In the present process, a semi-milled Fourdrinier papermaking machine is used. First, a 1% solution of the biodegradable chemical plasticizer is prepared as described in Example 1 above. Second, 3% by weight aqueous NSK suspension / NSK = northern softwoods kraft pulp = northern softwood kraft cellulose /. we make it in a traditional fresh pulp. The NSK slurry is slightly purified / refined / and added to the NSK material wire, dry fibers to a 1% by weight permanent resin solution of 2% wet strength / Kymene 557H from Hercules Incorporated of Wilmington, DE. The adsorption of Kymene 557H on NSK fiberboard is assisted by an in-line mixer. After the in-line mixer 1 ^z% carboxymethyl cellulose solution was deposited in a ratio of 0.2%, it increases the dry strength of the fibrous substrate on a dry fiber basis. The adsorption of carboxymethylcellulose on the NSK fiber pulp can be assisted by an in-line mixer. Then, the chemical plasticizer mixture / DEDTDMAC / PEG / 1% solution is added to the NSK slurry to dry fibers in a ratio of 0.1% by weight. The adsorption of the chemical softener on the NSK fiber paste can be assisted by an in-line mixer. The NSK suspension is diluted to 0.2% using a propeller pump. Thirdly, a 3% w / w CTMP suspension / CTMP = chemically modified thermo mechanical pulp / chemically modified thermo-mechanical pulp / prepared in a conventional fresh pulp. Pegosperse nonionic surfactant is incorporated into the pelletizer at a rate of 0.2% by weight of dry fibers.

A 1% solution of the chemical softening mixture is introduced into the CTMP

V * • · · e «··· ·

- 46 "« "· ··" in the material conductor, in front of the material pump, in a proportion of 0.1% by weight of dry fibers. The adsorption of the chemical softening mixture on the CTMP fiber suspension can be assisted by an in-line mixer. The CTMP suspension is diluted to 0.2% with a propeller pump. The treated pulp mixture / NSK / CTMP / a in the rack was mixed and layered on a Fourdrinier screen to form an initial paper web. The dewatering is carried out through the Fourdrinier sieve and is assisted by a deflector and suction filters. The Fourdrinier screen has 5 shed satin fabrics, 84 machine direction and 76 transverse single strand yarns / inch. The initial wet paper web is transferred from the Fourdrinier sieve with a fiber density of about 22% at the transfer point to a photopolymer screen with 240 linear sieve cells per square inch, a 34% sieve region, and a 14 micron photopolymer depth. Further dewatering is carried out with vacuum-assisted water extraction until the paper web has a fiber density of 28%. The patterned web is dried by passing air through to a fiber density of about 65% by weight. The paper web is then bonded to a Yankee dryer surface with a sprayed crepe adhesive consisting of a 0.25% aqueous polyvinyl alcohol solution. The fiber density is increased to about 96% and the paper web is scraped dry with a scraper. The scraper has a slope of about 25 ° and is positioned relative to the Yankee dryer at an entry angle of about 81 °. Yankee Dryer is about 244 meters / min • ···· * »μ · ·· • ·

- Run at 47 speeds. The dry paper web is wound at 214 meters per minute.

Paper towel products are formed from two layers of paper web, pressed and laminated, using polyvinyl alcohol adhesive. The paper towel has a square weight of about 26 fr / 3M square feet, about 0.2% biodegradable chemical plasticizer mixture and about 1.0% permanent wet strength resin. The paper towel thus produced is soft, absorbent and highly moist.

Table 1 summarizes the retention amounts and mean particle size of the DEDTDMAC / PEG-400 vesicle dispersion and the same if only PEG-400 is added to the fiber suspension.

Table 1

PEG DEDTDMAC / PEG for suspension for vesicle dispersion

PEG retention 80 in the product /% / 5 Quantity of retention of DEDTDMAC in the product /% / 85 Medium grain size / micron / 0.4

j__példa

The purpose of this example is to illustrate a method of using dry-drying and laminating paper production methods to produce soft and absorbent toilet paper, biodegradable with a 400 / PEG-400 / mixture of diester diphaglycylkyl dimethylammonium chloride / DEDTDMAC / and polyethylene glycol. treated with a chemical plasticizer and a periodic wet strength resin.

In the practice of the method according to the invention, a semi-sized Fourdrinier papermaking machine is used. First, as described in Example 1, a 1% solution of the biodegradable chemical plasticizer is prepared. Second, a 3% w / w aqueous NSK suspension is prepared in a conventional fresh pulp. The NSK suspension is slightly cleaned / refined / and periodic wet strength resin / National starch 78-0080, National Starch and Chemical Corporation of New York, NY / 2% solution is introduced into the NSK material line for dry fibers 0 , 75% by weight. The adsorption of the periodic wet strength resin to NSK fibers is assisted by an in-line mixer. The NSK suspension is diluted to a density of about 0.2% by means of a propeller pump. Third, a 3 wt% aqueous suspension of eucalyptus fibers is prepared in a conventional fresh pulp. A 1% solution of the chemical softening mixture is introduced into the material line of the eucalyptus suspension prior to the pump, in a dry weight ratio of 0.2% by weight. The adsorption of the biodegradable chemical softening mixture to the eucalyptus fibers can be assisted by an in-line meier. The eucalyptus suspension is diluted with a propellant pump to a density of about 0.2%.

The treated pulp mixture thus treated is mixed in a 30% NSK / 70% eucalyptus / riser cabinet and initialized on a Fourdrinier screen to form an initial paper web. Drainage is done through the Fourdrinier sieve and is assisted by a deflector and suction cupboards. The Fourdrinier screen has a satin fabric configuration of 5 sheds with 84 machine direction or 76 transverse single strand yarns. The initial paper web is transferred from the Fourdriner screen at a transfer point of about 15% fiber to a photopolymer screen that employs 562 linear times per square inch.

It contains 40% sieve knot zones and 9 microns depth of photopolymer. Further dewatering is carried out with vacuum-assisted water extraction until the paper web has a fiber density of about 28%. The patterned web is dried by air overflow to a fiber density of about 65% by weight. The paper web is then bonded to a Yankee dryer surface by spraying a crepe adhesive consisting of 0.25% aqueous polyvinyl alcohol. The fiber density is increased to about 96% and the paper web is creped with a scraper. The scraper has a slope of about 25 ° and is positioned relative to the Yankee dryer • ·

- 50 entry angles of about 81 °. The Yankee dryer is operated at a speed of about 244 meters per minute. The dry paper web is wound at 214 meters per minute.

The web is processed into a single layer silk crepe paper product. The paper has a square mass of about 18 - # / 3M square feet, about 0.1% biodegradable chemical softening mixture, and about 0.2% periodic wet strength resin. It is important that the so-called silk crepe paper is made of soft, absorbent and wipes and / or toilet paper.

Table 2 below summarizes the retention quantities and the effervescent particle size of the DEDTDMAC / PEG vesicle dispersion as compared to those obtained when PEG-400 alone is added to the pulp.

Table 2

PEG DEDTDMAC / PEG for suspension for vesicle dispersion

Retention rate of PEG in the product /% / 5 75

Retention rate of DEDTDMAC in product /% / - 85

Medium grain size / micron /

0.4 • ·

- Example 51 6 _i

The purpose of this example is to illustrate a method of using a dry-drying paper-making technique to produce a soft and absorbent toilet paper composed of a mixture of diester difaggyualkyl dimethylammonium chloride / DEDTDMAC /, polyethylene glycol 400 / PEG-400 / and a dry strength resin. containing a biodegradable chemical plasticizer mixture.

In the practice of the method according to the invention, a semi-sized Fourdrinier papermaking machine is used. First, as described in Example 1, a 1% solution of the biodegradable chemical plasticizer is prepared. Secondly, a 3% w / w aqueous NSK suspension is prepared in a conventional fresh pulp. The NSK suspension is slightly cleaned / refined / dry strength resin / Acco 514 or Acco 711, sold by American Cyanamid Company of Fairfield, OH / 2% solution added to NSK material web at 0.2 wt% dry fiber . The adsorption of dry strength resin to NSK fibers is assisted by an in-line mixer. The NSK suspension is diluted with a propeller pump to a density of about 0.2%. Third, a 3% w / w eucalyptus aqueous suspension is prepared in a conventional fresh pulp. A 1% solution of the chemical softening mixture is introduced into the material conduit of the eucalyptus fiber suspension before the material pump, to a dry fiber content of 0.2% by weight. The adsorption of the biodegradable chemical plasticizer mixture can be assisted by an in-line mixer of eucalyptus ros52. The eucalyptus suspension is diluted with a propeller pump to a density of about 0.2%.

The treated pulp mixture thus treated is mixed in a 30% NSK / 70% eucalyptus / racket and formed into a Fourdrinier screen to form an initial paper web. The dewatering is carried out through the Fourdrinier sieve, with a deflector and suction cups. The Fourdrinier screen has a 5 shed satin fabric configuration, 84 machine direction and 76 transverse single-strand yarns / inch. The initial wet paper web is transferred from the Fourdrinier sieve at a transmission point of about 15% fiber density to a photopolymer screen having 562 linear sieve cells per square inch, 40% sieve knot zone, and 9 micron photopolymer depth. Further dewatering is carried out with vacuum-assisted water extraction until the paper web has a fiber density of about 28%. The patterned web is preheated to about 65% by weight of fiber through air overflow. The paper web is then bonded to a Yankee dryer surface by spraying a crepe adhesive comprising 0.25% aqueous polyvinyl alcohol. The fiber density is increased to about 96% and the paper web is scraped dry with a scraper. The scraper blade has a slope of about 25 ° and is positioned relative to the Yankee dryer to provide an entry angle of about 81 °. The Yankee dryer is operated at a speed of about 244 meters per minute. THE

wrap the dry paper web at 214 meters per minute.

The two layers of the paper web are converted into silk crepe paper products and coiled together using a layering bonding technique. The silk crepe paper has a square mass of about 23 # / 3M / square foot and contains about 0.1% biodegradable chemical softening mixture and about 0.1% dry strength resin. It is important that the silk crepe paper so produced is soft, absorbent, and suitable for face and / or toilet tissue.

Table 3 below summarizes the retention amounts and mean particle size of the DEDTDMAC / PEG vesicle dispersion compared to the data obtained when PEG-400 is added to the pulp.

. table

PEG DEDTDMAC / PEG for suspension for vesicle dispersion

Retention rate of PEG in the product /% / 5 75

Retention rate of DEDTDMAC in product /% / - 80

Medium grain size / micron /

0,4 • · · · · · «· · · · · · · · · · · · · ·

- Example 54 7 _x _

The purpose of this example is to illustrate a method using a conventional drying paper making method for producing soft and absorbent toilet paper, which is diester dihydrogenated tallowalkyldimethylammonium chloride / DEDHTDMAC /, polyethylene glycol 400 / PEG-400 / and dry strength. was treated with a biodegradable chemical softening composition comprising a resin mixture.

In the practice of the method according to the invention, a semi-sized Fourdrinier papermaking machine is used. First, according to the procedure described in Example 3, a 1% solution of the biodegradable chemical softener is prepared. Second, a 3% w / w aqueous NSK suspension is prepared in a conventional fresh pulp. The NSK suspension is slightly purified / refined, and a dry strength resin / Acco 514 or Acco 711, product / 2% solution of American Cyanamid Company of Wayne, is added to the NSK material line to dry fibers 0.2 % by weight. The adsorption of dry strength resin to NSK fibers is assisted by an in-line mixer. The NSK suspension is diluted with a propeller pump to a density of about 0.2%. Third, a 3% w / w eucalyptus aqueous suspension is prepared in a conventional fresh pulp. A 1% solution of the chemical softening mixture is applied to the material line of the eucalyptus before the material pump, to a dry fiber content of 0.2% by weight. The adsorption of the chemical softener • · · · · · can be facilitated by in-line mixers of the eucalyptus fibers. The eucalyptus suspension is diluted with a propellant pump to a density of about 0.2%.

The treated pulp mixture thus treated was mixed in a 30% NSK / 70% eucalyptus / riser cabinet and layered on a Fourdrinier screen to form an initial paper web. The dewatering is done through the Fourdrinier sieve using deflector and suction cups. The Fourdrinier screen has a 5 shed satin fabric configuration, 84 machine direction and 76 transverse single-strand yarns / inch. The initial wet paper web is transferred from the Fourdrinier screen at a transfer point of about 15% fiber density to a conventional felt. Further dewatering is carried out with vacuum-assisted water extraction until the fibrous density of the paper web is about 35%. The paper web is then bonded to a Yankee dryer surface.

The fiber density is increased to about 96% and the paper web is scraped dry with a scraper. The scraper blade has a slope of about 25 ° and is positioned relative to the Yankee dryer to provide an entry angle of about 81 °. The Yankee dryer is operated at a speed of about 244 meters per minute. The dry paper web is wound at 214 meters per minute.

The two layers of the paper web are made of silk crepe paper products and layered together using a layering process. Weight per square meter of paper - 56 • ··· »· ···· · * · · · · · · · · · · · · · · · · · ··· · · · ·· ··· · Contains .23 l / 3M square foot, about 0.1% biodegradable chemical softening mixture and about 0.1% dry strength resin. It is important that the paper made in this way is soft, absorbent, and suitable for face and / or toilet paper.

Table 4 below summarizes the retention amounts and mean particle size of the DEDHTDMAC and PEG-400 vesicle dispersion compared to the data obtained when only PEG-400at is added to the fiber suspension.

Table 4

PEG DEDHTDMAC / PEG for suspension for vesicle dispersion

Retention of PEG in the product /% / 5 70

Retention rate of DEDHTDMAC in product /% / - 75

Medium grain size / micron /

0.5 • ···· «

Claims

1. A paper product comprising a sheet of fibrous cellulosic material and containing from 0.005 to 5.0% by weight of biodegradable chemical softening composition per fibrous cellulosic material, which is a mixture of the following components:

(a) a quaternary ester amine of formula (I) or (11), wherein each substituent is (C 1 -C 6) alkyl or hydroxyalkyl or a mixture thereof, preferably C 1 -C 3 alkyl, most preferably methyl; each R 1 is C 14 -C 22 hydrocarbon or a mixture thereof, preferably C 16-18 alkyl; each R 1 is C 12-20 hydrocarbon or a mixture thereof, preferably C 14 -C 16 alkyl; and a compatible anion, preferably chloride or methyl sulfate; and / b / a polyhydroxy compound such as glycerol or polyethylene glycol or polypropylene glycol having an average molecular weight of 200-4000, preferably 200-1000, most preferably

200-600;

the weight ratio of the quaternary ester amine compound to the polyhydroxy compound in the mixture is from 1: 0.1 to 0.1: 1, preferably from 1: 0.3 to 0.3: 1, most preferably from 1: 0.7 to 0.0; 7: 1, in addition, the polyhydroxy compound is mixed with the quaternary ester amine compound at a high temperature at which the quaternary · ··· «·

The ester amine 58 and the polyhydroxy compound are miscible.

2. The paper product of claim 1, wherein the quaternary ester amine compound is diester di / non-hydrogenated / naphthalyldimethylammonium chloride, diester di / allyl hydrogenated / phosphoric allyl dimethyl ammonium chloride, diester -dihydrogenated / partially hydrogenated dimethylammonium chloride, diester dihydrogenated tallowkyl dimethylammonium chloride, diester difaggyualkyl dimethyl ammonium methyl sulfate or diester dihydrogenated tallowalkyldimethylammonium methyl sulfate.

The paper product according to claim 1 or 2, wherein the polyhydroxy compound is mixed with the quaternary ester amine compound in a liquid phase.

4. Referring to 1-3. A paper product according to any one of claims 1 to 4, wherein the quaternary ester amine compound is mixed with the polyhydroxy compound at a temperature of at least 50 ° C, more preferably at a temperature of 50 to 100 ° C.

5. A paper product according to any one of claims 1 to 3, wherein the mixture of the quaternary ester amine compound and the polyhydroxy compound is diluted with a liquid carrier to a concentration of 0.01 to 25% by weight of the chemical softening composition.

6. The paper product of claim 5, wherein the quaternary ester amine compound and the polyhydroxy compound are present as particles dispersed in the liquid carrier, and the quaternary ester amine compound and the polyhydroxy compound are preferably of a fine particle size. 0.01 to 10 microns, most preferably 0.1 to 1.0 microns.

A paper product according to claim 5 or 6, wherein the liquid carrier has a temperature of 4O-

8 ° C and the pH of the liquid carrier is less than 4.

.

red product, paper.

1-7 A towel, toilet paper or facial tissue according to any one of claims 1 to 5

9. A biodegradable chemical plasticizer composition comprising a mixture of the following components:

(a) a quaternary ester amine of formula (I) or (11), wherein each substituent is (C 1 -C 6) alkyl or hydroxyalkyl or a mixture thereof, preferably C 1 -C 3 alkyl, most preferably methyl; each substituent is a C 14 -C 22 hydrocarbon group or a mixture thereof, preferably a C 16 -C 18 alkyl group; each R 1 is C 12-20 hydrocarbon or a mixture thereof, preferably C 14 -C 16 alkyl; and X is a compatible anion, preferably chloride or methyl sulfate ion; and / b / a polyhydroxy compound, such as glycerol, or polyethylene glycol or polypropylene glycol, which is said to have a ?,? · · · · · · · · · · · · · ·· «·

- 60 molecular weights of 200-4000, preferably 200-1000, most preferably 200-600;

the weight ratio of the quaternary ester amine compound to the polyhydroxy compound in the mixture is from 1: 0.1 to 0.1: 1, preferably from 1: 0.3 to 0.3: 1, most preferably from 1: 0.7 to 0.0; 7: 1, in addition, the polyhydroxy compound is mixed with the quaternary ester amine compound at a high temperature where the quaternary ester amine compound and the polyhydroxy compound are miscible.

10. The chemical softening composition of claim 9, wherein the quaternary ester amine compound is diester di / non-hydrogenated / phosphorus alkyldimethyl ammonium chloride, diester di / allyl hydrogenated / phosphoric allyl dimethyl ammonium chloride. , diester / partially hydrogenated / alkynyl dimethyl-1-ammonium chloride, diester dihydrogenated tallowkyl dimethyl ammonium chloride, diester diphagal allyl dimethyl ammonium methyl sulfate or diester dihydrogenated tallowalkyldimethylammonium methyl sulfate.

The chemical softening composition according to claim 9 or 10, wherein the mixture of the quaternary ester amine compound and the polyhydroxy compound is diluted with a liquid carrier to a concentration of 0.0125.0% by weight of the chemical softening composition; such a mixture of quaternary ester amine compound and polyhydroxy compound * * · · · · · * * · · · · · · · · · · · ·

- is present in the form of particles dispersed in a liquid carrier; and the average particle size of the quaternary ester amine compound and the polyhydroxy compound is preferably from 0.01 to 10 microns, most preferably from 0.1 to 1.0 microns.

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