WO2003044270A2

WO2003044270A2 - Soft absorbent tissue

Info

Publication number: WO2003044270A2
Application number: PCT/US2002/012074
Authority: WO
Inventors: Kou-Chang Liu
Original assignee: Kimberly-Clark Worldwide, Inc.
Priority date: 2001-11-15
Filing date: 2002-04-17
Publication date: 2003-05-30
Also published as: AR036928A1; US20030127208A1; TW200300189A; AU2002316041A8; WO2003044270A3; TW591159B; US6599393B1; AU2002316041A1

Abstract

A tissue product having improved hand feel and good wettability is produced by printing onto one or both sides of the tissue an aqueous emulsion containing a hydrophilically-modified amino-functional polydimethylsiloxane. The hydrophilically-modified amino-functional polydimethylsiloxane structure has one or more pendant groups containing ethylene oxide moieties.

Description

SOFT ABSORBENT TISSUE CONTAINING HYDROPHILICALLY-MODIFIED AMINO- FUNCTIONAL POLYSILOXANES

Background of the Invention

In the field of soft tissues, such as facial tissue and bath tissue, it is well known that the application of polysiloxanes to the surface of the tissue can impart an improved surface feel to the tissue. However, polysiloxanes are also known to impart hydrophobicity to the treated tissue. Hence, it is difficult to find a proper balance between softness and wettability, both of which are desirable attributes for tissue, particularly bath tissue.

Summary of the Invention

It has now been discovered that the wettability of a tissue can be improved with minimal negative impact on the surface feel of the tissue by treating one or both outer surfaces of the tissue with a particular group of hydrophilically-modified amino-functional polysiloxanes. More specifically, suitable polysiloxane structures have one or more pendant groups and/or one or both terminal groups which contain an amine derivative. The general structure of the hydrophilically-modified amino-functional polysiloxanes of this invention is as follows:

R₂_ r__ si — O — ]_n— [— S Sii — O — ]_m- - Si— R₂— A

[EO]_r

[PO]_s

[R₄]t

B wherein

R-i is a Ci to C₈ straight chain, branched, cyclic alkyl radical;

R₂, R₃, and R₄ are independently a C₂ to C₁₀ straight chain, branched, cyclic, unsubstituted or substituted alkylene diradical; m = 0 to 10,000; n = 20 to 100,000; r = 1 to 10,000; s = 0 to 10,000; t = 0 or 1 ;

"A" is a N R₅ R₆, a (N R₇ R₈ R₉)⁺ X^", a OCOR₈R₉; a O-SO₃R.,; a PO₃ Ru R_i2; or a COOR₁₄ radical; when m = 0, R₅ and R₆ are independently a radical of CO R₁₅, COO Rι₅, CON R₁₅ R-j₇,

CORi₆ -COR₁₇; or -R₁₈-COORι₇; when m > 0, R₅ and R₆ are independently a radical of hydrogen, d to C₈ alkyl, CO R₁₅,

COO R₁₅, CONR₁₅ Rι₇, COR₁₆ -COR₁₇ or -R₁₈ -COOR₁₇;

R₇, and R₈ are independently a d to C₆ alkyl radical;

R₉ is a Ci to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical, or a

SO₂PhR₁₀ where Ph is a phenyl group;

R₁₀ is a Ci to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical;

"X" is a halide, a sulfate or other counter ion;

Ru and R₁₂, are independently a C-i to C₆ alkyl radical;

R₁₄ is a hydrogen, a Ci to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical;

R ₅ and R₁₇are independently a Ci to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical;

R-ie, Ri8 are independently a Ci to C₈ ethylene diradical; and

"B" is a hydrogen, an amino acid or an aminoacid derivative, a C-i to C₆ straight chain, branched, cyclic alkyl radical or independently a radical of "A". Representative species within the foregoing general structure include the following:

(1)

CH₃ CH₃ CH₃ CH₃ CH₃

I cr I I I I cr

C₁₆H₃₃ N⁺ R₂ — [— Si — O — ]_n— [— Si — O - ]_m — Si — R₂ — N C₁6 H₃₃

CH₃ CH₃ R₃ CH_a CH₃

[EO]r [PO]s

[R₄]t

B

(2)

CH₃ CH₃ CH₃ CH₃ CH₃

I cr I | | | cr

C₂H₅ N⁺ C₃H₆ —I— Si — O — ]_n— [— Si — O— ]_m— Si— C₃H^N⁺C₂H₅

[EO]_r

CH₂

I cr

CH₃ N⁺CH₃

(3)

CH₃ CH₃ CH₃

I I

H₂ N R₂ — [— Si — O ^■]n— [— Si — O — ]_m— Si— R₂— NH₂

CH₃ R₃ CH₃

[EO]_r [PO]s

B

(4)

CH₃ CH₃ CH₃

RnO₃SO — R₂— [— Si — O — ]_n— [— Si — O — ]_m— Si— R₂— OSO3R₁₁ CH₃ R₃ CH₃

[EO]_r

[PO]_s

OSOsR-n CH₃ CH₃ CH₃

Rι₂ CO₂ R₂ — [_ Si — O — ]_n— [— Si — O — ]_m— S -R₂— O₂CR₁₅

CH₃ R₃ CH₃

[EO]_r

[PO]s [R₄]t B

(6)

CH₃ CH₃ CH₃

I I I

HO₂C Rs— {— Si — O — ]_n— {— Si — O— ]_m— Sk— R₂— CO₂H

CH₃ R₃ CH₃

[EO]_r [PO]_β

[fj lt

B (7)

CH₃ CH₃ CH₃

CH3NHCONH— Rs— [— Si— O— ]_n— [— Si— O— ]m— i— R₂— HNOCNHCH₃

CH₃ C₃H₆ CH₃

[EO]_r

[PO]s

H

(8)

CH₃ CH₃ CH₃

C₂H₅OCONH R₂— [— Si— O— ]_n- — Si— O— ]_m— Si— R₂— HNOCOC₂H₅

CH₃ C₄H₈ CH₃

[EO]_r [PO]_s H

(9)

CH₃ CH₃ CH₃

I

C₂H₅NHCOO — R₂— [— Si— O— ]_n- — Si— O— ]_m— Sk-R₂— OOCHNC2H5

[EO]_r

[PO]s

C=O HNC₂H₅

(10)

CH₃ CH₃ CH₃

C₂H₅CONH Rz— [— Si— O— ]_n- — Si— O— ]_m— Si— R₂— HNCOC₂H₅

CH₃ R₃ CH₃

[EO]_r

[PO]s

B

(11)

CH₃ CH₃ CH₃

I I

(C₂H₅CO)₂N R₂— [— sμ-o— ]_n— [— sμ- -]_m_ Si— R₂— N(COC₂H₅ )₂

CH₃ R₃ CH₃

[EO]_r

[PO]s

B

(12)

CH₃ CH₃ CH₃

H N R_? Si — O ._]n_ r_ si — O — ]_m— S -R₂— NH₂ CH₃ R₃ CH₃

[EO]_r

R₄

I

NH₂

(13)

CH₃ CH₃ CH₃ CH₃ CH₃ x- I I I x-

C₁₈H₃₇PhO₂SN⁺— C₃Hr- [— Si— O]_n- ₃ Hrie6 -N⁺SO₂PhC₁₈H₃₇

[EO]_r H

(14)

U₂ P 11 12

(15)

CH₃ CH₃ CH₃ CH₃

I cr I | | cr

C₁₆H₃₃ N⁺ R₂ — [— Si — O — ]_n —Si — R₂— N⁺ C₁₆ H₃₃

(16)

CH₃ CH₃ CH₃ CH₃

I i- I I l ι-

C₂H₅ N⁺ R₂ — [— Si — O — ]_n —Si — R₂— N⁺ C₂H₅

CH₃ CHa CH₃ CHa

(17)

CH₃ CH₃ CH₃ CH₃ x- I I I I x-

C₁₂H₂5PhO₂SN⁺— Ra— [— Si— O]_n— Si— R₂— N⁺SO₂PhC₁₂H₂₅ CH₃ CH₃ CH₃ CH₃

(18)

CH₃ CH₃

I I

(CH₃)₂NCONH F - [_ Si— O— ]_n— Si— R₂— HNOCN(CH₃)₂

CH₃ CH₃ (19)

CH₃ CH₃

C₂H₅OOCNH R₂— [— Si— O— ]_n— Si— R₂— HNCOOC₂H5

CH₃ CH₃

The derivitized amino-functional polydimethylsiloxanes described above can be applied to the tissue web alone or in conjunction with other chemicals, such as bonders or debonders. They can be applied to the tissue web, particularly an uncreped throughdried web, by spraying or printing. Rotogravure printing of an aqueous emulsion is particularly effective. Add-on amounts can be from about 0.5 to about 15 dry weight percent, based on the weight of the tissue, more specifically from about 1 to about 10 dry weight percent, still more specifically from about 1 to about 5 weight percent, still more specifically from about 2 to about 5 weight percent. The distribution of the deposits of the derivitized amino-functional polydimethylsiloxanes is substantially uniform over the printed surface of the tissue, even though the surface of the tissue, such as in the case of uncreped throughdried tissues, may be highly textured and three- dimensional.

The Wet Out Time (hereinafter defined) for tissues of this invention can be about 15 seconds or less, more specifically about 10 seconds or less, still more specifically about 6 seconds or less, still more specifically about 5 seconds or less, still more specifically from about 4 to about 8 seconds. As used herein, "Wet Out Time" is related to absorbency and is the time it takes for a given sample to completely wet out when placed in water. More specifically, the Wet Out Time is determined by cutting 20 sheets of the tissue sample into 2.5 inch squares. The number of sheets used in the test is independent of the number of plies per sheet of product. The 20 square sheets are stacked together and stapled at each corner to form a pad. The pad is held close to the surface of a constant temperature distilled water bath (23 +/-2° C), which is the appropriate size and depth to ensure the saturated specimen does not contact the bottom of the container and the top surface of the water at the same time, and dropped flat onto the water surface, staple points down. The time taken for the pad to become completely saturated, measured in seconds, is the Wet Out Time for the sample and represents the absorbent rate of the tissue. Increases in the Wet Out Time represent a decrease in absorbent rate.

The "Differential Wet Out Time" is the difference between the Wet Out Times of a tissue sample treated with a derivitized amino-functional polydimethylsiloxane and a control tissue sample which has not been treated. The Differential Wet Out Time, for purposes of this invention, can be about 10 seconds or less, more specifically about 5 seconds or less, still more specifically about 3 seconds or less, still more specifically about 2 seconds or less, and still more specifically about 1 second or less.

The ratio of the Differential Wet Out Time to the add-on amount of the derivitized amino- functional polydimethylsiloxane can be about 3 seconds per weight percent or less, more specifically about 1 second per weight percent or less, still more specifically about 0.5 second per weight percent or less.

Tissue sheets useful for purposes of this invention can be creped or uncreped. Such tissue sheets can be used for facial tissues, bath tissues or towels. They can have one, two, three or more plies. The basis weight of the tissue product can be from about 25 to about 50 grams per square meter. If used for bath tissue, a single ply tissue having a basis weight of from about 30-40 grams per square meter is particularly suitable.

Brief Description of the Drawings

Figure 1 is a schematic diagram of an uncreped throughdried process for making bath tissue in accordance with this invention.

Figure 2 is a schematic diagram of the post-manufacturing method of handling the uncreped throughdried web and the rotogravure coating process used to apply the derivitized amino-functional polydimethylsiloxane emulsion in accordance with this invention.

Detailed Description of the Drawings

Referring to Figure 1, shown is a schematic flow diagram of a throughdrying process for making uncreped throughdried tissue sheets. Shown is the headbox 1 which deposits an aqueous suspension of papermaking fibers onto an inner forming fabric 3 as it traverses the . forming roll 4. Outer forming fabric 5 serves to contain the web while it passes over the forming roll and sheds some of the water. The wet web 6 is then transferred from the inner forming fabric to a wet end transfer fabric 8 with the aid of a vacuum transfer shoe 9. This transfer is preferably carried out with the transfer fabric traveling at a slower speed than the forming fabric (rush transfer) to impart stretch into the final tissue sheet. The wet web is then transferred to the throughdrying fabric 11 with the assistance of a vacuum transfer roll 12. The throughdrying fabric carries the web over the throughdryer 13, which blows hot air through the web to dry it while preserving bulk. There can be more than one throughdryer in series (not shown), depending on the speed and the dryer capacity. The dried tissue sheet 15 is then transferred to a first dry end transfer fabric 16 with the aid of vacuum transfer roll 17. The tissue sheet shortly after transfer is sandwiched between the first dry end transfer fabric and the transfer belt 8 to positively control the sheet path. The air permeability of the transfer belt is lower than that of the first dry end transfer fabric, causing the sheet to naturally adhere to the transfer belt. At the point of separation, the sheet follows the transfer belt due to vacuum action. Suitable low air permeability fabrics for use as transfer belts include, without limitation, COFPA Mononap NP 50 dryer felt (air permeability of about 50 cubic feet per minute per square foot) and Asten 960C (impermeable to air). The transfer belt passes over two winding drums 21 and 22 before returning to pick up the dried tissue sheet again. The sheet is transferred to the parent roll 25 at a point between the two winding drums. The parent roll is wound onto a reel spool 26, which is driven by a center drive motor.

Particularly suitable methods of producing uncreped throughdried basesheets for purposes of this invention are described in U.S. 6,017,417 issued January 25, 2000 to Wendt et al. and U.S. 5,944,273 issued August 31, 1999 to Lin et al., both of which are herein incorporated by reference.

Figure 2 illustrates a suitable method for applying the derivitized amino-functional polydimethylsiloxane to the tissue basesheet. Shown is the parent roll 25 being unwound and passed through two calender nips between calender rolls 30a and 31a and 30b and 31b. The calendered web is then passed to the rotogravure coating station comprising a first closed doctor chamber 33 containing the hydrophilically-modified amino-functional polydimethylsiloxane emulsion to be applied to a first side of the web, a first engraved steel gravure roll 34, a first rubber backing roll 35, a second rubber backing roll 36, a second engraved steel gravure roll 37 and a second closed doctor chamber 38 containing the derivitized amino-functional polydimethylsiloxane emulsion to be applied to the second side of the web. If both sides of the web are to be treated, the two emulsions can be the same or different. The calendered web passes through a fixed-gap nip between the two rubber backing rolls where the derivitized amino-functional polydimethylsiloxane emulsion is applied to the web. The treated web is then passed to the rewinder where the web is wound onto logs 40 and slit into rolls of bath tissue. Examples

Example 1

In order to further illustrate this invention, an uncreped throughdried tissue is produced • using the methods described in Figures 1 and 2 and is treated with a hydrophilically-modified amino-functional polydimethylsiloxane as set forth in structure 12 described above.

More specifically, a single-ply, three-layered uncreped throughdried bath tissue is made using eucalyptus fibers for the outer layers and softwood fibers for the inner layer. Prior to pulping, a quaternary ammonium softening agent (C-6027 from Goldschmidt Corp.) is added at a dosage of 4.1 kg/Mton of active chemical per metric ton of fiber to the eucalyptus furnish. After allowing 20 minutes of mixing time, the slurry is dewatered using a belt press to approximately 32% consistency. The filtrate from the dewatering process is either sewered or used as pulper make-up water for subsequent fiber batches but not sent forward in the stock preparation or tissue making process. The thickened pulp containing the debonder is subsequently re-dispersed in water and used as the outer layer furnishes in the tissue-making process.

The softwood fibers are pulped for 30 minutes at 4 percent consistency and diluted to 3.2 percent consistency after pulping, while the debonded eucalyptus fibers are diluted to 2 percent consistency. The overall layered sheet weight is split 30%/40%/30% among the eucalyptus/refined softwood/ eucalyptus layers. The center layer is refined to levels required to achieve target strength values, while the outer layers provide the surface softness and bulk. Parez 631 NC is added to the center layer at 2-4 kilograms per ton of pulp based on the center layer.

A three-layer headbox is used to form the wet web with the refined northern softwood Kraft stock in the two center layers of the headbox to produce a single center layer for the three- layered product described. Turbulence-generating inserts recess about 3 inches (75 millimeters) from the slice and layer dividers extending about 1 inch (25.4 millimeters) beyond the slice are employed. The net slice opening is about 0.9 inch (23 millimeters) and water flows in all four headbox layers are comparable. The consistency of the stock fed to the headbox is about 0.09 weight percent.

The resulting three-layered sheet is formed on a twin-wire, suction form roll, former with forming fabrics (12 and 13 in Figure 1) being Lindsay 2164 and Asten 867a fabrics, respectively. The speed of the forming fabrics is 11.9 meters per second. The newly-formed web is then dewatered to a consistency of about 20-27 percent using vacuum suction from below the forming fabric before being transferred to the transfer fabric, which is travelling at 9.1 meters per second (30% rush transfer). The transfer fabric is an Appleton Wire T807-1. A vacuum shoe pulling about 6-15 inches (150-380 millimeters) of mercury vacuum is used to transfer the web to the transfer fabric.

The web is then transferred to a throughdrying fabric (Lindsay Wire T1205-1 ) previously described in connection with Figure 2 and as illustrated in Figure 9). The throughdrying fabric is travelling at a speed of about 9.1 meters per second. The web is carried over a Honeycomb throughdryer operating at a temperature of about 350°F. (175°C.) and dried to final dryness of about 94-98 percent consistency. The resulting uncreped tissue sheet is then wound into a parent roll.

The parent roll is then unwound and the web is calendered twice. At the first station the web is calendered between a steel roll and a rubber covered roll having a 4 P&J hardness. The calender loading is about 90 pounds per lineal inch (pli). At the second calendering station, the web is calendered between a steel roll and a rubber covered roll having a 40 P&J hardness. The calender loading is about 140 pli. The thickness of the rubber covers is about 0.725 inch (1.84 centimeters).

The calendered single-ply web is then fed into the rubber-rubber nip of the rotogravure coater to apply the hydrophilically-modified amino-functional polydimethylsiloxane emulsion to both sides of the web. The aqueous emulsion contains 40% of a derivitized amino polydimethylsiloxane, 8% surfactant, 0.5% antifoaming agent, 0.5% preservative, and the balance water. The gravure rolls are electronically engraved, chrome over copper rolls supplied by Specialty Systems, Inc., Louisville, Kentucky. The rolls have a line screen of 200 cells per lineal inch and a volume of 6.0 Billion Cubic Microns (BCM) per square inch of roll surface. Typical cell dimensions for this roll are 140 microns in width and 33 microns in depth using a 130-degree engraving stylus. The rubber backing offset applicator rolls are a 75 Shore A durometer cast polyurethane supplied by American Roller Company, Union Grove, Wisconsin. The process is set up to a condition having 0.375 inch interference between the gravure rolls and the rubber backing rolls and 0.003 inch clearance between the facing rubber backing rolls. The simultaneous offset/offset gravure printer is run at a speed of 2000 feet per minute using gravure roll speed adjustment (diferential) to meter the polysiloxane emulsion to obtain the desired addition rate. The gravure roll speed differential used for this example is 1000 feet per minute. This process yields an add-on level of 2.5 weight percent total add-on based on the weight of the tissue. The tissue is then converted into bath tissue rolls. Sheets from the bath tissue rolls have a silky, lotiony hand feel and a Wet Out Time of 4.8 seconds. (Similarly made tissues without the treatment of this invention have a Wet Out Time of about 4.0 seconds.) The ratio of the Differential Wet Out Time to the weight percent add-on amount is 0.32. Example 2

An uncreped throughdried tissue is made substantially as described above with the following exceptions: (1) the overall layered weight is split 20%/60%/20% among the eucalyptus / refined softwood / eucalyptus layers; (2) no Parez is added to the center layer; (3) the add-on level of the hydrophilically-modified amino-functional polydimethylsiloxane is 3.0 weight percent; (4) the structure of the hydrophilically-modified amino-functional polydimethylsiloxane is as set forth in structure 9 above; and (5) the hydrophilically-modified amino-functional polydimethylsiloxane constitutes 40 weight percent of the aqueous emulsion used to deliver the hydrophilically-modified amino-functional polydimethylsiloxane to the tissue. The resulting bath tissue product obtained has a silky, lotiony hand feel and a Wet Out Time of 5 seconds.

Example 3

An uncreped throughdried tissue is produced similarly as described in Example 1 with the following exceptions: (1) prior to pulping, a polysiloxane of structure 2 is added to the eucalyptus fibers at a dosage of 2 kg/Mton of active chemical per metric ton of fiber; (2) the addon level of the hydrophilically-modified amino-functional polydimethylsiloxane is 1.5 weight percent; (3) the structure of the hydrophilically-modified amino-functional polydimethylsiloxane printed onto the tissue is as set forth in structure 13 above; and (4) the hydrophilically-modified amino-functional polydimethylsiloxane constitutes 20 weight percent of the aqueous emulsion used to deliver the hydrophilically-modified amino-functional polydimethylsiloxane to the tissue. The resulting bath tissue product obtained has a silky, lotiony hand feel and a Wet Out Time of 4.2 seconds.

It will be appreciated that the foregoing description and examples are not to be construed as limiting the scope of this invention, which is defined by the following claims and all equivalents thereto.

Claims

We claim:

1. A tissue containing a polysiloxane having the following general structure:

A — R₂ — [— Si — O — ]_n— [— Si — O — ]_m— Sh-R₂— A

[EO]_r [PO]s

[R₄]t

B

wherein

R-i is a C-[ to C₈ straight chain, branched, cyclic alkyl radical;

"A" is a N R₅ R₆, a (N R₇ R₈ R₉)⁺ X-, a OCOR₈R₉; a O-SOaR^ a PO₃ R-,-, R₁₂, or a COOR₁₄ radical; when m = 0, R₅ and R₆ are independently a radical of CO R₁₅, COO R₁₅, CON R-i₅ R₁₇, CORι₆ •

COR₁₇; or -R₁₈-COORι₇; when m > 0, R₅ and R₆ are independently a radical of hydrogen, C-i to C₈ alkyl, CO R-|₅, COO

R₁₅, CONR₁₅ Rι₇, COR₁₆ -COR₁₇ or -R₁₈ -COOR_i7;

R₇, and R₈ are independently a C-i to C₆ alkyl radical;

R₉ is a C-i to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical, or a

SO₂PhR-|₀ where Ph is a phenyl group;

R₁₀ is a C-_\ to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical;

"X" is a halide, a sulfate or other counter ion; Ru and R₁₂, are independently a Ci to C₆ alkyl radical;

R-ι₄ is a hydrogen, a C-i to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical;

R₁₅ and R₁₇ are independently a Ci to C₃₀ straight chain, branched, substituted or unsubstituted alkyl radical;

R₁₆, R₁₈ are independently a d to C₈ ethylene diradical; and

"B" is a hydrogen, an amino acid or an aminoacid derivative, a Ci to C₆ straight chain, branched, cyclic alkyl radical or independently a radical of "A".

2. The tissue of claim 1 wherein the Wet Out Time is about 10 seconds or less.

3. The tissue of claim 1 wherein the Wet Out Time is about 7 seconds or less.

4. The tissue of claim 1 wherein the Wet Out Time is about 5 seconds or less.

5. The tissue of claim 1 wherein the Wet Out Time is from about 4 to about 8 seconds.

6. The tissue of claim 1 having from about 0.5 to about 15 dry weight percent of the derivitized amino-functional polysiloxane.

7. The tissue of claim 1 having from about 1 to about 10 dry weight percent of the derivitized amino-functional polysiloxane.

8. The tissue of claim 1 having from about 1 to about 5 dry weight percent of the derivitized amino-functional polysiloxane.

9. The tissue of claim 1 having from about 2 to about 5 dry weight percent of the derivitized amino-functional polysiloxane.

10. The tissue of claim 1 wherein the ratio of the Differential Wet Out Time to the add-on amount of the derivitized amino-functional polysiloxane is about 3 seconds per weight percent or less.

11. The tissue of claim 1 wherein the ratio of the Differential Wet Out Time to the add-on amount of the derivitized amino-functional polysiloxane is about 1 second per weight percent or less.

12. The tissue of claim 1 wherein the ratio of the Differential Wet Out Time to the add-on amount of the derivitized amino-functional polysiloxane is about 0.5 second per weight percent or less.

13. The tissue of claim 1 wherein the tissue is an uncreped throughdried tissue.

14. The tissue of claim 1 wherein both sides of the tissue are printed with the same derivitized amino-functional polysiloxane.

15. The tissue of claim 1 wherein the derivitized amino-functional polysiloxane printed on one side of the tissue is different than the derivitized amino-functional polysiloxane printed on the other side of the tissue.

16. The tissue of claim 1 wherein A is a NR₅R₆ radical.

17. The tissue of claim 1 wherein A is a N(R₇R₈R₉)^+I_ radical.

18. The tissue of claim 1 wherein A is a OCOR₈R₉ radical.

19. The tissue of claim 1 wherein R₅ and R₆ are independently a hydrogen radical.

20. The tissue of claim 1 wherein R₅ and R₆ are a C C₈ radical.

21. The tissue of claim 1 wherein R₅ and R₆ are a COR₁₅ radical.

22. The tissue of claim 1 wherein R₅ and R₆ are a COOR ₅ radical.

23. The tissue of claim 1 wherein R₅ and R₆ are a CONR₁₅R₁₇ radical.

24. The tissue of claim 1 wherein R₅ and R₆ are a COR₁₆-COR-|₇ radical.

25. The tissue of claim 1 wherein R₅ and R₆ are a R₁₈-COOR₁₇ radical.

26. The tissue of claim 1 wherein B = A.

27. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃ CH₃ CH₃

I cr I I I I cr

C₁₆H₃₃ N⁺ R₂ — [— Si — O — ]_n— [— Si — O — ]_m— Si— R₂— N⁺ C₁₆ H₃₃

CH₃ CH₃ R₃ CH₃ CH₃

[EO]_r

[R₄]t

B

28. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃ CH₃ CH₃

I cr I I I I cr

C₂H₅ N⁺ C₃H₆ — {— Si — O - -]_n— [— Si -O- -]m — Si — C3H6 — N C₂Hδ

[EO]_r

[PO]s C=O CH₂

I cr

CH₃ N⁺CH₃

C- 1,66 H πss

29. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

H₂ N R₂ — [— Si — O — ]_n— [— Si — O — ]_m— Si— R₂— NH₂

CH₃ R₃ CH₃

[EO]_r

[PO]s

[R₄]t

B

30. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

R 0₃SO R₂— [— Si — O — In— [— Si — O — ]_m— Si— R₂— OSO₃Rn

I I I

CH₃ R₃ CH₃

[EO]_r

[PO]_s

[R₄]t

31. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

R₁₂ CO₂ — R₂ — [— Si — O — ]_n— [— Si — O — ]_m— Si— R₂— O₂CR₁₂ CH₃ R₃ CH₃

[EO]_r [PO]₈

[R₄]t

B

32. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

HO₂C — R₂— [— Si — O — ]_n— [— Si — O— ]_m— Si— R₂— CO₂H CH₃ R₃ CH₃

[EO]_r

B

33. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃ CH₃NHCON — HNOCNHCHS

[EO]_r

H

34. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

I

C₂H₅OCONH Rz— [— Si— O— ]_n- -]_m— Si— R₂— HNOCOC₂H₅

CH₃ C₄H₈ CH₃

[EO]_r [PO]s

H

35. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

C₂H₅NHCOO R₂— [— Si— O— ]_n- -Si— O— ]_m— Sh-R₂— OOCHNC₂H₅

CH₃ C H₈ CH₃

[EO]_r [PO]s C=O HNC₂H₅

36. The tissue of claim 1 wherein the polysiloxane has the following structure:

CHs CHs CH₃

C₂H₅CONH Rz-i— Sk-O— ]_n- -Si— O- — ]m — i — R₂- -HNCOC₂H₅

CH₃ R₃ CH₃

[EO]_r

[Ppiβ

B

37. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

(C₂H₅CO)₂N Rz— [— Si— O— ]_n— [— Si— O— ]_m— Si— R₂— N(COC₂H₅ )₂

CH₃ R₃ CH₃

[EO]_r

[R₄]t

B

38. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

CH₃ R₃ CH₃

[EO]_r

R₄ NH₂

9. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CHs CH₃ CH₃ CH₃ x- I I I I I x-

C₁₈H₃₇PhO₂SN⁺— CsHe— [— Si— O]_nH:-Si— O]_m— S -C₃H₆— N⁺SO₂PhC₁₈H₃₇ CH₃ CH₃ C₃H₈ CHs CH₃

[EO]_r H

40. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃

R₁₂ RιιO₃P R₂ — [ — Si — O — ]_n — [ — Si — O — ]_m — Si — R₂ — PO₃R-ι-|Rι₂

CH₃ R₃ CH₃

I

[EO]_r

41. The tissue of claim 1 wherein the polysiloxane has the following structure:

CHs CHs CH₃ CH₃

I cr I I I cr

C-i₆H₃₃ N R₂ - ^• [— Si — O — ]_n — Si — R₂— N⁺ C₁₆ H₃₃

CHs CH₃ CH₃ CH₃

42. The tissue of claim 1 wherein the polysiloxane has the following structure:

CHs CH₃ CHs CH₃

I r I I I r

C₂H₅ N⁺ R₂ — [— Si — O — ]_n —Si — R₂— N⁺ C₂H₅

I I I I

CH₃ CHs CHs CH₃

43. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃ CH₃ CH₃ x- I I I I x-

C₁₂H₂₅PhO₂SN⁺— Rz— [— Si— O]_n— Si— R₂— N⁺SO₂PhC₁₂H₂₅ CH₃ CH₃ CH₃ CH₃

44. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃

I I

(CH₃)₂NCONH Rz— [— Si— O— ]_n— Sh-R₂— HNOCN(CH₃)₂

CH₃ CH₃

5. The tissue of claim 1 wherein the polysiloxane has the following structure:

CH₃ CH₃

C₂H₅OOCNH — Rz- {— Sh-O— ]_n— Sh-R₂— HNCOOC₂H₅

CH₃ CH₃