MXPA00007078A - Soft absorbent tissue products - Google Patents

Abstract

Amine-modified polysiloxanes are applied to the opposite outer surfaces of a tissue product, such as the two outer surfaces of a 3-ply facial tissue, providing improved softness to the surfaces and a degree of hydrophobicity to prevent wet through of liquids during use. However, the degree of hydrophobicity is controlled by the chemical structure of the amine-modified polysiloxane and/or by blending the amine-modified polysiloxane with a more hydrophilic modified polysiloxane such that liquid is still allowed to enter the tissue structure in a reasonably short time to be absorbed by the center ply, but the absorption in combination with the hydrophobicity of the other outer surface substantially delays the liquid from passing completely through the tissue product.

Description

ABSORBENT AND SOFT TISSUE PRODUCTS Background of the Invention In the manufacture of tissue products, including tissue and bathroom facepieces, the industry has made considerable efforts to improve tact characteristics to fill the consumer's desire for "soft" tissues. There are primary methods to improve the softness of tissues through chemical additives. First, there are chemical softening agents that can be added to the supply prior to the formation process to reduce the stiffness of the base sheet and / or deliver improved surface feel characteristics. Second, there are chemicals that can be applied to the tissue surface after the sheet has been formed to provide an improved surface sensation.

However, in addition to the softness, another desirable attribute for both the facial tissue and the bathroom tissue is the ability to keep the hand protected during use. Therefore, since both the softness and the protection for the hand are key consumer benefits for the tissue product for the consumer, there is a need for a unique chemical system that can deliver both attributes.

Synthesis of the Invention It has now been discovered that multi-layer tissue base sheets treated topically with one or more suitable amine-modified polysiloxanes result in a softer tis, through both mechanisms of reduced base sheet stiffness and improved surface feel. , with a controlled water repellency and a sufficient absorbency to provide a tactile protection during use. The modified amine polysiloxanes preferably reside on the outer surface of the tissue layers to which the modified polysiloxanes are applied, either as a result of hydrogen bonding, charge attraction or other chemical interaction, thereby providing a Smooth benefit over the surface and providing a degree of water or liquid repellency. However, when the liquid n penetrates the outer surface of the tissue, the liquid rapidly absorbed by the central untreated portion of the tissue is transmitted outward in the x-y plane of the tissue. At the same time, the presence of the amine-modified polysiloxane on the opposite surface delays the additional penetration of liquid to the exterior of the tissue, thereby essentially trapping the liquid at the center of the tissue. This "one-way valve" effect protects the user's hands from getting dirty during normal use, and at the same time provides a benefit of softness. The combination of softness, liquid repellency and absorbency is unique and beneficial to the consumers.

However, not all amine-modified polysiloxanes are suitable for the purposes of this invention. It is necessary to impart the proper balance d hydrophilicity and hydrophobicity to the surface of the tissue in order to adequately delay the penetration into the liquid, but still allow sufficient penetration to allow the inner part of the tissue to absorb the liquid. The desired balance can be achieved by altering one or more of the following factors to increase or decrease the hydrophobicity (1) molecular weight the amine modified polysiloxane can be increased to increase hydrophobicity and decreased to increase hydrophilicity; (2) the mole percent of the amine functional groups within the amine-modified polysiloxane molecule can be changed to increase or decrease the hydrophobicity; (3) the aggregate amount of the amine-modified polysiloxane applied to the surface of the tissue can be increased to increase the hydrophobicity; and (4) the amine modified polysiloxane can be mixed with a more hydrophilic material, such as the modified polysiloxane as a polyether modified polysiloxane, to decrease the hydrophobicity. By balancing these factors, those skilled in the chemical arts can achieve polysiloxane modified with amine and modified polysiloxane mixtures which achieve the tissue properties of this invention.

Therefore in one aspect, the invention resides in a soft tissue product having two or more layers, said tissue product having a module in the direction of the machine (hereinafter defined) of about 30 kilograms less, wet outer area (hereinafter defined) d about 2 square inches or greater, a moisture passing time (hereinafter defined) of about 1 seconds or greater. Such tissue products have the proper balance and softness (as measured by the MD module) and the absorbency (as measured by the wet transfer time and wet exterior area) to keep the user's hands protected from liquids during the use.

More specifically, the invention resides in a soft tissue product having two or more layers and side facing surfaces topically treated with an amine-modified polysiloxane, said tissue product having a module in the machine direction around 3 kilograms or less, a wet outer area of about one square inch or greater, and a wet transfer time of about 15 seconds or more.

More specifically, the wet exterior area may be around 3 inches or greater, more specifically d about 4 inches or greater; and even more specifically d from about 2 square inches to about 6 square inches. Also more specifically, the wet transfer time can be 20 seconds or more, more specifically d about 30 seconds or more, more specifically d about 45 seconds or more, and even more specifically from about 15 to about 60 seconds. Also more specifically, the MD module can be around 2 ~ kilograms or less; even more specifically from around d 5 to around 20 kilograms.

In another aspect, the invention resides in a method for making a controlled, soft multi-layer tissue product of d absorbency comprising: a) forming an aqueous suspension of papermaking fibers; b) depositing the aqueous fiber suspension on a forming fabric to form a fabric; c) drying the tissue to form a tissue sheet; d) combining the tissue sheet with one or more similar tissue sheets to form a multi-layer tissue base sheet having two outer surfaces; and e) topically treating both outer surfaces of the tissue surface with an aqueous emulsion of an amine-modified polysiloxane to form a tissue product, said tissue product having a wet exit area of about 2 square inches or larger and a time of wet transfer of about 15 seconds or more.

As used here, the "MD" module is a measure of the softness of the tissue sheet and is the slope of at least one straight line of squares between 70 and 157 gram points for charging against percent of elongation d the sample. The module values in the direction of the machine are obtained using conventional tension test instruments (for example an integrated Sintech / 2 computer test system). A single facial tissue is cut in the direction of the machine to a width of 3 inches with a die cut. The length of the test sample must exceed the length of gauge (distance between the jaws of the voltage tester) by at least 2 inches. Test sample n must have no rips or creases and must be clean and have parallel edges. The tension tester jaws are opened and the test specimen is placed between the jaws straight and centered. The jaws are closed on the sample the test protocol is initiated. The sample is pulled at a third of the normal test speed (10 inches per minute). When the test load reaches 0.5% of the full scale load, the elongation is measured to correct for any loosening in the test sample. At that point, the crosshead changes speed and continues at the normal test speed. The data is collected until a maximum load is reached and the load falls to 65% of the maximum load. A suitable voltage tester can be obtained from Sintech Inc. of P.O. Box 14226 of Research Triangle Park, North Carolina 27709-4226.

The means for determining the "wet transfer time" and the "wet exterior area" will be described in detail with reference to the drawings.

The tissue products or of this invention may have two strata, three strata, four strata or more. The products of three strata are preferred because the outer layers can have their faces facing out treated with the polysiloxane or modified polysiloxanes according to this invention. The resulting stratum strata product has two soft and liquid repellent outer surfaces and an inner absorbent stratum. This allows the liquid not only to be absorbed by the inner layer but also to be trapped in the space between the strata, which further reduces the possibility of the user experiencing moisture through the tissue during use. Particularly suitable tissue products include facial tis, bathroom tissue, similar kitchen towels. These products are suitably made using conventional papermaking fibers. Their individual strata can be in layers or homogeneous, pressed wet or dried continuously.

The amine-modified polysiloxane materials which are suitable for the purposes of this invention have the following general formula: where x and y are integers > 0. The mole ratio of x to (+ y) can be from 0.005 percent to around 25 percent. The groups can be C 6 higher alkyl substituents. Additionally, R2 and Rs may be hydroxyl or C-_ higher alkyl alcohol substituents. The R?, - preferred moieties include C ^. The R 10 moiety may include an amine-related functional group such as amine, imin and / or amide.

For example, the amino-modified polysiloxane can be polysiloxane wherein the R 10 moiety contains a d-amine group per substituent or two amine groups or more substituent, separated by a branched linear alkyl chain of C? or older.

Modified polysiloxane materials which are suitable for mixing or combining with the amine-modified polysiloxane or polysiloxanes for the purposes of balancing the hydrophobicity according to this invention have the following general formula: where x and y are integers > 0. The mole ratio of x to (+ y) can be from 0.005 percent to around 25 percent. The R-9 moieties may be Cx or higher alkyl substituents. Additionally, R2 and R5 can be hydroxyl C? 6 major alkyl alcohol substituents. Preferred Rx R9 moieties include C-C4. The R1X moiety may include organic functional groups such as ether, polyether, amine ester, imine, amide or other functional groups, including the alkyl and alkenyl analogues of such functional groups.

As an example, the half RX1 can be a functional group of polyether of the generic form -R12 - (R13-0) a - (R14-0) b R15; wherein R12, R13 and R14 are Cx alkyl chains or greater R15 may be hydrogen or an alkyl group CC ^, and "a" and "b may be integers from 1 to 100, more specifically from 10 to 30 .

The viscosity range of the modified polysiloxane with amine, which is indicative of the molecular weight can be from about 25 centipoise to about 2,000,000 centipoise or higher, more specifically from about 100 to about 1,000,000 centipoise.

Suitable methods for applying the modified polysiloxane or polysiloxanes to the surface of the tissue include spraying, printing and coating. Co-etched printing is preferred because of the control it offers with respect to the amounts added to the tissue surface. The amount of polysiloxane or modified polysiloxanes applied to the surface of the tissue will depend on the particular modified polysiloxane. However, the appropriate aggregate amounts are from about 0.1 to about 5 percent per pes based on the dry weight of the tissue product., ma specifically from about 0.5 to about 3 po cent by weight and even more specifically from about 0.7 d to about 2% by weight. It is preferable to first emulsify the modified polysiloxane (s) in water using the appropriate surfactant before applying the emulsion to the surface of the tissue. Even though the modified polysiloxanes preferably reside on the surface of the tissue to which they are applied, the polysiloxanes inherently migrate so that even the middle stratum of a three layer tissue product may contain some of the silicone material. However, such amounts are much less than the amount on the outer surface of the tissue so that the central layer remains substantially hydrophilic and can transmit and absorb the liquid.

In order to further optimize and balance the softness of the tactile protection and the absorbency benefits of modified polysiloxane treatment, the two or more mixtures of the modified polysiloxane materials can be applied to the surface of the tissue. In a particular example a mixture of polysiloxane modified with hydrophobic amin and a polysiloxane modified with hydrophilic polyether can be used to adjust the wet transfer time of the finished tis product. The ratio of the modified polysiloxane to amin for the polyether modified polysiloxane can be from about 100 percent to about 10%, more specifically from 100% to about 50%.

Those familiar with the art of polymers will appreciate that the molecular weight (viscosity), the degree of substitution of the selected species for the various R groups and their chain lengths, the molar ratio of the "X" and "Y" components of a modified modified polysiloxane species, and by mixing two or more species of modified polysiloxane can be varied to affect the hydrophobicity of the modified polysiloxane to be applied to the surface of the tissue in order to achieve the wet transfer times and the desired wet outer areas in accordance with this invention.

Brief Description of the Drawings Figure 1 is a schematic representation of apparatus used to measure the wet transfer time and wet areas as described herein.

Figure 2 is a plan view of the sample cover illustrated in Figure 1.

Figure 3 is a bar chart illustrating the wet transfer time for tissues of this invention and comparison to certain other tissues.

Figure 4 is a bar diagram illustrating the wet outer area for tissues of this invention compared to other tissues of Figure 3.

Detailed Description of the Drawings Referring to the drawings, the method for determining the wet transfer time and the outdoor wet area will be described. In general, the method involves placing a measured quantity of an inked liquid on the upper surface of a tissue sample and measuring the time it takes for the liquid to pass through the sample to activate a wet senso placed at the bottom of the tissue. That time is the wet transfer time. At this point in time, the extent to which the inked liquid will have to be transmitted in the x-y direction of the tissue will be visible as a circular or elliptical groove. The area of the point is the wet outer area.

Figure 1 schematically illustrates the equipment set up to carry out the test procedure shown in a wet sensor 1 which rests on a flat surface and is connected to a humidity light indicator 2. The specific humidity sensor is a controller liquid perception Cole-Parmer Liqui-Sense 77096-00 manufactured by Barnant Company, of Barrington, Illinois with a liquid perception sensor Cole-Parmer 77095-00. The humidity sensor sensitivity is calibrated to respond to 0.2 millimeter of the test liquid (described below) according to the manufacturer's instructions. The tissue sample 3 which has been folded in half and placed on top of the moisture sensor is secured with two Lexan side weights and 5 placed on both sides of the humidity sensor. Each side weight measures 3/4 of an inch by 1/4 of an inch in the cross section and is 4 inches long. These weights are placed so that the folded tissue sample rests against the surface of the moisture sensor, but is not under tension. On top of the sample is a 4 inch by 1 / inch 6-inch Lexan sample cover as illustrated further in Figure 2. The cover d sample has a conical hole 7 through the center measuring 3/8 inch in diameter on the top surface and a 1/1 inch in diameter on the bottom surface. Because the thickness of the humidity sensor is slightly less than the 1/4 inch thickness of the lateral weights, the support d sample primarily rests on the lateral weights.

Placed on top of the sample cover is a video camera 8 (JVC TK-1070U Color Video Camera made in Japan by JVC). The output of the video camera is connected to the recorder of the video cassette 9 (Panasonic AG-1960 Prolin distributed by Panasonic Industrial Co., of Secaucus, New Jersey) and a color monitor 10 (Panasonic CT-1381-Y Color Vide Display) . The video camera is placed on a tripod d so that the humidity light indicator 2 is visible within the view of the video camera.

The test liquid used to carry out the test is a Hercules sized green tester available from Hercules Incorporated, of Wilmington, Delaware. The liquid d test has the following properties measured at 22 ° C viscosity of 10 centipoise when measured using a Cynchro-leetrie viscometer from Brookfield Model RVT with a No. 1 spindle at a speed of 50 revolutions per minute; a surface tension of 60.5 dynes per centimeter when measured using a duNouy ring tensiometer (Físhe Scientific 20 surface tensiometer); pH of 7.3; and a specific conduction of 1 Siemens micro per centimeter.

To carry out the test to determine the wet transfer time and the wet outdoor area, the video photograph is adjusted so that the photograph of the sample cube measures 6 inches x 6 inches on the video monitor. The liquid sense controller unit is placed so that the alarm light (humidity indicator light can be seen clearly on the video screen.) A sample of the tissue product to be tested is folded in half, s placed On the humidity sensor, it is secured with the side weight, and covered with the sample cover as previously shown and described.

(VCR) starts to work. Using a micropipette, 0. milliliters of the test liquid are placed in the hole of the sample cover and the time measurement of the test is started. When the moisture monitor alarm light is on, the time in seconds is the wet transfer time for that sample. After that point the video cassette recorder stops. Using the pause and running characteristics of the video, the video image is adjusted to the frame where the alarm was activated showing the size of the point created by the inked test liquid. The area of the ink image on the video screen is that point in time, expressed in square inches is the wet outer area. Because the shape of the ink images is generally elliptical, the area can be easily determined by measuring the main and minor axis of the ellipse and calculating the area. However, if greater precision is desired, it will be appreciated that this is also possible by calculating the area using more sophisticated image analysis techniques.

Figures 3 and 4 are bar charts illustrating the wet transfer time and the wet exterior area for tissues made by the following examples and various commercial tissues. As shown, the tissues of this invention have a unique combination of superior water repellency (as measured by relatively high values for wet transfer time) and high absorbency (as measured by relatively high values for the outer area). wet).

And emplos Example 1 (Control). A stratum tissue of three strata having a finished basis weight of 22.7 pounds by 2,880 square feet and a supply consisting of 65% hardwood and 35% softwood fibers was printed on both sides with an aqueous emulsion of modified polysiloxane (FTS-226 manufactured by Witco Corporation, of Greenwich Connecticut) through a simultaneous rotograbad printing process. The modified polysiloxane aqueous emulsion contained about 20% by weight of a polysiloxane modified with amino, about 20% by weight of polysiloxane modified with polyether, about 57% by weight of water, about 2 by weight of emulsifiers, around 0.75% by weight of a biocide package and a small amount of a buffer agent to adjust the pH of the final emulsion in the range of 6.5-7.5. The ratio of the percent of polysiloxane modified with amino to polysiloxane modified with polyether fu 50/50.

The gravure rolls were electronically engraved, chromium-plated copper rolls supplied by Southern Graphics Systems, of Louisville, Kentucky. The roller had a line screen of 360 cells per inch line and a volume of 1.5 billion cubic microns (BCM) per square inch of roller surface. The typical cell dimensions for this roller were 65 microns in length, 11 microns wide and 13 microns deep. The rubber backed offset applicator rolls were a 75 Shore A hardness polyurethane supplied by the American Rolle Company of Union Grove, Wisconsin. The process was set to a condition that has a 0.375 inch interference between the gravure rolls and the rubber backing rolls and a 0.003 inch gap between the backing rolls of the rubber cover. The offset / simultaneous offse gravure printer was run at a speed of 200 feet per minute. This process gave an aggregate level of 1.0% by total weight added based on the weight of the tissue. The resulting soft tis product had a wet transfer time of 2 seconds and a wet exterior area of 0.9 square inches. _ The module in the machine direction was about 16.54 kilograms.

Example 2 (This Invention). A tissue product was prepared as described in Example 1, except that the modified polysiloxane aqueous emulsion (silicon emulsion Y-14344 from Witco Corporation) was a 1: 1 po weight mixture of an aqueous modified polysiloxane emulsion ( silicon emulsion Y-14264 from Witco Corporation) and a second modified polysiloxane aqueous emulsion (silicone emulsion Y-1427 from Witco Corporation). More specifically, the first modified polysiloxane aqueous emulsion contained about 32% by weight of a modified amino polysiloxane, about 63.2% by weight of water, about 3.2% by weight of an emulsifier package, about 0.75% by weight of a biocide package about 0.8% by weight of a freeze-thaw stabilizer and a buffering agent to carry the p within the range of 6.5-7.5. The second modified polysiloxane aqueous emulsion contained about 24% by weight of an amino-modified polysiloxane, about 11% by weight of a mixture of two polyether-modified polysiloxanes, about 61.2% by weight of water, about 2.4% by weight of an emulsifier package, about 0.75% by weight of a biocide package, about 0.6% by weight of a freeze-thaw stabilizer and a sufficient buffered agent to bring the pH into 6.5-7.5. The proportion of percent polysiloxane modified with polyolefin-modified polysiloxane per cent was 84/16.

The resulting soft tissue product had a wet transfer time of 22.8 seconds and a wet exterior area of 3.8 square inches. The module in the direction of the machine was 14.18 kilograms.

Example 3 (This Invention). A tissue product was prepared as described in example 1, except that the modified polysiloxane aqueous emulsion (silicon emulsion Y-14316 from Witco Corporation) was a mixture of 9: 1 po weight of a first modified polysiloxane aqueous emulsion. (silicon emulsion Y-14264 from Witco Corporation) and an aqueous modified polysiloxane second emulsion (silicone emulsion Y-14275 from Witco Corporation). More specifically, the first modified polysiloxane aqueous emulsion contained about 32% by weight of a modified amino polysiloxane, about 63.2% by weight of water, about 3.2% by weight of an emulsifying packet, about 0.75% by weight of a biocide package about 0.8% by weight of a freeze-thaw stabilizer and a buffering agent to carry the p within the range of 6.5-7.5. The second modified polysiloxane aqueous emulsion contained about 24% by weight of an amino-modified polysiloxane, about 11% by weight of a mixture of two polyether-modified polysiloxanes, about 61.2% by weight of water, about 2.4% by weight of an emulsifier package, about 0.75% by weight of a biocidal package, about 0.6% by weight of a freeze-thaw stabilizer and a sufficient buffered agent to bring the pH into 6.5-7.5. The proportion of percent polysiloxane modified with polyolefin-modified polysiloxane per cent was 97/3.The resulting soft tissue product had a wet transfer time of 31.7 seconds and a wet exterior area of 5.3 square inches. The module in the direction of the machine was 17.24 kilograms.

Example 4 (This Invention). A tissue product was prepared as described in Example 1 except that the modified polysiloxane aqueous emulsion contained about 32% by weight of an amino-modified polysiloxane around 63.8% by weight of water, about 3.2% by weight of water. an emulsifier package, about 0.2% by weight of a biocide package and about 0.8% by weight of a stabilized freeze-thaw. (Silicon emulsion Y-1424 from Witco Corporation). The ratio of percent modified polysiloxane to amino to percent polysiloxane modified with polyether was 100/0.

The resulting soft tissue product had a wet transfer time of 53.4 seconds and a wet outer area of 4.6 square inches. The module in the direction of the machine was 11.65 kilograms.

Example 5 (Commercial Tissue). A sample of tis® facial Kleenex (from Kimberly-Clark Corporation) was tested as discussed above. The tissue had a wet transfer time d 2. 0 seconds and a wet exterior area of 1.1 square inches Example 6 (Commercial Tissue). A sample of tis ® ® facial Kleenex Cold Care with a lotion facial tissue (strata) was tested as discussed above. The tissue had a wet transfer time of 15.1 seconds and a wet outer area of 1.3 square inches.

Example 7 (Commercial Tissue). A sample of tis® facial soft and strong Puffs was tested as discussed above The tissue had a wet transfer time of 8.1 seconds and a wet outside area of 1.0 square inches.

Example 8 (Commercial Tissue). A sample of tis® Facial Puffs Advanced Extra Strength was tested as discussed above. The tissue had a wet transfer time of 2 seconds and a wet exterior area of 1.2 square inches.

Example 9 (Commercial Tissue). A sample of tis ® -facial Puffs Plus was tested as discussed above. The tis had a wet transfer time of 6.8 seconds and a wet outdoor area of 0.9 square inches.

Example 10 (Commercial Tissue). A sample of tis® facial Scotties (3 strata) was tested as discussed above The tissue had a wet transfer time of 1.2 seconds and a wet exterior area of 0.8 square inches.

It will be appreciated that the foregoing examples, given for purposes of illustration, are not to be considered as limiting the scope of this invention which was defined by the following claims and all equivalents thereof.

Claims (14)

R E I V I N D I C A C I O N S

1. A soft tissue product having two or more layers, said tissue product has a module in the direction of the machine of about 30 kilograms or less, a wet outer surface of about 2 square inches or greater and its wet transfer time about 15 seconds or more.

2. The tissue product, as claimed in clause 1, characterized in that it also comprises a central layer.

3. The tissue product, as claimed in clause 1, characterized in that the wet outer area is about 3 square inches or greater.

4. The tissue product, as claimed in clause 1, characterized in that the wet outer area is about 4 square inches or greater.

5. The tissue product, as claimed in the. clause 1, characterized in that the wet outer area is from about 2 to about 6 square inches.

6. The tissue product, as claimed in clause 1, characterized in that the wet transfer time is around 20 seconds or more.

7. The tissue product, as claimed in clause 1, characterized in that the wet transfer time is around 30 seconds or more.

8. The tissue product, as claimed in clause 1, characterized in that the wet transfer time is about 45 seconds or more.

9. The tissue product, as claimed in clause 1, characterized in that the wet transfer time is from about 15 to about 60 seconds.

10. A soft tissue product having two or more layers and two faces facing outwardly treated topically with an amine-modified polysiloxane, said tissue product has a module in the machine direction of about 30 kilograms or less, an area wet exterior d about 2 square inches or more and a wet transfer time of about 15 seconds or more, wherein the amine-modified polysiloxane has the following formula: where x and y are integers > 0; The mole ratio of x to (x + y) is from 0.005 percent to around 25 percent; Rx, R3, R4, and R6-R9 are C or higher alkyl d substituents; R2 and R5 are C-L p greater alkyl, Cx or higher alkyl alcohol d or hydroxyl substituents; Y R10 is an alkyl chain of CS or more that comprises one or more functional groups selected from the group consisting of amine, imine and / or amide.

11. The tissue product, as claimed in clause 10, characterized in that Rxo comprises one or more amine groups separated by an alkyl chain of x major.

12. The tissue product, as claimed in clause 10, characterized in that the polysiloxane modified with amine is mixed with another modified polysiloxane of the formula: where x and y are integers > 0; The mole ratio of x to (x + y) is from 0. 005 percent to around 25 percent; R1 # R3, R4 and R6-R9 are Cx or higher alkyl substituents; R2 and Rs are x or higher alkyl, C or higher alkyl alcohol, or hydroxyl substituents; Y R1X is an alkyl chain or greater than or comprising one or more organic functional groups selected from the group consisting of ether, polyether, ester, amine, imine amide and the alkyl and alkenyl analogs of such functional groups.

13. The tissue product, as claimed in clause 12, characterized in that u is of the general formula -R12- (R13-0) a- (R14-0) b -R15; wherein R12, R13 and R14 are Cx or higher alkyl chains, R15 is hydrogen or a Cx-C4 alkyl group, and "a" and "b" are integers from 1-100.

14. A method for making a multi-strand tissue product of controlled absorbency, which comprises: a) forming an aqueous suspension of paper fibers; b) depositing the aqueous fiber suspension on a forming machine to form a fabric; c) drying the tissue to form a tissue sheet; d) combining the tissue sheet with one or more similar tissue sheet to form a multiple stratum tissue base sheet having two exterior surfaces; and e) topically treating both outer surfaces of the tissue surface with an aqueous emulsion of a modified polysiloxane co amine to form a tissue product, said tis product having a wet exit area of about 2 square inches or greater and a time of wet transfer around 15 seconds or more. SUMMARY The amine-modified polysiloxanes are applied to the opposing outer surfaces of a tissue product such as the two outer surfaces of a three-layer facial tissue, providing improved surface smoothness and a degree of hydrolybicity to prevent wetting of the tissues. liquids during use. However, the degree of hydrophobicity is controlled by the chemical structure of amine-modified polysiloxane and / or by mixing the amine-modified polysiloxane with a modified polysiloxane plus hydrophilic so that the liquid is still allowed to enter the tissue structure. in a reasonably short time to be absorbed by the central stratum, but the absorption and combination with the hydrophobicity of the other outer surface essentially retards that the liquid passes completely through the tissue product.