JP2001508503A - Tissue paper containing selectively placed chemical additives - Google Patents

Abstract

  (57) [Summary] A chemically reinforced paper structure having a discontinuous pattern of the chemical composition is disclosed. The paper structure has a cellulosic substrate, such as tissue paper. The substrate has a profile of two or more different heights. The chemical composition contains a chemical softener composition or a surfactant composition and is selectively positioned to fit well at one of the cellulosic substrate heights, preferably the higher height area. . This paper structure is suitable for use as a bath or toilet tissue.

Description

DETAILED DESCRIPTION OF THE INVENTION        Tissue paper containing selectively placed chemical additives                                Field of the invention   The present invention relates to a chemically strengthened paper comprising a cellulose substrate and a chemical papermaking additive. Regarding the structure. More specifically, the present invention relates to microsections having two or more different heights. A cellulosic substrate comprising a zone. Chemical papermaking additives have different paper structure heights It is taken in so as to match one of them well.                                Background of the Invention   Cells, such as toilet tissue paper, paper towels, and decorative paper Consumables made from loin substrates are an integral part of modern society. Typically, These products have important physical properties that should be considered acceptable to consumers Need to be The exact mixing of key properties and the absolute value of each property will vary with the nature of the product. Nevertheless, flexibility, wet and dry strength, absorbency, and aesthetics are still unbiased This is the desired property. Flexibility (softness) brings out a pleasant touch, and the product The product may become rough or abrasive when touched by skin or other sensitive surfaces. This is one aspect of the textile web that guarantees that it does not feel strange. Strength when used The ability of a structure to maintain the physical integrity of the structure. Absorbent fiber structure A property of the fibrous structure that gains body and maintains its fluid for an acceptable period of time. Aesthetics are defined by the consumer when the product is viewed alone or in the context of the product. It focuses on the psycho-visual reactions that occur.   The most common method for producing tissue paper products is wet papermaking. This In such a process, each fiber is first suspended in a slurry diluted with water. This The slurry then removes most of the water, leaving a thin, relatively uniform weight of the initial wafer. Placed on a perforated screen to form a tube. This initial web is then Various methods are used to form the finished tissue paper web. (Or) dried. As part of this process, the molded or dried web is , Usually glued to a drying drum and subsequently to give the desired properties At the drying equipment.   Many existing moisturized products are in the scope of the description above. For example Examples of webs that are soft, strong, absorbent, and have two or more different microregions: Lawrence H. Sanford, issued January 31, 1967. Sanfor d) and James B. Sison (Jamus B. Sisson) U.S. Pat. No. 6; Peter G. Ayes, issued August 10, 1976 rs) US Pat. No. 3,974,025; issued Nov. 30, 1976. George Morgan, Jr. ) And Thomas F. Rich ( Thormas F. Rich) U.S. Patent No. 3,994,771; March 4, 1980. Paul D. Trokhan Trokhan) U.S. Pat. No. 4,191,6. 09 and Paul D. Trokhan, issued on January 20, 1987. D. Trokhan) can be found in U.S. Pat. No. 4,637,859. These documents are characterized by a repeating pattern of high and low areas. are doing. The area with this height can be discontinuous or continuous. Low ward In the area, the web is used during papermaking using the pattern-conveying fabric or the protruding part of the belt. It was made by compressing locally.   Other bulky soft tissue papers are available on November 17, 1981 Jerry E. Karstens Carstens) U.S. Pat. No. 4,300,981 And R. Wells, issued April 3, 1984. R. Wells) and Thomas A. Hensler. Henster) U.S. Pat. 40,59 No. 7 discloses it.   Chemically composed of a cellulosic substrate with the characteristics of chemical fortification applied to it Reinforced paper structures are known in the prior art. For example, peeling to papermaking furnish Combining the use of an agent and a resilient release agent to avoid bulk compaction, Obtaining a high, soft, absorbent tissue paper, May 1974 J, L, Salvucci, Jr. issued on the 21st US Patent No. 3 , 812,000.   Chemical strippers, such as those intended by Salbakki, see above, and their kinetics The theory is, for example, a typical Friemark issued on August 28, 1973, etc. U.S. Pat. No. 3,755,220 issued May 29, 1974 to U.S. Pat. No. 3,844,880 to Meisel et al. U.S. Pat. No. 4,158,594 issued to Becker et al. It has been disclosed.   Tissue paper is treated with a cationic surfactant to further enhance flexibility For non-cationic surfactants. For example, departure September 25, 1990 U.S. Pat. No. 4,959,125 to Spendel in US Pat. Spendel, U.S. Pat. No. 4,940,51, issued Jul. 10, 990. No. 3 teaches using a non-cationic, preferably non-ionic, surfactant. Processing tissue paper enhances tissue paper flexibility A method for doing so is disclosed.   Tissue paper, especially bulky and patterned densified tissue paper The flexibility of the paper is enhanced by various reagents such as vegetable oils, animal oils, synthetic oils, and especially Can be improved by treating with a polysiloxane material, which is referred to as silicone oil It is known. For example, Ampurusky (A) published on October 22, 1991 See U.S. Pat. No. 5,059,282 to Mpulski). This Ann Pulsky's patent specification states that polysiloxanes can be used on wet tissue paper webs. A compound (preferably at a fiber concentration of about 20% to about 35%). The process is disclosed. These polysiloxane compounds are Gives a silky, soft feel.   The above methods generally produce acceptable product characteristics, but the product characteristics Can be further improved. However, the latest products and possible enhancements The method of making a finished product suffers from several disadvantages. For example, strong tissue The chemicals used in paper and paper webs are often diluted slurry of water and fibers. Added before the first deposition on the forming screen. This is additive additive It is a convenient and economical way to enter. However, absorption support or flexibility improvements Other chemicals, for the sake of goodness, are also used in the so-called wet ・ It is widely used to add to the end. Used for developing weight characteristics Because of the complex nature of each chemical, the chemicals are often contradictory Interact. These chemicals are mutually desirable on cellulose fibers. It can compete for the destructive properties inherent to clothing and even fibers. For example, flexible Chemicals that impart properties often reduce the natural tendency of the fiber to bind to other fibers. Thus, it reduces the functional strength of the resulting web. Chemical abstract The advantages of both the method and the product when paper additives are introduced at the wet end are both Keep it low.   Additives introduced at the wet end of the process must If so, it must be maintained by cellulosic fibers. this is To the ionic charge, most preferably the negative ionic charge inherent in cellulose. It is performed using a chemical having an attractive positive ionic charge. Web features Many additives that could improve the properties are not charged. like this If chemicals are introduced into the dilute fiber slurry at the wet end of the process, Conclusion As a result, the fibers are weakened, which exacerbates the interference problem described above.   Discloses a method for adding a powerful agent and softener to the wet end of the papermaking process Examples of such patent specifications include Phan and Ton issued on June 29, 1993. Trokhan U.S. Pat. No. 5,223,096 and 1993 U.S. Pat. No. 5,217,576 issued to Phan on June 8, 2008. . These wet-end steps typically involve the incorporation of strong and soft reagents. To any potential undesirable undesirable interactions of the drug. Do not prevent.   Another disadvantage of adding any chemical to the wet end of this process is that Will be distributed throughout the web if retained. Often active It is desirable to add only the components to the surface of the web. This is, for example, a lubricating soft material Is desired. Applying only to the surface guarantees efficient use of the material and for that reason Is because consumers only interact with the surface by contact. Suitable for surface The application may also include other materials, such as a strong additive that is best contained in the center of the sheet. Also prevents interference with excipients.   Chemical paper additives should be added to the cellulosic substrate to form a wet web Can also. For example, a chemical additive may be applied to a cellulose substrate from an aqueous solution of a drug. , Can be dried to form a chemically strengthened paper structure. Unfortunately The above method of adding a drug to a cellulosic substrate also provides a uniform or homogeneous This results in distribution. This uniform or homogeneous distribution of the drug is two tall To negate the performance advantages provided by the cellulose substrate having the above microscopic area Become.   The present invention overcomes all of the above disadvantages and provides desirable additional advantages. In particular, Adding functional chemicals in a manner consistent with the microscopic area of the cellulose can It has been found to maximize the performance advantages of paper with area. For example, described below As mentioned above, chemical softeners are used to enhance the function of the Optimally added to   Typically, the chemical composition is applied to the cellulosic substrate by spraying or printing. Is done. Unfortunately, it is difficult to spray chemical compositions onto substrates in precise patterns It is. Printing of chemical compositions on substrates is sharper and more precise than can be obtained by spraying Pudding with a raised pattern or gravure cell Need a troll. The printing roll with the rising protrusion and the gravure plate is Unless the pattern is particularly desirable for substrates such as capillaries, the added chemical The pattern of the composition is changed to the pattern corresponding to the projections of the print roll and the gravure plate. To be defined. It is also very important to match the pattern to be printed to the micro area of the substrate. Difficult.   The problem is that too many prints, one for each desired pattern, This can be solved by using rolls and gravure plates. However, such preparations are not If only short-term operation is desired, the cost of To the point where it becomes economically impossible to prepare a roll or gravure.   Therefore, tissue papers, especially those with a bulky and high density pattern, Predetermined micro-areas of tissue paper are applied to (1) a commercial paper machine, (2) Non-toxic and environmentally friendly (3) the desired tensile strength of tissue paper, using a gentle chemical composition; A method that can be implemented in such a way as to maintain its absorbency and low lint properties Is chemically desirable.   What is important is that according to the present invention, a functional chemical is added to a desired micro area. Enhances the desired functional properties without adversely affecting other properties It is possible. For example, increase tensile strength without adversely affecting flexibility. Or, alternatively, it can be soft without adversely affecting the tensile strength. Softness can be improved.   It is an object of the present invention to provide a soft and absorbent toilet paper product It is in.   It is an object of the present invention to provide a soft and absorbent cosmetic tissue paper product. To provide.   It is an object of the present invention to provide a soft and absorbent paper towel product.   An object of the present invention is to provide a cellulose substrate having two different heights. It has the above minute area, and incorporates the chemical papermaking additive to match this minute area. It is to provide a paper structure.   A further object of the invention is to provide flexibility, strength, absorbency and aesthetics or their properties Incorporates chemical paper additives into tissue paper to enhance the combination of To provide an improved process.   A further object of the present invention is to maximize the performance advantages of papers with multiple zones. Chemical papermaking to match the fine area of the tissue paper It is to provide an improved process for incorporating the agent.   The above and other objects will be described in detail below by using the present invention. As achieved.                                Summary of the Invention   The invention comprises a cellulose substrate, wherein the substrate has more than one height, Wherein the height defines a first pattern and the second height has a second pattern. It has a reinforced paper structure. Each height has one or more areas of cellulosic substrate . The non-migrating chemical paper additive is one that corresponds to one height of the cellulosic substrate. It is distributed to the above areas.   In a particularly preferred embodiment, the higher height corresponds to the discontinuity zone and the lower Corresponds basically to a continuous mesh portion. In this example, For example, chemical paper additives may be preferred, for example, for improved flexibility and / or absorbency. If intended above, it is distributed to the higher area of the discontinuity. Similarly, move No chemical paper additive is continuous low if e.g. intended to improve strength Can be added to the area. Further, as described in detail below, the chemical The mechanically reinforced paper structure is preferably through-air dried.                             BRIEF DESCRIPTION OF THE FIGURES   This specification concludes the claims, which particularly point out the invention and which clearly call for protection. It should be noted that the present invention will be described with reference to the following description in connection with the related drawings. I believe it will be better understood.   FIG. 1 shows a continuous cellulosic network and the discontinuous chemicals therein. With the location of the papermaking additive, a broken top view of the paper structure according to the present invention,   2 is a cutaway elevation view along line 2-2 of FIG. 1,   FIG. 3 is a schematic illustration of an elevation of one device used to manufacture the structure of the present invention.                             Detailed description of the invention   As illustrated in FIG. 1, a paper structure 20 chemically reinforced in accordance with the present invention comprises: Formed with a substantially flat cellulosic substrate and a chemical papermaking additive 24. Chemical papermaking Additive 24 is typically added to cellulose substrate 22 in the form of an aqueous solution as shown in FIG. available. Referring to FIG. 3, the solution 40 has a unique pattern on the cellulose substrate 22. Is given to Once the aqueous solution 40 has been added to the cellulose substrate, the chemical papermaking The moisture remaining in the cellulosic substrate together with additive 24 is ultimately Removed.   Referring again to FIG. 1, the cellulosic substrate 22 comprises a cellulosic structure, preferably This is a tissue paper web. Cellulose substrates have a basis weight and / or density And a number of different micro areas 34 and 38. This area 34 and 38 Arbitrarily disposed on the substrate 22 is such that the cellulose substrate 22 is visually flat. Acceptable as long as the chemical paper additive does not move in good agreement with each microarea .   The cellulosic substrate 22 according to the present invention is capable of forming two distinct densities. It has possible micro areas 34 and 38. Preferably, the areas 34 and 38 are An essentially continuous network 32 and discontinuities 36 within this essentially continuous network. Are arranged so as to be arranged as shown in FIG. As used herein, substantially Extending throughout the cellulosic substrate 22 in one or both of its major dimensions. Area 32 is considered to be "essentially a continuous mesh." On the contrary , Non-continuous areas 36 are considered "discontinuous." The discontinuous area 36 is Protruding outwardly to the far end of section 32, which essentially forms a continuous mesh Is out.   Preferably, the discontinuous area 36 and the essentially continuous mesh area 32 are non-uniform. It is arranged in a repeating pattern. By "not ragged", the area 32 And 36 are considered to be predictable and result from the production of known and predetermined features. It is considered to have resulted. By "repeat", putter The cellulose is formed more than once in the cellulose substrate 22. However, if When the lulose substrate 22 is provided to the consumer, it is relatively small and the pattern is comparable. If the large or paper structure 20 is provided to the consumer as an integral object, The pattern will appear to appear only once on the cellulose substrate 22. Better Preferably, areas 34 and 38 of cellulosic substrate 22 are dense and essentially continuous meshes. Area 32 and discontinuous low density areas 36 in this essentially continuous mesh area 32 Preferably, a discontinuous low density region 36 and an essentially continuous The mesh area 32 is on a different plane, as described below.   For the embodiments described herein, from about 2 to about 155 per square centimeter Meters of low density discontinuity 36 (10 to 1000 discontinuities per square inch) 36) (preferably those with a chemical papermaking additive), more preferably Is about 16 to 109 low density discontinuities 36 (100 Cellulosic substrates 22 having a discontinuity of 36 to 700 per square inch are suitable. Has been found to be true.   The cellulose substrate 22 according to the present invention has a contour with two or more different heights 26. I do. The “height” of the cellulose substrate 22 is a local deviation from a flat surface. The substrate height 26 can be adjusted by placing the substrate on a flat horizontal surface that acts as a reference surface. Required. The different heights 26 of the cellulosic substrate correspond to the different density zones 3 described above. 4 and 38, which may or may not match, the cellulose substrate 22 It is determined as the height difference in the direction above the reference plane and the reference plane perpendicular to the main dimension.   Preferably, the areas 34 and 34 defined based on different densities and different heights 26 and 38 match. Therefore, the discontinuous low-density area 36 also has a high From the density region 34, the height 26 increases. However, this is Suitable embodiments exist where the density discontinuity 36 does not match the specific density height 26 It should be recognized that it is possible.   The cellulosic substrate 22 according to the present invention is composed of cellulosic fibers. Of the other two relatively small dimensions (along the longitudinal axis of the fiber) And perpendicular to the longitudinal axis of the fiber). Very long, so the linearity is rough. If you examine the fiber with a microscope, It turns out that the other two dimensions are smaller than the main dimensions of the fiber, These other small dimensions need not be substantially equal and the fiber axis It does not have to be constant over the entire length. The important thing is that the fiber Bends around the fiber, bends against other fibers, and Thus, it is only dispersed on the papermaking net (or equivalent).   Cellulose substrate 22 may be shrunk and wrinkled as desired, Good. If the cellulosic substrate 22 shrinks and wrinkles, the substrate is essentially a continuous network. 32, it becomes a waveform in the Z direction and shrinks. With such a waveform, A wrinkle occurs, and the difference 26 in the height of the wrinkle corresponds to the height difference 2 obtained in the dimensions described later. Compared to 6, it is considered very small. However, this does The attached cellulose substrate 22 has a height higher than the crepe-processed corrugations and small corrugations. Embossing, through-air drying, etc. may be performed to create the low difference 26. Shrinkage An example of a method for producing a tissue paper product which has been through-dried without processing is disclosed in January 1995. Kimberly-Clark Corporation's European Patent Application No. 677 611 A2, which is hereby incorporated by reference. Included in the description. Such a structure that is air-dried without shrinkage and wrinkles, Suitable for practicing the invention.   Fibers composed of cellulosic substrate 22, such as polyolefins or polyesters Synthetic fibers may be used, but preferred are cotton linters, rayon or bagasse. Cotton linters, more preferably soft wood (zoosperms or conifers) or hardwood Wood pulp such as high quality wood (angiosperms or deciduous trees). A material obtained by combining a material and a cellulose material may be used. As used herein In other words, the cellulose substrate 22 is not limited to the above-listed fibers. If it has 0 weight percent or more, or 50 volume percent or more, Loin. " Length about 2. 0 to about 4. 5mm, diameter about 2 5 to about 50 millimeter softwood fiber and less than about 1 millimeter in length Wood pulp fiber comprising hardwood fiber having a diameter of about 12 to about 25 mm Is found to be easy to use for the cellulose substrate 22 described below.   If wood pulp fibers were selected for the cellulosic substrate 22, the fibers Fibers are treated with chemical methods, such as the sulfite, sulfate, and soda methods, and Manufacture using any pulp manufacturing method, including mechanical methods such as ground wood Can be. Alternatively, the fiber may be manufactured by a combination of chemical and mechanical methods, or Is good for recycling. The type, combination and treatment of the fibers used It is not fatal.   The cellulose substrate 22 according to the present invention is microscopically flat in two dimensions, It has a certain thickness in the dimensional direction. However, this third dimensional thickness is initially Cellulose substrate with relatively large or initial two-dimensional dimensions compared to the two-dimensional dimensions of Compared with the production capacity of No. 22, it is relatively small.   Cellulose substrate 22 according to the present invention may have a single layer, May be stratified according to the type. However, it should be recognized that the present invention Any or all two or more monolayers made on the basis of In other words, they may be connected so as to face each other.   Of course, it should be recognized that the woven or non-woven material must meet the stated density requirements. In order to satisfy the above, it can be appropriately used as the cellulose substrate 22. .   Cellulose substrate 22 having zones 34 and 38 of different densities can be made by well-known conventional techniques. By locally increasing the density of an area by embossing, or Vacuuming or releasing pressure into a suitable mold after air drying as is well known in the art It may be obtained by reducing the density of a certain area. This Similarly, they have different heights 22 in a direction substantially perpendicular to the plane of the cellulose substrate 22. The cellulose substrate 22 can be embodied by embossing as is well known in the art, As is well known in the art, vacuum is applied after air drying or pressure is released into a suitable mold. The method may be used again to implement the method.   Preferably, the chemically reinforced paper structure of the present invention is through-dried. In particular A preferred through-dried cellulosic substrate 22 is disclosed in Jul. 16, 1985 It is manufactured on the basis of Rokuhan U.S. Pat. No. 4,529,480. This U.S. Pat. The purpose of indicating the through-dried cellulose substrate 22 and different heights 26 The purpose of the present invention is to provide a method for making a particularly preferred cellulose substrate 22 in accordance with the present invention. For reference, are incorporated herein by reference. Trokhan in U.S. Pat. Cellulose substrates 22 made according to 529,480 correspond to one another. It has a discontinuity zone 36, both of which are relatively low in density and increase in height 26. Increase (or decrease).   The cellulosic substrate 22 preferably has a height difference between the different areas 34 and 38. Is about 0. 13 millimeters (0. 005 inches). This height 26 is As is well known, a microtome mirror or stereoscopic three-dimensional sweep without pressure limitation It is measured using an image of an electron microscope mirror.   The chemical papermaking additive 24 may be added to the cellulose substrate in an aqueous solution, emulsion, or suspension. It is added in the form of turbidity. For example, the aqueous solution 40 containing the chemical papermaking additive 24 , As shown in FIG.   The specific type of chemical papermaking additive 24 depends on the type of chemical papermaking additive 24 desired. Applied to the turn and does not move, and therefore flows into and transfers to different parts of the cellulose substrate. Make the desired pattern (like a uniform coating) without moving the line or other movement Unless altered to impair the useful placement of the papermaking additive 24, the present invention Is not fatal. Chemical papermaking additive 24 can be used during drying, even in dry conditions. Preferably, it does not move when wet.   Referring to FIG. 2, the aqueous solution 40 containing the chemical papermaking additive 24 is preferably Is applied to the discontinuous low density area 38 of the cellulose substrate 22 in a predetermined pattern. It is arranged so that it does not move overlapping the area. Other patterns, such as cellulose based Substantially only one major dimension of the texture 22 (ie, longitudinal, lateral, or diagonal thereof) Semi-continuous pattern forming lines extending over the entire line) is possible, but discontinuous A pattern having the chemical papermaking additive 24 located only in the low density region 38 is preferred. In this preferred embodiment, the relatively dense areas are the non-moving chemical papermaking additives. 24 are substantially absent.   Referring again to FIG. 3, a chemically reinforced paper structure according to the present invention is shown in the illustrated device. It may be made using the device 50. The illustrated device 50 has three axially rotatable rotors. 52, 54 and 56, preferably mutually parallel longitudinal axes, metalling rolls 52, a transfer roll 54, and an anvil roll 56 . The three rolls 52, 54 and 56 form a nip 58 and a gap 60. A nip 58 is provided between the metering roll 52 and the transfer roll 54. You. Gap 60 is between transfer roll 54 and anvil roll 56 .   The metering roll 52 is provided on a reservoir 62 of the liquid reservoir 40. Labia Roll. The axial rotation causes metering roll 52 to move Of the cells of the metering roll 52 by means of the collector blade 41. The liquid precursor 40 is received from a reservoir 62 for precisely leveling the filling, Later, a specific amount of the aqueous solution 40 is sent to the transfer roll 54. Cellulose group The material 22 is formed of a transfer roll 54 uniformly coated with the aqueous solution 40 and an ambience. Pass between Le Rolls 56. Applying aqueous solution 40 containing chemical papermaking additive 24 Significantly contoured areas 36 and 38 of the cellulosic substrate 22 to be sought Together with the remainder of the cellulose substrate 22 on the anvil roll 56, Projecting in the direction of the transfer roll 54, Contact. As will be apparent to those skilled in the art, the transfer roll 54 and the By increasing or decreasing the clearance of the clearance 60 of the invil roll 56, a small amount and a large amount The component 40 of the aqueous solution is applied to the contoured raised area of the cellulosic substrate 22 as described above. Print by contacting the transfer roll and the anvil roll respectively. , Can be applied. Similarly, the shape of the metering roll 52 is changed. e Then, the amount of the aqueous solution 40 applied to the cellulose substrate 22 is changed at a certain gap 60. be able to. Alternatively, it is clear that the aqueous solution 40 is By spraying, immersing the transfer roll 54 in the aqueous solution 40, etc. Application, thereby eliminating the need for metering rolls 54, or Of the gap 60 formed between the tarling roll 52 and the anvil roll 56 By printing directly from the metering roll 52 to the substrate 22 in the aqueous solution May be given to the transfer roll.   Cellulose substrate 22 comprises transfer roll 54 and anvil roll 56. When passing through the gap 60, the aqueous solution 40 contacts the outer edge of the transfer roll 54. Only those areas of the cellulosic substrate that have a height 26 sufficient to apply. Tran The spur roll 54 is on an anvil roll 56 of the cellulosic substrate 22. Do not touch parts. Therefore, these portions of the cellulose substrate 22 are 0 does not apply.   By adjusting the gap 60, different amounts of the aqueous solution 40, and finally the dried The applied chemical papermaking additives to the raised areas of the cellulose substrate 22. Can be. Generally, for the embodiments described herein, the discontinuity 36 Aqueous solution applied within the range of about 1 to 500 milligrams per square centimeter 40 has been found to be suitable.   Once the cellulose substrate 22 to be used for the paper structure 20 is selected based on the behavior of the consumer If so, the benefits will become apparent. In particular, different areas 34 and 38 of height 26 (1 One area 34 contacts the anvil roll 56 and the other area 38 The cellulose substrate 22 according to the present invention (with contact with the roll 54) Offers some advantages not offered. First, contains chemical paper additive 24 Having a special pattern of aqueous solution, such as gravure pattern or radially extending protrusions Cellulose substrate 2 without the need for transfer rolls 54 for transfer. 2 Can be arranged. Typically, a metering roll with a pattern 54 is more difficult and costly to manufacture than a plain metering roll 54 Take it.   A second advantage of the present invention is that it has flexibility, and this flexibility is For those who may not want to use the transfer roll 54, the chemical papermaking Match the pattern to the area of the cellulose substrate 22 where the additive 24 is to be applied That you can do it. Such a match, even under ideal manufacturing conditions This can be extremely difficult to achieve, as different areas of the cellulosic substrate 22 It occurs almost exclusively on a microscopic scale. Actual production is even more complicated, The reason is that the pitch of the different areas 32 and 36, and thus the chance of a mismatch, is due to the substrate 2 2 as it is pulled through the device 50, the basis weight of the cellulosic substrate 22, And other manufacturing parameters. Explained in FIG. The production of the present invention by the process involves the chemical papermaking additive 24 Make sure that it fits exactly into the area.   Third, a change in the pattern of the chemical papermaking additive 24 applied to the cellulose substrate 22 is desired. In one case, one with a transfer roll 54 with a smooth outer edge and no pattern The device 50 can be used for multiple patterns. Have different contours Cellulose substrate 22 is placed between transfer roll 54 and anvil roll 56. It is inserted into the gap 60 and the gap of the gap 60 appropriately adjusted. transfer· Roll 54 is obtained with a smooth surface and a mere change of cellulose substrate 22. The preparation of any desired pattern to be performed can be continued. Once the specific cellulose Once the substrate 22 is selected, such flexibility in manufacturing is not available in the prior art. Is not something.   Several modifications based on the present invention are possible. For example, if desired, basically A continuous mesh area 32 and a discontinuous area 36 that varies based on basis weight rather than density. A lulose substrate 22 can be made. If such a cellulose substrate 22 is selected US Patent No. to Johnson et al., Issued April 30, 1985, No. 4,514,345, or Trokhan published on September 14, 1993. khan) et al., U.S. Pat. No. 5,245,025. The two patents describe cellulose having different areas based on basis weight. Is incorporated herein by reference for the purpose of indicating how to make substrate 22 . Alternatively, a plurality of different heights 26 above (or below) an essentially continuous mesh area 32 Is feasible. The chemical component 24 has a specific minimum height 2 6 or only in discrete amounts 3 depending on the height. 6 can be applied.                             Chemical papermaking additives   Used for multi-elevational tissue paper of the present invention The chemical papermaking additive for making is preferably a strong additive, an absorbent additive, Selected from the group consisting of agents, aesthetic (texture) additives, and mixtures thereof It is. Each of these types of additives is described below. A) Powerful additive   The strong additive is a permanent wet strong resin, a temporary wet strong resin, a dry strong additive, and, It is selected from the group consisting of these mixtures.   Where permanent wet strength is desired, chemical papermaking additives may include the following groups of chemicals: I.e., polyamide epichlorohydrin, polyacrylamide, insolubilized Polyvinyl alcohol; urine formaldehyde; polyethylene imine; Selected from Tosan polymer. Polyamide epichlorohydrin resin is a cation A wet strength resin, which has been found to be particularly useful. Suitable type Such resins are disclosed in US Pat. No. 3,700,623 issued Oct. 24, 1972. And U.S. Pat. No. 3,772,076 issued Nov. 13, 1973. Light Both patent specifications are directed to Caim. , Incorporated herein by reference. Useful polyamide epichlorohydride One commercial source of phosphorus resin is Hercules I, Willington, Delaware. nc, under the trade name (Kymeme) 557H. Such resins are commercially available.   Polyacrylamide resins have also proven useful as wet strength resins . These resins are disclosed in U.S. Pat. No. 3,556,932, and Williams (W. U.S. Pat. No. 3,556,933 to U.S. Pat. The specification is incorporated herein by reference. Polyacrylamide resin One commercial source is American Cyanamid, Sanford, Connecticut The company has purchased one such resin under the trade name of Parez 631NC (registered trademark). It is commercially available under the registered trademark.   Still other water-soluble cationic resins that have found utility in the present invention are urea-phophores. Formaldehyde and melamine formaldehyde resins. These multifunctional More common functional groups on resins are amino groups and methylol groups bonded to nitrogen. Nitrogen-containing functional groups. Polyethyleneimine type resins are also useful in the present invention. It is.   If temporary wet strength is desired, the chemical paper additive may be a chemical from one of the following groups: That is, a cationic dialdehyde starch-based resin (for example, Nippon Carlit Co., Ltd.) Manufactured by Caldas, National Starch 78-0080 or Cobond 1000, Are manufactured by National Starch and Chemical Corporation ) And dialdehyde starch. Improved starch temporary moisture Wet strength resin is also disclosed in U.S. Pat. No. 4, issued to Solarek et al. , 675, 395, incorporated herein by reference. Have been. A preferred temporary wet strength resin is Bjorkqu, published January 1, 1991. ist), including the resins described in U.S. Pat. No. 4,981,557; Thus, it is incorporated herein. Another example of a preferred temporary wet strength resin is Pal Parez® 750B, which is commercially available from SciTech. An improved polyacrylamide resin.   If dry starch is desired, the chemical papermaking additives may include the following groups of chemicals: Polyacrylamide (e.g., American Shea, Wayne, NJ) A combination of Namido Cipro 514 and Axo Strength 711); starch (eg, Corn starch or potato starch); polyvinyl alcohol (eg Airbol 540, manufactured by Air Products Inc, Allentown, Lubania); Guar or locust bean gum; and / or carboxymethyl cellulose (For example, Aqualon CM from Aqualon, Wilmington, Del.) CT). In general, any suitable Starch is characterized by its water solubility and hydrophilicity. Exemplary starch material The ingredients are corn starch, but are not intended to limit the range of suitable starch materials, and Potato starch, a waxy corn industrially known as amioca starch -Starch is particularly preferred. Amioka starch is common corn starch The difference is that Amioka starch is completely amylopectin, whereas Corn starch contains both ampropectin and amylose is there. The various unique properties of Amioka starch are described in H. Shopmeyer (H. H. Schopmeyer); "Amika-starch from waxy corn"; Industry December 1945, pp. 106-108 (Vol. Pp. 1476-1478) ). The starch is preferably granular, but granular or dispersed. Can be shaped. This starch is boiled enough to induce swelling of the particles. Is preferred. More preferably, the starch particles are separated from the starch particles by boiling or the like. Scattered Swell to just before. Such highly swollen starch particles are “sufficiently boiled” Should be referred to as Dispersion conditions are generally starch particle size, particle crystal It can vary depending on the degree of oxidation and the amount of amylose present. sufficient Boiled amioca starch is, for example, a water-soluble slurry having a starch particle concentration of about 4%. By boiling at about 190 ° F. for about 30 to about 40 minutes. Can be adjusted. Other available exemplary starch materials are available from National Ann. Entered from De Chemical Company (Bridgewater, NJ) It has a group containing nitrogen, such as an amino group and a methylol group attached to the nitrogen. The modified cationic starch as modified. Such modified starch Up to now, flour materials have mainly been pulp for increased wet and / or dry strength. Used as finished sample additive. However, tissue and tissue When applied to paper webs, these are the same modified starch material wet -Has a reduced effect on wet strength with regard to endo addition. Such modified starch material The latter has generally been preferred because of the belief that the ingredients are more expensive than unmodified starch. This These wet and dry strength resins are added by the process described in the present invention. It may be added to the pulp furnish. It is important to understand that pulp furnish The addition of chemical compounds, such as the wet strength and temporary wet strength resins described above, is useful in the present invention. It is optional and not essential for the implementation of the development That is.   Strong additives may be added alone to the tissue paper web, In addition to, before, after or after the addition of the absorptive and / or aesthetic additives Is also good. Drying of other sheets under the same conditions except for binderless treatment More than an effective amount of a strong additive to control Preferably, starch is added to the sheet. Preferably, about 0 of the strong additive . 01% to about 2.0% is retained on the dry sheet calculated on a dry fiber weight basis More preferably, about 0.1% of the strong additive material, preferably starch-based. 1% to about 1.0% is retained. B) Soft additives   Chemical softening additives include lubricants, plasticizers, cationic release agents, non-cationic release agents, And mixtures thereof. In the present invention, as a softening additive Suitable release agents for all applications are related to the preference for cationic surfactants. It contains both thione and a non-cationic surfactant. Non-cationic surfactant Contains anionic, nonionic, and zwitterionic surfactants. Preferably The surfactant does not substantially migrate to the old position after tissue paper production, Tissue paper that may otherwise result from the inclusion of surfactants This is for preventing the characteristics of the above from changing after production. This includes, for example, storage, shipping, The use of surfactants that have a higher melting temperature than commonly encountered at the time of sale, And use of embodiments of the tissue paper of the present invention; Higher melting temperatures.   Tissue paper web to achieve the flexibility and tensile strength benefits mentioned above The amount of non-cationic surfactant added to the product depends on the constant tensile strength of the final product. Correspondingly, from the lowest effective level required to provide such benefits to about 2%; From about 0.01% to about 2% of the non-cationic surfactant is retained on the web; More preferably from about 0.05% to about 1.0%; most preferably not more than about 0.05% About 0.3%. The surfactant is preferably an alkyl chain having 8 or more carbon atoms. Have Exemplary anionic surfactants are linear alkyl sulfonates, and And alkylbenzene sulfonates. Exemplary nonionic surfactants are Roda Inc. Crodesta (Cro) available from New York, NY desta) ® alkyl diluents including alkyl glycoside esters; 19 U.S. Pat. No. 4,011, issued to W.K. Langdon et al. No. 389, alkyl diluent ethers; Glyco Chemicals, Inc. Pegosperse® 200 available from (Greenwich, CT) Alkyl polyethoxyl esters such as ML; available from Shell Chemical Company Alkyl polyethoxyl ethers such as Nono Neodol R25-12 and S Tell; ICI America Inc. Sorbitan such as Span 60 available from the company Esters and ethoxyl sorbitanes, also available from ICI America Ter, propyl sorbitan ester, ethoxyl and propoxyl sorbitan Sterol mixture, and polyethoxysorbitan alcohol. Alkyl poly distribution Glycosides are particularly preferred for use in the present invention. The example fields listed above Surfactants are merely exemplary in nature and limit the scope of the invention. It does not mean.   Any surfactant other than a chemical papermaking additive for emulsifying surfactant materials will be Referred to as `` surfactants '' and present as an emulsifying component of emulsified chemical papermaking additives Any surfactant that will be referred to hereinafter as an "emulsifier". Surfactant is a tip Paper, alone or simultaneously with, after, or with other chemical papermaking additives. There is no problem even before the addition. In a typical process, if other additives are present, The surfactant is added to the cellulosic substrate at the same time as the other additives. Also, phosphorus Text with a relatively low concentration of binder to control the coating and / or increase tensile strength. It may be desirable to treat a release agent containing tissue paper. You. As used herein, the term "binder" is used to refer to any of a variety of previously known types. Referenced as dry and wet strength additives. If used, remove the binder. At the same time, after, or before the release agent or absorbent aid, Added to the paper. Preferably, the binder is exfoliated on tissue paper Agents (eg, this binder is a diluent added to tissue paper webs) (Contained in the aqueous solution).   If a chemical softener that acts mainly to give a smooth feeling is desired Then, the softener is the next group of chemicals, namely organic materials (such as inorganic oils). Material, or wax such as paraffin or carnuba, or lanolin), and poly Siloxane (Ampulski US Pat. No. 5,059,282) Such as compounds described herein and incorporated herein by reference. ). Suitable polysiloxane compounds for use in the present invention Details are described below.   Tissue paper to get the above softness and slippery benefits ・ The degree of polysiloxane compound added to the web will depend on the constant tensile strength of the final product. As a criterion, dry starting from the minimum effective amount required to achieve the benefits described above It is in the range of up to about 2% by weight, preferably about 0.01% to About 2% of the siloxane compound is retained on the web, more preferably about 0.02% To about 1.0%, most preferably from about 0.03% to about 0.3%. You. The polysiloxane compound preferably has siloxane weight units of the structure You. Where R₁And R_TwoIs an independent siloxane monomer unit, Each independently represents hydrogen or any alkyl, allyl, alkenyl, alkaryl, araki , Cycloalkyl, hydrocarbon halogen compounds, or other functional groups Can be. Any of such functional groups may be substituted or unsubstituted. Attention Functional group R of any monomer unit₁And R_TwoIs the corresponding of the next adjacent monomer unit. The functionality may be different from the above. In addition, polysiloxanes are linear, branched It may have a chain or ring structure. Functional group R₁And R_TwoHasa In addition, it can independently be another silicon functionality, such as, for example, a limited one. But not siloxane, polysiloxane, silane, polysiloxane, etc. . This functional group R₁And R_TwoAre, for example, alcohols, carboxylic acids, aldehydes, And may contain any of a variety of organic functionalities, including amine and amide functionalities. And a reactive silicon compound. Exemplary alkyl groups are methyl, d Tyl, propyl, butyl, pentyl, hexyl, octyl, and These are similar groups. Exemplary alkyl groups are vinyl, allyl, and Is a group similar to Exemplary allyl groups are phenyl, diphenyl, naphthyl And similar groups. Exemplary alkaryl groups are benzyl, alpha Phenylethyl, betaphenylethyl, alphaphenylbutyl, and These are similar groups. Exemplary cyclic alkyl groups are cyclobutyl, cyclope An alkyl group, a cyclohexyl group, and similar groups. Exemplary halogen Fluorinated hydrocarbon groups include chloromethyl, bromoethyl, ethyl tetrafluoride, and ethyl fluoride Group, ethyl trifluoride group, ethyl trifluoride group, oxylyl hexafluoride group, and the like. A similar group. References disclosing polysiloxanes include March 1, 1958. Gien, U.S. Pat. No. 2,826,551, issued 1 day, 1976 U.S. Pat. No. 3,964,500 to Drakoff, issued on June 22. U.S. Patent No. 4,364,83 to Pader, issued December 21, 1982. 7, U.S. Patent No. 7, issued Oct. 22, 1991, Ampulksi et al. Patent No. 5,059,282 and Wools issued on September 28, 1960 There is Woolston UK Patent No. 849,433. All these patents Incorporated herein by reference. Further incorporated by reference herein. Petrarch Systems Inc. (1984) There are pages 181 to 217 of silicon compounds published in the year 2000. The entire Sun is described in detail.   If a chemical softener having the function of mainly giving plasticity to the structure is desired, The softener is replaced by the next group of drugs, namely polyethylene glycol (e.g., PEG 400); dimethylamine; and glycerin Can be.   If a cationic softener whose main function is release is desired, the next group of chemicals That is, a positive quaternary ammonium compound (dimethylated tallow Dimethylammonium (DTDMAMS) or dihydrogenated tallow Umchloride (DTDMAC), both of Witco, Greenwich, Connecticut ・ Manufactured by Corporation; Verocel 579 (Stenungsund, Sweden) (Manufactured by Eka Novell, Inc.); incorporated herein by reference. No. 4,351,699 to Osborn and US Pat. No. 4,447,294; and / or DTDMM S or a diester derivative of DTDMAC).   In particular, quaternary ammonium has the formula:           (R₁)_4-m-N⁺-[R_Two]_mX^-   here   m is 1 to 3;   Each R₁Is C₁Or C₈Alkyl group, hydroxyalkyl group, hydrocarbyl Or a substituted hydrocarbyl group, an alkoxylated group, a benzyl group, or A mixture of these;   Each R_TwoIs C₉Or C₄₁Alkyl group, hydroxyalkyl group, hydrocarbyl Or a substituted hydrocarbyl group, an alkoxylated group, a benzyl group, or A mixture of these; and   X^-Is any softener-compatible anion suitable for use in the present invention. You.   Preferably, each R_TwoIs C₁₆Or C₁₈Alkyl groups, most preferably each R_TwoIs straightforward Chain C₁₈Is an alkyl group. Preferably R₁Is a methyl group, and X^-Is chloride or Is methyl sulfate. Optionally, R_TwoSubstitutes should be derived from vegetable oils Can be.   Quaternary ammonium compounds with ester function that can be reduced to soil by decay Has the formula:           (R₁)_4-m-N⁺-[(CH_Two)_n-Y-R_Two]_mX^-   here   Each Y = -O- (O) C- or -C (O) -O-;   m = 1 to 3; preferably m = 2;   Each n = 1 to 4; preferably n = 2;   Each R₁Is a short chain C₁Or C₆, Preferably C₁Or C_Three, Alkyl group Is, for example, a methyl group (most preferred), an ethyl group, a propyl group, and mixtures thereof. A hydroxyalkyl group, a hydrocarbyl group, a benzyl group or a Mixed,   Each R_TwoHas a long chain and is at least partially unsaturated (more than about 5 and less than 100 IV, from about 10 to about 85 IV) hydrocarbyl, or substituted A hydrocarbyl substituent and a counterion, X^-Is mutually soluble with any softener Any anion of the ability, such as acetate, chloride, bromide, methyl Sulphate, formate, sulphate, nitrate and the like.   Preferably, most of the R_TwoHas 18 to 24 carbon atoms (C₁₈-C_{twenty four}) Chain Of 90% or more aliphatic acyl groups. More preferably, most of the R_TwoIs charcoal Prime number 18, carbon number 22 (C₁₈, C_{twenty two}), And mixtures thereof at 90% or more. Selected from the group consisting of aliphatic acyls.   Other types of suitable quaternary ammonium compounds are published December 12, 1995. Kimberly-Clark Corporation, European Patent No. 0 688 911 No. A2, which is hereby incorporated by reference. Has been captured.   Tertiary amine softener compounds can also be used in the present invention. Suitable tertiary amine soft An example of a softener is James River Corporation, issued March 21, 1995. No. 5,399,241 to James River Corp. And this US patent is incorporated herein by reference. C) Absorbent additive   If an absorption enhancer is desired to enhance the rate of absorption, the enhancer may be Chemicals, ie, polyethoxylates (eg, PEG400); alkyl ethoxyls Esters (eg Pegosperss 20 available from Lonza Inc.) 0ML); alkyl ethoxyl alcohols (eg, Neodol); Rupoliethoxylinonylphenol (for example, Lone Pollenk / GAF) Igepearl CO), ethoxylate trimethylpentanediol, and / or Spendel U.S. Pat. Nos. 4,959,125 and 4,944. No. 5,513, which can be selected from the materials described in US Pat. Patent specifications are incorporated herein by reference. Surfactants, release agents, If the softener reduces wetting, apply a wetting agent, such as a second surfactant, It may be added to the liquid. For example, for the production of soft wettable paper, sorbita Mixing stearic acid ester with alkyl polyethoxyl alcohol Can be.   Water-soluble polyhydroxy compounds can also be used as absorption enhancers and / or wetting agents Noh. Examples of suitable water-soluble polyhydroxy compounds for use in the present invention Are glycerol, polyglycerol having a weight average molecular number of 150 to 800, and And a weight average molecular weight of about 200 to about 400, preferably about 200 to 1000. , Most preferably, 200 to 600 polyoxyethylene and polyoxypropylene. There is Len. Polyoxyethylene having a weight average molecular weight of about 200 to about 600 is Particularly preferred. The above-mentioned polyhydroxy compounds may be used. For example, glyce Mix of roll and polyglycerol, mix of glycerol and polyoxyethylene Substances, mixtures of polyglycerol and polyoxyethylene, etc. are useful in the present invention. It is. Particularly preferred polyhydroxy compounds are those having a weight average molecular weight of about 400. Lioxyethylene. This material is a trademark of "PEG-400" Commercially available from Union Carbide, Durban, Ga.   If an absorption enhancer is desired to reduce the rate of absorption, the absorption enhancer should be Product, i.e., an alkyl ketene dimer (e.g., Wilmington, Del.) Aquapel R360XC Emuljo manufactured by Hercules Emulsion); Fluorocarbon (for example, a 3M company located in Minneapolis, MN). Chigard), hydrophobic silicon (e.g., Dow Corni, Midland, Michigan) PDMS DC-200 manufactured by Co., Ltd.), fluorinated telomers (for example, Delaware). Zonil 7040) manufactured by DuPont of Wilmington, Alaska, etc. You can choose.   Absorbent additives can be used alone or in combination with strong additives. Lees Flour-based strong additives are seen as preferred binders for use in the present invention. I've been out. Preferably, the tissue paper is treated with an aqueous starch solution . In addition to reducing the fuzziness of finished tissue paper products, low Concentrations of starch are also likely to be produced by the addition of high concentrations of starch. Toughness) without increasing the tensile strength of tissue paper Let This is also the case for tips that have been increased in strength by conventional methods of increasing tensile strength. Ash paper, for example by increasing the refining of pulp, or other dry The strength and softness of the sheet are higher than those of the sheet whose tensile strength has been increased by the addition of additives. sex Provide tissue paper with improved (softness) relationship. The result is Applications where starch has traditionally not made softness a critical property, such as cardboard, sacrificing flexibility This is surprising because it was used to increase the strength of the steel. In addition, starch is added to printing paper or writing paper to improve surface printability. Used as a filler. D) Aesthetic (feel) additives   If an aesthetic additive is desired, the aesthetic additive may comprise the following group of drugs: , Inks, dyes, fragrances, opacifiers (such as TiO_TwoOr calcium carbonate), increased fluorescence It can be selected from whitening agents, and mixtures thereof.   Paper texture can also be improved using the method described in the present invention. ink , Dyes and / or fragrances are subsequently added to the tissue paper web It is preferably added to the water-soluble components to be added. Aesthetic additives can be used alone or It may be added in combination with soft and / or strong additives.                                  Analytical method   As used herein, the amount of treatment chemicals retained on the tissue paper web The analysis can be performed in any manner permitted by the prior art. For example, tee The concentration of polysiloxane retained in the paper can be adjusted using an organic solvent. Solvent extraction of polysiloxane followed by atomic absorption spectroscopy It can be measured by determining the concentration of silicon in the liquid, a nonionic surfactant, For example, the concentration of alkyl glucoside can be extracted with an organic solvent, followed by gas chromatography. Can be measured by determining the concentration of surfactant in the extract The concentration of on-surfactant, e.g. linear alkyl sulfonate, is extracted with water and subsequently The concentration of starch can be measured by colorimetric analysis of the extract. Decomposes to glucose with milases and then uses colorimetric analysis to determine glucose concentration Can be measured. These methods are exemplary, and tissue pages Others useful for determining the concentration of a particular component held by par It does not mean the exclusion of the law.   The hydrophilicity of tissue paper is generally due to the wetness of tissue paper. We refer to it as a tendency. The hydrophilicity of tissue paper is By determining the length of time it takes for the paper to completely wet the paper Can be quantified to some extent. This length of time is referred to as "wetting time". Wet For the purpose of performing consistent and reproducible tests of the wet time, The following procedure can be used for the Approximately 11.1 cm x 12 cm (about 4/3/8 inch x 4/3/4 inch) Saved sample unit sheet (test paper samples Environmental conditions are 23 ± 1 ° C, as specified in Method T402 of the TAPPI standard. Secondly, fold it four times so that the corners are adjacent to each other. From about 1.9 cm (about 0.75 inches) to about 2.5 cm (about 1 inch) Third, rub the spherical sheet into distilled water of 23 ± 1 ° C. Fourth, start the timer immediately on the surface of the main part, and fourthly, wet the spherical sheet. When the timer is completed, stop the timer and read the time. Completion of wetting is a visual observation .   The preferred hydrophilicity of a tissue paper depends on its intended end use. For tissue paper used in various applications, such as toilet paper Once the toilet is flushed, it takes a relatively short time to prevent clogging. It is desirable to be completely wetted. Preferably, the wetting time is no more than 2 minutes. More preferably, the wetting time is 30 seconds or less. Most preferably, the wetting time is 1 It is 0 seconds or less.   The hydrophilic properties of the embodiments of the tissue paper of the invention are, of course, measured immediately after production. May be specified. However, the substantial increase in hydrophilicity After the first two weeks after production, ie following the production of the tissue paper, Occurs after two weeks. Therefore, the above-mentioned wetting time is preferably At the end of two weeks. Therefore, at the end of the two week period at room temperature, The wet time is referred to as the "two week wet time".   The density of tissue paper, as this term is used herein, is Divide the basis weight (mass / unit area) of the paper by the thickness and use the appropriate This is the average value of the density calculated by performing various unit conversions. Tissue paper thickness As used herein, the compressive load of this paper is 15.5 g / cm.^Two (95g / in^Two) Is the thickness when receiving. A suitable instrument for the measurement is a pencil Twing Albert in Zip Code 19154, Philadelphia, Vania -Thickness gauge model 89-100 manufactured by Instrument Company.   The following examples illustrate the practice of the invention, but are intended to limit the invention. It is not intended.                                   Example 1   Prototype scale fourdrinier wiremaking is used in the practice of the present invention. NSK (Northern region Conifer crafts from the United States (eg, Weyerhaeuse, Tacoma, WA) r)) Grand Prairie supplied by Corporation )) 3% by weight of water-soluble slurry is made in a conventional repulper I can do it. Temporary wet strength resin (i.e., National, New York, NY) Nationals marketed by Le Starch and Chemical Corporation Le Starch 78-0080) at a rate of 0.75% by weight of dry fiber At NSK Stock Pipe). Temporary wet strength resin for NSK fiber Adsorption is enhanced with an in-line mixer. This NSK slurry is Dilute to a concentration of about 0.2% with a pump. Eucalyptus trees (for example, Aracul of Brazil 3% by weight aqueous slurry of Aracruq fiber is used in conventional repulpers I can do it. This eucalyptus slurry is concentrated with a fan pump. Diluted to about 0.2%. The components of each furnish are separated by a separate layer in the head box. That is, eucalyptus fiber is sent to the outer layer and NSK is sent to the inner layer. Are deposited on the fourdrinier wire to form the webs, each layer corresponding to a basis weight. Prolapse Water occurs on the fourdrinier wire and is supported by deflectors and vacuum boxes. Fourdrinier Wye The ya has five sheeps and is satin woven. This satin woven has 33 warp yarns and weft yarns. With 30 pieces, this number is the value per centimeter. Initial wet web Has a fiber concentration of about 18% at the delivery point from the fourdrinier wire and is sent to the second papermaking belt. Can be Second papermaking belt has preferred mesh surface and deflection conduit Endless belt. This papermaking belt has a photopolymer network on a porous fabric element. Made by forming, this woven element is made of polyester, No. 5,334,289 to Trokhan. Based on 4 sheep, 2 layers type, 20 warp (MD) filaments per 1 cm, weft (CD) is 18 filaments, the US patent specification of which Are incorporated herein by reference. The filament has a diameter of 0.22 in the longitudinal direction mm and the diameter in the horizontal direction is 0.28 mm. Knuckle about 3 for photosensitive polymer fabric 5% area, 87 pieces per square centimeter (562 pieces per square inch) Linear Idaho Cells <Linear Idaho Cells.> The pattern of the daho cell is the rice of Trokhan and others issued on May 7, 1996. This is described in detail in FIG. 19 of US Pat. No. 5,514,523. State patent specifications are incorporated herein by reference. Used in this process The photosensitive resin used is MEH-1000, which is located in Wilmint, Delaware. Methacrylate marketed by Mac Damid Imaging Technology, Inc. It is a urethane resin. This papermaking belt has a total thickness of about 1.2 mm. 0.2 mm is the pattern of the photosensitive polymer, and this pattern is It extends upward.   The initial web is placed on a papermaking belt, passes through a vacuum dewatering box, The web is transported through the lier and then sent to the Yankee Dryer. Be included. Other process and machine conditions are listed below. The fiber concentration is Approximately 27% after the water box. It is about 65% before being sent to the liar, and 0.25% of polyvinyl alcohol A crepe adhesive consisting of an aqueous solution is sprayed by the application, and the web is Before dry creping by a doctor blade, the fiber concentration is estimated to be 98 % To increase. The doctor blade has a bevel of about 25 degrees and a Yankee ・ This Yankee dryer is located at a position where the compression angle of the dryer is about 81 degrees. Is operated at about 177 ° C. (about 350 ° F.), and this Yankee dryer It runs at about 800 feet per second. Dry creped web Then passes between two calendar rolls. These two calendar rows Is biased by weight and has a surface velocity of about 201 meters per minute (660 feet per minute) Driven by The web to be calendered is a reel (also with a surface speed of about 201 (Operated at 660 ft / min) and then used To be served. Deflection material by distribution roll There are five components of the chemical additive added: water, legal oil (Texaco ・ High-speed turbine oil marketed by Oil Company), ADGEN EN) TA100 (a surfactant commercially available from Witco Corporation) Stearyl dimethyl ammonium chloride), cetyl alcohol (Protector & ・ Chain 16 chain aliphatic alcohol marketed by Gambling Company And glycerol. The relative proportions of these five components are legal oil 6 . 1% by weight, Adgen 0.3% by weight, Cetyl alcohol 0.2% by weight, glycero 31.3% by weight of water and water are the balance. Water solubility added to papermaking belts The flow rate per unit volume of the chemical additive component is about 6.21 liters / hour-meter (about 0. 50 gallons / hour-lateral feet). This wet web is water soluble chemical Upon contact with the additive component, the fiber concentration is about 25% based on the total web weight. You.   This web is converted to a single layer tissue paper product. This tissue • Paper is about 18 # / 3M square feet (18 # / 3M Sq Ft) Glycerol in the knuckle area of this tissue paper 1% and about 1% of legal oil and distributed throughout this tissue paper. About 0.2% wet strength resin. The important thing is made in this way Tissue paper is soft and absorbs well, decorative paper and toilet paper It is suitable for use as a par.                                   Example 2   A prototype scale Fourdrinier wire machine is used in the practice of the present invention. NSK (Northern region Conifer craft (eg, Tahoe, WA) 3% by weight water-soluble slurry supplied by Ration Co., Ltd. Is made in a conventional repalper. Temporary wet strength resin (ie, -National Starch and Chemical Corporation, New York, York 2% solution of National Starch 78-0080 It is added to the NSK stock pipe at a rate of 0.75% of the dry fiber weight. NS The adsorption of the temporary wet strength resin to the K fiber is enhanced with an in-line mixer. This Of NSK is diluted to a concentration of about 0.2% with a fan pump. eucalyptus A 3% by weight aqueous slurry of tree (eg, Aracles, Brazil) fiber is a conventional slurry. It is made in a repulper. Eucalyptus slurry is concentrated by fan pump Diluted to about 0.2%. Each furnish component is separated by a separate layer in the head box. That is, eucalyptus is sent to the outer layer and NSK is sent to the inner layer) It is deposited on a fourdrinier wire to form. Dehydration is caused by the fourdrinier wire and Supported by reflectors and vacuum boxes. Fourdrinier wire has five sheeps and satin weave This satin weave has 33 warp yarns and 30 weft yarns. It is the value per centimeter. The initial web is the fiber at the delivery point from the fourdrinier At a concentration of about 18% and sent to a second papermaking belt. This second papermaking belt is preferred An endless belt having a mesh surface and a deflection conduit. This papermaking belt is polyester This fabric is made by forming a network of photosensitive polymer on a porous fabric element made of The material element is a process disclosed in US Pat. No. 5,334,289 to Trokhan. 20cm warp yarn (MD), weft yarn (MD) CD) is 18 filaments, the U.S. Pat. Thus, it is incorporated herein. This filament has a vertical diameter of about 0.2 2 mm, 0.28 mm in diameter in the lateral direction. About 35% of photosensitive polymer fibers Knuckle area and 87 pieces per square centimeter (562 pieces per square inch) linear ・ It has an Idaho cell, and the pattern of this linear Idaho cell is 1996 US Patent No. 5,514,523 to Trokhan, issued May 7, 2007. 19, which is hereby incorporated by reference herein. Is embedded. The photosensitive resin used in this process is Wilmington, Delaware Methacryluree marketed by MacDam Imaging Technology, Inc. It is MEH1000 of a tan resin. The papermaking belt has a total thickness of 1.2 mm 0.2 mm is the pattern of the photosensitive polymer, and this pattern is It extends above the element.   The initial web is placed on a papermaking belt, passes through a vacuum dewatering box, The web is transported through the lier and then the web is sent over the Yankee dryer I will. Other process and machine conditions are listed below. Vacuum dehydration About 27% after packing and sent to Yankee dryer by the action of pre-dryer. It is about 65% before being incorporated, and is made of 0.25% aqueous solution of polyvinyl alcohol. Crepe adhesive is sprayed by the applicator and the fiber concentration It increases to an estimated 98% before being creped dry on a tar blade. Doctor -The blade has a bevel of about 25 degrees and about a Yankee dryer. At a position where the compression angle is 81 degrees, the Yankee dryer is at 177 ° C (about 350 ° C). ° F), the Yankee dryer operates at approximately 244 meters per minute (800 (Every minute). The dried creped web is then turned into two calenders Pass between the rolls. The two calender rolls are mutually biased by the weight of the rolls. And operates at a surface speed of about 201 meters per minute (660 feet per minute) . The calendered web is reeled (also at a surface speed of about 201 meters per minute ( Operated at 660 feet per minute) and then ready for use.   The aqueous solution containing the chemical additive components is continuously added to the top of the calender roll. available. The composition of the water-soluble chemical additive added to this calender roll is , Three components: water, quaternary ammonium compounds (e.g., Witco -The company marketed under the trade name "Varisoft 137" (Hydrogenated) tallow dimethyl ammonium methyl sulfate) and glycerol It is. The relative ratio of these three components is 100% for “Varisoft 137”. %, Glycerol is 40% by weight, and water is the remaining amount. This web is this web When the web comes into contact with the composition of the water-soluble chemical additive, the fibers based on the total weight of the web The fiber concentration is about 98%.   This web is converted to a one-layer tissue paper product. This tissue • The paper has a basis weight of about 18 # / 3M Sq Ft, and this tissue paper About 1% glycerol and about 0.2% quaternary ammonium in the pillow area The compound softener is also distributed throughout the tissue paper at about 0.1%. Contains 2% temporary wet strength resin. The important thing was made in this way For use as tissue paper decorative paper and / or toilet paper Suitable That is.                                   Example 3   A prototype scale Fourdrinier is used in the practice of the present invention. NSK (Northern region needles Tree craft (e.g., Wayahosa Corporation of Tacoma, Washington) 3% by weight aqueous slurry supplied from Made in the pulsar. Temporary wet strength resin (ie New York National Starch and Chemical Corporation of New York Commercially available National Starch 78-0080) is NSK's stock pipe. At a rate of 0.75% of the dry fiber weight. Temporary wet strength on NSK fiber The adsorption of the power resin is enhanced by the in-line mixer. This NSK sla Lee is diluted with a fan pump to a concentration of about 0.2%. Eucalyptus trees (eg bra A 3% by weight aqueous slurry of fiber (Jill's Alacules) is used in a conventional repulper. Is made up of This eucalyptus slurry is about 0.2% concentration by fan pump Diluted in Each component of the furnish is separated by a separate layer (the (Eucalyptus is sent to the outer layer and NSK is the center layer.) Deposited to form an initial web of Dehydration is caused by the fourdrinier wire and Supported by reflectors and vacuum boxes. Fourdrinier wire has five sheeps and satin weave This satin weave is a single strand of 33 warp yarns and 30 weft yarns. The number is a value per centimeter. Initial wet web is long wire The fiber is fed to the second papermaking belt at a fiber concentration of about 18% at the delivery position. This second papermaking belt is an endless belt having a preferred mesh surface and a deflection line. This Papermaking belts form a network of photosensitive polymers on a porous textile element Made from polyester, this textile element is made of polyester, Trokhan 4-hingle bilayer based on the process disclosed in U.S. Pat. No. 5,334,289 to U.S. Pat. With 20 (warp) and 18 (weft) filaments per centimeter And This US patent is incorporated herein by reference. This filament is vertical The direction is about 0.22 mm in diameter, and the lateral direction is 0.28 mm in diameter. Photosensitive polymer Fibers have about 35% knuckle area and 87 cells per square cm (562 cells per square inch). ), And the linear Idaho cell has 199 US Patent No. 5,514,523 to Trokhan, issued May 7, 2006 This U.S. patent is hereby incorporated by reference in its entirety. You. The photosensitive resin used in this process is MEH-1000, which is a Delaware Commercialized by Wilmington's MacDamd Imaging Technology Inc. Methacrylic urethane resin. The total thickness of the papermaking belt is about 1.2m m, 0.2 mm of which is the pattern of the photosensitive polymer, It extends above the object element.   The initial web is on a papermaking belt, passes through a vacuum dewatering box, Transported through the ears, after which the web was sent over the Yankee dryer It is. Other steps and conditions are described below. Fiber concentration in vacuum dehydration box About 27% later, sent to Yankee dryer by the action of pre-dryer About 65% before; clay consisting of 0.25% aqueous solution of polyvinyl alcohol The adhesive is sprayed by an applicator; the fiber concentration is Before being dried and creped in the mold, it rises to an estimated 98%. Doctor Blade, Has a bevel of about 25 degrees and a compression angle of about 81 degrees with respect to the Yankee dryer Position; the Yankee dryer is operated at about 350 ° F (177 ° C) Yankee dryers operate at about 244 meters per minute (about 800 feet per minute) It is. The dried creped web then passes between two calender rolls. The two calender rolls are mutually biased by roll weight, and about 201 It is operated at a surface speed of Torr per minute (660 feet per minute). Calendared The web is reeled (also at a surface speed of about 201 meters per minute (660 feet per minute) It is wound up and used.   The aqueous solution with the chemical additive component is an emulsion distribution ・ Before the papermaking belt comes into contact with the initial web via the roll, It is continuously added to the knuckle area. Extracted by distribution role Five types of water-soluble chemical additive compositions added to the knuckle area of the paper belt Ingredients: water, legal oil (commercially available from Texaco Oil Company) High-speed turbine), ADOGEN TA100 (Witco Corporation) Distearyl dimethyl ammonium chloride), cetyl Alcohol (charcoal available from Procter & Gamble Company) (A linear aliphatic alcohol having a prime number of 16) and a water-soluble dye composition. This The relative proportions of the following are 6.1% by weight of legal oil, 0.3% by weight of adgen, Chill alcohol 0.2% by weight, water-soluble dye composition 0.2% by weight, water remaining is there. Volumetric flow rates of compositions of water-soluble chemical additives added to papermaking belts. Is approximately 6.21 liters per hour per meter (approximately 0.50 gallons per hour and lateral feet) It is. The fiber concentration of the wet web is determined by the amount of water soluble chemical additive When contacted with the composition, it is about 98% based on the total weight of the web.   This web is converted to a one-layer tissue paper product. This tissue The paper has a basis weight of about 18 # / 3M Sq Ft and a temporary wetness of about 0.2% Contains moisturizing resin. The important thing is that the tissue The vapor is soft, absorbent, aesthetically improved, and used for cosmetics and toilets. That it is suitable for use as tissue for tissue.                                   Example 4   A prototype scale Fourdrinier wire machine is used in the practice of the present invention. NSK (Northern region Crafting softwood lumber (e.g., Wearhosa Corporation, Tacoma, WA) 3% by weight of water-soluble slurry supplied by Created in the next repalper. Temporary wet strength resin (ie Newyo National Starch and Chemical Corp. in New York, NY A 2% solution of National Starch 78-0080) available from It is added to the NSK stock pipe at a rate of 0.75% of the dry fiber weight. this Adsorption of temporary wet strength resin on NSK fiber is enhanced by in-line mixer . This NSK slurry is diluted to a concentration of about 0.2% with a fan pump. You A 3% by weight aqueous slurry of potassium (eg, Aracles, Brazil) is Made in pulper. This eucalyptus slurry is concentrated with a fan pump. It is diluted to about 0.2%. Each furnish composition is separated in a head box. Layer (ie eucalyptus is sent to the outer layer, NSK is sent to the more central layer) Deposited to form three layers of initial web on the mesh wire. Dehydration, fourdrinier Occurs through the tube and is assisted by a deflector and vacuum box. Long net The ear has five sheeps and is satin-woven, and this satin-woven is 33 in the vertical direction, It has 30 monofilaments per centimeter in the transverse direction. Early wet cormorants Ebb was fed from a fourdrinier wire to a second papermaking belt at a fiber concentration of about 18% at the delivery position. Transported to This second papermaking belt consists of a network of photosensitive polymers on a porous textile element. Made by forming a structure, this woven element is made of polyester, The process disclosed in US Pat. No. 5,334,289 to Trokhan. 20 (vertical) and 18 (horizontal) per centimeter And the U.S. patent specification is incorporated herein by reference. You. The photosensitive resin used in this step is MEH-1000, which is McDermid Imaging Technology In of Wilmington, IA This is a methacrylic / urethane resin commercially available from Company c. Total thickness of papermaking belt Is about 1.2 mm, and 0.2 mm is the pattern of the photosensitive polymer. The turns extend above the porous textile element.   The initial web passes through a vacuum dewatering box on a papermaking belt, and is blow-dried pre-dried. The web is then transported to a Yankee dryer. It is. Other process and machine conditions are listed below. The fiber weight is Approximately 27% after the box, and due to the action of the pre-dryer, the Yankee dryer About 65% before being carried over; creping adhesive Composed of 0.25% aqueous solution and sprayed by applicator; fiber concentration The degree is estimated to be about 98% before the web is dried and creped with a doctor blade. To rise. The doctor blade has an oblique angle of about 25 degrees and the Yankee At a compression angle of about 81 degrees to the ear; the Yankee dryer is about 1 Operating at 77 ° C (about 350 ° F), this Yankee dryer is about 244 meters It runs at a speed of about 800 feet per minute. The dried creped web is then Pass between two calendar rolls. These two calendar rolls are rolls Deviated by weight, running at a surface speed of about 201 meters per minute (660 feet per minute) Turned. The web used for the calendar is a reel (this also has a surface speed of about 201 meters) Per minute (operated at 660 feet per minute) and then ready for use You.   The aqueous solution containing the chemical additive composition is applied to the Yankee Dry To the surface of the web prior to the initial web transport. Yang by spraying equipment The water-soluble chemical additive composition applied to the surface of the key dryer has three components. Minutes, i.e., water, Airvol 50 (Ellentown, PA) A products and chemicals marketed polyvinyl alcohol), And Cypro 711 (American Shea, Wayne, NJ) (Polyacrylamide dry strong resin supplied by Namide Co., Ltd.). This The relative proportions of the three components are 0.125% by weight of polyvinyl alcohol, It is 0.125% of acrylamide dry strong resin and the remaining amount of water. Yankee ·dry The flow rate of the water-soluble chemical additive composition applied to the surface of the yarn is about 0.11 gallon / Minute / lateral foot. Wet initial web has a total average moisture content of 1 pound fiber 0.67 pounds of water.   This web is converted to a one-layer tissue paper product. This tissue ・ Paper has a basis weight of fiber gram per square meter (about 18 pounds of fiber per 30 square meters) 00 feet) and is predominantly distributed in the low area of this tissue product. About 0.01% dry strength resin. The important thing is that Tissue paper is soft and absorbent, aesthetically improved, and Suitable for use as decorative paper and / or toilet tissue paper That is.

────────────────────────────────────────────────── ─── Continuation of front page    (81) Designated countries EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, L U, MC, NL, PT, SE), OA (BF, BJ, CF) , CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, S D, SZ, UG, ZW), EA (AM, AZ, BY, KG) , KZ, MD, RU, TJ, TM), AL, AM, AT , AU, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, G B, GE, GH, HU, IL, IS, JP, KE, KG , KP, KR, KZ, LC, LK, LR, LS, LT, LU, LV, MD, MG, MK, MN, MW, MX, N O, NZ, PL, PT, RO, RU, SD, SE, SG , SI, SK, SL, TJ, TM, TR, TT, UA, UG, UZ, VN, YU (72) Inventors Melvin, Joe, Brian             Cincinnati, Ohio, United States             Chi, Burdett Avenue # 3 1382

Claims (1)

[Claims]   1. Having two heights, a first height defining a first pattern, and a second height A cellulose substrate defining a second pattern, wherein each of said heights has one or more areas; ;   In said one or more areas corresponding to said one height of said cellulose substrate A chemically reinforced paper structure comprising a non-migrating chemical papermaking additive.   2. The one height corresponds to a discontinuous area, and the other height is basically continuous. A chemically reinforced paper structure according to claim 1, which corresponds to a reticulated structure.   3. 3. The method of claim 1 wherein said immobile chemical paper additive is in said discontinuous zone. 3. The chemically reinforced paper structure of claim 2.   4. The chemical papermaking additive is a strong additive, an absorbent additive, a softening additive, an aesthetic additive. Claim 1 selected from the group consisting of excipients and mixtures thereof On paper chemically reinforced paper structure.   5. 5. The chemical according to claim 4, wherein said chemical papermaking additive is a softening additive. Reinforced paper construction.   6. The softening additive is a lubricant, a plasticizer, a cationic release agent, a non-cationic release agent And a compound selected from the group consisting of: and mixtures thereof. Chemically reinforced paper structure.   7. 7. The chemical according to claim 6, wherein said softening additive is a non-cationic release agent. Reinforced paper construction.   8. The non-cationic release agent is sorbitan ester, ethoxy sorbitan ester Stel, propoxyl sorbitan ester, mixed ethoxyl and propoxy Selected from the group consisting of silsorbitan esters and their mixtures A chemically reinforced paper structure according to claim 7.   9. The chemical additive according to claim 6, wherein the softening additive is a cationic softening agent. Enhanced paper structure.   10. 9. The ninth aspect, wherein the cationic softener is a quaternary ammonium compound. A chemically reinforced paper structure according to paragraph.   11. The cation softener is a diester quaternary ammonium compound. 10. A chemically reinforced paper structure according to claim 9, wherein:   12. 5. The method according to claim 4, wherein said chemical papermaking additive is a strong additive. A chemically strengthened paper structure.   13. The strong additive is a permanent wet resin, a temporary wet strong resin, a dry strong additive. 13. The method according to claim 12, wherein the group is selected from the group consisting of: and a mixture thereof. Of chemically strengthened paper structure.   14． The strong additive is polyamide epichlorohydrin resin, polyacrylic resin. Permanent wet strength selected from the group consisting of luamide resins, and mixtures thereof. 14. The chemically reinforced paper structure of claim 13 which is a force resin.   15. Claims: The strong additive is a temporary wet strength resin based on starch. The chemically reinforced paper structure of claim 14.   16. 5. The method according to claim 4, wherein said chemical papermaking additive is an absorption additive. A chemically strengthened paper structure.   17． The absorption additive is a polyhydroxy compound, a polyethoxylate, Kill ethoxy ester, alkyl ethoxyl alcohol, alkyl polyethoxy Lunonylphenol, ethoxyltrimethylpentanediol, and mixtures thereof 17. The chemically fortified product of claim 16 selected from the group consisting of compounds. Paper structure.   18. 9. The method according to claim 1, wherein the absorption additive is an alkyl ethoxyl alcohol. 18. The chemically reinforced paper structure of claim 17.   19. 18. The method according to claim 17, wherein the absorption additive is a polyhydroxy compound. On paper chemically reinforced paper structure.   20. The polyhydroxy compound is glycerol, polyglycerol, Glue made of polyoxyethylene, polyoxypropylene, and mixtures thereof 20. A chemically reinforced paper structure according to claim 19 selected from paper.   21. 5. The composition according to claim 4, wherein said chemical papermaking additive is an aesthetic additive. A chemically strengthened paper structure.   22. The aesthetic additives include inks, dyes, fragrances, opacifiers, optical brighteners, and 22. The compound according to claim 21, which is selected from the group consisting of A chemically strengthened paper structure.   23. 23. The chemically fortified composition of claim 22, wherein said aesthetic additive is a dye. Paper structure.   24. 7. The method according to claim 6, wherein said lubricant additive comprises a silicon compound. Of chemically strengthened paper structure.   25. The claim wherein the silicon compound is silicon having an amino group. 25. The chemically reinforced paper structure of claim 24.   26. Having a basically continuous network area and discontinuous areas disposed therein; The essentially continuous network defines a first height, and the discontinuity area is a second height. A cellulose substrate that defines   Transfer at the one or more areas corresponding to the one height of the cellulose substrate Through-dried chemically reinforced paper structure with immobile chemical papermaking additives Build.   27. The chemical papermaking additive is applied to one of the areas by contact with a roll The chemical method according to claim 1, which is made based on a method comprising a printing step. Enhanced paper structure.   28. The chemical papermaking additive is applied to one of the areas by contact with a roll 3. The method according to claim 2, wherein the method is performed based on a method having a printing step. Enhanced paper structure.   29. The chemical papermaking additive is applied to one of the areas by contact with a roll 27. The chemistry of claim 26, made based on a method comprising the step of printing. Reinforced paper construction.