BRPI0707823A2 - product and process for treating a substrate - Google Patents

Abstract

PRODUCT, AND, PROCESS FOR TREATING A SUBSTRATE A method for treating a substrate is described. According to one aspect, the method includes applying a polymeric coating to a substrate, and causing the polymeric coating to contact a heated surface while the coating is still wet. Optionally, the polymeric coating may include a crosslinkable material, and a crosslinking agent may be used to promote crosslinking. The polymeric coating doubles the heated surface. Also presented is a product produced according to the method described. The product is characterized by having empty spaces under the coating surface.

Description

"PRODUCT, Ε, PROCESS FOR UMSUBSTRATE TREATMENT"

REFERENCE TO RELATED APPLICATION

This application claims the priority benefit under 35 U.S.C. paragraph 119 (e) of the provisional application of serial number 60 / 776,114 filed February 23, 2006, which is incorporated herein by reference in its entirety.

BACKGROUND OF THE INVENTION

The present disclosure relates to a method for treating a substrate having a polymeric film forming composition. More particularly, the presentation relates to a method for producing paper or cardboard, composed of the steps of applying a polymeric film-forming coating on a substrate, and placing the polymeric coating on a heated surface while the polymeric coating is still damp. The resulting polymeric layer has a smooth surface with voids (eg bubbles) just below the surface. In certain embodiments, the polymeric coating may be comprised of a crosslinkable hydrogel, and a crosslinking solution may be applied to the polymeric coating on the substrate surface, thereby forming at least one partially crosslinked polymeric coating and then contacting it with a heated surface. The current presentation also refers to a treated substrate product.

Paper is made by a essentially continuous production process, where a dilute aqueous suspension of cellulosic fibers flows into the wet end of a papermaking machine and a consolidated continuous-length dry sheet continuously emerges from the dry end of the papermaking machine. The wet end of the paper making machine is composed of one or more main boxes, a drainage section and a pressing section. The dry end of a modern papermaking machine is comprised of a number of steam-heated rotating casing rollers distributed along a displacement path of a continuous coil sheet under a heat-conserving cover structure. Although there are numerous design variations for each of these sections of the papermaking machine, the most important commercially among the variants is the "Fourdrinier" machine where the box discharges a large jet of suspension onto the moving screen with an extremely fine mesh.

The screen is constructed and driven by an endless belt that is displaced over a number of rollers or support sheets. A pressure differential across the screen from the side in contact with the suspension and the opposite eye draws water from the suspension through the screen as that section of the screen travels along a portion of the screen route circuit table. dilution of the suspension is extracted, the fibrous constitution of the suspension is accumulated on the surface of the fabric like a damp but substantially consolidated blanket. Upon arrival at the end of the screen circuit table length, the blanket has already accumulated sufficient mass and tensile strength to contain a small physical space between the screen and the first press roll. The first press roll moves the web to a first press space where the larger volume of water remaining in the web is removed by pressing in the roll gap. One or more additional pressing intervals may be followed.

From the pressing section, the continuous web, now generally characterized as a continuous web, enters the drying section of the paper machine to thermodynamically remove the remainder of the water.

Generally speaking, the most important fibers for papermaking are obtained from softwood and hardwood tree species. However, fibers obtained from straw or bagasse in certain cases have been used. Chemical and mechanical fiber stripping processes, well known in the prior art, are used for the separation of fibers from the natural growth composition for papermaking. Paper-making fibers obtained by chemical fiber separation processes and methods are generally referred to as chemical pulp, while papermaking fibers derived from mechanical fiber separation methods may be called ground wood pulp or mechanical pulp. There are also combined fiber separation processes such as semi-chemical, thermochemical or thermomechanical ones. Any of the three species may have the fibers separated by chemical or mechanical methods. However, some species and processes of fiber separation are more economically or functionally suitable than others.

An important difference between chemical and mechanical pulp is that mechanical pulp can be passed directly from the fiber separation stage to the papermaking machine. Chemical pulp, on the other hand, should have at least mechanically separated fibers washed and sieved after chemical digestion. Usually, the pulp chemistry is also refined mechanically after being sieved and before the papermaking machine. Additionally, the average fiber length of mechanical pulp is, as a rule, shorter than that of chemical pulp. However, fiber length is also largely dependent on the wood species from which the fiber originates. Softwood fibers are generally three times longer than hardwood fibers.

The most important properties of a specific paper are largely determined by the species of feedstock used and the manner in which the papermaking machine and continuous sheet forming process treat these feedstocks. Important operating factors in the continuous sheet forming mechanism are the main box and the screen.

Coated paper or cardboard used for printing and packaging generally requires high levels of polish, excellent softness, and excellent printability, as well as certain strength and stiffness characteristics.

If coated paper or cardboard has a high stiffness, it can easily pass through high speed printing or packaging machines with less agglomeration in the feed. Higher stiff paper can be used advantageously in books, magazines, and catalogs because it provides a stiff or heavier feel similar to a book cover. For packaging, rigidity is required to maintain the structural integrity of the cardboard product during filling and subsequent use.

The stiffness is closely related to the basis weight and density of the paper. There is a general tendency for stiffness to increase when the base weight increases, and it is reduced when the density of the pulp increases. Stiffness and other properties can be improved by increasing the base weight. However, this would result in a product that uses more fibers, which would increase cost and weight. Therefore, high stiffness coated paperboard or cardboard with a moderate basic weight is desirable. Paper with a moderate basic weight is also more economical because less raw material is used. In addition, weight-based shipping costs are lower for low base weight paper.

In addition to the high stiffness, the coated paper or paperboard that must be printed often requires high polishing and softness. For coated paper or paperboard to have such quality characteristics, the density typically must be increased to a certain extent to allow a printing surface. usable. Softness is usually obtained through calendering. However, calendering will cause a reduction in caliber, which typically results in a corresponding reduction in sharpness. The calendering process deteriorates paper stiffness by significantly reducing gauge and increasing density. The backing sheet for conventional grades of coated paper is typically heavily thickened through calendering to produce a sufficiently low surface roughness to produce an industry acceptable coated final softness. These calendering processes, including the treatment of a wet pile, may increase the density by as much as 20% to 25%.

Thus, the relationship between polish and stiffness and between softness and stiffness are generally inversely proportional to each other for a given amount of fiber per unit area. Unpacking grades are sold based on size, so production processes that reduce size (increasing paper density) reduce sales price. Processes that cause a smaller gauge reduction save material costs. The caliber is measured in "points" where a point = 0.001 inches. For example, the conventional 10 point paper production method requires the use of paper having a thickness greater than 12 points prior to calendering. It would be desirable to be able to produce a finished paper having approximately the same thickness as the initial substrate.

Improvements in the calendering process include wet gradient calendering, hot calendering, soft calendering, and slightly improved stiffness through belt calendering for a given caliber, but do not change the fundamental relationship between caliber, stiffness, softness, and the printing properties.

Various proposals have been made to improve the stiffness of paper or coated cardboard without printing calendering. For example, various proposals include high levels of softwood in the feedstock, the addition of specially prepared fibers in the feedstock, the addition of highly branched polymers within the feedstock, and large quantities of copolymer starch or latex with a transitioning temperature. raised glass (commonly referred to as "Tg") within the coating formulation.

However, the potential disadvantages of these stiffness improvement methods are that, while being useful for improving the stiffness of the paper, they could potentially degrade the softness, wettability, and / or printability of the obtained coated paper.

Because of the reasons mentioned above, it has been very difficult to achieve satisfactory paper stiffness without increasing density. Other methods can be used for altering the bias / softness ratio in the grades of paper and cardboard. Applying a paper coating is a very common way to improve paper surface properties without causing the drastic increases in paper density typically associated with the required calendering levels to achieve a certain level of softness. Preferably, the coated end surface should be uniform to produce acceptable appearance and printing properties.

Therefore, it would be desirable to produce a paper or paperboard product having the desired properties, while maintaining the initial sheet density or minimizing the increase in density. In addition, it would be desirable to produce a paper or paperboard. exhibited improved softness without the concomitant increase in density associated with conventional softness creation methods. Casting coating methods exist for producing very soft surfaces, but these methods typically operate at slower production speeds than the speed of various papermaking machines.

SUMMARY OF PRESENTATION

In one embodiment, a product is disclosed which includes a substrate with a coating on the substrate. The coating includes a water soluble polymer and a release agent. There are voids formed inside the liner.

In another embodiment, a product is disclosed which includes a substrate with a coating on the substrate. The coating includes a water soluble polymer and essentially no elastomeric material. There are voids formed within the coating.

In another embodiment, a product is disclosed which includes a substrate with a coating on the substrate. The coating includes a surface, and the surface has a Sheffield softness of less than about 300 units. There are voids formed beneath the surface of the jacket.

In another embodiment, a product is disclosed which includes a substrate with a coating on the substrate. The coating includes a water soluble polymer, a release agent, and essentially no elastomeric materials. The coating includes a surface, and the surface has a Sheffield softness of less than about 300 units. There are empty spaces formed beneath the surface of the coating.

In another embodiment, a process for treating a substrate is disclosed. A wet film of aqueous polymer solution is applied to the substrate. The aqueous polymeric solution is immobilized by contacting it with a heated surface to cause the aqueous polymeric solution to boil, and to at least partially dry the aqueous polymeric solution.

In another embodiment, a process for treating a substrate is disclosed. And applied on the substrate a wet film aqueous polymeric dissolution. The aqueous polymeric solution is immobilized by contacting it with a heated surface to cause the aqueous polymeric solution to boil and form voids remaining in the aqueous polymeric solution, and to at least partially dry the aqueous polymeric solution.

In another embodiment, a process for treating a substrate is disclosed. An aqueous polymer solution coating is applied to the substrate as a wet film. The coating includes water soluble polymer and a release agent. The film is immobilized by contacting it for less than about 3 seconds with a heated surface above 150 ° C to cause the aqueous polymeric solution to boil and empty spaces in the film, and at least to dry. partially the movie.

In another embodiment, a process is presented for the

treatment of a substrate. An aqueous polymer solution coating is applied to the substrate as a wet film. The coating includes water-soluble polymer and essentially no elastomeric material. The film is immobilized by contacting it with a heated surface for less than about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymer solution to boil and form voids in the film, and at least partially dry the film.

In another embodiment, a process for treating a substrate is disclosed. An aqueous polymer solution coating is applied to the substrate as a wet film. The coating includes water-soluble polymer and essentially no elastomeric material. The film is immobilized by contacting it with a heated surface for at least about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymer solution to boil and form voids in the film, and at least partially dry the film. The aftercoating surface has a Sheffield softness of less than about 300 units. In another embodiment, a process for treating a substrate is presented. An aqueous polymer solution coating is applied to the substrate as a wet film. The coating includes a water soluble polymer, a release agent, and essentially no elastomeric material. The film is immobilized by contacting it with a heated surface for less than about 3 seconds, with a temperature above about 150 ° C, to cause the aqueous polymeric solution to boil to form voids in the film, and to at least partially dry the film. The coating surface after drying has a Sheffield softness of less than about 300 units.

In another embodiment, a process for treating a cellulosic substrate is disclosed. A wet film of aqueous polymer solution is applied to the substrate. The aqueous polymer solution includes at least about 60% dry weight water soluble polymer and up to 10% dry weight release agent. The aqueous polymeric solution is immobilized by contacting it with a heated surface for less than about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymeric solution to boil and empty spaces in the solution. aqueous polymeric solution, and at least partially dry the aqueous polymeric solution.

BRIEF DESCRIPTION OF DRAWINGS

Fig. 1 is a schematic view of an apparatus for treating a polymeric coated substrate according to an embodiment of the present invention.

Figs. 2-9 are cross-sectional micrographs showing amorphology of samples made in accordance with one embodiment of the invention, having a topcoat.

Figs. 10 - 12 are cross section micrographs showing the morphology of samples made according to one embodiment of the invention.

Figs. 13-14 are surface micrographs made by electron scanning microscopy showing the morphology of the samples made in accordance with one embodiment of the invention.

The figs. 15-16 are surface micrographs made by back scattering scanning electron microscope showing amorphology of samples made in accordance with one embodiment of the invention.

Fig. 17 is a graph showing the distribution of void space dimensions in samples made according to one embodiment of the invention.

DETAILED DESCRIPTION OF THE INVENTION

In describing preferred embodiments, certaterminology will be used for clarity. Such terminology is intended to include not only the embodiments cited but all technical equivalents operating in a similar manner for a similar purpose to achieve a similar result. Citation of any document should not be considered as an admission that it is prior art with respect to the present invention. Unless otherwise indicated or unless the context otherwise suggests, all weights, percentages, and proportions are by weight.

The present disclosure relates to a method for treating a substrate with a film-forming polymeric coating. More particularly, the presentation relates to a method for the manufacture of paper or cardboard, composed of the steps of applying a polymeric coating to a substrate, and placing the polymeric coating on a heated surface while the polymeric coating is still damp. Boiling water in the polymeric coating causes voids to form beneath the surface, but the dofilm surface is soft. Paper or cardboard produced in accordance with certain embodiments of the present invention exhibits desired levels of surface smoothness and smoothness without significant increase in basic paper density. In some embodiments, the polymeric coating may include a crosslinkable material and a crosslinkable solution may be applied to the polymeric coating on the surface of the substrate, thereby forming at least one partially crosslinked polymeric film forming composition. In such cases, the polymeric coating is typically primarily it may be applied to the continuous sheet and then the crosslinking solution is applied before the treated continuous sheet contacts the heated surface. For polymers with very weak crosslinking, it may be possible to provide the crosslinking solution in the coating itself.

An advantage of treating a polymeric film-forming substrate according to the present invention relates to the improvement in smoothness and / or smoothness that can be obtained without a significant increase in density or a reduction in leaf size. Heavy calendering of the continuous pulp paper sheet associated with conventional techniques for the production of a paper having comparable printing properties to conventional coated papers is not required. In addition, even when the continuous web of paper pulp is soft, much lower pressures may be applied to provide similar printing properties on papers with increased stiffness. According to certain embodiments of the present invention, the web of cellulose paper is softened such that the size is not reduced by more than about 7% and is typically reduced by about 2% to 5%. By comparison, conventional coated papers typically are calendered prior to coating at much higher pressures, which cause a density increase of about 20 to 25%. According to one aspect of the invention, continuous pulping of cellulose paper may be calendered to a Parker Print Surf softness of between about 2 and 6 microns prior to application of the polymeric film. However, substrates with higher Parker values may be used. Print Surf '. For example, a "Parker Print Surf" softness substrate of around 9 microns could be used. "ParkerPrint Surf" softness is determined according to the TAPPIT 555 om-99 standard.

Fig. 1 illustrates apparatus 10 useful in practicing certain embodiments of the invention. A substrate 12 undergoes surface treatment with the crosslinkable polymeric coating 14 to form a polymeric coating layer 16 on the substrate 12. While the polymeric coating is still damp, an optional crosslinking solution 18 may be applied to the polymeric coating layer16. thereby forming a cross-linked polymeric coating 20 on the substrate 12. The polymeric coating 20 is typically at least partially cross-linked. The polymeric coating is still damp before it is brought into contact with the polished drum 22 by pressing the continuous sheet 12 against the drum surface with a depression application roller 24. Heat from the drum surface causes boiling within the wet polymer coating of so that voids are formed in the polymer under the surface. The crosslinking solution causes the polymeric coating to be crosslinked and gel over a substantially continuous film or layer. Typically, the resulting film will exhibit improved resistance to the base sheet. The treated polymeric sheet may not be completely dry and as such it may be directed through a secondary heater 26. Any type of secondary heating device may be used which is capable of drying the treated sheet without adversely affecting the sheet properties. The treated sheet emerges from secondary heaters 26 as a film-polymer treated substrate 28 characterized by improved smoothness and softness.

Optionally, additional coating processes 30 (and other processes such as coating, polishing calendering, etc.) may be used for forming a coated product 32.

As shown in fig. 1, the web involves a substantial portion of the hot polished drum 22. The amount of wrapping may depend on the operating conditions, such as web speed, the moisture content of the polymer film forming composition 20, the temperature of the drum, and the like. process factors. A small amount of contact time may be sufficient with the hot polished drum 22. In addition to providing the substrate in continuous foil form, it may also be provided in sheet form.

The crosslinkable polymeric coating and optional crosslinking solution may be applied by various techniques such as dip coating, stick coating, scraper blade coating, gravure roll coating, reverse roll coating, measured size pressing, soft roll coating. , extrusion coating, curtain coating, spray coating and the like. Crosslinkable polymeric coating and crosslinking solutions may be applied by the same coating technique or different methods may be used for each.

An embodiment according to the present invention is based on coagulation or gelation that occurs between polyvinyl alcohol and borax. According to this type of system polyvinyl alcohol (PVOH) is an example of a crosslinkable polymer and a borax solution is an example of a corresponding crosslinking solution. As soon as the PVOH 14 solution is applied, with approximately 25% solids and about 5 g / m 2 dry coverage, the crosslinker solution 16 is applied at a solid rate in solution to produce at least about 0 borax coverage, 1 g / m2 dry. This wet cross-linked polymeric film 20 is then contacted with a hot polished drum 22 by applying pressure of the continuous sheet 12 against the surface of the common pressure-applying roller 24. The surface temperature of the drum is less around 150 ° C, or according to certain embodiments, at least about 190 ° C, so that the coating can be dried free of the drum surface. The contact time of the polymeric film with the drum may be in the range of up to about 3.0 seconds, more especially about 0.5 - 2.0 seconds. This is a sufficient time for the polymeric film to be immobilized and solidified so that the surface of the polymeric film has a smooth flat finish equivalent to the drum surface. Immobilization of the polymeric film less partially includes drying of the film. The coating is not necessarily completely dry when it comes out of the drum, so further drying may be required 26. The continuous sheet then continues through the process and may receive additional layers of coating, for example conventional coatings, before being rolled. The polymeric coating may be applied as a single layer or as two or more layers. Limited experience also suggests that a polymeric film may be immobilized or solidified only with momentary contact with the heated drum, as can be achieved by using a pressure roll 24 to press the continuous sheet 12 against the hot drum 22 without any further wrapping of the sheet. continuous around the drum. However, it is considered that some development may be practiced in the hot drum, and optionally a filter 23 may be used to assist in pressing the continuous sheet into contact with the hot drum. If a felt 23 is used to assist the continuous web contact with the hot drum, then the felt 23 may be loaded between pressing hole 24 and the heated drum 22.

Contact between the polymeric film and the hot drum causes boiling to occur within the polymeric film, creating voids or bubbles in the film. Spacing conditions should be adjusted so that boiling occurs. Satisfactory results were obtained in the laboratory with an existing press roll, a 9 inch (22.86 cm) wide web, and empty space loads of about 2 to about 15 pounds (0.90 to 6.8 kg) per linear inch (2.54 cm). Depending on the dorolo press hardness and the diameters of the hot drum and the pressure roll, conditions may need to be adjusted.

Specific examples of crosslinker polymers useful in certain embodiments of the present invention include crosslinkable hydrogels. The following crosslinkable hydrogels are especially useful: starch, cornstarch in the form of wax, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginates. One or more polymers chosen from those described above may be used. The crosslinkable polymer is typically applied in dissolution form usually as an aqueous solution. The concentration of the solution polymer is not especially limited but can easily be determined by one of ordinary skill in the art. For example, a 20% starch solution may be used as described below. The crosslinkable polymer may be applied to produce a surface coverage (dry basis) of from about 3 to about 15 gsm (g / m2) and more particularly from about 4 to about 8 gsm. According to special embodiments of the present invention, the crosslinkable polymer may be used in an amount ranging from about 60% to about 100% by weight of dry materials.

Specific examples of crosslinkers include borates, aldehydes, ammonium salts, calcium compounds and derivatives thereof. Oreticulators, if used, typically may be applied as a solution and usually as an aqueous solution. The concentration of the crosslinker in the solution is not especially limited but can be readily determined by one of ordinary skill in the art. The crosslinker may be applied to produce a surface coverage (dry basis) of from about 0.1 to about 0.5 gsm, more especially from about 0.2 to about 0.3 gsm.

The temperature of the heated surface is in excess of that typically used for melt coating. The higher temperature should allow higher operating speeds. It is anticipated that paper or cardboard produced in accordance with certain embodiments of the present invention may be produced at speeds in the range of from about 750 to 3,000 fpm, more especially from about 1,500 to 1,800 fpm. Although we do not wish to be bound by theory, the higher temperature and residence time are chosen such that the coating composition is heated to its boiling temperature and it appears that when the coating comes to a boil there is an increase in the contact area between the coating and the coating. the drum. Increased contact results in a surface heated by the polymeric film that has improved softness and polishing. In addition, the treated surface is receptive to paint. Boiling of the coating when being softened on the surface of the polished drum appears to significantly improve the polish and softness of the substrate treated by the finished polymeric film.

The polymeric coating on the substrate is typically pressed against the heated surface for sufficient time to allow the coating to boil and then be adjusted to a smooth, polished finish. According to special embodiments, the contact time of the polymeric film formed in the drum is within the range of up to about 3.0 seconds, more especially up to about 2.0 seconds, and more especially up to about 0.5 seconds.

The polymeric coating may also include one or more pigments. Examples of useful pigments include, but are not limited to, acaulim, talc, calcium carbonate, calcium acetate, titanium dioxide, clay, zinc oxide, alumina, aluminum hydroxide and synthetic silica, with crystalline silica, amorphous silica or finely divided silica being examples thereof. Organic pigments may also be used.

The crosslinkable polymeric coating and / or crosslinker solution may further include one or more release agents. Specific examples of release agents useful herein include, without limitation, waxes such as petroleum, vegetable, animal and synthetic waxes, fatty acid metal soaps such as metal stearates, long chain alkyl derivatives such as fatty esters, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers such as polyolefins, silicone polymers, fluoropolymers and natural polymers, fluorinated compounds such as fluorinated fatty acids and combinations thereof. A person of ordinary skill in the art can readily determine the amount of release agent to be used in a specific application. Typically, the coating may contain from about 0.3 to 10% deliberative agent, more especially about 2 to 5% by weight. Weight. Instead of or releasing the release agent in the coating, the release agent may be sprayed onto the coating surface or applied to the heated dot surface. If a non-stick surface may be applied to the heater by a release agent or other means then application of a release agent to the coating or to the coating surface may not be necessary.

The polymeric coating used in certain embodiments of the present invention, wherein at least the aforementioned polymer is contained, is generally prepared as an aqueous composition. An appropriate relationship between those ingredients is different, depending on the polymer composition, the conditions of application and so on. but it has no specific limitation as to whether the treated treated paper can meet the quality required for its intended use. In addition, the polymeric coating according to certain embodiments of the present invention may optionally contain additives such as a dispersant, water retention agent, thickening agent, defoaming agent, preservative, dye, water-proof, a wetting agent, a drying agent, an initiator, a plasticizer, a fluorescent dye, an ultraviolet absorbent, a release agent, a lubricant, and a cationic polyelectrolyte.

According to a specific embodiment of the present invention, the substrate is treated with the polymeric coating near a central region of the papermaking machine, such as the pressing and sticking position. In addition, the apparatus for applying the polymeric coating on the substrate may be placed relative to the paper machine so that it can apply the polymeric film to any surface of the continuous paper forming sheet. More than one apparatus may be used for applying the polymeric film to each side of the continuous paper forming sheet.

These advantages allow the use of lightly corrugated paper or paperboard, thereby preserving stiffness while providing good printing properties.

The base sheet is typically formed from fibers used commercially for such purpose, and according to specific embodiments, include unbleached or bleached kraft pulp. The paper may consist of hardwood or softwood or a combination thereof. The basic weight of the cellulose fiber layer may range from about 30 to about 500 gsm, and more especially from about 150 to about 350 gsm. The base sheet may also contain organic and inorganic fillers, sizing agents, retention agents, and other auxiliary agents as is known in the art. The final paper product may contain one or more layers of cellulose fibers, film-polymeric layers and, according to certain embodiments, other functional layers. The present invention, according to certain embodiments, produces paper or paperboard coated on one or both sides. for printing or packaging whose "Parker Print Surf" softness after coating and finishing processes when measured according to the paper and pulp test method TAPPI nr. 5A, is less than about 2 - 3 microns.

The paper or cardboard described herein may additionally be produced with one or more additional coatings. A topcoat containing conventional components may be produced to improve certain properties of the paper or cardboard. Examples of such conventional components include pigments, binders, fillers and other special additives. The topcoat, when present, may be applied at much lower coating weights than conventional coatings and still provide similar printing properties. Therefore, the topcoat weight may be around 4 to 9gsm as a single coating. coating or about 8 to 18 gsm with two layers of coating. In contrast, conventional coated papers typically require about 10 to 20 gsm as a single coating layer or 18 to 30 gsm as two coating layers to produce comparable surface properties. The paper or cardboard may also be coated on the side of the sheet having the untreated surface.

Having presented the teachings of the present presentation, it will now be illustrated by way of specific examples which should not be construed as limiting the scope of the claims in any way.

A base sheet having a caliber of about 10 points, a Parker Print Surf (PPS) value of about 9 microns (10 kg pressure with a soft back) and a Sheffield softness of about 310 can be treated according to certain embodiments of the present invention to produce a treated sheet having improved softness with only minimal gauge reduction. The base sheet may be treated by applying a PVOH solution of approximately 25% solids to the base sheet to produce a dry coverage of about 5 g / m2. Thereafter, the crosslinker solution may be applied at a rate and with solids in the solution to produce a borax coverage of at least about 0.1 g / m 2 dry. The wet, cross-linked polymeric film may be brought into contact with a hot polished drum by pressing the sheet against the drum surface. The surface temperature of the drum may be at least about 190 ° C. The coating would be dried and released from the drum surface. The time of contact of the polymeric film with the drum would typically be in the range of about 0.5 - 2.0 seconds. The treated sheet would have a caliber between about 9.6 and 10.0 points, a PPS value of about 2.4 to 3.0 and a softness of about 140 - 170.

In a preferred embodiment, a starch solution may be used as the polymeric material in the polymeric coating.

One aspect of the presentation refers to a method of producing paper or cardboard. According to one embodiment of the invention, the method includes applying a polymeric coating composed of a crosslinkable hydrogel to a substrate, applying a cross-linking solution to the polymeric coating on the substrate surface, thereby forming at least one partially polymeric film-forming coating. cross-linking and placing the film-forming polymer coating in contact with a heated surface while the film-forming polymer coating is still damp. The heated surface may be a hot polished drum having a soft finish. The temperature of the heated surface typically is within a range of from about 150 ° C to about 240 ° C. Higher temperatures may be used, for example, up to about 300 ° C. The heated surface temperature according to certain embodiments is within a range. 180 ° to about 200 ° C, and according to certain embodiments, is at least about 190 ° C.

According to special embodiments of the invention, the cross-linked polymer may be chosen from the group consisting of starch, cornstarch, protein, polyvinyl alcohol, casein, gelatin, soy protein, ealginates. According to certain aspects of the present invention, the crosslinkable polymer may be used in amounts ranging from about 60 to about 100% by weight of the dry materials.

In some manifestations, the crosslinker may be a borate or borate derivative, such as borax, sodium tetraborate, boric acid, boric acid phenyl, or boric butyl acid. The crosslinker may be used in amounts ranging from about 1 to about 12%, based on the crosslinker.

The present invention is also directed to papers produced according to the described method. Treated papers are characterized by improved softness together with relatively small increases in density compared to the original sheet.

As it is desirable to have the coating moist when contacting the heated drum, the coating may be moistened, for example by applying water. One method is to spray water over his coatings before contacting the hot drum. However, in certain embodiments, it may be possible to operate without any further humidification.

In certain embodiments, starch may be used as a soluble opolymer. In certain embodiments, amid-based coatings may be successfully operated without a crosslinker, and good results may be obtained without gelation (also called coagulation).

A starch solution containing 2 - 5% of a deliberation agent was contacted with a heated drum under the conditions described above. Under certain conditions, if humidification of the coating is desired, only water such as spraying may be used and good reproduction of the polished surface may be produced. If the coating solids are sufficiently few, the process works without a spray of water for humidification. A 20% solids starch coating was applied to the continuous sheet and placed in contact with a heated drum, and produced a good reproduction.

Starch coatings containing 25% and 30% solids were tested. Both of these coatings were released from the drum without any adhesion, but with good surface reproduction. The 25% solids coating showed moderate reproduction, but the 30% solids coating was not very soft. It appears that a certain amount of water present on the surface may help to propagate boiling over the entire coating. Below a certain amount of surface water, localized surface areas may still have sufficient boiling to produce a good reproduction of the dotambor surface, but other surface areas do not. Therefore, without surface spraying with water spray, when solids increase above 20%, the percentage of surface area reproducing the soft surface of the drum is reduced with increasing coating solids, until about 30% coating Solids produce little or no surface softness. If sufficient water is sprayed onto the 30% solids coating surface prior to contact with the heated drum, full surface reproduction can be achieved.

We would expect that this ratio could also be affected by the absorption capacity of the raw material, coating weight, coating viscosity and process speed. It could be possible to establish the effects of these parameters through further experiments.

The examples described above were performed with a chrome surface on the heated drum. The examples described below were performed after the drum was again coated on the surface with a tungsten carbide coating. In each of these examples, several "runs" were made to get the data. A run consists of the drum to be heated to approximately 190 ° C, a spray level will be set, the liner applied to the continuous sheet by a feed stick method, optionally followed by a humidification spray (which optionally may contain crosslinking agent), and then the continuous sheet will be put in contact with drum at 35 fpm. The drum temperature during a run ranged from 180 ° C to 190 ° C. During a run, the only variable that was changed was the weight of the coating applied by the feed rod. Changes were made to the coating type, coating solids content, level of dispersion in the different test runs and equipment. The weight of the jacket was measured by differential weighing and is recorded as bone-dry. Some of the experiments were performed with the crosslinker in the coating itself, for example, when a material such as starch that did not crosslink strongly was used.

Example 1

A minimally pressed base sheet with a basis weight of 111 lbs / 3,000 ft2 was used as a substrate on which to apply and treat single coat compositions. The first coating was CELVOL 203S polyvinyl alcohol (PVOH) with 95% dry weight and 5% Emtal 50 VCS, a triglyceride used as a release agent. The coating solids constituted 20% by weight. The coat was applied by a feeding stick. The table is a list of samples and test conditions. Sample 1.1 was made by spraying the coating with a crosslinking solution containing 3 wt% borax 1 wt% castor oil as the release agent. The dispersion rate was 48 ml / min. The sample replicated the drum well and was released without sticking. Significant improvements in softness have been achieved with minimal loss of caliber. For sample 1.2, the conditions were the same, except that no borax was used in the spray solution. Without the borax to crosslink the polyvinyl alcohol, the uncoated surface coating, and part of the film remained on the drum surface. clearly shows the benefit of polyvinyl alcohol crosslinking.

TABLE

Samples and test conditions

<table> table see original document page 25 </column> </row> <table>

In another run, carboxymethyl cellulose (CMC) was replaced by polyvinyl alcohol for comparison of polymer performance. Carboxymethyl cellulose was FINFIXX 30, which could only be made with 7% solids due to the viscosity of the coating. The coating was shaped with 95% polymer and 5% Emtal. Samples 1.3 and 1.4 are two different coating weights sprayed with a 48 ml / min borax spray. The coating replicated the drum surface well and was completely released from the drum. The softness was improved with a minimum caliber, but the softness was not as good as with polyvinyl alcohol. For the run that produced sample 1.5, no sprinkler borax was used. The coating replicated well the drum surface and was completely released from the drum. The softness has been improved by removing the chest. This showed that a non-crosslinked coating could be replicated and released from the drum, indicating that materials other than crosslinkable materials could be used in this process.Example 2

A minimally pressed base sheet having a basis weight of 111 lbs / 3,000 ft2 was used as a substrate on which to apply and treat simple coating compositions. The first coating was 95% dry weight CLEER-COTE 625 starch (a modified viscosity waxy cornstarch) and 5% Emtal 50 VCS5 with a triglyceride as the release agent. Coatings solids constituted 20% by weight. The coating was applied by means of a feed rod. Sample 2.1 was made by spraying the coating with a crosslinker solution containing 3% by weight of thorax and 1% by weight of a sulfonated castor oil as a deliberate agent. The spray rate was 46 ml / min. The sample replicated the drum and was released from the drum without adhering. Significant improvements in softness were achieved with minimal loss of caliber. Samples 2.2,2.3, 2.4 and 2.5 were prepared with different coating weights from the same coating, but the spray contained no borax. All samples replicated the surface well and were completely released from the drum. Samples 2.6 and 2.7 were executed without any sprinkling. The samples replicated the surface well and were completely released from it. The smoothness values were not so good, but the samples still had significantly improved smoothness with minimal reduction in gauge. This demonstrates that the process can be performed without any dehumidifying spray.

Example 3

This experiment was a continuation of example 2, exploring the effects of coating solids. Samples 3.1 and 3.2 were run with a 23% solids coating with no humidification spray. Good replication and good deliberation were obtained. For samples 3.3 and 3.4, the coating solids were increased to 25.7%, again being applied without any dehumidifying spray. Complete release was obtained but incomplete surface replication was obtained. Based on visual inspection, only about 90 - 95% of the surface replied to the drum. For samples 3.5 and 3.6, this same 25.7% solids coating was performed and a 48 ml / min humidification spray was applied. Full-surface replication and softness values were greatly improved. For samples 3.7 through 3.12, a 30% solids coating was used.

When no humidification spray (3.7) was used, a complete release was obtained, but only a small percentage of the surface was replicated. When a 48 ml / min humidification spray (3.8) was used, replication was greatly improved, but the surface was still mottled with a poor replication area.

When the humidification spray was increased to 98 ml / min (3.9, 3.10 & 3.12), replication was complete and softness was greatly improved with a minimum reduction in caliber. Thereafter, the solids of the coating were reduced. With 17.5% solids in the coating (3.13, 3.14) without any application of humidification spraying, good liberation and complete replication were achieved. At 10% solids (3.15) without any spraying application of humidification, the low viscosity of the coating led to reduced coating weight and increased coating absorption on the sheet, and thus poor replication occurred.

Samples of the soft products, produced using seam as the 20% solids polymeric coating, were top coated with a conventional pigmented clay coating (about two thirds of clay and one third of carbonate with a latex binder applied on a single coating approximately 10 pounds / 3,000 ft2) applied over the soft polymeric layer. These samples were then selected for examination of the coating layer morphology. The cutting was made by freezing the samples in nitrogenous liquid, and then splitting the samples in two (freeze fracture). The broken edges of the samples (for example, the sectioned sections) were then examined under a microscope.

The micrographs revealed that there are voids in the polymeric coating layer as shown in Figures 2 to 9 which include measuring bars to indicate their scale. For Figures 2 - 5, the microscope extension was 1000 times, and the measuring bars were 20 microns long. In Figure 2, as an example, the structure as shown includes a cardboard substrate 110. The thickness of the substrate generally extends below the area of the micrograph. Because of the freeze fracture process, substrate 110 as shown in the micrographs is sometimes separated or partially separated from polymeric layer 120. Thus, the upper boundary of substrate 110 can only be shown approximately by the dashed distance that represents the substrate.

In these samples, polymeric coating layer 120 was applied onto substrate 110, and was dried against a heated drum as described above. The topcoat 130 was then applied and dried. The term "polymeric coating" is used herein to describe that applied layer as described above, which then contacted a heated drum while it was wet. The term "topcoat" is used to describe the outer layer, which has been applied as a layer. Of course, the "topcoat" could be applied in more than one layer and could be of coating materials other than those used herein.

The voids 121 are evident in the polymeric coating layer 120, as seen in figures 2-9. Figure 2, for example, shows several voids 121 in the polymeric coating layer 120, with voids appearing to be approximately 5 to 20 microns in lateral dimension. It is considered that its size within the fractured sample is approximately in the same range. Void spaces typically appear to be "flat" in the "vertical" direction, that is, going to the thickness of the sample. The voids also appear to have relatively soft, and usually thin "walls". These thin walls are quite similar as seen between adjacent voids. When a void wall is adjacent to the topsheet 130, its thickness may be difficult to see but its presence may be reduced by the smaller soft outline of the topsheet 130 adjacent the void.

Figure 3 is an example micrograph showing various voids 121 in the polymeric coating layer. The voids appear to extend over an equivalent area of no more than the metadata of the coated surface area. The polymeric coating layer is not well defined in this micrograph.

Figure 4 is an example micrograph showing various voids 121 in the polymeric coating layer 120. The void walls appear to be relatively thin, as evidenced by a somewhat translucent appearance on the walls of two void spaces.

For figures 5-9, the microscope magnification was 500 times and the measuring bars were 50 microns long. Figure 5 shows various voids in the polymer layer 120, with individual measurement bars showing dimensions of the chosen spaces, for example, generally moving left to right, measurements of 10.5 microns at vertical distance, 36 microns at lateral distance, 10.6 microns vertical distance, and 36.3 microns in lateral distance. Again the voids appear to extend over an equivalent area of approximately half the area of the coated surface.

Figure 6 shows another sample with similar measurement bars, for example, generally moving from the right-hand left, measurements of 8.66 microns in vertical distance, 32.1 microns in lateral distance, 11.8 microns in vertical distance, and 22, 7 microns lateral conductance. Measurements like these in figures 5 and 6 were obtained for use in the graph discussed later in figure 17.

Figure 7 shows the voids 121 in the polymer layer 120, including several showing a generally flat appearance. The voids appear to extend over an equivalent area close to the total area of the coated surface. Figure 8 shows another sample with voids of similar width 121. The wall areas of the various voids are visible. Fig. 9 shows yet another sample where the voids 121 appear to extend over an area equivalent to almost the area of the coated surface.

Other samples of soft products produced using seam as the 20% solids polymeric coating were not top coated. These samples were cut for examination of the coating layer morphology. The cut was made by freezing the samples in liquid nitrogen, and then breaking the samples in two (freezing fracture). The edges of part of the samples (for example, the cut sections) were then examined under a microscope as shown in Figures 10 to 12, which includes measuring bars to indicate their scale. The microscope extension was 1000 times, and the measuring bars were 20 microns long. Figure 10 shows the polymeric layer 120, which contains the voids 121 and has a very soft outer surface. The polymeric layer is on a cardboard substrate 110, and is shown as one of cellulose fibers 112. The thickness of the substrate generally extends below. of the micrographic area.

Figures 11 and 12 show additional micrographs of samples that were polymer coated but not topically coated. Again, the softness of the polymeric layer 120 is evident, as are the voids at the bottom 121. The void walls often coincide with the surface of the polymeric coating.

Figure 13 (200-fold magnification) and Figure 14 (500-fold magnification) show the surface of the samples as seen in a scanning electron microscope. These samples were not coated with topcoat 130. Larger strand-like structures 122 that appear as a mesh or mesh are individual voids in the polymer layer 120. The polymeric layer here appears essentially transparent except for the empty-space walls.

Figures 15 and 16 show the surface of the samples as seen in a backscattered scanning electron microscope. These samples did not receive a topcoat 130. Larger bead-like structures 112 are substrate cellulose fibers 110. Smaller cell-like structures 122 appearing as a mesh or thin mesh are the walls of the individual voids in the polymer layer 120. The polymeric layer here appears essentially transparent except for the walls of the voids. The voids appear to be distributed over the entire surface.

Figure 17 is a graph showing the distribution of void sizes based on approximately 90 measurements of void width (lateral dimension) and height (a vertical dimension in micrographs). The measurements show an average void space width (measured in the direction parallel to the sample thickness) of about 19 microns, with a standard deviation of about 9 microns. The measurements show an average void height (measured in the direction going "within" the sample thickness) of about 10 microns, with a standard deviation of about 4 microns.

These empty space dimensions appear to be representative of the samples studied here. However, they do not mean to be limiting because changes in materials or processing conditions may have other dimensions.

It is hypothesized that vapor bubbles create these voids while the liner is in contact with the heated drum, and the bubbles may produce a force to help keep the liner in contact with the drum. The resulting voids typically help to bridge the gap between the roughened IlO substrate layer and the heated drum soft surface. Thus, the dry polymeric coating has a soft replicated surface which is softer than the substrate layer 110. It appears that many or most of the voids remain intact when topcoat 130 is applied. Thus, the topcoat may eventually be softer because of the relatively softer lower polymer layer 120. This is seen as an advantage gained by the invention. In addition to the possible influence of voids and ancillaries on creating a smooth replicated surface, voids may also contribute to lower product density.

The conditions in the space between the press roll 24 and the hot drum 22 may influence the formation of voids in the polymeric coating. Depending on the hardness of the press roll, and the diameters of the press roll and hot drum, it may be necessary to adjust the feed in this space (for example, the PLI feed over the space) to boil in this gap, which creates the voids.

The polymer coated paper or cardboard created by this process may be used whenever a soft substrate or a finished product is desired. The polymer coated paper or cardboard may be used as such (for example as shown in figures 10-16) or may be used as a substrate for additional coatings or other treatments to be applied (for example the topcoat 130 shown in figures 2 - 9, or other coatings) thereon. Additional materials or finishing processes may be applied to the polymer coated paper or paper, with or without additional coatings. For example, one or more additional coatings may be applied, as is typical with the base coat, topcoat, and triple coating of conventional paper or cardboard substrates. Calendering processes may be applied before or after additional optional coatings. For example, one or more additional coatings may be applied, followed by a calendering step.

Methods of producing and using polymer coated material according to the invention should be readily apparent from the material description and process as set forth herein. No further discussion or illustration deemed material or method detail is deemed necessary.

While the preferred embodiments of the invention have been described and illustrated, it should be apparent that various modifications may be made to the embodiments and implementations of the invention without departing from the spirit or scope of the invention. Although the preferred embodiments illustrated herein have been described in connection with a paper or cardboard substrate, these embodiments may be readily implemented in accordance with the invention in other structures, including, without limitation, textiles, nonwoven cloths, fibrous materials, polylactic acid substrates, and porous movies.

It should be understood, therefore, that the invention is not limited to the specific embodiments set forth (or apparent from the presentation) herein, but are limited only by the claims appended hereto.

What is claimed as new and desired to be protected by US patent letters is characterized by the fact that it constitutes:

Claims (162)

1. Product, characterized in that it comprises: a substrate; a first coating on the substrate, wherein the first coating includes a water-soluble polymer and a release agent, and where voids are formed within the first coating. Product according to Claim 1, characterized in that the first coating pellet contains essentially no elastomeric material. Product according to Claim 1, characterized in that the substrate pellet includes cellulose. Product according to Claim 1, characterized in that the substrate pellet comprises at least one of a paper, cardboard, fabric, fibrous material, porous material, porous film, or polylactic acid. Product according to Claim 1, characterized in that the water-soluble polymer pellet comprises a crosslinkable polymer. Product according to Claim 1, characterized in that the first coating pellet includes a cross-linking agent. Product according to Claim 6, characterized in that the cross-linking agent phage comprises at least one of borax, borates, aldehydes, ammonium salts, calcium compounds, and derivatives thereof. Product according to Claim 1, characterized in that the first coating pellet comprises on a dry weight basis at least about 60% water-soluble polymer and up to 10% release agent. Product according to Claim 1, characterized in that the water-soluble polymer pellet comprises at least one of starch, corn protein, protein, polyvinyl alcohol, casein, gelatin, soy protein, ealginate. Product according to claim 1, characterized in that the release agent comprises at least one of wax, oil wax, vegetable wax, animal wax, synthetic wax, acid-metal soap, metal stearates, long chain alkyl derivatives, esters. fatty acids, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids and combinations thereof. Product according to Claim 1, characterized in that it is further composed of a second coating on the first coat. Product according to Claim 11, characterized in that the second coating comprises at least one of pigment, binder and filler. Product according to claim 1, characterized in that the first coating includes a surface of at least 50% of the surface of the first coating and has subsurface voids having a transverse dimension of at least 5 microns. Product according to Claim 1, characterized in that the substrate comprises a continuous sheet. Product according to Claim 1, characterized in that the substrate comprises a sheet. Product according to Claim 1, characterized in that the first coating includes a surface with a Sheffield softness of less than about 300 units. Product according to Claim 1, characterized in that the first coating includes a surface with a Sheffield softness of less than about 200 units. Product according to claim 1, characterized in that the first coating includes a surface with a Sheffield softness of less than about 150 units. 19. Product, characterized in that it comprises: a substrate; A first coating on the substrate, wherein the first coating includes a water-soluble polymer and essentially no elastomeric material, and where voids are formed within the first coating. Product according to claim 19, characterized in that the substrate includes cellulose. Product according to claim 19, characterized in that the substrate includes at least one of paper, cardboard, fabric, fibrous material, porous material, porous film, or polylactic acid. Product according to claim 19, characterized in that the water-soluble polymer includes a crosslinkable polymer. Product according to Claim 19, characterized in that the first coating includes a cross-linking agent. Product according to Claim 23, characterized in that the cross-linking agent is composed of at least one of the boraxes, borates, aldehydes, ammonium salts, calcium compounds, and derivatives thereof. Product according to Claim 19, characterized in that the first coating includes, based on dry weight, at least about 60% water-soluble polymer and up to 10% deliberative agent. Product according to Claim 25, characterized in that the release agent comprises at least one of a wax, a petroleum wax, a vegetable wax, animal wax, synthetic wax, fatty acid metal soap, metal stearates, alkyl chain derivatives. long, fatty esters, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations thereof. A product according to claim 19, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Product according to Claim 19, characterized in that the first coating comprises starch. Product according to Claim 19, characterized in that it comprises a second coating on the first coating. Product according to Claim 19, characterized in that the second coating comprises at least one of pigment, binder, and filler. Product according to Claim 19, characterized in that the first coating comprises a surface of at least 50% of the surface of the first coating and has subsurface voids having a transverse dimension of at least 5 microns. Product according to Claim 19, characterized in that the substrate comprises a continuous sheet. Product according to Claim 19, characterized in that the substrate comprises a sheet. Product according to claim 19, characterized in that the first coating includes a surface with a Sheffield softness of less than about 300 units. Product according to Claim 19, characterized in that the first coating comprises a surface with a Sheffield softness of less than about 200 units. A product according to claim 19, characterized in that the first coating includes a surface with a Sheffield softness of less than about 150 units. 37. Product, characterized in that it is composed of: a substrate; a first coating on the substrate, where the first coating includes a surface, where the surface has a Sheffield softness of less than about 300 units, and where voids are formed under the surface of the first coating. Product according to Claim 37, characterized in that the first coating comprises essentially no elastomeric material. Product according to claim 37, characterized in that the substrate includes cellulose. Product according to claim 37, characterized in that the substrate comprises at least one of paper, cardboard, tissue, fibrous material, porous material, porous film, or polylactic acid. Product according to Claim 37, characterized in that the first coating comprises a crosslinkable polymer. Product according to Claim 37, characterized in that the first coating includes a cross-linking agent. Product according to Claim 42, characterized in that the cross-linking agent is composed of at least one of the boraxes, borates, aldehydes, ammonium salts, calcium compounds, and derivatives thereof. A product according to claim 37, characterized in that the first coating includes, on a dry weight basis, at least about 60% water-soluble polymer and up to 10% deliberative agent. Product according to Claim 44, characterized in that the release agent comprises at least one of wax, oil wax, vegetable wax, animal wax, synthetic wax, acid-metal soap, metallic stearates, long chain alkyl derivatives, esters. fatty acids, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations of the same. Product according to claim 37, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Product according to Claim 37, characterized in that the first coating comprises starch. Product according to claim 37, characterized in that at least 50% of the surface of the first coating has subsurface voids having a transverse dimension of at least 5 microns. Product according to claim 37, characterized in that the substrate comprises a continuous sheet. Product according to Claim 37, characterized in that the substrate comprises a sheet. Product according to Claim 37, characterized in that the surface has a Sheffield softness of less than about 200 units. Product according to Claim 37, characterized in that the surface has a Sheffield softness of less than about 150 units. 53. Product, characterized in that it comprises: a substrate; a first coating on the substrate, where the first coating includes a water-soluble polymer, a release agent, and essentially no elastomeric material, where the first coating includes a surface, where the surface has a Sheffield softness of less than about 300 units, and where the voids are formed beneath the first surface finish. Product according to Claim 53, characterized in that the substrate includes cellulose. A product according to claim 53, characterized in that the substrate includes at least one of paper, cardboard, fabric, fibrous material, porous material, porous film, or polylactic acid. Product according to Claim 53, characterized in that the water-soluble polymer includes a crosslinkable polymer. A product according to claim 53, characterized in that the first coating includes a crosslinking agent. Product according to claim 57, characterized in that the cross-linking agent is composed of at least one of the boraxes, borates, aldehydes, ammonium salts, calcium compounds and derivatives thereof. Product according to Claim 53, characterized in that the first coating includes, based on dry weight, at least about 60% water-soluble polymer and up to 10% deliberative agent. Product according to claim 53, characterized in that the release agent comprises at least one of wax, oil wax, vegetable wax, animal wax, synthetic wax, acid-metal soap, metallic stearates, long chain alkyl derivatives, esters. fatty acids, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations of the same. Product according to claim 53, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Product according to Claim 53, characterized in that the first coating comprises starch. Product according to claim 53, characterized in that at least 50% of the surface of the first coating has subsurface voids having a transverse dimension of at least 5 microns. A product according to claim 53, characterized in that the substrate comprises a continuous sheet. Product according to Claim 53, characterized in that the substrate comprises a sheet. 66. Product according to claim 53, characterized in that the surface has a Sheffield softness of less than about 200 units. Product according to Claim 53, characterized in that the surface has a Sheffield softness of less than about 150 units. 68. A process for treating a substrate, characterized in that it comprises: applying to the substrate a wet film of an aqueous polymer solution; and the immobilization of the aqueous polymeric solution by bringing the aqueous polymeric solution into contact with a heated surface to cause the aqueous polymeric solution to imbibe, where the immobilization includes at least partial drying of the aqueous polymeric solution. Process according to Claim 68, characterized in that the wet film is in contact with the heated surface for less than about 3 seconds. 70. The method of claim 68, wherein the wet film is in contact with the heated surface for less than about 2 seconds. Process according to Claim 68, characterized in that the wet film is in contact with the heated surface for at least about 0.5 seconds. Process according to Claim 68, characterized in that the heated surface is at a temperature above about 150 ° C. Process according to claim 68, characterized in that the wet film of the aqueous polymeric solution is in contact with a heated surface with a temperature above about 150 ° C for less than about 3 seconds. 74. A process for treating a substrate, characterized in that it comprises: applying to the substrate a wet film of an aqueous polymeric solution, immobilization of the aqueous polymeric solution by placing the aqueous polymeric solution in contact with a heated surface to cause that the aqueous polymer solution enters soaking and forms voids remaining in the aqueous polymer solution, where the immobilization includes at least partial drying of the aqueous polymer solution. Process according to Claim 74, characterized in that the wet film is in contact with the heated surface for less than about 3 seconds. Process according to Claim 74, characterized in that the wet film is in contact with the heated surface for less than about 2 seconds. Process according to claim 74, characterized in that the wet film is in contact with the heated surface for less than 0.5 seconds. Process according to claim 74, characterized in that the heated surface is at a temperature above about 150 ° C. A process according to claim 74, characterized in that the wet film of the aqueous polymeric solution is in contact with a heated surface with a temperature above about 150 ° C for less than about 3 seconds. 80. A process for treating a substrate, characterized in that it comprises: applying to the substrate a first coating of an aqueous polymeric solution as a wet film, wherein the first coating includes a water-soluble polymer and a release agent, the immobilization of the by contacting it with a surface heated for less than about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymer solution to boil and form voids in the film, where immobilization includes at least partial drying dofilm. 81. The method of claim 80, wherein the film is in contact with the heated surface for less than about 2 seconds. Process according to claim 80, characterized in that the film is in contact with the heated surface for less than about 0.5 seconds. Process according to claim 80, characterized in that the substrate includes cellulose. Process according to Claim 80, characterized in that the aqueous polymer solution contains essentially no elastomeric material. Process according to claim 80, characterized in that the substrate comprises at least one of paper, cardboard, fabric, fibrous material, porous material, porous film, or polylactic acid. Process according to Claim 80, characterized in that the water-soluble polymer includes a cross-linkable polymer. Process according to Claim 80, characterized in that the cross-linking agent is included in the first coating or is applied to the first coating before the film is contacted with the heated surface. A process according to claim 88, characterized in that the cross-linking agent is comprised of at least one of the boraxes, borates, aldehydes, ammonium salts, calcium compounds, and derivatives thereof. Process according to Claim 80, characterized in that the first coating includes, based on dry weight, at least about 60% water-soluble polymer and up to 10% deliberative agent. A process according to claim 80, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Process according to Claim 80, characterized in that the first coating includes starch. A process according to claim 80, characterized in that the release agent comprises at least one of wax, oil wax, vegetable wax, animal wax, synthetic wax, acid-metal soap, metal stearates, long chain alkyl derivatives, esters. fatty acids, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations of the same. Process according to claim 80, characterized in that it is further composed of the application of a second coating after at least partial drying of the film. Process according to Claim 93, characterized in that the second coating comprises at least one of pigments, binders and fillers. A method according to claim 80, characterized in that the first coating includes a surface and at least 50% of the surface of the first coating has subsurface voids having a transverse dimension of at least 5 microns. A process according to claim 80, characterized in that the substrate comprises a continuous sheet. Process according to Claim 80, characterized in that the substrate comprises a sheet. Process according to Claim 80, characterized in that the first coating includes a surface with a Sheffield softness of less than about 300 units. Process according to Claim 80, characterized in that the first coating includes a surface with a Sheffield softness of less than about 200 units. Process according to Claim 80, characterized in that the first coating includes a surface with a Sheffield softness of less than about 150 units. 101. A process for treating a substrate, characterized in that it comprises: applying to the substrate a first coating of an aqueous polymeric solution as a wet film, wherein the first coating comprises a water-soluble polymer and essentially no elastomeric material; contacting a heated surface for less than about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymer solution to boil and form voids in the film where immobilization includes at least partial drying dofilm. 102. The method of claim 101 wherein the film is in contact with the heating surface for less than about 2 seconds. Process according to Claim 101, characterized in that the film is in contact with the heating surface less than about 0.5 seconds. Process according to Claim 101, characterized in that the substrate includes cellulose. Process according to claim 101, characterized in that the substrate comprises at least one of paper, cardboard, fabric, fibrous material, porous material, porous film, or polylactic acid. A process according to claim 101, characterized in that the water-soluble polymer includes a cross-linkable polymer. A process according to claim 101, characterized in that a crosslinkable agent is included in the first coating or is applied to the first coating before the film is brought into contact with the heated surface. Process according to Claim 107, characterized in that the cross-linking agent is composed of at least one of borax, borates, aldehydes, ammonium salts, calcium compounds and derivatives thereof. Process according to Claim 101, characterized in that the first coating includes, based on the dry weight, at least about 60% water-soluble polymer and up to 10% release agent. 110. The process of claim 109 wherein the release agent comprises at least one toothpaste, petroleum wax, vegetable wax, animal wax, synthetic wax, fatty acid metal soap, metal stearates, long chain alkyl derivatives, fatty esters, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations thereof. Process according to Claim 101, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Process according to Claim 101, characterized in that the first coating comprises starch. 113. The method of claim 101 further comprising further applying a second coat after at least partial drying of the film. 114. The method of claim 113, wherein the second coating comprises at least one pigment, binder, and filler. Process according to claim 101, characterized in that the first coating includes a surface and at least 50% of the surface of the first coating has voids of the subsurface having a transverse dimension of at least 5 microns. Process according to Claim 101, characterized in that the substrate comprises a continuous sheet. 117. The method of claim 101 wherein the substrate comprises a sheet. Process according to Claim 101, characterized in that the first coating comprises a surface with a Sheffield softness of less than about 300 units. Process according to Claim 101, characterized in that the first coating comprises a surface with a Sheffield softness of less than about 200 units. 120. The method according to claim 101, characterized in that the first coating includes a Sheffield soft surface less than about 150 units. 121. A process for treating a substrate, characterized in that it comprises: applying to the substrate a first coating of an aqueous polymeric solution as a wet film, immobilizing the film by contacting it with a heated surface for less than about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymeric solution to boil and form voids in the film, where the immobilization includes at least partial drying of the film, where the first coating includes a surface, where the The surface of the first coating after drying has a Sheffield softness of less than about 300 units. 122. The method of claim 121, wherein the film is in contact with the heating surface for less than about 2 seconds. 123. The method of claim 121, wherein the film is in contact with the heating surface less than about 0.5 seconds. Process according to Claim 121, characterized in that the substrate includes cellulose. Process according to Claim 121, characterized in that the substrate comprises at least one of paper, cardboard, fabric, fibrous material, porous material, porous film, or polylactic acid. Process according to Claim 121, characterized in that the aqueous polymeric solution contains essentially no elastomeric material. A process according to claim 121, characterized in that the aqueous polymeric solution includes a polymerizable linker. Process according to Claim 121, characterized in that a cross-linking agent is included in the first coating or applied to the first coating before the film is brought into contact with the heated surface. A process according to claim 128, characterized in that the cross-linking agent is composed of at least one of borax, borates, aldehydes, ammonium salts, calcium compounds and derivatives thereof. Process according to Claim 121, characterized in that the first coating includes, based on the dry weight, at least about 60% of the water-soluble polymer and up to 10% of the release agent. Process according to claim 130, characterized in that the release agent comprises at least one toothpaste, petroleum wax, vegetable wax, animal wax, synthetic wax, fatty acid metal soap, metal stearates, long chain alkyl derivatives, fatty esters, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations thereof. Process according to Claim 121, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Process according to Claim 121, characterized in that the first coating comprises starch. A method according to claim 121, further comprising a second coating after at least partial drying of the film. Process according to Claim 134, characterized in that the second coating comprises at least one pigment, binder, and filler. 136. The method of claim 121, wherein at least 50% of the surface of the first coat has subsurface voids having a transverse dimension of at least 5 microns. Process according to Claim 121, characterized in that the substrate comprises a continuous sheet. Process according to Claim 121, characterized in that the substrate comprises a sheet. Process according to Claim 121, characterized in that the surface of the first coating has a Sheffield softness of less than about 200 units. Process according to Claim 121, characterized in that the surface of the first coating has a Sheffield softness of less than about 150 units. 141. A process for treating a substrate, characterized in that it comprises: applying to the substrate a first coating of an aqueous polymeric solution as a wet film, wherein the first coating includes a water-soluble polymer, a release agent, and essentially no elastomeric material, immobilizing the film by contacting it with a heated surface for less than about 3 seconds at a temperature above about 150 ° C to cause the aqueous polymer solution to boil and form voids in the film where The immobilization includes at least the partial drying of the film, where the first coating includes a surface, where the surface of the first coating after drying has a Sheffield softness of less than about 300 units. 142. The method of claim 141 wherein the film is in contact with the heating surface for less than about 2 seconds. 143. The method of claim 141, wherein the film is in contact with the heating surface for less than about 0.5 seconds. Process according to Claim 141, characterized in that the substrate includes cellulose. Process according to Claim 141, characterized in that the substrate comprises at least one of paper, cardboard, fabric, fiber material, porous material, porous film, or polylactic acid. A process according to claim 141, characterized in that the water-soluble polymer includes a cross-linkable polymer. A process according to claim 141, characterized in that a crosslinking agent is included in the first coating or applied to the first coating before the film is brought into contact with the heated surface. A process according to claim 147, characterized in that the cross-linking agent is composed of at least one of borax, borates, aldehydes, ammonium salts, calcium compounds and derivatives thereof. A process according to claim 141, characterized in that the first coating includes, based on the dry weight, at least about 60% water-soluble polymer and up to 10% release agent. Process according to claim 141, characterized in that the release agent comprises at least one toothpaste, petroleum wax, vegetable wax, animal wax, synthetic wax, fatty acid metal soap, metal stearates, long chain alkyl derivatives, fatty esters, fatty amides, fatty amides, fatty acids, fatty alcohols, polymers, polyolefins, silicone polymers, fluoropolymers, natural polymers, fluorinated compounds, fluorinated fatty acids, and combinations thereof. 151. Process according to claim 141, characterized in that the first coating comprises at least one of starch, waxy maize, protein, polyvinyl alcohol, casein, gelatin, soy protein, and alginate. Process according to Claim 141, characterized in that the first coating comprises starch. Process according to Claim 141, characterized in that it is further composed of the application of a second coating after at least partial drying of the film. Process according to Claim 153, characterized in that the second coating comprises at least one pigment, binder, and filler. Process according to Claim 141, characterized in that at least 50% of the surface of the first coat has voids of the subsurface having a cross-sectional dimension of at least 5 microns. Process according to Claim 141, characterized in that the substrate comprises a continuous sheet. Process according to Claim 141, characterized in that the substrate comprises a sheet. Process according to claim 141, characterized in that the surface of the first coating has a Sheffield softness of less than about 200 units. Process according to Claim 141, characterized in that the surface of the first coating has a Sheffield softness of less than about 150 units. 160. A process for treating a substrate, characterized in that it comprises: providing a cellulosic substrate, applying to the substrate a wet film of aqueous polymeric solution, wherein the aqueous polymeric solution is composed of at least about 60% soluble polymer. dry weight based water, and up to 10% dry weight based release agent, immobilization of the aqueous polymer solution by contacting the same with a heated surface for less than about 3 seconds at a temperature above about 150 ° C. ° C to cause the aqueous polymer solution to boil and form voids in the aqueous polymer solution, where immobilization includes at least partial drying of the aqueous polymer solution. A process according to claim 160, characterized in that the aqueous polymer solution is in contact with the heated surface for less than about 2 seconds. Process according to claim 160, characterized in that the aqueous polymeric solution is in contact with the heated surface for less than about 0.5 seconds.