JPH06502818A - Method for forming oil-repellent coated sheets and products thereof - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Method for forming oil-repellent coated sheets and products thereof 1. Field of invention The present invention is useful for sheet decoration and more particularly for standard lightweight cellulose sheets. Concerning the decoration of materials such as (paper). The present invention also provides an edge for sheets or films. For embossing and more specifically from decorative surfaces of sheets or films. Concerning repelling the ile.

Description of prior art Cellulose sheets are usually decorated by imprinting methods. achieve some kind of special effect To achieve this, the printing method requires special inks and relatively complex printing procedures. . In addition, some decorative effects cannot be achieved by imprinting methods.

One very desirable decorative effect is the iridescent color produced by the diffraction grating. It's a visual effect. Di rec tor of the Br1tish R Sir John Barton, oyal Mint (ca. 1770) This noticeable effect is due to the fact that the surrounding light changes its color by reflection from the diffraction grating. This occurs when the light is diffracted into components. Diffraction gratings are closely and regularly spaced grooves (5,000 to 11,000 grooves per cm) embossed on the reflective surface. formed when

In recent years, this diffraction grating technology has been used to create two-dimensional holograms that create the illusion of a three-dimensional image to the observer. It has been used in the formation of 1' roughy images. This holographic image technique The technique can create very attractive displays.

Furthermore, the economics of forming holographic images depend significantly on economies of scale. The concept of discouraging counterfeiting using holographic images is widespread. I have found a good use for it.

The original diffraction grating is then densely deposited onto a polished metal surface using a special “ruler”. formed by cutting large, evenly spaced lines.

by subsequently shaping the moldable material to the master grating surface. A technique has been developed to replicate the master grating. More recently, Phil The surface of the film is thermally softened and then a diffraction grating or hologram is placed on top of the softened surface. Run the thermoplastic film through an embossing roller that imparts an image of the film. Now you can emboss them by In this way, there is virtually no A sheet of limited length is mounted on its surface with a diffraction grating or holographic image. It can be decorated. The decorated surface of the polymer can be used as a diffraction grating without any additional treatment. It is usually sufficiently reflective that the optical effect of This is because the incident light This is because it is reflected by the surface of the decorated surface. For the purposes of this application, The term grating includes holographic images based on grating technology. .

Unfortunately, such unprotected diffraction gratings have grooves on their surface that can be removed by almost any material. and its iridescent light, especially when it becomes filled with oily substances. would lose its scientific effectiveness. More specifically, it will be handled by humans. On a decorated surface, the ≠ skin area normally present on a human finger is fills the grooves in the unprotected surface and from the part of the surface covered by the sucor This will remove the iridescent effect.

decorated by coating the decorated surface with a protected transparent polymeric layer The presence of the decorated layer itself should be avoided if skin oils should not enter the grooves in the surface. It has been found that the presence of light will destroy the iridescent optical effect.

This problem can be solved by plating an unprotected grooved surface to form a reflective surface and The next solution is to coat the plated surface with a protective layer. can. Although the resulting product retains an iridescent effect, the plating method is very expensive. and introduce numerous practical problems in the production of embossed sheets.

These and other difficulties experienced with prior art chemical methods are overcome by the present invention. It was removed in a novel way by

It is therefore an object of the present invention to ensure that oil deposited on a surface is repelled from the surface. The objective is to provide a decorative surface system that

Another object of the invention is that the oil deposited on the surface is Optical light produced by a bossed diffraction pattern or holographic image The objective is to provide a decorative surface system that does not interfere with the effect.

In view of the above-mentioned and other purposes that will become apparent as the description progresses, The invention comprises the combinations and steps of steps hereinafter described and claimed. and sequence and composition details, and the exact nature of the invention disclosed herein. Changes in the embodiments may depart from the spirit of the invention (and the scope of what is claimed). It is understood that this can be done within.

Summary of the invention In achieving the above-mentioned and related objects, the present invention provides for Provides embossing. This coating has a perceivable heat It is a heat-sensitive material with plastic properties. The term “thermoplastic” refers to When used hereinafter, it shall be construed to include such materials.

Said paper is advantageously supplied with a thermoplastic coating. this heat Plastic coatings are typically produced by intaglio or reverse roll processes. applied in a water-based or other suitable liquid.

The actual formation of the coating is formed from a dispersion of polymer spheres in a volatile liquid. The process begins by spreading a prepared pre-membrane composition onto an oil-absorbing paper substrate. Probably. Subsequently, the substrate covered with the pre-membrane is heated to volatilize the liquid and release the porous material. The remer particles are melted together. The resulting coating is a coated surface It absorbs the oil deposited on it and repels the oil onto the paper substrate which absorbs the oil. It is a porous membrane that can be skipped. Since this film is thermoplastic, it can be It can be embossed to form a diffraction grating or a holographic image. this is , must be done without destroying the porosity of the membrane. Fill with the best oil Skipping properties occur when the membrane has a broken or cracked surface after embossing. was observed. The optical effect or image produced is deposited on the surface of the coating. It will not be destroyed by accumulated oil. The reason is 1. soil oil is on the surface The oink that is repelled from the surface and lies underneath will adhere well to the decorative surface. And when applied lightly, it interferes with the decorative effect produced by the embossing. do not have.

Preferred pre-membrane coating compositions include lipophilic polymers such as styrene polymers. It is an aqueous dispersion of spheres. Applicants prefer dispersions of substantially uniform particle size. and generally larger particle sizes provide improved oil-repelling properties. observed to bring about sex. The most preferred dispersion is styrene/acrylic Consists of 0.5 micron diameter spheres of copolymer. The coating composition also Typical ingredients include primers, plasticizers, emulsifiers, dispersants, pigments, and defoamers. cormorant. Although the plasticizer is sufficient to give the membrane adhesion to the substrate, it does not block the membrane. It will be present in a minimal amount that is insufficient to have nucleating properties.

Brief description of the drawing FIG. 1 is a schematic diagram illustrating the coating operation, and FIG. 2 is a diagram illustrating the coated substrate of FIG. FIG. 3 is a perspective view of one form of embossing; FIG. 5 is a perspective view of an alternative form of embossing, and FIG. 5 shows the substrate and preliminary membrane layer. Figure 6 is a cross-sectional view of the laminate in which the pre-membrane coating is melted to form a porous membrane. It is a cross-sectional view of the laminate after forming, FIG. 7 is a cross-sectional view of the laminate after embossing, and FIG. 8 is a cross-sectional view of the laminate after embossing. Cross section of the laminate after human skin oil has been deposited onto the embossed surface and FIG. 9 shows a laminate showing oil being repelled from a knee-possessed surface. In the cross-sectional view of Figure 10 shows the oil splashed onto and absorbed by the substrate. FIG. 3 is a cross-sectional view of the layered material.

Description of preferred embodiments A preferred embodiment of the invention begins with the coating method described in FIG.

For example, a standard paper sheet 10 may be supplied with the upper side of the paper sheet 10 from the supply box 12. Thermoplastic pre-membrane coating by pouring a liquid pre-membrane mixture onto surface 13. 11. Thermoplastic coating 11 is also supplied by supply box 12. Solvent or water using intaglio or reverse roll method, as shown schematically in It can also be given in the base.

The thickness of paper sheet 10 typically varies from about 40 microns to about 100 microns.

Paper sheet 10 may also be cardboard having a thickness of up to about 750 microns (note +25.4 microns = 0.001 inch). Coat of thermoplastic coating 11 The printing weight is sufficient to accept and retain the micro-embossed image. There must be. The rougher the paper, the thicker the thermoplastic coating is required. On the other hand, the higher the coating weight, the more It tends to increase curl. Regarding the coating weight of thermoplastic coating 11 The preferred range was determined to be approximately 3 to 20 grams per square meter. . In a preferred embodiment of the invention, the paper sheet provides strength and strength for the final product. , as you will see later, it absorbs oil which attracts oil through the coating. It will give you both characteristics. A first very strong layer (e.g. a polymeric film) layer of paper) and a second oil-absorbing paper layer between the first layer and the coating. It would also be possible to form a body.

Other oil-absorbing substrates such as non-woven fabrics can also be used in the present invention instead of paper. May be used.

Referring now to FIG. 2, once coating 11 is applied to the upper surface of paper substrate 10, 13, the coated substrate is coated with a coating 11 in which the outer layer is liquid-bearing. The body is volatilized and the coating is melted or sintered into a porous membrane.

Use additional heat to ensure proper heating, softening and melting or sintering. can be done. Special features include infrared heaters that can be placed away from the surface being softened. Appropriate for Such a heater is about i,oo.

Operates at a heater surface temperature of ’F.

The thermoplastic (thermally deformable) coating 11 has a temperature well above its softening temperature. It must be heated thoroughly. When using coated paper, coating 11 The practical limit for heating is about 230°C (450'F). Above this temperature , the paper substrate begins to deteriorate. In operation, coating 11 typically has a thickness of about 12 Should be heated to a temperature of 0°C to 177°C (250°F to 350°F) was determined and this range is combined and embossed in the method of the present invention. represents a preferred range for most thermoplastic coatings.

During this heating operation, the pre-membrane mixture is coalesced. This merging method is The mixture still remains after the cooling operation and the melting of the thermoplastic particles that are the main component of the pre-membrane mixture. including volatilization of any water (or other liquid carrier) present in the The code to generate The coating is a porous membrane that is firmly attached to the substrate.

will normally be fed directly to the embossing stem. However, the generation The laminate is then cooled and stored for embossing at some later time. It may also be possible to do it in between.

The softened and melted laminate can be fed directly to the embossing step. , more energy efficient and therefore preferred.

Referring now to Figure 3, once the outer layer of thermoplastic has been softened and porous Once the film has been fused, an embossing device is used for decoration. this The device includes a heated hot platen 32, an embossing roll 31 and a pressure nib roll 3. Use 3. The embossing roller 31 applies the desired embossing onto its surface. It is a conventional embossing master with Everturn. This pattern is hard Engraving, embossing or on the surface of the roller 31 by the material by attaching patterned plastic film or metal foil to - or produced on multiple rollers. The embossing roller 31 is soft. When in contact with the embossed plastic surface 11, the embossed pattern on the paper Transferred to coating 11. At the same time, contact with relatively cold rollers cooling. This cooling action causes the coating to de-emboss. Prevents coating from running away after cleaning. The result is decorated and polymer coated It is paper.

The temperature of the embossing master (embossing roller 31) is should be lower than the softening temperature of the ring 11. However, embossed The temperature of the embossing roller 31 is such that the coating 11 is hardened before embossing is completed. It shouldn't be that low. Embossing roller 31 (embossing master ), its thermal conductivity and specific heat, embossing entube pressure, The viscoelastic properties, the operating speed, and the coating immediately before contact with the embossing roller 31 It has been found that the heating temperature can vary depending on the temperature at which it is heated. many strange Despite the number, the applicant has developed an embossing master (roller) in the method of the invention. The preferred temperature of the roller 31) is about 66°C below the temperature of the thermoplastic coating 11. It was determined that the temperature was between 150°F and 208°F. present invention In the context of the method, this generally reduces the preferred web temperature to about 100°C (2 12°F) to 200°C (392°F).

In the alternative arrangement of FIG. 4, the take-off roller 34 is coated with a thermoplastic coating. In order to allow longer contact between the ring 11 and the embossing roll 31 added. This longer contact time allows for better cooling of the embossed surface allows for easy separation of the web from the embossing roll and can be Prevents coating glue flow and loss of embossed patterns. pressure The nip roller 33 may be metal, or the surface may be made of an elastic material such as rubber. may be covered. Pressure knit roller 33 and embossing roller 31 The force applied between the two rollers is Must be in the range of approximately 501 bs per inch (PLI) to approximately 1,0 OOPLI. No. Pressure is applied between the knitting roller 33 and the embossing roller 31. The force applied may advantageously be between 50 and 300 PLI, more preferably between about 100 and 2 It is 00PLI.

This latter range approximately corresponds to about 40 to 9 Qlbs per square inch. − The contact pressure between the singing cylinders or rollers is pumps per square inch. It is often reported in pounds per line inch (PLI) rather than pounds per line inch (PLI).

This is because the exact width (i.e. area) of contact between the two rollers is usually not known. However, the force applied at the contact length is generally known.

The surface of the embossing roller (roller 31) is embossed with an embossed pattern. It must be hard and resist deformation to be preserved during processing steps.

The opposing roller, i.e. the nip roller 33, must be rigid (but also somewhat It must be soft and elastic. This is because the nip roller 33 is embossed. This makes it possible to apply an almost evenly distributed pressure to the back of the sheet. Nippro 33 typically has a Shore A Juro of about 70-80 or somewhat higher. Extremely hard (and has a hardness meter reading of ASTM D-412) Ensure that evenly distributed pressure is obtained on the back of the sheet being embossed. It was decided that the material should not be so hard as to interfere with the material. Embossing roller 3 1 and nip roller 33 come into contact with the sheet to achieve embossing. time is typically about 8 milliseconds (e.g. for a 1/2 inch wide contact area) is 300ft/m1n) to about 0. 2 milliseconds (e.g. 1/8 inch wide contact area It is in the range of 300ft/m1n).

Various decorative effects can be achieved by embossing.

If the diffraction pattern is not continuous, appropriate modification of the embossing roller will can provide a matte background. Instead, the embossed pattern is Coating the areas where embossed decoration is not desired, e.g. insword also can also be partially filled with transparent lacquer.

Turning now to a more microscopic view of the method and product of the present invention, FIG. a paper sheet with a coating 11 of a pre-membrane mixture before melting of the material 11; An enlarged cross-sectional view of the base body 10 is shown. FIG. 5 constitutes the main components of the pre-membrane mixture 11 Thermoplastic spheroids (sphero 1ds) 37, 38, 39 and 40 are shown. vinegar. These spheroids form the coating on the substrate 10 prior to melting of the coating. form a ting.

FIG. 5 shows that it includes the upper surface 13 of the substrate 10 and the lower layer of the uncured coating 11. It must be understood that it is symbolic in that it shows the interface between Noriyoshi Typically, the spheres are stacked on top of the substrate to a depth of more than 40 spheres, resulting in a core The tings are approximately 20 microns thick.

FIG. 6 is a cross-sectional view of the laminate after coating 11 has been melted to form a porous membrane. shows. The spheroid present in Figure 5 has pores 46, 47, 48 and 49 rotated. are fused together in such a way that they are formed between ellipsoids, and these pores , passes from the upper surface 14 of the coating 11 to the lower surface 15 of the coating 11. do. The lower surface of the coating 11 is of course in contact with the upper surface 13 of the substrate 10. ing.

In a preferred embodiment, after melting, the microporous membrane coating: approximately 20 microns thick (from top to bottom) and approximately 100 microns between pores. It would be Kron. The pores are approximately 5 microns wide and extend across the coating surface. forming an interconnected three-dimensional network of transpositions that connect to the for simplicity , the pores are shown as capillaries running from the top to the bottom of the coating. However, the pore structure is more complex, such as the interconnected cracks in J. It should be understood that The applicant claims that the final surface structure is a polymer particle dispersion depending on the choice of liquid (see Example 1 below) and drying and embossing conditions. I observed that. The longer the drying time, the higher the embossing temperature. The higher the amount, the more time it takes to slough off the oil. It tends to increase. In general, cracked or cracked surfaces are It has the property of repelling oil.

Figure 7 shows that the upper or decorative surface of the coating 11 has been embossed. FIG. 6 shows an enlarged cross-sectional view of the laminate according to the present invention. Embossing is shown as groove 51 There is. Typically the grooves are 1 micron peak to peak and 0.5 microns wide. Ron is deep.

FIG. 8 shows human skin oil 50 deposited on top surface 14 of coating 11. FIG. 2 shows an enlarged cross-sectional view of the laminate of the present invention. This oil is added to the embossed surface. The groove 51 is penetrated and the oil and then the coating 11 forms. Since the refractive index of the thermoplastic materials used does not differ greatly, the grooves under the oil Visual effects are effectively erased.

FIG. 9 shows that oil wets the internal surface of pore 46 and is attracted to it. As a result, the oil is drawn down into the pores and towards the substrate 10. An enlarged cross-sectional view of the layered material is shown.

FIG. 10 shows that oil 50 is effective from the upper surface of coating 11 along pores 46. The laminate of the invention is repelled by the target and completely absorbed by the substrate 10. An enlarged cross-sectional view is shown. The result is a visual effect on the upper surface of the coating before This means that the interfering oil has been completely removed from the upper surface of the coating. Ru. Applicants have proposed a method for passing finger oil from a surface to an oil-absorbing substrate. Approximately 0. Typical permeation rates of 5 to 3 minutes were observed.

A key element of the invention is the coating on the decorative or embossed surface. microporous core that is suitable to absorb into its pores all the oil deposited on the It is The polymer from which the membrane is formed has a pore surface that is lipophilic. They must form pores that attract human skin oils. or must be wetted by it. In a preferred embodiment, this The membrane is made of uniformly sized thermoplastic polymer particles, which can absorb oil. formed by the melting of a membrane into a skin that is full of pores or small racks. Will.

As can be seen from Example 1 below, a particle size of about 0.5 microns is preferred.

Applicants also note that the microporous coating of the present invention also allows gas to pass through but repels water ( It was recognized that it has hydrophobic (hydrophobic) power. This also allows breathing while preventing dehydration Its utility as a selective membrane in packaging products (surface embossing) (with or without processing).

In a preferred embodiment, the pre-membrane mixture is dispersed in water by a plasticizer. uniform 0.5 micron diameter polystyrene spheroids, colored pigment dispersion (if desired for appearance) and certain other processing aids.

When this coating is applied to a paper substrate and dried at 130°C (266°F) In this process, polystyrene particles are melted together and formed into a transparent material containing small interconnecting racks. Leaves a clear film. These cracks allow all surface oil to enter the membrane. and then flicked into the underlying paper substrate. This coating is Can be stored after melting, supported or thermally embossed immediately after melting. Ru.

Premembrane mixtures of the present invention will typically contain the following components:

1. Binder: Uniform polystyrene particles (Morton International An aqueous dispersion of Lytron 2502) from It is solid. Lytron alone has good oil absorption and dries transparent. It becomes a clear film. However, it exhibits curl when applied to paper. More and high cohesive and adhesive strength are also preferred. This binder (and its aqueous carrier) ) is approximately 80% by weight of the total dry coating weight. Lytron series Therein, the applicant states that the particles are preferably of small diameter (both 0.1 micron and less). I observed that something must happen. A diameter of 0.5 microns is most preferred.

2. Plasticizer: For example, butylbenzyl phthalate to soften the coating. is required. This reduces curl and reduces the glass transition temperature. It also lowers the embossing temperature) and adds shine to the coating. plasticity The agent is less than 5% by weight of the dried coating and the finished product that the coating adheres to the paper without causing blocking in is kept to the minimum amount possible.

3. Emulsifier: For example, a nonionic emulsifier to make the plasticizer compatible with the polystyrene dispersion. alkylphenyl polyether alcohol (T from Rohm and Haas) Rinton X-100) is required. The emulsifier is 5% of the weight of the plasticizer or may be 0.2% of the total mixture.

4. Pigment dispersion: For example, toluidene red (AJT 222 DaY Glo Co 1 or Comp) may be added directly to the polystyrene/plasticizer mixture.

5 Dispersant 9 For example DISPER 8E from Daniel Products AYD W-28 was plasticized to make the pigment dispersion compatible with the polystyrene mixture. should be added to the agent/polystyrene mixture.

6. Defoaming agent 9 For example, Bubble Break from Witco Corp. r748 is incorporated into the mixture after plasticizer addition.

Formulation data/ Plasticizers should be loaded with emulsifiers. Then plasticize the binder under gentle stirring Add to the agent. Add half of the defoamer, followed by the dispersant, to this mixture. It is possible. Slowly add the pigment dispersion followed by the remainder of the defoamer to this mixture. It's okay to do that.

Various data: Two other latexes have been found to have oil-absorbing properties: 1. Aqueous dispersion of polyvinyl butyral (Butvar BR from Monsanto) liquid. This coating formed a very sticky film.

2. Carboxylated acrylic copolymer latex (BF Gutdrich) Hycar 26315) has slower oil absorption than Lytron. there was.

Addition of primer to the formulation adds adhesive strength to the coating.

Paper bonding is enhanced when dried at lower temperatures (110°C versus 130°C). It will be done. However, the reduction in gloss and emboss definition occurs as a result.

Formulation A Oil-absorbing embossable coating (transparent) wt% Binder polystyrene pigment dispersion Lytron 2502 from Monsanto 95.00 Rohm and Haas? et al. 100.00 Formulation B Oil-absorbing embossable coating (red transparent) wt% Day Glo Co1or Corp 15.8 Dispersant Daniel Pr Disperse AYD W-280,3100,00 from oducts Formulation C oil-absorbing embossable coating (white translucent) wt% WFD-610214・5 Dispersant Disperse AYD W from Daniel Products -280,25100,00 Formulation D Oil-absorbing embossable coating (green transparent) wt% 49T70 2.0 from Morton Pigment dispersion (Phthalo Green) Day Gl.

Co1or Corp, from AIT 544 16.2 Dispersant Disperse AYD W from Daniel Products -280,3100,00 Formulation E Oil-absorbing embossable coating (yellow transparent) heavy amount% 49T70 2.0 from Morton Pigment dispersion (Yellow) Day Glo A from Co1orCorp IT 385 15.5 Dispersant Dis from Daniel Products perse AYD W-28 Region 2 Defoamer Bu from Witco Corp. bble Breaker 748 0.6 All of the above formulations are fully functional It is. Formulation E with appropriate selection of colored pigments gives the best combination of properties . It is melted by heating to 110°C (230°F) and is highly effective. It is possible to produce a film of The preferred paper is a high wet strength clay ) coated paper.

The invention may be further understood by reference to the following comparative examples and the variances in Table 1. liquid and latex in the production of micro-embossed coated paper. To evaluate the properties of the mer itself, it was used without additives or modifiers. child These dispersions were spread over 1 square meter using a rod wrapped with #12 wire. 5ibille 5tenay white clay coated paper (On e Newbury St, Peabody, Massachusetts 0 1960). Dry the sample in an oven at 130°C for 20 seconds 120 using a diffraction embossed plated mylar master. Embossed at °C. The quality of the embossing from the embossed coating Peeling of the master was evaluated.

Embossed coated paper with skin oil smeared on the surface and diffraction pattern Test for oil splash by measuring the time it takes to reappear. did. Adhesion of the coating to the paper is applied by finger pressure and rapidly pulled 3M MAGIC tape (Minnesota Mining & Mf g, Co,).

The embossed surfaces were photographed at x200x to show their void structure. Ta.

Both LYTRON and ROPAQUE styrene/acrylic copolymer dispersions He showed the ability to jump. In the LYTRON dispersion, oil is easily blown away. Efficiency generally increased with increasing particle size.

LYTRON and ROPAQUE samples showed crab king.

In contrast, BUTVARBR, which showed no cracking, was very slow. He only gave me a moment. Best results are achieved with excellent oil repellency and metal transfer. LYTRON 25σ12 dispersion with low M blocking and good adhesion Obtained by liquid.

In the embossing and adhesion column of Table 1, "G" indicates "good" and "F" indicates " "P" indicates "Possible" and "MT" indicates plated embossed Shows the movement of metal from the fabrication master, which corresponds to the movement of metal from the embossing master. This is a sign of poor peeling.

ADCOTE6LJH61A is manufactured by Morton Chemical Co., Chicago, Illinois. It is a styrene/acrylic copolymer dispersion. 37R345 is Morton Chemi High molecular weight ethylene interpolymer dispersion from Cal Corporation. UNOCAL 3512 is B, F, Gutdrich Chemical of Cleveland, Ohio. This is an acrylic polymer dispersion from Co., Ltd.

The binders in Table 2 below were coated on paper, dried and as in Example 1. It was embossed to look like this. All of the embossed media produced is oil absorbent was observed to be lacking.

1. Polyvinyl butyrate (PVB solution B-72/Monsanto) 2. Sulfona Nitrocellulose ink containing mido plasticizer (Santicizer MHP) 3. PVB containing isodecyl diphenyl phosphate (Sant 1size r　148) 4. PVB containing IA, xyl adipate (Santicizer 3 67/Monsanto) 5. Vinyl chloride/vinyl acetate terpolymer solution (VAGH/Union Carbide ) 6. Ethylene vinyl acetate copolymer emulsion (Polybondx34-2 1/Morton) 7. Acrylic ester copolymer emulsion (Hycar 26315/Gutsu Doritsi) 8. Acrylic emulsion (Rhop 1 ex LC-4010-Muando Haas) 9. Polyurethane aqueous dispersion (Neores R-960/1ei) 10. Vinyl chloride latex (Airflex 4514/Air Products) 11. Styrene acrylic copolymer emulsion (Nacrylic78-63 34/National) 12. Acrylic ester copolymer emulsion (Hycar 26084/G) Tsudoritschi) 13. Blend of styrene acrylic copolymer emulsion and polystyrene dispersion (Nat-78su 41F4 Null/Lytron 2502 Morton) 14, Acrylic copolymer emulsion (Neocryl Bt-24/1ci ) 15. Polystyrene solution (18-210/Amoco) Other aspects of the invention will be apparent to those skilled in the art. should be obvious. In addition to its various decorative uses, the inventive oil-absorbing coated sheets for applications where protection against counterfeiting is desired (e.g. commercial bills) It can also be used in This technology also has fragile substrates that would indicate constitutional reform. It can also be used to manufacture packaging where constitutional amendments are obvious by using can.

Therefore, it is not intended that the invention be limited to the preferred embodiments set forth herein. It is not intended, but rather that the invention be defined by the claims and their equivalents. Ru.

Having thus described the invention, it is claimed as novel and patentable. The following are things that should be protected by law:

FIG. 4 international search report Continuation of front page (81) Specified times EP (AT, BE, CH, DE.

DK, ES, FR, GB, GR, IT, LU, NL, SE), 0A (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, SN , TD, TG), AU, BB, BG, BR, CA, C3, FI, HU, JP, KP.

LK, MC, MG, MN, MW, No, PL, RO, SD, SU

Claims (13)

[Claims] 1. A. base body B. an oil-absorbing layer associated with a substrate having an oil-absorbing surface; C. A decorative layer having a first side and a second side, where the second side is attached to the substrate. attached and the decorative layer passes from the first side to the second side through the decorative layer. is formed from a porous membrane with pores that pass through the membrane, and each pore has a decorative attracts oil from the first side of the layer and transports the oil to the oil-absorbing layer. (having a surface suitable for) for decorative or informational purposes. coated sheet. 2. The coat according to claim 1, wherein the substrate and the oil-absorbing layer are a single sheet. sheet that has been exported. 3. The first side of the decorative layer is embossed to form a grating or hologram. A coated sheet according to claim 1, wherein the coated sheet is 4. Porous membranes are polymer particles partially melted together to form pores 2. A coated sheet according to claim 1, wherein the coated sheet is formed from: 5. 5. The coated sheet of claim 4, wherein the pores have a lipophilic surface. 6. 5. The coated sheet of claim 4, wherein the particles include a styrene polymer. 7. A. providing a substrate, where the substrate is suitable for absorbing oil; having a first surface), B. providing a coating of a pre-membrane composition onto the first surface; C. heating the coating to heat the coating on the first side away from the substrate and on the substrate; into a porous membrane with a second side adjacent to the membrane (where the membrane having an internal surface suitable for transport from the first surface of the membrane to the second surface of the membrane) forming a coated sheet for decorative or informational use, comprising How to do it. 8. 8. The method of claim 7, wherein the pre-membrane composition comprises polymer particles in a liquid carrier. . 9. 8. The method of claim 7, wherein the pre-film composition comprises uniform spherical particles. 10. 10. The method of claim 9, wherein the spherical particles are of about 0.5 micron diameter. . 11. The pre-membrane composition can be coated without causing blocking of the sheet. The claimed invention contains a plasticizer in an amount suitable to provide effective adhesion of the porous membrane to the substrate. The method described in Range 7. 12. Step C. followed by embossing and diffraction of the first side of the coating. 8. A method according to claim 7, forming a grating or a hologram. 13. Step C. followed by thermally softening the first side of the coating. 8. The method of claim 7, wherein the porosity of the membrane is maintained during embossing.