Method for vapor deposition of hydrophobic films on surfaces

Abstract

A solid composition having a solid state film forming substance mixed with an inert carrier. The composition is heated in a vacuum chamber to evaporate the film forming substance by sublimation to form a molecular beam of amphiphilic molecules which settle on a substrate surface within the chamber and bond thereto while self-assembling into a thin film.

Description

BACKGROUND OF THE INVENTION

[0002] This application relates to the art of film forming compositions and to methods for applying films to substrates. The invention is particularly applicable to film forming compositions that contain solid state alkylsilsesquioxane polymers and to methods for applying such polymers to substrates, and will be described with particular reference thereto. However, it will be appreciated that the application has broader aspects and that at least certain features can be used with other polymers and methods.

[0003] Polymerizable amphiphilic molecules having the intrinsic ability to self-assemble into a thin film are well known in both solution phase and gas phase. By way of example, descriptions of such materials and their ability to form thin films are contained in: W. C. Bigelow et al, J. Colloid. Sci., 1,513-538 (1946); L. H. Lee, J. Colloid. & Interface Sci., 27, 751-760 (1968); E. E. Polymeropoulos et al, J. Chem. Phys., 69, 1836-1847 (1978); J. Sagiv, U.S. Pat. No. 4,539,061; J. Phys. Chem. 70, 2937 (1966); Trans. Faraday. Soc., 63, 2549 (1967); J. Phys. Chem., 73, 2372 (1969); Langmuir, 7, 923 (1991); Langmuir, 9, 3518 (1993) and Langmuir, 13, 1877 (1997). Disclosures of molecular beam deposition of coatings on substrates are found in the following U.S. Pat. Nos. 4,001,858; 4,181,544; 4,330,360; 4,681,773; 4,800,100; and 5,064,520. The disclosures of these publications and patents are hereby incorporated herein by reference. Compositions and methods for applying hydrophobic ultra thin films of self-assembling amphiphilic molecules to substrates are described in commonly assigned U.S. Pat. Nos. 5,078,791; 5,166,000; 5,173,365; 5,204,126; 5,219,654; 5,300,561; 5,766,698; and 5,897,918. The disclosures of these patents are hereby incorporated herein by reference.

[0004] Use of the compositions and methods disclosed in the above literature and patents typically results in the formation of a mono-layer thin film on a substrate surface. Inter-molecular interactions in both solution phase and gas phase under a low vacuum make it difficult to use these compositions and methods to form multi-layer films. In addition, the use of these compositions requires cleaning of the substrate surface and/or the vacuum chamber after formation of the film.

[0005] Compositions and methods disclosed in the above literature and patents are very sensitive to moisture, and require special packaging, handling and processing. These prior art processes also expose the entire substrate surface to the film forming substance and result in a film over the entire surface of the substrate. There is no choice of selecting a certain substrate surface or shape for film formation other than by masking.

[0006] In the compositions and methods disclosed in the above literature and patents, highly reactive self-assembling amphiphilic monomer substances are used to form the films. It would be desirable if these monomers could be partially polymerized to reduce their high reactivity to moisture while still being capable of acting as self-assembling amphiphilic molecules to form thin films.

[0007] Compositions with organic polymer molecules and self-assembling amphiphilic polymer substances for use in forming multi-layer thin films have been reported in the literature. By way of example, silsesquioxanes made from different monomer silanes and alkylsilanes are disclosed in Chem. Rev., 95 1431-1442 (1995) and Chem. Rev., 95, 1409-1430 (1995), and references cited therein and in J. Am. Chem. Soc., 119, 3135-3143 (1997). The disclosures of these publications are hereby incorporated herein by reference.

[0008] Methods for applying multi-layer thin films of organic polymers and self-assembling amphiphilic polymer substances inside ultra high vacuum chambers are known in the fields of optoelectronics, flat panel displays, thin film transistors and lasers as disclosed in J. Am. Chem. Soc., 120, 8563-8564 (1998) and Chem. Rev., 97, 1793-1896 (1997), and references cited therein. The disclosures of these publications are hereby incorporated herein by reference.

[0009] Use of the above methods and compositions requires the use of materials having extremely high purity. Therefore, a very complicated purification procedure is required that includes the use of a vacuum chamber at an ultra high vacuum of 1×10−7 to 1×10−11 torr.

[0010] It would be desirable to have a process and composition for use in applying hydrophobic thin films of self-assembling amphiphilic polymer substances to surfaces in a manner that is very fast, efficient and cost effective. It also would be desirable to have a process that is capable of coating only one surface at a time with a film of controlled thickness. It also would be desirable to have a process that could be used at a much lower vacuum than the ultra high vacuum mentioned in the previous references. It also would be desirable to have a process where cleaning of the excess coating material inside the vacuum chamber automatically takes place during the coating process. It would be desirable to have a coating composition of self-assembling amphiphilic polymer substances that is easy to handle and use. It also would be desirable to have a composition that is very stable at room temperature and humidity, and does not require special protection from temperature or moisture. It would be yet another desirable characteristic to have a composition, and process that is user friendly and environmentally safe. It would be another desirable characteristic to have a composition and process in which a single component material of very high purity is not required. It further would be desirable to have a coating composition that is easy to dispose of after it has been used.

SUMMARY OF THE INVENTION

[0011] In accordance with the present application a stable solid state coating composition includes a solid state film forming polymer having self-assembling amphiphilic molecules. In one arrangement, the film forming polymers are alkylsilsesquioxanes which are prepared in accordance with known procedures, such as disclosed in J. Am. Chem. Soc., 119, 3135-3143 (1997), the disclosure of which is hereby incorporated herein by reference.

[0012] A pure film forming substance in accordance with the present application evaporates very rapidly when heated and this makes it difficult to control the thickness of a film that is formed by the evaporated molecules. Therefore, the film forming substance preferably is mixed with an inert carrier, such as a metal oxide, that is stable at high temperatures and does not react with moisture or with the film forming substance.

[0013] The composition of film forming polymer powder mixed with a metal oxide powder is compressed into a tablet or compressed into a metal cup. The film forming polymer preferably is 10-50% by weight of the composition.

[0014] The amount of film forming substance in the composition that is compressed into a tablet or compressed into a metal cup usually is in the range of 0.5 to 5.0 grams, and more preferably 0.5 to 1.0 grams. Obviously, larger or smaller amounts may be used for some purposes.

[0015] When a metal cup is used and packed with compressed composition according to the present application, the volume of the cup usually is 0.5 to 2.0 milliliters. Obviously, other sizes may be used for some purposes.

[0016] A substrate is coated with a thin film of amphiphilic molecules in accordance with the present application by placing the composition of the present application in a vacuum chamber with a substrate to be coated. A high vacuum of 1×10−4 to 1×10−6 torr is established and maintained within the vacuum chamber during the coating process. When the desired vacuum is established, the composition is heated within the vacuum chamber to evaporate the film forming substance from a solid state to a vapor state by sublimation. The evaporated material forms a molecular beam of amphiphilic molecules that settle on the substrate surface and self-assemble into a continuous thin film that bonds to the substrate surface. The thickness of the film is controlled by the evaporation rate of the film forming substance and time.

[0017] A variety of different substrate materials can be coated with thin films of amphiphilic polymer molecules by using the method and composition of the present application. Suitable substrate materials include, but are not necessarily limited to, glass, ceramic, porcelain, plastics, glass or plastic lenses, glass slides, sun glasses, safety glasses, precision optical parts, lenses with anti-reflective coatings, or flat sheets or other surfaces, and certain polished metal surfaces such as silicon, aluminum, germanium, chromium, titanium and zirconium.

[0018] It is a principal object of the present invention to provide an improved coating composition that contains a solid state film forming substance of amphiphilic molecules for use in providing hydrophobic thin films on substrate surfaces.

[0019] It is also a principal object of the invention to provide an improved method for providing hydrophobic thin films on substrate surfaces.

[0020] It is another object of the invention to provide a method that permits coating of substrate surfaces one side at a time.

[0021] It is a further object of the invention to provide a method that can be used to provide substrate-surfaces with multi-layer self-assembled films of controlled thickness.

[0022] It is also an object of the invention to provide a method that does not require an ultra high vacuum.

[0023] It is an additional object of the invention to provide a composition of the type described that is easy to handle, transport and use. It is another object of the invention to provide such a composition that is very stable at normal temperature and humidity.

[0024] It is yet another object of the invention to provide a method and composition that is user friendly and environmentally safe.

[0025] It is also an object of the invention to provide a method wherein excess coating material is removed from the vacuum chamber during the coating process.

[0026] It is also an object of the present invention to provide a coating composition that is easy and safe to dispose of.

[0027] It is also an object of the invention to use a mixture of amphiphilic polymers to create good hydrophobic films on surfaces.

BRIEF DESCRIPTION OF THE DRAWING

[0028] The drawing is a diagrammatic illustration of a vacuum chamber in which the coating method of the present application as carried out.

DESCRIPTION OF REPRESENTATIVE EMBODIMENTS

[0029] It will be understood that the explanations provided herein are for purposes of disclosing representative embodiments of the invention and not for purposes of limiting same.

[0030] As used in the context of this application, a film forming substance is one containing amphiphilic polymeric molecules that are capable of self-assembly on a substrate surface and of bonding thereto by virtue of the high affinity that the polar groups in the polymeric molecules have for the polar groups on the substrate surface. An amphiphile contains a polar region and a non-polar region, and amphiphiles that can be used to form film in accordance with the present application include, but are not necessarily limited to, the following:

[0031] The polar segment of the amphiphile can be a corboxylic acid, alcohols, thiols, amides, primary, secondary, tertiary amines, silane derivatives and sulfonates.

[0032] The non-polar or a polar component typically consists mainly of alkyl and alkyl ether or fluorinated alkyl and alkyl ether groups. The alkyl chain also may have other polymerizable moieties in it.

[0033] In one arrangement, the film forming substance is prepared by the hydrolysis and polymerization of monomers using known procedures as disclosed in the aforementioned literature. The typical monomers used in the present application consist essentially of RmSiXn where the non-polar R is a substituted silane or siloxane, or an alkyl, a per-fluorinated alkyl, an alkyl ether, or a per-fluorinated alkyl ether group of 6-20 carbon atoms and most preferably 10-20 carbon atoms, where X is selected from the group consisting of halogens, hydroxy, alkoxy and acetoxy groups, and where m is 1-3, n is 1-3 and m+n equal 4.

[0034] In another example, the monomer used to make the stable solid state film forming alkylsilsesquioxane polymer is RmSiXn, where R is C18, X is an ethoxy group, m is 1-3, n is 1-3 and m+n equal 4.

[0035] By way of example, octadecyltrichlorosilane is used to make a stable solid state film forming amphiphilic polymer substance. Octadecyltrichlorosilane is added dropwise to a stoichometric excess of water held at about 5° C. and with good stirring. In the beginning, the material hydrolyzes and suspends in the water solution. After about 15 minutes it rises to the top of the water as a white flaky material and is left standing for 30-45 minutes. The precipitate is collected by suction filtration, thoroughly washed with water to remove residual hydrochloric acid, and dried under a vacuum at room temperature which usually is in the range of 18-32° C. A mixture of different siloxane polymers is obtained as mentioned in the literature, and the polymers still have some unreacted active hydroxy groups.

[0036] The white flaky material is then heated at 160-180° C. for 1 hour at a vacuum not lower than 1×10−2 to 5×10−2 torr. A lower vacuum would be 1×10−1 torr, and higher vacuums would be 1×10−3 to 1×10−7. During this process, most of the residual water and possibly the water between different polymer layers is removed. This step is necessary to obtain a polymer that provides a very uniform film deposition rate in the high vacuum process. Without this dehydration step, the deposition rate is not constant due to the release of excess water from the substance during the coating process. However, it is not desirable to obtain nearly 100% dehydration as might be obtained if the vacuum and/or temperature are too high, or if the dehydration time is too long.

[0037] The cooled solid polymer material is crushed to a fine powder and mixed with an inert binder such as a metal oxide powder to obtain a homogeneous mixture. Titanium dioxide powder, such as P25 available from . Degussa Corporation, is a suitable binder. Other binders that may be useable include silica and alumina. The important characteristic of the binder is that it should be one that does not react to moisture or with the film forming substance, and is stable at high temperatures of 300° C. and greater so that it does not evaporate when the composition is heated to evaporate the film forming polymer by sublimation.

[0038] The thoroughly mixed polymer powder and metal oxide powder are combined so that the polymer powder is 10-50% by weight of the composition, more preferably 20-40% by weight of the composition, and most preferably 25-30% by weight of the composition. The homogeneous mixture is compressed into a tablet or placed in a container such as a small metal cup and compressed therein. The tablet or the homogeneous mixture compressed into the cup is used inside the vacuum chamber for coating substrates with thin films. The metal cup may be of such metals as copper, aluminum and tin, but is not necessarily limited thereto.

[0039] In the method of the present application, substrates to be coated are placed inside the vacuum chamber, along with the composition of the present application, and a high vacuum of 1×10−4 to 1×10−6 torr is established inside the vacuum chamber. The substrate preferably is rotated while the composition is heated to evaporate the solid state film forming substance by sublimation. This establishes a molecular beam of amphiphilic molecules which settle on the substrate surface and attach or bond thereto by way of covalent bonding, hydrogen bonding and/or van der Waals forces while self-assembling into a continuous thin film. The rate of the deposition is set at 0.1-1.0 nm/sec by controlling the heat and evaporation rate, and is monitored by the use of an optical balance located within the vacuum chamber or by other deposition rate monitors such as a vacuum microbalance or quartz-crystal oscillator. A multi-layer thin film having a uniform thickness of 3-100 nm may be obtained. When the film has reached the desired thickness, heating of the coating composition is stopped and the chamber is vented so that the coated substrates can be removed. This method provides a very uniform hydrophobic thin film on substrate surfaces.

[0040] The method of the present application may be used to provide a thin film over other coatings such as anti-reflective coatings and mirror coatings. For example, the composition of the present application may be placed within a vacuum chamber at the same time as a composition for forming an anti-reflective coating or a mirror coating. The anti-reflective or mirror coating is first evaporated to provide the substrates, such as lenses, with an anti-reflective or mirror coating. The composition of the present application then is evaporated to provide a continuous thin film over the anti-reflective coating or mirror coating. Thus, the substrate is sequentially coated with different films without removing it from the vacuum chamber.

[0041] A vacuum chamber used to practice the method of the present application may be of the type manufactured by Satis, Denton or Zeiss for use in depositing anti-reflective coatings on lenses. The metal cup containing the composition may be heated with an electron beam gun, a resistance heater, an induction heater or another heat source. The tablet may be placed in a crucible within the vacuum chamber and similarly heated to evaporate the solid state film forming substance by sublimation. Preferably, neither the substrate nor the vacuum chamber are heated before or during the deposition process, and the only heat produced within the chamber is that used to evaporate the film forming substance. Thus, the temperature within the vacuum chamber during the entire process normally is well below 100° C.

[0042] The drawing shows a typical vacuum chamber A having a suitable door for providing access to the interior 10 thereof in a known manner. A conduit 12 communicating with the vacuum chamber interior 10 is connected with a vacuum pump for establishing and maintaining a desirable vacuum within the vacuum chamber.

[0043] A rotatable shaft 14 extends through a packing gland 16 to interior 10 of chamber A and has a mechanical gripping device 18 thereon for gripping the outer periphery of a substrate B. Any of the known mechanical clips and holders may be used for holding one or more substrates to be coated, as well as vacuum holders in which one or more substrates, such as lenses, are held to a rotatable support by a vacuum acting on the rear surfaces of the substrates, the vacuum being applied through a hollow shaft 14 and a plurality of spaced-apart ports in a hollow disc holder.

[0044] A metal cup 20 containing the composition of the present application, or a crucible holding a composition tablet, is positioned on a support 22 having a suitable heater associated therewith for heating the composition to a temperature of 100-300° C. and more preferably 150-200° C. After establishing a desirable vacuum of 1×10−4 to 1×10−6 torr in the vacuum chamber, the heater is energized and the solid state film forming substance in the composition evaporates by sublimation to form a molecular beam 24 of amphiphilic molecules which settle on substrate surface 26 that faces toward the source 20 of the molecular beam. The opposite surface 28 of the substrate B is not coated with the film forming substance. The amphiphilic molecules settle on substrate surface 26 and bond thereto as by covalent bonding, hydrogen bonding and/or van der Waals forces while simultaneously self-assembling into a continuous thin film. The operation is continued for a period required to form a desired film thickness the chamber is then vented and the coated substrates are removed.

[0045] Controlling the heat source used to evaporate the film forming substance controls the evaporation rate which in turn controls the deposition rate of the amphiphilic molecules on the substrate surface. The percent of film forming substance in the composition also may be varied to vary the evaporation and deposition rates.

[0046] The substrate preferably is located between the source of the molecular beam and the vacuum port with the surface to be coated facing toward the molecular beam so that the molecules in the beam engage the substrate surface as they travel toward the vacuum port. The substrate is rotated at a rate of one revolution per 1-10 seconds (6-60 revolutions per minute), and more preferably one revolution per 2-5 seconds (12-30 revolutions per minute). Removal of excess coating material from the substrate or the vacuum chamber is not necessary. The used composition cup or tablet is simply removed and replaced for coating a new batch of substrates.

[0047] By way of example, the film forming substance that is made from RmSiXn may be one in which R is an alkyl chain containing 12 carbon atoms and X is Cl. R also may be a per fluorinated alkyl group containing 12 carbon atoms. R also may be a per fluorinated alkyl chain with X being chloride. R also may be an alkyl chain with 16 carbon atoms. A mixture of different monomers containing alkyl chains ranging from 6 to 12 carbon atoms may be hydrolyzed to provide a film forming substance that is a mixture of different materials that are then mixed with an inert binder powder. Durable and uniform films with excellent hydrophobic properties are obtained using such materials.

[0048] Although the invention has been shown and described with reference to representative embodiments, it is obvious that alterations and modifications will occur to others skilled in the art upon reading and understanding of this application. Therefore, it is to be understood that the invention may be practiced otherwise than as specifically described herein while remaining within the scope of the claims.

Claims

36. A method of coating substrate surfaces with a hydrophobic thin film of amphiphilic molecules or amphiphilic polymers comprising the steps of positioning a substrate and a solid state film forming substance of amphiphilic molecules or amphiphilic polymers within a chamber, evaporating the film forming substance to produce a film forming vapor of amphiphilic molecules or amphiphilic polymers, and allowing the amphiphilic molecules or amphiphilic polymers in the vapor to settle on the substrate surface and self-assemble thereon into a hydrophobic thin film.

37. The method of claim 36 including the step of rotating said substrate while said amphiphilic molecules or amphiphilic polymers in said vapor settle thereon within said chamber.

38. The method of claim 36 including the step of maintaining the temperature within said chamber at less than 100° C.

39. The method of claim 36 wherein said step of evaporating is carried out to provide a film formation on the substrate surface at a rate of 0.1-1.0 nanometers of film thickness per second.

40. The method of claim 39 wherein the film formation rate is 0.4-0.6 nanometers of film thickness per second.

41. The method of claim 36 wherein said method is carried out for a time to provide the substrate with a film having a thickness of 3-100 nanometers.

42. The method of claim 41 wherein the method is carried out for a time to provide the substrate with a film having a thickness of 6-15 nanometers.

43. The method of claim 36 including the step of maintaining the chamber at a vacuum of 1×10−4 to 10−6 torr.

44. The method of claim 36 wherein the step of positioning a solid state film forming substance of amphiphilic molecules or amphiphilic polymers within a chamber is carried out by positioning within the chamber a composition that includes a mixture of an inert powder and a powdered film forming substance of amphiphilic molecules or amphiphilic polymers.

45. The method of claim 44 wherein the step of positioning a composition in the chamber is carried out by positioning the composition in the form of a compressed tablet.

46. The method of claim 44 wherein the step of positioning a composition in the chamber is carried out by positioning the composition compressed within a metal cup.

47. The method of claim 44 wherein the step of positioning a composition is carried out by positioning a composition that includes a mixture of a metal oxide powder and a powdered film forming substance of amphiphilic molecules or amphiphilic polymers.

48. The method of claim 47 wherein the step of positioning a composition is carried out by positioning a composition that contains 10-50% by weight of the powdered film forming substance of amphiphilic molecules or amphiphilic polymers.

49. The method of claim 36 wherein the step of positioning a film forming substance in the chamber is carried out by positioning in the chamber a tablet of inert material that carries the film forming substance of amphiphilic molecules or amphiphilic polymers.

50. A method of coating substrate surfaces with a hydrophobic thin film of amphiphilic molecules or amphiphilic polymers comprising the steps of positioning within a chamber a substrate and a solid inert material that carries a film forming substance of amphiphilic molecules or amphiphilic polymers, heating the inert material to evaporate the film forming substance and produce a film forming vapor of amphiphilic molecules or amphiphilic polymers, and allowing the amphiphilic molecules or amphiphilic polymers in the vapor to settle on the substrate surface and self-assemble thereon into a hydrophobic thin film.

51. The method of claim 50 including the step of maintaining the temperature within the chamber below 100° C.

52. The method of claim 50 including the step of maintaining the chamber at a vacuum of 1×10−4 to 1×10−6 torr.

53. A method of coating substrate surfaces with a hydrophobic thin film of amphiphilic molecules or amphiphilic polymers comprising the steps of positioning within a chamber a substrate and a film forming substance of amphiphilic molecules or amphiphilic polymers interspersed in at last a portion of a body of inert material, evaporating the film forming substance to produce a film forming vapor of amphiphilic molecules or amphiphilic polymers, and allowing the amphiphilic molecules or amphiphilic polymers in the vapor to settle on the substrate surface and self-assemble thereon into a hydrophobic thin film.

54. The method of claim 53 including the step of rotating said substrate while said amphiphilic molecules or amphiphiloc polymers in said vapor settle thereon within said chamber.

55. The method of claim 53 including the step of maintaining the temperature within said chamber at less than 100° C.

56. The method of claim 53 wherein said step of evaporating is carried out to provide a film formation on the substrate surface at a rate of 0.1-1.0 nanometers of film thickness per second.

57. The method of claim 56 wherein the film formation rate is 0.4-0.6 nanometers of film thickness per second.

58. The method of claim 53 wherein said method is carried out for a time to provide the substrate with a film having a thickness of 3-100 nanometers.

59. The method of claim 56 wherein the method is carried out for a time to provide the substrate with a film having a thickness of 6-15 nanometers.

60. The method of claim 53 including the step of maintaining the chamber at a vacuum of 1×10−4 to 1×10−6 torr.

61. The method of claim 53 wherein said step of positioning a film forming substance within said chamber is carried out by positioning within the chamber a forming substance of amphiphilic molecules or amphiphilic polymers interspersed in at least a portion of an inert body of particulate material.

62. The method of claim 53 wherein the step of positioning a film forming substance within the chamber is carried out by positioning within the chamber a solid state body that includes a mixture of an inert powder and a powdered film forming substance of amphiphilic molecules or amphiphilic polymers.

63. The method of claim 53 wherein the step of positioning a film forming substance within the chamber is carried out by positioning within the chamber a solid state film forming substance of amphiphilic molecules or amphiphilic polymers interspersed in at least a portion of the body of inert material.

64. The method of claim 53 wherein the step of positioning a film forming substance in the chamber is carried out by positioning a compressed tablet of an inert material carrying a film forming substance of amphiphilic molecules or amphiphilic polymers.

65. The method of claim 53 wherein the step of positioning a film forming substance in the chamber is carried out by positioning the film forming substance and the inert material compressed within a cup.

66. The method of claim 53 wherein the step of positioning a film forming substance is carried out by positioning a composition that includes a mixture of a metal oxide powder and a powdered film forming substance of amphiphilic molecules or amphiphilic polymers.

67. The method of claim 53 wherein the step of positioning a film forming substance is carried out by positioning a combined film forming substance and inert material that contains 10-50% by weight of the film forming substance of amphiphilic molecules or amphiphilic polymers.

68. The method of claim 53 wherein the step of positioning a film forming substance is carried out by positioning a combined film forming substance and inert material that contains 0.5-5.0 grams of film forming substance of amphiphilic molecules or amphiphilic polymers.

69. A method of coating substrate surfaces with a hydrophobic thin film of amphiphilic molecules or amphiphilic polymers comprising the steps of positioning within a chamber a substrate and a tablet of inert material that carries a film forming substance of amphiphilic molecules or amphiphilic polymers, heating the tablet to evaporate the film forming substance and produce a film forming vapor of amphiphilic molecules or amphiphilic polymers, and allowing the amphiphilic molecules or amphiphilic polymers in the vapor to settle on the substrate surface and self-assemble thereon into a hydrophobic thin film.

70. The method of claim 69 wherein said step of positioning a tablet that carries a film forming substance is carried out by positioning a tablet that carries an alkylsilsesquioxane polymer.

71. The method of claim 69 wherein said step of positioning a tablet is carried out by positioning a tablet of compressed particulate material and the film forming substance is carried by the tablet.

72. The method of claim 69 wherein said step of positioning a tablet is carried out by positioning a compressed tablet of inert material carrying film forming substance of amphiphilic molecules or amphiphilic polymers.

73. The method of claim 69 wherein said step of positioning a tablet is carried out by positioning a tablet that carries a solid state film forming substance of amphiphilic molecules or amphiphilic polymers.

74. The method of claim 69 wherein said step of positioning a tablet is carried out by positioning a tablet and a film forming substance with at least a portion of the tablet having the film forming substance of amphiphilic molecules or amphiphilic polymers interspersed therein.

75. The method of claim 69 wherein said step of positioning a tablet is carried out by positioning a tablet that carries 0.5-5.0 grams of film forming substance of amphiphilic molecules or amphiphilic polymers.

76. The method of claim 69 wherein said step of positioning a tablet is carried out by positioning a tablet that carries 10-50% by weight of the film forming substance of amphiphilic molecules or amphiphilic polymers.