Internally-coated porous webs with controlled positioning of modifiers therein

• US 5,869,172 A
• Filed: 05/17/1995
• Issued: 02/09/1999
• Est. Priority Date: 03/14/1988
• Status: Expired due to Term

• Current Assignee: Nextec Applications Incorporated
• Original Assignee: Nextec Applications Incorporated
• Inventors: Caldwell, J. Michael
• Primary Examiner(s): Bell, James J.
• Application Number:
  US08/442,983
• Time in Patent Office: 1,364 Days
• Field of Search: 2/83, 2/114, 2/901, 128/849, 128/888, 424/402, 424/404, 428/240, 428/242, 428/260, 428/272, 428/274, 428/283, 428/290, 428/306.6, 428/305.5, 428/308.4, 428/311.1, 428/311.5, 428/311.7, 428/315.5, 428/317.9 , 428/907, 428/920, 523/103, 523/122, 602/48, 602/50, 604/367, 604/372
• US Class Current: 428/306.6
• CPC Class Codes: A61F 13/00063 comprising medicaments or additives, e.g. odor control, PH control, debriding, antimicrobic drug delivery dressings A61K9/70; chemical aspect of the additives A61L15/00
• CPC Class Codes: A61F 13/49003 Reusable, washable fabric diapers
• CPC Class Codes: A61F 13/51405 treated or coated, e.g. with moisture repellent agent
• CPC Class Codes: A61F 13/51476 being three-dimensional, e.g. embossed, textured, pleated, or with three-dimensional features, like gathers or loops
• CPC Class Codes: A61F 13/5148 having an impervious inner layer and a cloth-like outer layer
• CPC Class Codes: A61F 2013/00255 with pores
• CPC Class Codes: A61F 2013/0074 containing foams
• CPC Class Codes: A61F 2013/00863 with pores
• CPC Class Codes: A61F 2013/00927 with biological activity, e.g. enzymes for debriding wounds or others, collagen or growth factors
• CPC Class Codes: A61L 15/26 Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds; Derivatives thereof A61L15/225 takes precedence
• CPC Class Codes: A61L 15/52 Water-repellants
• CPC Class Codes: B05C 11/02 Apparatus for spreading or distributing liquids or other fluent materials already applied to a surface ; Controlling means thereforB05C7/00 takes precedence; Hand tools for such purposes B05C17/10; Control of the thickness of a coating by spreading or distributing liquids or other fluent materials already applied to the coated surfacecontrolling supply of liquid or other fluent material B05C11/10
• CPC Class Codes: B05C 11/04 with blades
• CPC Class Codes: B05C 3/18 only one side of the work coming into contact with the liquid or other fluent material B05C3/02 takes precedence
• CPC Class Codes: C08J 2205/05 Open cells, i.e. more than 50% of the pores are open
• CPC Class Codes: C08J 2427/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
• CPC Class Codes: C08J 2433/00 Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Derivatives of such polymers
• CPC Class Codes: C08J 2475/00 Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
• CPC Class Codes: C08J 2483/00 Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• CPC Class Codes: C08L 83/04 Polysiloxanes
• CPC Class Codes: C14C 11/00 : Surface finishing of leather
• CPC Class Codes: C14C 9/00 : Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
• CPC Class Codes: D04H 1/42 : characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
• CPC Class Codes: D04H 1/58 : by applying, incorporating or activating chemical or thermoplastic bonding agents, e.g. adhesives in combination with needling D04H1/488
• CPC Class Codes: D04H 1/587 : characterised by the bonding agents used
• CPC Class Codes: D04H 1/64 : the bonding agent being applied in wet state, e.g. chemical agents in dispersions or solutions
• CPC Class Codes: D06B 15/08 : by scraping
• CPC Class Codes: D06M 15/256 : containing fluorine
• CPC Class Codes: D06M 15/263 : of unsaturated carboxylic acids; Salts or esters thereof
• CPC Class Codes: D06M 15/3568 : containing silicon
• CPC Class Codes: D06M 15/564 : Polyureas, polyurethanes or other polymers having ureide or urethane links; Precondensation products forming them
• CPC Class Codes: D06M 15/643 : containing silicon in the main chain
• CPC Class Codes: D06M 15/653 : modified by isocyanate compounds
• CPC Class Codes: D06M 15/657 : containing fluorine
• CPC Class Codes: D06M 2101/06 : cellulosic
• CPC Class Codes: D06M 2101/12 : Keratin fibres or silk
• CPC Class Codes: D06M 2101/26 : Polymers or copolymers of unsaturated carboxylic acids or derivatives thereof
• CPC Class Codes: D06M 2101/32 : Polyesters
• CPC Class Codes: D06M 2101/34 : Polyamides
• CPC Class Codes: D06M 2200/12 : Hydrophobic properties
• CPC Class Codes: D06N 3/0002 : characterised by the substrate
• CPC Class Codes: D06N 3/047 : with fluoropolymers
• CPC Class Codes: D06N 3/12 : with macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds , e.g. gelatine proteins
• CPC Class Codes: D06N 3/128 : with silicon polymers
• CPC Class Codes: D21H 17/59 : obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon
• CPC Class Codes: D21H 19/32 : obtained by reactions forming a linkage containing silicon in the main chain of the macromolecule
• CPC Class Codes: D21H 25/06 : of impregnated or coated paper D21H25/08 takes precedence
• CPC Class Codes: Y10S 428/907 : Resistant against plant or animal attack
• CPC Class Codes: Y10S 428/92 : Fire or heat protection feature
• CPC Class Codes: Y10S 977/788 : Of specified organic or carbon-based composition
• CPC Class Codes: Y10T 428/249954 : With chemically effective material or specified gas other than air, N, or carbon dioxide in void-containing component
• CPC Class Codes: Y10T 428/249955 : Void-containing component partially impregnated with adjacent component
• CPC Class Codes: Y10T 428/249958 : Void-containing component is synthetic resin or natural rubbers
• CPC Class Codes: Y10T 428/249962 : Void-containing component has a continuous matrix of fibers only [e.g., porous paper, etc.]
• CPC Class Codes: Y10T 428/249965 : Cellulosic
• CPC Class Codes: Y10T 428/249978 : Voids specified as micro
• CPC Class Codes: Y10T 428/249986 : Void-containing component contains also a solid fiber or solid particle

Abstract

Improved processes are provided for treating a porous substrate (especially a fabric) to produce novel internally coated porous materials. During treatment, a curable thixotropic material and one or modifying materials are applied to the porous substrate as an impregnant. The treatment imparts specific properties to the end product material. Selection of the modifier material is based on the particular end use application. Sufficient energy is directed to the impregnant and porous substrate to cause the impregnant to flow into the porous substrate and force the modifier to specific positions within the substrate.

Claims

1. An article comprising a porous web that has been treated with a curable, shear thinnable, thixotropic polymeric material and with one or more modifiers, said material being at least partially cured, said modifiers being selectively positioned within the web, and at least some of the pores of said web being open.

2. The article of claim 1, wherein the modifier is selectively positioned substantially on one surface of the porous web.

3. The article of claim 1, wherein said modifier alters the functional properties of said article.

4. The article of claim 1, wherein said modifier is selected from biocides, therapeutic agents, adhesive agents, processing agents, humidity-controlling agents, water repellents, ion-exchange agents, light-reflective agents, dyes and pigments, mildew-resistance agents, conductive agents, proteins, hand-altering agents, blood repellents, flexibility-inducing agents, light fastness-inducing agents, rot-resistant agents, stain-resistant agents, grease-resistant agents, ultraviolet-absorbing agent, fillers, flattening agents, electrical conductive agents, thermal conductive agents, flame retardants, antistatic agents, sub-micron particulate matter, electromagnetic shielding agents or radio frequency shielding agents.

5. The article of claim 4, wherein the biocide is selected from halogens and halogen-based compounds, antibiotics, anti-virals, nonoxynol-9, phenols and phenolic compounds, quaternary ammonium salts, zinc oxide, Z-N-octyl-4-isothiazole-3-one, phenyl mercuric acetate, skin disinfectants, water disinfectants, air disinfectants, gaseous disinfectants, clothing disinfectants, methyl dimethyl propoxylene ammonium chloride, polyiodides, acid salts derived from hydrochloric, methanesulfonic, ethanesulfonic, isoethionic, lactic or citric acids, or trichlorocarbon.

6. The article of claim 4, wherein the light reflective agent is selected from titanium oxide or zinc oxide.

7. The article of claim 4, wherein the mildew resistant agent is selected from thiazolylbenzimidazole, zinc phosphite, phenols, benzothiazoles or organosilicon quaternary ammonium salts.

8. The article of claim 4, wherein the hand-altering agent is selected from proteins or polyolefin fibers or fabrics.

9. The article of claim 4, wherein the filler is selected from carbon, molecular sieves, fumed silica or colloidal silica.

10. The article of claim 4, wherein the flame retardant is selected from aluminum hydroxide, borax, tetrakis(hydroxymethyl)phosphonium chloride, potassium hexafluoro zirconate, potassium hexafluoro titanate, polyamides, polyimides, poly-parabanic acid, polyether sulfones, polyether ether ketones, polyetherimides, fluoroplastic resin films, polyphenylene sulfide, magnesium hydroxide, silicone-treated magnesium oxide, polybenzimidazole, flame-durable fibers, carbon or carbonizable compositions, retardant powder fillers, kaolin, gypsum, hydrated clay, polypropylene, polybutylene, metal carboxyl salts containing at least 6 carbon atoms, calcium compounds, barium atoms, strontium atoms, salts of inorganic acids, polyolefins, copolymers of polystyrene or polycarbonates, polyesters, polyamides, polycaprolactams, ionomers, polyurethanes, acrylonitrile-butadiene-styrene polymers, acetal resins, ethylene-vinylacetate resins, polymethylpentene, polyphenylene oxide, or polyphenylene oxide-polystyrene blends.

11. The article of claim 4, wherein the ultraviolet absorbing agent is selected from benzophenones, benzotriazoles, cinnamic acid esters, benzoxazoles, 4-thiazolidones, titanium dioxide or zinc oxide.

12. The article of claim 4, wherein the antistatic agent is selected from fatty acid esters and their derivatives, long-chain amines, amides, quaternary ammonium salts, polyoxyethylene derivatives, polygloycols and their derivatives, polyhydric alcohols and their derivatives or epoxides and glycol ethers thereof.

13. The article of claim 4, wherein said processing agent is selected from cross-linking inhibitors, rheological agents, polyvinyl alcohol or hydrophilic polymers.

14. The article of claim 1, wherein said modifier contains reactively available sites.

15. The article of claim 14, wherein the reactively available sites of the modifier are oriented outwardly from a surface of the porous web.

16. The article of claim 14, wherein said reactively available sites are capable of binding an agent.

17. The article of claim 14, wherein said modifier is selected from polyurethane, phenolic resins, polyurea resins, polyolefins, polyamides, polysiloxanes, polysulfides, polyvinyl esters or polyacetal resins.

18. The article of claim 16, wherein said modifier is polyurethane.

19. The article of claim 18, wherein said agent is iodine.

20. The article of claim 16, wherein said agent is an airborne organic contaminant.

21. The article of claim 14, wherein said modifier is biologically active.

22. The article of claim 21, wherein said biologically active modifier is selected from proteins, antibodies or enzymes.

23. The article of claim 16, wherein said agent is biologically active.

24. The article of claim 23, wherein said biologically active agent is selected from proteins, antibodies or enzymes.

25. The article of claim 14, wherein said reactively available sites catalyze a chemical reaction.

26. The article of claim 14, wherein said reactively available sites are capable of binding one or more proteins.

27. The article of claim 14, wherein said reactive sites are capable of binding one or more antibodies.

28. The article of claim 1, wherein said modifier promotes adhesion between the curable, thixotropic material containing one or more modifiers therein and the web.

29. The article of claim 1, wherein the modifier alters the surface chemistry of the article.

30. The article of claim 29, wherein said surface chemistry modifier is selected from the group consisting of fluorochemical compounds, proteins, anti-static agents, blood repellants, grease resistant agents.

31. The article of claim 1, wherein said modifier promotes the release of an agent from the web.

32. The article of claim 31, wherein said agent is a biologically active compound.

33. The article of claim 32, wherein the modifier is a hydrogel.

34. The article of claim 32, wherein the modifier is a fluorochemical compound.

35. The article of claim 1, wherein said thixotropic material comprises a polymer selected from polysiloxanes, polyurethanes, fluorosilicones, modified polyurethane silicones, modified silicone polyurethanes, acrylics or polytetrafluorethylene.

36. The article of claim 1, wherein said curable, thixotropic material containing one or more modifiers therein comprises a diluent.

37. The article of claim 36, wherein said diluent is selected from the group consisting of water, low molecular weight silicones, low molecular weight ketones or aromatics.

38. The article of claim 1, wherein said web is flexible.

39. The article of claim 1, wherein said web is rigid.

40. The article of claim 1, wherein said web is selected from foam, paper, leather or filtration membrane.

41. The article of claim 1, wherein said porous web is a fabric.

42. The article of claim 41, wherein said fabric is a woven fabric.

43. The article of claim 41, wherein said fabric comprises natural fibers.

44. The article of claim 41, wherein said fabric comprises synthetic fibers.

45. The article of claim 41, wherein said fabric is a non-woven fabric.

46. The article of claim 1, wherein said curable, thixotropic material and one or more modifiers forms a discontinuous film.

102. The article of claim 1, wherein the modifier is localized on one surface of the porous web.

47. A porous article comprising:

a porous web having a plurality of web members with interstices therebetween;

an at least partially cured material derived from a curable, shear thinnable, thixotropic polymeric material which forms;

a thin film substantially encapsulating at least some of the web members leaving at least some of the interstices open, or

a substantially continuous internal layer; and

one or more modifiers, wherein said modifier(s) is selectively positioned within the web.

48. The article of claim 47, wherein the modifier is selectively positioned substantially on one surface of the porous web.

49. The article of claim 47, wherein the modifier is selectively positioned substantially within the encapsulated material.

50. The article of claim 47, wherein the modifier is selectively positioned substantially on one surface of the encapsulated material.

51. The article of claim 47, wherein said modifier(s) projects through the surface of the encapsulated material.

52. The article of claim 47, wherein the substantially continuous internal layer is positioned close to a surface of the porous web.

53. The article of claim 47, wherein the modifier is selectively positioned substantially on one surface of the substantially continuous internal layer.

54. The article of claim 47, wherein the modifier is selectively positioned substantially within the substantially continuous internal layer.

55. The article of claim 47, wherein said modifier alters the functional properties of said article.

56. The article of claim 47, wherein said modifier is selected from biocides, therapeutic agents, adhesive agents, processing agents, humidity-controlling agents, water repellents, ion-exchange agents, light-reflective agents, dyes and pigments, mildew-resistance agents, conductive agents, proteins, hand-altering agents, blood repellents, flexibility-inducing agents, light fastness-inducing agents, rot-resistant agents, stain-resistant agents, grease-resistant agents, ultraviolet-absorbing agents, fillers, flattening agents, electrical conductive agents, thermal conductive agents, flame retardants, antistatic agents, sub-micron particulate matter, electromagnetic shielding agents or radio frequency shielding agents.

57. The article of claim 56, wherein the biocide is selected from halogens and halogen-based compounds, antibiotics, anti-virals, nonoxynol-9, phenols and phenolic compounds, quaternary ammonium salts, zinc oxide, Z-N-octyl-4-isothiazole-3-one, phenyl mercuric acetate, skin disinfectants, water disinfectants, air disinfectants, gaseous disinfectants, clothing disinfectants, methyl dimethyl propoxylene ammonium chloride, polyiodides, acid salts derived from hydrochloric, methanesulfonic, ethanesulfonic, isoethionic, lactic or citric acids, or trichlorocarbon.

58. The article of claim 56, wherein the light reflective agent is selected from titanium oxide or zinc oxide.

59. The article of claim 56, wherein the mildew resistant agent is selected from thiazolylbenzimidazole, zinc phosphite, phenols, benzothiazoles or organosilicon quaternary ammonium salts.

60. The article of claim 56, wherein the hand-altering agent is selected from proteins or polyolefin fibers or fabrics.

61. The article of claim 56, wherein the filler is selected from carbon, molecular sieves, fumed silica or colloidal silica.

62. The article of claim 56, wherein the flame retardant is selected from aluminum hydroxide, borax, tetrakis(hydroxymethyl)phosphonium chloride, potassium hexafluoro zirconate, potassium hexafluoro titanate, polyamides, polyimides, poly-parabanic acid, polyether sulfones, polyether ether ketones, polyetherimides, fluoroplastic resin films, polyphenylene sulfide, magnesium hydroxide, silicone-treated magnesium oxide, polybenzimidazole, flame-durable fibers, carbon or carbonizable compositions, retardant powder fillers, kaolin, gypsum, hydrated clay, polypropylene, polybutylene, metal carboxyl salts containing at least 6 carbon atoms, calcium compounds, barium atoms, strontium atoms, salts of inorganic acids, polyolefins, copolymers of polystyrene or polycarbonates, polyesters, polyamides, polycaprolactams, ionomers, polyurethanes, acrylonitrile-butadiene-styrene polymers, acetal resins, ethylene-vinylacetate resins, polymethylpentene, polyphenylene oxide, or polyphenylene oxide-polystyrene blends.

63. The article of claim 56, wherein the ultraviolet absorbing agent is selected from benzophenones, benzotriazoles, cinnamic acid esters, benzoxazoles, 4-thiazolidones, titanium dioxide or zinc oxide.

64. The article of claim 56, wherein the antistatic agent is selected from fatty acid esters and their derivatives, long-chain amines, amides, quaternary ammonium salts, polyoxyethylene derivatives, polygloycols and their derivatives, polyhydric alcohols and their derivatives or epoxides and glycol ethers thereof.

65. The article of claim 56, wherein said processing agent is selected from cross-linking inhibitors, rheological agents, polyvinyl alcohol or hydrophilic polymers.

66. The article of claim 47, wherein said modifier contains reactively available sites.

67. The article of claim 66, wherein the reactively available sites of the modifier are oriented outwardly from a surface of the porous web.

68. The article of claim 66, wherein said reactively available sites are capable of binding an agent.

69. The article of claim 66, wherein said modifier is selected from polyurethane, phenolic resins, polyurea resins, polyolefins, polyamides, polysiloxanes, polysulfides, polyvinyl esters or polyacetal resins.

70. The article of claim 69, wherein said modifier is polyurethane.

71. The article of claim 70, wherein said agent is iodine.

72. The article of claim 68, wherein said agent is an airborne organic contaminant.

73. The article of claim 66, wherein said modifier is biologically active.

74. The article of claim 73, wherein said biologically active modifier is selected from proteins, antibodies or enzymes.

75. The article of claim 68, wherein said agent is biologically active.

76. The article of claim 75, wherein said biologically active agent is selected from proteins, antibodies or enzymes.

77. The article of claim 66, wherein said reactively available sites catalyze a chemical reaction.

78. The article of claim 66, wherein said reactively available sites are capable of binding one or more proteins.

79. The article of claim 66, wherein said reactive sites are capable of binding one or more antibodies.

80. The article of claim 47, wherein said modifier promotes adhesion between the curable, shear thinnable thixotropic material containing one or more modifiers therein and the web.

81. The article of claim 47, wherein the modifier alters the surface chemistry of the article.

82. The article of claim 81, wherein said surface chemistry modifier is selected from the group consisting of fluorochemical compounds, proteins, anti-static agents, blood repellants or grease resistant agents.

83. The article of claim 47, wherein said modifier promotes the release of an agent from the web.

84. The article of claim 83, wherein said agent is a biologically active compound.

85. The article of claim 84, wherein the modifier is a hydrogel.

86. The article of claim 84, wherein the modifier is a fluorochemical compound.

87. The article of claim 47, wherein said thixotropic material comprises a polymer selected from polysiloxanes, polyurethanes, fluorosilicones, modified polyurethane silicones, modified silicone polyurethanes, acrylics or polytetrafluorethylene.

88. The article of claim 47, wherein said curable, thixotropic material containing one or more modifiers therein comprises a diluent.

89. The article of claim 88, wherein said diluent is selected from the group consisting of water, low molecular weight silicones, low molecular weight ketones or aromatics.

90. The article of claim 47, wherein said web is flexible.

91. The article of claim 47, wherein said web is rigid.

92. The article of claim 47, wherein said web is selected from foam, paper, leather, filtration membrane, or laminate.

93. The article of claim 47, wherein said porous web is a fabric.

94. The article of claim 93, wherein said fabric is a woven fabric.

95. The article of claim 93, wherein said fabric comprises natural fibers.

96. The article of claim 93, wherein said fabric comprises synthetic fibers.

97. The article of claim 93, wherein said fabric is a non-woven fabric.

98. The article of claim 47, wherein said curable, thixotropic material and one or more modifiers forms a discontinuous film.

99. The article of claim 47, wherein said internal layer has a thickness in the range of 0.01 micron up to 50 microns.

100. The article of claim 47, wherein said porous internal layer has a pore size of up to about 10 microns.

101. The article of claim 47, wherein the thickness of the thin film varies in a controlled gradient through the thickness of the web.

103. The article of claim 47, wherein the modifier is localized at one or more selected positions within the web.

104. The article of claim 47, wherein the modifier is localized on one surface of the porous web.

105. The article of claim 47, wherein the modifier is localized within the encapsulated material.

106. The article of claim 47, wherein the modifier is localized on one surface of the encapsulated material.

107. The article of claim 106, wherein the modifier projects through the surface of the encapsulated material.

108. The article of claim 47, wherein the modifier is localized on one surface of the substantially continuous internal layer.

109. The article of claim 47, wherein the modifier is localized within the substantially continuous internal layer.

110. A method of controllably applying a combination of treating materials to a porous web, said method comprising:

applying a curable shear thinnable, thixotropic material to said porous web;

applying one or more modifiers to said porous web; and

subjecting said thixotropic material and modifier(s) to sufficient energy to cause the thixotropic material and modifier(s) to flow into the porous web, and selectively position said modifier(s) within the web, wherein at least some of the interstitial spaces of said web remain open.

111. The method according to claim 110 wherein said web is pretreated with said modifier, prior to applying said curable, thixotropic material thereto.

112. The method according to claim 110 wherein said modifier and said curable, thixotropic material are applied to said web in combination.

113. The method according to claim 110 wherein said modifier is applied to said web after applying said curable, thixotropic material thereto.

114. The method according to claim 113 wherein said curable, thixotropic material is subjected to shear thinning conditions prior to application of said modifier to said web.

115. The method according to claim 114 wherein said modifier is pressured into the web.

116. The method according to claim 110, wherein said thixotropic material and said modifier(s) are applied to the surface of the porous web.

117. The method according to claim 110, wherein said modifier alters the functional properties of the resulting article.

118. The method according to claim 110, wherein said modifier alters the functional properties of said curable, thixotropic material containing one or more modifiers therein.

119. The method according to claim 110, wherein said modifier is selected from the group consisting of biocides, therapeutic agents, adhesive agents, humidity-controlling agents, water repellents, ion-exchange agents, light-reflective agents, dyes and pigments, mildew-resistant agents, conductive agents, proteins, hand-altering agents, blood repellents, flexibility-inducing agents, light fastness-inducing agents, rot-resistant agents, stain-resistant agents, grease-resistant agents, ultraviolet-absorbing agent, fillers, flattening agents, electrical conductive agents, thermal conductive agents, flame retardants, antistatic agents, processing agents, electromagnetic shielding agents, and radio frequency shielding agents.

120. The method according to claim 110, wherein said modifier contains reactively available sites.

121. The method according to claim 120, wherein said reactively available sites are capable of binding an agent.

122. The method according to claim 118, wherein said curable, thixotropic material comprises a diluent.

123. The method according to claim 122, wherein said diluent is selected from the group consisting of water, low molecular weight silicones, low molecular weight ketones or aromatics.

124. The method according to claim 122, where said energy is sufficient to drive the diluent from the curable, thixotropic material.

125. The method according to claim 110, wherein said porous web has a plurality of web members with interstices therebetween and wherein the curable, thixotropic material and one or more modifiers forms a thin film substantially encapsulating at least some of the web members.

126. The method according to claim 110, wherein said porous web has a plurality of web members with interstices therebetween and wherein the curable, thixotropic material and one or more modifiers forms a substantially continuous, internal layer.

127. The method according to claim 125, wherein the curable, thixotropic material and one or more modifiers further form a substantially continuous, internal layer.

128. The method according to claim 125, wherein said energy causes a variation in thin film thickness in a controlled gradient through the thickness of the web.

129. The method according to claim 126, wherein the internal continuous layer is positioned close to the application surface of the porous web.

130. The method according to claim 126, wherein the internal continuous layer is positioned close to the surface opposing the application surface of the porous web.

131. The method according to claim 110, wherein the modifier is selectively positioned substantially on the application surface of the porous web.

132. The method according to claim 110, wherein the modifier is selectively positioned substantially on the surface opposing the application surface of the porous web.

133. The method according to claim 125, wherein the modifier is selectively positioned substantially within the encapsulated material.

134. The method according to claim 125, wherein the modifier is selectively positioned substantially on one surface of the encapsulated material.

135. The method according to claim 125, wherein said modifier(s) projects through the surface of the encapsulated material.

136. The method according to claim 126, wherein the modifier is selectively positioned substantially on one surface of the internal, continuous layer.

137. The method according to claim 126, wherein the modifier is selectively positioned substantially within the internal, continuous layer.

138. The method according to claim 120, wherein the reactive sites of the modifier are oriented outwardly from a surface of the porous web.

139. The method according to claim 110, wherein said energy is provided by subjecting the curable, thixotropic material containing one or more modifiers therein and web to shearing conditions.

140. The method according to claim 138, wherein the shearing conditions are provided by passing the web and curable, thixotropic material containing one or more modifiers therein in contact with one or more blades at a predetermined angle with respect to the blades.

141. The method according to claim 140, wherein one or more of the blades is flexible.

142. The method according to claim 140, wherein one or more of the blades is rigid.

143. The method according to claim 139, wherein the shearing conditions are provided by passing the web and curable, thixotropic material containing one or more modifiers therein through rollers at a controllable pressure.

144. The method according to claim 110, further comprising at least partially curing said thixotropic material.

145. The method according to claim 144, wherein the energy for curing is provided by thermal energy, electron beam, microwave, electromagnetic radiation or ultrasonic energy.

146. The method according to claim 110, wherein said porous web comprises carpet fibers.

147. The method according to claim 146, wherein said carpet fibers are combed prior to applying said curable, thixotropic composition and one or more modifiers thereto, and once again prior to curing the composition after shear thinning thereof.

148. The method according to claim 110, wherein the modifier is localized on the application surface of the porous web.

149. The method according to claim 110, wherein the modifier is localized on the surface opposing the application surface of the porous web.

150. The method according to claim 125, wherein the modifier is localized within the encapsulated material.

151. The method according to claim 125, wherein the modifier is localized on the surface of the encapsulated material.

152. The method according to claim 125, wherein the modifier projects through the surface of the encapsulated material.

153. The method according to claim 126, wherein the modifier is localized on one surface of the internal continuous layer.

154. The method according to claim 126, wherein the modifier is localized within the internal continuous layer.