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1. (WO2019006409) COMPOSITES IMPRIMÉS EN 3D À PARTIR D'UNE SEULE RÉSINE PAR EXPOSITION À LA LUMIÈRE CONFIGURÉE
Note: Texte fondé sur des processus automatiques de reconnaissance optique de caractères. Seule la version PDF a une valeur juridique

CLAIMS

WHAT IS CLAIMED IS:

1. A process for making a composite polymer composition, said process comprising:

providing a light polymerizable liquid composition comprising:

a first polymerizable component;

a second polymerizable component, and

a photoinitiator,

the light polymerizable liquid composition characterized by a liquid ratio of the first polymerizable component to the second polymerizable component;

generating a first polymer region having a first ratio of the first polymerizable component to the second polymerizable component by exposing the light

polymerizable liquid composition to a first exposure of light characterized by a first exposure region; and

polymerizing the light polymerizable liquid composition in a second region different than the first region and adjacent to, contacting, or overlapping with the first exposure region, wherein the second region has a second ratio of the first

polymerizable component to the second polymerizable component,

wherein the liquid ratio, the first ratio, and the second ratio are different.

2. The process of claim 1, wherein polymerizing the light polymerizable liquid composition in the second region generates a second polymer, and wherein the first polymer is characterized by one or more different polymer properties than said second polymer.

3. The process of claim 2, wherein the one or more different polymer properties are selected from the group consisting of: Tg, storage modulus, Young's modulus, elongation to break, elongation to yield, or any combination of these.

4. The process of claim 2, wherein the first polymer is characterized by a Tg that is from 2 °C to 50 °C greater than the second polymer from 5 °C to 50 °C greater than the second polymer, from 5 °C to 40 °C greater than the second polymer, from 5 °C to 30 °C greater than the second polymer, from 5 °C to 20 °C greater than the second polymer, from 5 "C to 10 °C greater than the second polymer, from 10 °C to 20 °C greater than the second polymer, from 10 °C to 50 °C greater than the second polymer, from 10 °C to 100 °C greater than the second polymer, from 1 °C to 100 °C greater than the second polymer, from 1 °C to 500 °C greater than the second polymer, from 10 °C to 500 °C greater than the second polymer, from 1 °C to 50 °C greater than the second polymer, from 1 °C to 40 °C greater than the second polymer, from 1 "C to 30 °C greater than the second polymer, from 1 °C to 20 °C greater than the second polymer, from 1 °C to 10 °C greater than the second polymer, or from 1 °C to 5 °C greater than the second polymer.

5. The process of claim 2, wherein the first polymer is characterized by a storage modulus that is from 1 MPa to 1,000 MPa greater than the second polymer, from 1 MPa to 500 MPa greater than the second polymer, from 1 MPa to 250 MPa greater than the second polymer, from 1 MPa to 200 MPa greater than the second polymer, from 1 MPa to 100 MPa greater than the second polymer, from 1 MPa to 50 MPa greater than the second polymer, from 1 MPa to 10 MPa greater than the second polymer, from 50 MPa to 200 MPa greater than the second polymer, from 50 MPa to 500 MPa greater than the second polymer, from 50 MPa to 1,000 MPa greater than the second polymer, from 100 MPa to 1,000 MPa greater than the second polymer, from 200 MPa to 400 MPa greater than the second polymer, from 200 MPa to 600 MPa greater than the second polymer, from 200 MPa to 1,000 MPa greater than the second polymer, or from 200 MPa to 2,000 MPa greater than the second polymer.

6. The process of claim 2, wherein the first polymer is characterized by an elongation to break that is from 10% to 1,000% greater than the elongation to break of the second polymer, from 10% to 500% greater than the elongation to break of the second polymer, from 10% to 100% greater than the elongation to break of the second polymer, from 10% to 50% greater than the elongation to break of the second polymer, from 20% to 1,000% greater than the elongation to break of the second polymer, from 30% to 1,000% greater than the elongation to break of the second polymer, from 50% to 1,000% greater than the elongation to break of the second polymer, or from 100% to 1,000% greater than the elongation to break of the second polymer.

7. The process of claim 1, wherein said step of exposing said light polymerizable liquid composition to said first exposure results in a polymerization induced phase separation in said light polymerizable liquid composition along one or more lateral directions.

8. The process of claim 1, wherein said first polymerizable component and said second polymerizable component are miscible in each other.

9. The process of claim 1, wherein said second polymerizable component is partially or fully immiscible in the first polymer.

10. The process of claim 1, wherein said first polymerizable component and said second polymerizable component are mono functional monomers, polyfunctional monomers or a combination of these.

11. The process of claim 1, wherein said first polymerizable component comprises one or more of a methacrylate monomer, an acrylate monomer, a thiol monomer, a vinyl acetate derivative monomer, a styrene monomer, a vinyl ether monomer or a combination of these; and wherein said second polymerizable component comprises one or more of an acrylate monomer, a thiol monomer, an allyl ether monomer, a vinyl acetate derivative monomer, a vinyl chloride monomer, an acrylonitrile monomer, a vinyl ether monomer, a vinyl silane (or siloxane) monomer, a butadiene monomer, a norbornene, a maleate monomer, a fumarate monomer, an epoxide monomer, an anhydride monomer, an hydroxyl monomer a combination of these.

12. The process of claim 1, wherein said first polymerizable component is provided in said light polymerizable liquid composition at a concentration selected over the range 10 to 90 wt% and said second polymerizable component is provided in said light polymerizable liquid composition at a concentration selected over the range 10 to 90 wt%.

13. The process of claim 1, wherein said light polymerizable liquid composition further

comprises one or more additives selected from the group consisting of additional polymerizable components, additional photoinitiators, thermal initiators, polymerization catalysts, surfactants, dispersants, viscosity modifiers, pigments, dyes, surface active compounds, fillers, particles, binders, or any combination of these.

14. The process of claim 1, wherein the first polymer, said second polymer, or both are formed by a free radical polymerization, ionic polymerization (cationic or anionic) or a combination of these.

15. The process of claim 2, wherein the first polymer is primarily formed by free radical polymerization and wherein the second polymer is primarily formed by ionic

polymerization (cationic or anionic).

16. The process of claim 2, wherein the first polymer is primarily formed by from photo- induced polymerization and wherein the second polymer is primarily formed by thermally induced polymerization.

17. The process of claim 1, wherein said first polymerizable component and said second

polymerizable component are characterized by a reactivity ratio greater than or equal to 1.

18. The process of claim 17, wherein said reactivity ratio is selected over the range of 1 to 10.

19. The process of claim 17, wherein said reactivity ratio results from differences in a

polymerization rate coefficient, concentration, functionality or any combination of these of said first polymerizable component and said second polymerizable component.

20. The process of claim 17, wherein said reactivity ratio results from differences in the solubility or diffusivity of said first polymerizable component and said second polymerizable component.

21. The process of claim 17, wherein said reactivity ratio results from differences in oxygen inhibition, light absorption, photoinitiator concentration or any combination of these for said self-polymerization reaction of the first polymerizable component and said polymerization reaction of the first polymerizable component and the second

polymerizable component.

22. The process of claim 1, wherein said first polymerizable component and said second polymerizable component each independently are characterized by a diffusivity in said light polymerizable liquid sufficient for a direct or additive manufacture process.

23. The process of claim 1, wherein at least a portion of said first exposure region, said second region or both independently have at least one lateral dimension less than or equal to 100 μιη.

24. The process of claim 1, wherein at least a portion of said first exposure region, said second region, or both independently have at least one lateral dimension of 50 μιη to 100 nm.

25. The process of claim 1, wherein said first exposure region comprises more than one first exposure area or wherein said second region comprises more than one second exposure area.

26. The process of claim 1, wherein said first exposure region is characterized by a light intensity of less than 20 mW/cm ; and wherein the second region is characterized by a light intensity equal to or greater than the light intensity of the first exposure region.

27. The process of claim 1, wherein the first exposure region is exposed to light more than once before the second region is exposed to light.

28. The process of claim 1, wherein said first exposure is generated via laser exposure,

holography, DLP projection, optical lithography, pulsed light or an combination of these.

29. The process of claim 1, wherein said step of polymerizing said light polymerizable liquid composition comprises exposing said light polymerizable liquid composition to a second exposure of light.

30. The process of claim 1, wherein said step of polymerizing said light polymerizable liquid composition characterized by the second region comprises exposing said light polymerizable liquid to thermal energy.

31. The process of claim 1 , comprising a method of direct or additive fabrication.

32. The process of claim 31, wherein said method of direct or additive fabrication uses a single light polymerizable liquid composition.

33. The process of claim 31, wherein said method of direct or additive fabrication is selected from the group consisting of: a stereolithographic (SLA) technique, a digital light processing (DLP) technique, a continuous liquid interface production technique, a micro- stereolithographic (μ-SLA) technique, a two photon polymerization technique, a material jetting technique, and a combination thereof.

34. The process of claim 33, wherein the method of direct or additive fabrication generates said polymer composition comprising a composite material.

35. The process of claim 31, wherein the method of direct or additive fabrication generates an orthodontic appliance comprising said polymer composition.

36. The process of claim 33, wherein after the second exposure is complete, a new layer is started.

37. The process of claim 33, wherein one of more of the layers uses only 1 exposure for that layer.

38. A method of making a composite polymer composition from a single resin, the process comprising:

providing a resin, the resin comprising a first monomer component and a second monomer component, the resin characterized by a resin ratio of the first monomer component to the second monomer component;

initiating a polymerization reaction by exposing the resin to a first exposure of light;

forming a first region having a first ratio of the first monomer component to the second monomer component; and

forming a second region having a second ratio of the first monomer component to the second monomer component, wherein the resin ratio, the first ratio, and the second ratio are different.

39. The method of claim 38, further comprising the step of polymerizing the second monomer component.

40. The method of any one of claims 38-39, wherein initiating the polymerization reaction comprises exposing the resin to a source of radiation.

41. The method of claim 40, wherein an object is placed between the first region and the

source of radiation.

42. The method of claim 41, wherein the object comprises a mask, a cover, a lens, a filter, or any combination thereof.

43. The method of any one of claims 40-42, wherein the source of radiation comprises

ultraviolet light, visible light, infrared light, microwave irradiation, laser exposure, holography, DLP projection, optical lithography, pulsed light, or a combination thereof.

44. The method of any one of claims 38-43, wherein the polymerization of the first monomer component forms a first polymer.

45. The method of any one of claims 39-44, wherein polymerizing the second monomer component forms a second polymer.

46. The method of any one of claims 39-45, wherein the polymerization reaction results in a polymerization-induced phase separation along one or more lateral directions.

47. The method of any one of claims 39-46, wherein the first region and the second region are separated by a concentration gradient.

48. The method of claim 47, wherein the concentration gradient comprises the concentrations of the first monomer component and the second monomer component.

49. The method of claim 47, wherein the concentration gradient comprises the concentration of the first polymer and the second polymer.

50. The method of any one of claims 38-49, further comprising the step of using a mask to selectively define the first region or the second region.

51. The method of any one of claims 39-50, wherein the polymerization of the second

monomer component uses a secondary photopolymerization.

52. The method of claim 51, wherein the secondary photopolymerization comprises the use of a mask, an overlapping region, a full blanket exposure, or a combination thereof.

53. The method of any one of claims 51-52, wherein the secondary photopolymerization uses a second source of radiation, said source of radiation comprising ultraviolet light, visible light, infrared light, microwave irradiation, or a combination thereof.

54. The method of any one of claims 51-53, wherein the polymerization of the first monomer and the polymerization of the second monomer use the same source of radiation.

55. The method of any one of claims 38-54, wherein the first monomer component and the second monomer component are miscible.

56. The method of any one of claims 38-55, wherein the first monomer component and the second monomer component are fully miscible.

57. The method of any one of claims 44-56, wherein the second monomer component is immiscible in the first polymer.

58. The method of any one of claims 44-57, wherein the second monomer component is fully immiscible in the first polymer.

59. The method of any one of claims 44-58, wherein the first monomer component is

immiscible in the first polymer.

60. The method of any one of claims 44-59, wherein the first monomer component is fully immiscible in the first polymer.

61. The method of any one of claims 38-60, wherein the first monomer component is

monofunctional, polyfunctional, or a combination thereof.

62. The method of any one of claims 38-61, wherein the second monomer component is monofunctional, polyfunctional, or a combination thereof.

63. The method of any one of claims 38-62, wherein the first monomer component comprises one or more of a methacrylate monomer, an acrylate monomer, a thiol monomer, a vinyl acetate monomer, a styrene monomer, a vinyl ether monomer, a derivative thereof, or a combination thereof.

64. The method of any one of claims 38-63, wherein the second monomer component

comprises one or more of an acrylate monomer, a thiol monomer, an allyl ether monomer, a vinyl acetate monomer, a vinyl chloride monomer, an acrylonitrile monomer, a vinyl ether monomer, a vinyl silane (or siloxane) monomer, a butadiene monomer, a norbornene, a maleate monomer, a fumarate monomer, an epoxide monomer, an anhydride monomer, a hydroxyl monomer, a derivative thereof, or a combination thereof.

65. The method of any one of claims 38-64, wherein from 10 to 90 wt% of the resin consists of the first monomer component.

66. The method of any one of claims 38-65, wherein from 10 to 90 wt% of the resin consists of the second monomer component.

67. The method of any one of claims 38-66, wherein the resin further comprises an additive.

68. The method of claim 67, wherein the additive is selected from the group consisting of a polymerizable component, a photoinitiator, a thermal initiator, a polymerization catalyst, a surfactant, a dispersant, a viscosity modifier, an optical absorber, a pigment, a dye, a surface active compound, a filler, a particle, a binder, or any combination thereof.

69. The method of any one of claims 38-68, wherein the polymerization reaction comprises ionic polymerization, free radical polymerization, or a combination thereof.

70. The method of claim 69, wherein the ionic polymerization comprises cationic

polymerization, anionic polymerization, or a combination thereof.

71. The method of any one of claims 44-70, wherein the first polymer is formed by free radical polymerization, ionic polymerization, photo-initiated polymerization, thermally induced polymerization, or a combination thereof.

72. The method of any one of claims 45-71, wherein the second polymer is formed by free radical polymerization, ionic polymerization, photo-initiated polymerization, thermally induced polymerization, or a combination thereof.

73. The method of any one of claims 44-72, wherein greater than 50% of the first polymer is formed by free radical polymerization.

74. The method of any one of claims 45-73, wherein greater than 50% of the second polymer is formed by ionic polymerization.

75. The method of claim 74, wherein the ionic polymerization comprises cationic

polymerization, anionic polymerization, or a combination thereof.

76. The method of any one of claims 44-72, wherein greater than 50% of the first polymer is formed by photo-initiated polymerization.

77. The method of any one of claims 45-73, wherein greater than 50% of the second polymer is formed by thermally induced polymerization.

78. The method of any one of claims 44-72, wherein greater than 50% of the first polymer is formed by thermally induced polymerization.

79. The method of any one of claims 45-73, wherein greater than 50% of the second polymer is formed by photo-initiated polymerization.

80. The method of any one of claims 38-79, wherein the first monomer component and the second monomer component have a ratio of reactivity, and wherein the ratio of reactivity of the first monomer component to the second monomer component is from 1:1 to 1:10,000, from 1:1 to 1:5,000, from 1:1 to 1:2,500, from 1:1 to 1:1,000, from 1:1 to 1:500, from 1:1 to 1:100, from 1:1 to 1:50, from 1:1 to 1:30, from 1:1 to 1:20, from 1:1.5 to 1:10,000, from 1:1.5 to 1:5,000, from 1:1.5 to 1:2,500, from 1:1.5 to 1:1,000, from 1:1.5 to 1:500, from 1:1.5 to 1:100, from 1:1.5 to 1:50, from 1:1.5 to 1:30, from 1:1.5 to 1:20, from 1:5 to 1:10,000, from 1:5 to 1:5,000, from 1:5 to 1:2,500, from 1:5 to 1:1,000, from 1:5 to 1:500, from 1:5 to 1:100, from 1:5 to 1:50, from 1:5 to 1:30, from 1:5 to 1:20, from 1:10 to 1:10,000, from 1:10 to 1:5,000, from 1:10 to 1:2,500, from 1:10 to 1:1,000, from 1:10 to 1:500, from 1:10 to 1:100, from 1:10 to 1:50, from 1:10 to 1:30, or from 1:10 to 1:20.

81. The method of any one of claims 38-80, wherein the first monomer component is from 1- fold to 10-fold more reactive than the second monomer component.

82. The method of claim 81, wherein the first monomer component is from 1-fold to 1000- fold, from 1-fold to 500-fold, from 1-fold to 100-fold, from 1-fold to 50-fold, from 1-fold to 10-fold, from 2-fold to 1000-fold, from 2-fold to 500-fold, from 2-fold to 100-fold, from 2-fold to 50-fold, from 2-fold to 10-fold, from 3-fold to 1000-fold, from 3-fold to 500-fold, from 3-fold to 100-fold, from 3-fold to 50-fold, from 3-fold to 10-fold, from 5- fold to 1000-fold, from 5-fold to 500-fold, from 5-fold to 100-fold, from 5-fold to 50-fold, from 5-fold to 10-fold, from 10-fold to 1000-fold, from 10-fold to 500-fold, from 10-fold to 100-fold, from 10-fold to 50-fold, from 50-fold to 1000-fold, from 50-fold to 500-fold, from 50-fold to 100-fold, or from 100-fold to 1000-fold more reactive than the second monomer component.

83. The method of claim 82, wherein the first monomer component is 2- fold to 5-fold more reactive than the second monomer component.

84. The method of any one of claims 80-83, wherein the difference in the reactivity of the first monomer component and the reactivity of the second monomer component comprises a difference in a polymerization rate coefficient, a difference in concentration, a difference in functionality, a difference in solubility, a difference in diffusivity of the first monomer component, a difference in diffusivity of the second monomer component, or any combination thereof.

85. The method of any one of claims 80-84, wherein the difference in the reactivity of the first monomer component and the reactivity of the second monomer component comprises a difference in oxygen inhibition, a difference in light absorption, a difference in

photoinitator concentration, or a combination thereof.

86. The method of any one of claims 80-85, wherein the first monomer component and the second monomer component comprise a diffusivity in the resin sufficient for direct or additive manufacturing.

87. The method of any one of claims 38-86, wherein the first region has at least one lateral dimension less than or equal to 500 μητ, less than or equal to 300 μητ, less than or equal to 200 μητ, less than or equal to 100 μητ, less than or equal to 50 μητ, or less than or equal to 20 μιη.

88. The method of any one of claims 38-87, wherein the second region has at least one lateral dimension less than or equal to 500 μητ, less than or equal to 300 μητ, less than or equal to 200 μητ, less than or equal to 100 μητ, less than or equal to 50 μητ, or less than or equal to 20 μιη.

89. The method of any one of claims 38-88, wherein the first region has at least one lateral dimension between 50 μιη and 100 nm, between 50 μιη and 250 μητ, between 100 μιη and 250 μητ, or between 100 μιη and 500 μιη.

90. The method of any one of claims 38-89, wherein the second region has at least one lateral dimension between 50 μιη and 100 nm, between 50 μιη and 250 μητ, between 100 μιη and 250 μητ, or between 100 μιη and 500 μιη.

91. The method of any one of claims 40-90, wherein the source of radiation initiates

polymerization of the first monomer component in a first exposure region.

92. The method of claim 91, wherein the source of radiation initiates polymerization of the second monomer component in a second exposure region.

93. The method of claim 92, wherein the first exposure region comprises a plurality of first exposure areas, or wherein the second exposure region comprises a plurality of second exposure areas.

94. The method of any one of claims 91-93, wherein the first exposure region is exposed to a first light intensity of less than 20 mW/cm .

95. The method of claim 94, wherein the second exposure region is exposed to a second light intensity, and wherein the second light intensity is equal to or greater than the first light intensity.

96. The method of any one of claims 91-95, wherein the first exposure region is exposed to the source of radiation before the second exposure region is exposed to the source of radiation.

97. The method of claim 96, wherein the first exposure region is exposed to the source of radiation more than once before the second exposure region is exposed to the source of radiation.

98. The method of any one of claims 91-97, wherein the first exposure region is exposed to laser exposure, holography, DLP projection, optical lithography, pulsed light, or a combination thereof.

99. The method of any one of claims 92-98, wherein the second exposure region is exposed to laser exposure, holography, DLP projection, optical lithography, pulsed light, or a combination thereof.

100. The method of any one of claims 91-99, wherein at least one of the first exposure region and the second exposure region are exposed to more than one exposure of light.

101. The method of any one of claims 92-100, wherein the second exposure region is exposed to thermal energy.

102. The method of any one of claims 38-101, further comprising the step of using a single additive manufacturing machine.

103. The method of claim 102, wherein the single additive manufacturing machine comprises a 3D printer.

104. The method of any one of claims 38-103, further comprising the step of fabricating the composite polymer composition using additive fabrication or direct fabrication.

105. The method of claim 104, wherein the additive fabrication and/or the direct fabrication uses a single light polymerizable liquid composition.

106. The method of any one of claims 104-105, wherein the additive fabrication and/or the direct fabrication comprises a stereolithographic (SLA) technique, a digital light processing (DLP) technique, a continuous liquid interface production technique, a micro- stereolithographic (μ-SLA) technique, a two photon polymerization technique, a material jetting technique, or a combination thereof.

107. The method of any one of claims 97-106, wherein a new layer is started after the second exposure region is exposed to the source of radiation.

108. The method of any one of claims 96- 107, wherein one or more regions use a single

exposure of radiation.

109. The method of any one of claims 38- 108, wherein the composite polymer composition comprises an orthodontic appliance.

110. A composite material made by any one of the methods of claims 38- 108.

111. The composite material of claim 110, wherein the first polymer comprises a storage

modulus at least 200 MPa greater than the storage modulus of the second polymer.

112. The composite material of any one of claims 110-111, wherein the first polymer comprises a fracture strain that is from 10% to 1,000% greater than the elongation to break of the second polymer, from 10% to 500% greater than the elongation to break of the second polymer, from 10% to 100% greater than the elongation to break of the second polymer, from 10% to 50% greater than the elongation to break of the second polymer, from 20% to 1,000% greater than the elongation to break of the second polymer, from 30% to 1,000% greater than the elongation to break of the second polymer, from 50% to 1,000% greater than the elongation to break of the second polymer, or from 100% to 1,000% greater than the elongation to break of the second polymer.

113. The composite material of any one of claims 110-112, wherein the strength of the

composite material is greater than that of the first polymer or the second polymer.

114. The composite material of any one of claims 110-113, wherein the flexibility of the composite material is greater than that of the first polymer or the second polymer.

The method of any one of claims 40-114, wherein the source of radiation comprises a wavelength of between 300 nm and 900 nm, between 300 nm and 800 nm, between 300 nm and 700 nm, between 300 nm and 600 nm, between 300 nm and 500 nm, between 300 nm and 450 nm, between 300 nm and 400 nm, between 400 nm and 800 nm, between 350 nm and 800 nm, between 350 nm and 600 nm, or between 350 nm and 500 nm.

115. The method of any one of claims 38-114, wherein the first region has a vertical dimension less than or equal to 500 μι , less than or equal to 300 μι , less than or equal to 200 μι , less than or equal to 100 μητ, less than or equal to 50 μητ, or less than or equal to 20 μιη.

116. The method of any one of claims 38-87, wherein the second region has a vertical

dimension less than or equal to 500 μητ, less than or equal to 300 μητ, less than or equal to 200 μητ, less than or equal to 100 μητ, less than or equal to 50 μητ, or less than or equal to 20 μιη.

117. The method of any one of claims 38-88, wherein the first region has a vertical dimension between 50 μιη and 100 nm, between 50 μιη and 250 μητ, between 100 μιη and 250 μητ, or between 100 μιη and 500 μιη.

118. The method of any one of claims 38-89, wherein the second region has a vertical

dimension between 50 μιη and 100 nm, between 50 μιη and 250 μητ, between 100 μιη and 250 μητ, or between 100 μιη and 500 μιη.

119. The method of any one of claims 38-118, wherein the resin is homogenous.

120. The method of any one of claims 38-118, wherein the resin ratio has a variation, and the variation is dependent on localization.

121. The method of any one of claims 38-118 or 119-120, wherein the first polymerizable

component can diffuse freely through the resin.

122. The method of any one of claims 38-118 or 119-121, wherein the second polymeriziable component can diffuse freely through the resin.

123. The method of any one of claims 38-118 or 119-122, wherein the first ratio is greater than the resin ratio, and the resin ratio is greater than the second ratio.

124. The method of any one of claims 38-118 or 119-122, wherein the first ratio is greater than the second ratio, and the second ratio is greater than the resin ratio.

125. The method of any one of claims 38-118 or 119-122, wherein the second ratio is greater than the resin ratio, and the liquid ratio is greater than the first ratio.

The method of any one of claims 38-118 or 119-122, wherein the second ratio is greater than the first ratio, and the first ratio is greater than the resin ratio.

The method of any one of claims 38-118 or 119-122, wherein the resin ratio is greater than the first ratio, and the first ratio is greater than the second ratio.

The method of any one of claims 38-118 or 119-122, wherein the resin ratio is greater than the second ratio, and the second ratio is greater than the first ratio.

The method of any one of claims 1-37, wherein the light polymerizable liquid composition is homogenous.

The method of any one of claims 1-37, wherein the liquid ratio has a variation, and the variation is dependent on localization.

1. The method of any one of claims 1-37 or 129-130, wherein the first polymerizable

component can diffuse freely through the light polymerizable liquid composition.

The method of any one of claims 1-37 or 129-131, wherein the second polymerizable component can diffuse freely through the light polymerizable liquid composition.

The method of any one of claims 1-37 or 129-132, wherein the first ratio is greater than the liquid ratio, and the liquid ratio is greater than the second ratio.

The method of any one of claims 1-37 or 129-132, wherein the first ratio is greater than the second ratio, and the second ratio is greater than the liquid ratio.

The method of any one of claims 1-37 or 129-132, wherein the second ratio is greater than the liquid ratio, and the liquid ratio is greater than the first ratio.

The method of any one of claims 1-37 or 129-132, wherein the second ratio is greater than the first ratio, and the first ratio is greater than the liquid ratio.

The method of any one of claims 1-37 or 129-132, wherein the liquid ratio is greater than the first ratio, and the first ratio is greater than the second ratio.

The method of any one of claims 1-37 or 129-132, wherein the liquid ratio is greater than the second ratio, and the second ratio is greater than the first ratio.