Reverse thermal gels as support for rapid prototyping

Abstract

The present invention relates to novel polymeric compositions that exhibit Reverse Thermal Gelation (RTG) properties for use as Support Materials (SM) in the manufacture of three-dimentional objects. These polymers are Temperature Sensitive Poolymers that respond with a significant change of properties to a small change in temperature. Temperature Sensitive Polymers exhibit cloud point (CP) or lower critical solution temperature (LCST) in aqueous solutions. Water-soluble Temperature Sencitive Polymers are chosen to give low viscosity liquid at low temperature when dissolved in water and by that to permit easy dispensing at low temperature. Rising the temperature above their gelation temperature (T gel ) will result in solidification of the composition. At its gel position the material has favorable characteristics as a support and building material. The gel layers have the appropriate toughness and dimensional stability to support the model layers during the building process. After the building process is completed the gel can be cooled down to a temperature below its T gel so the gel can liquefy and be removed easily by rinsing with a water.

1 . A composition suitable for supporting and/or building a three-dimentional object, said composition comprising: 
 at least one Temperature Sensitive Polymer; and    at least one surface-active agent,    wherein said composition exhibits Reverse Thermal Gelation (RTG) properties.    
     
     
         2 . The composition according to  claim 1 , wherein said Temperature Sensitive Polymer is a water-soluble Temperature Sensitive Polymer.  
     
     
         3 . The composition according to  claim 2 , wherein said water-soluble Temperature Sensitive Polymer is an ABA triblock oligomer, wherein A and B are oligomers.  
     
     
         4 . The composition according to  claim 3 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         5 . The composition according to  claim 3 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         6 . The composition according to  claim 3 , wherein A and B comprise aliphatic polyether and/or polyester units.  
     
     
         7 . The composition according to  claim 3 , wherein A is poly(ethylene oxide) and B is poly(propylene oxide).  
     
     
         8 . The composition according to  claim 2 , wherein said water-soluble Temperature Sensitive Polymer is a multi blocks polymer of (ABA-X) m , organized at random or repetitive configuration, wherein A and B are oligomers, m is an integer of 1-30, and X is a chain extender.  
     
     
         9 . The composition according to  claim 8 , wherein said X is selected from the group consisting of di, tri and poly carboxylic acids, diacyl halides, triphosgene or any combination thereof.  
     
     
         10 . The composition according to  claim 8 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         11 . The composition according to  claim 8 , wherein A ia a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         12 . The composition according to  claim 8 , wherein said multi block polymer of ABA is a polyurethane, a polycarbonate, a polyester or any combination thereof.  
     
     
         13 . The composition according to  claim 2 , wherein said Temperature Sensitive Polymer is a poly(N-substituted (meth)acrylamide).  
     
     
         14 . The composition according to  claim 13 , wherein said poly(N-substituted (meth)acrylamide) is a poly (N-isopropyl (meth)acrylamides).  
     
     
         15 . The composition according to  claim 2 , wherein said Temperature Sensitive Polymer is a poly vinyl alcohol derivetive, hydroxypropyl methylcellulose, ethyl hydroxyethyl cellulose (EHEC) or any combination thereof.  
     
     
         16 . The composition according to  claim 1 , wherein said surface-active agent is capable of resucing the surface tension of said composition to about 30 dyne/cm.  
     
     
         17 . The composition according to  claim 1 , wherein said surface-active agent is a silicon surface-active agent additive, a fluoro-based surface-active agent or a combination thereof.  
     
     
         18 . The composition according to  claim 1 , wherein said composition further comprises: 
 at least one photo curable reactive component;    at least one photo-initiator; and    at least one stabilizer.    
     
     
         19 . The composition according to  claim 18 , wherein said photo curable reactive compound is a (meth)acrylic component.  
     
     
         20 . The composition according to  claim 19 , wherein said (meth)acrylic component is a (meth)acrylic monomer, a (meth)acrylic oligomer, or a combination thereof.  
     
     
         21 . The composition according to  claim 19 , wherein said (meth)acrylic component is a polyetheline glycol mono or di (meth)acrylated, polyether triacrylate or any combination thereof.  
     
     
         22 . The composition according to  claim 18 , wherein said reactive component is a water miscible component that is, after irradiation or curing, capable of dissolving or swelling upon exposure to water or to an alkaline or acidic water solution.  
     
     
         23 . The composition according to  claim 22 , wherein said water miscible component is an acryloyl morpholine, a (meth)acrylated urethane oligomer derivative of polyethylene glycol, a partially (meth)acrylated polyol oligomer, an (meth)acrylated oligomer having hydrophilic substituents or any combination thereof.  
     
     
         24 . The composition according to  claim 23 , wherein said hydrophilic substituent is an acidic substuent, an amino substituent, a hydroxy substituent, or any combiination thereof.  
     
     
         25 . The composition according to  claim 19 , wherein said (meth)acrylic component is beta-carboxyethyl acrylate.  
     
     
         26 . The composition according to  claim 19 , wherein said reactive component is a molecule having one or more vinyl ether substituents.  
     
     
         27 . The composition according to  claim 26 , wherein said vinyl ether substituent is hydroxy-butyl vinyl ether.  
     
     
         28 . The composition according to  claim 18 , wherein said photo-initiator is a free radical photo-initiator, a cationic photo-initiator, or any combination thereof.  
     
     
         29 . The composition according to  claim 28 , wherein said free radical photo-initiator is benzophenone, an acylphosphine oxide, an alpha-amino ketone or any combination thereof.  
     
     
         30 . The composition according to  claim 28 , wherein said cationic photo-initiator is selected from the group consisting of aryldiazonium salts, diaryliodonium salts, triarylsulphonium salts, triarylselenonium salts and triarylsolphonium hexafluoroantimonate salts.  
     
     
         31 . The composition according to  claim 28 , wherein said photo-initiator further comprises a co-initiator component.  
     
     
         32 . The composition according to  claim 31 , wherein said co-initiator component is triethanol amine.  
     
     
         33 . The composition according to  claim 18 , wherein said co-initiator component is triethanol amine.  
     
     
         34 . A method for building a three-dimentional object by three dimentional printing, said method comprising the steps of: 
 dispensing a building composition comprising: 
 at least one Temperature Sensitive Polymer; wherein said composition exhibits Reverse Thermal Gelation (RTG) properties; and  
 at least one surface-active agent; and  
   gelating said building composition by increasing temperature to above the gelation temperature of said composition, thereby constructing said three dimentional object.    
     
     
         35 . The method according to  claim 34 , wherein said Temperature Sensitive Polymer is a water-slouble Temperature Sensitive Polymer.  
     
     
         36 . The method according to  claim 35 , wherein said water-soluble Temperature Sensitive Polymer is an ABA triblock oligomer, wherein A and B are oligomers.  
     
     
         37 . The method according to  claim 36 , wherein A is a hydrophilic oligomer and B ia hydrophobic oligomer.  
     
     
         38 . The method according to  claim 36 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         39 . The method according to  claim 36 , wherein A and B comprise aliphatic polyether and/or polyester units.  
     
     
         40 . The method according to  claim 36 , wherein A is poly(ethylene oxide) and B is poly(propylene oxide).  
     
     
         41 . The method according to  claim 35 , wherein said water-soluble Temperature Sensitive Polymer is a multi block polymer of (ABA-X) m , organized at random or repetitive configuration, wherein wherein A and B arer oligomers, m is an integer of 1-30, and X is a chain extender.  
     
     
         42 . The method according to  claim 41 , wherein said X is selected from group consisting of di, tri and poly isocyanates, di, tri and poly carboxylic acids, diacyl halides, triphosgene or any combination thereof.  
     
     
         43 . The method according to  claim 41 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         44 . The method according to  claim 41 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         45 . The method according to  claim 41 , wherein said multiblock polymer of ABA is a polyurethane, polycarbonate, polyester or any combination thereof.  
     
     
         46 . The method according to  claim 35 , wherein said Temperature Sensitive Polymers are poly (N-substituted (meth)acrylamides).  
     
     
         47 . The method according to  claim 46 , wherein said poly (N-substituted (meth)acrylamide is poly (N-isopropyl (meth)acrylamides).  
     
     
         48 . The method according to  claim 35 , wherein said Temperature Sensitive Polymer is a poly vinyl alcohol derivative, hydroxypropyl methylcellulos, Ethyl hydroxyethyl cellulose (EHEC) or any combination thereof.  
     
     
         49 . The method according to  claim 34 , wherein said surface-active agent is capable of reducing the surface tension of said composition to about 30 dyne/cm.  
     
     
         50 . The method according to  claim 34 , wherein said surfacce-active agent is a silicon surface-active agent additive, a fluoro-based surface-active agent or a combination thereof.  
     
     
         51 . The method according to  claim 34 , wherein said composition further comprises: 
 at least one photo curable reactive component;    at least one photo-initiator; and    at least one stabilizer,    wherein said method further comprises the step of curing said building composition, thereby increases the strength of said building composition.    
     
     
         52 . The method according to  claim 51 , wherein said photo curable reactive component is a (meth)acrylic component.  
     
     
         53 . The method according to  claim 52 , wherein said (meth)acrylic component is a (meth)acrylic monomer, a (meth)acrylic oligomer, or a combination thereof.  
     
     
         54 . The method according to  claim 52 , wherein said (meth)acrylic component is a polyethylene glycol mono or di (meth)acrylated, polyether triacrylate or any combination thereof.  
     
     
         55 . The method according to  claim 51 , wherein said reactive component is a water miscible component that is, after irradiation or curing, capable of dissolving or swelling upon exposure to water or to an alkaline or acidic water solution.  
     
     
         56 . The method according to  claim 55 , wherein said water miscible component is an acryloyl morpholine, a (meth)acrylated urethane oligomer derivative of polyethylene glycol, a partially (meth)acrylated polyol oligomer, an (meth)acrylated oligomer having hydrophilic substituents, or any combinatioin thereof.  
     
     
         57 . The method according to  claim 56 , wherein said hydrophilic substituents is an acidic substituent, an amino substituent, a hydroxy substituent or any combination thereof.  
     
     
         58 . The method according to  claim 52 , wherein said (meth)acrylic component is beta-carboxyethyl acrylate.  
     
     
         59 . The method according to  claim 52 , wherein said reactive component is a molecule having one or more vunyl ether substituents.  
     
     
         60 . The method according to  claim 59 , wherein said vinyl ether substituent is hydroxy-butyl vinyl ether.  
     
     
         61 . The method according to  claim 51 , wherein said photo-initiator is a free radical photo-initiator, a cationic photo-initiator, or any combination thereof.  
     
     
         62 . The method according to  claim 61 , wherein said free radical photo-initiator is benzophenone, an acylphosphine oxide, an alpha-amino ketone or any combination thereof.  
     
     
         63 . The method according to  claim 61 , wherein said cationic photo-initiator is selected from the group consisting of aryldiazonium salts, diaryliodonium salts, triarylsulphonium salts, triarylselenonium salts, triarylsolphonium hexafluoroantimonate salts.  
     
     
         64 . The method according to  claim 61 , wherein said photo-initiator further comprises a co-initiator component.  
     
     
         65 . The method according to  claim 64 , wherein said co-initiator component is triethanol amine.  
     
     
         66 . The method according to  claim 51 , wherein said stabilizer is 4-methoxy phenol.  
     
     
         67 . A method for supporting a three-dimentional object during construction, said method comprising the step of: 
 contacting said object with a support composition, said support composition comprising: 
 at least one Temperature Sensitive Polymer, wherein said support composition exhibits Reverse Thermal Gelation (RTG) properties; and  
 at least one surface-active agent; and  
   gelating said support composition by increasing temperature to above the gelation temperature of said composition, thereby supporting said three dimentional object.    
     
     
         68 . The method according to  claim 67 , further comprising the step of removing said support composition after construction of said object by cooling said support composition to a temperature below the gelation temperature of said compositioni.  
     
     
         69 . The method according to  claim 67 , wherein said construction comprises Rapid Prototyping (RP), Rapid Manufacturing (RM) or Rapid Tooling (RT).  
     
     
         70 . The method according to  claim 67 , wherein said construction comprises rapid tooling (RT), wherein said rapid tooling (RT) comprises 
 building a casting mold with said support composition for holding said object; and    building said object in said mold.    
     
     
         71 . The method according to  claim 70 , further comprising the step of removing said mold by cooling said support composition to a temperature below the gelation temperature of said composition.  
     
     
         72 . The method according to  claim 67 , wherein said construction comprises Rapid Manufacturing (RM), wherein said rapid manufacturing (RM) comprises direct manufacturing of finished parts.  
     
     
         73 . The method according to  claim 67 , wherein said Temperature Sensitive Polymer is a water-soluble Temperature Sensitive Polymer.  
     
     
         74 . The method according to  claim 73 , wherein said water-soluble Temperature Sensitive Polymer is an ABA triblock oligomer, wherein A and B are oligomers.  
     
     
         75 . The method according to  claim 74 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         76 . The method according to  claim 74 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         77 . The method according to  claim 74 , wherein A and B comprise aliphatic polyether and/or polyester units.  
     
     
         78 . The method according to  claim 74 , wherein A is poly(ethylene oxide) and B is poly(propylene oxide).  
     
     
         79 . The method according to  claim 73 , wherein said water-soluble Temperature sensitive Polymer is a multi block polymer of (ABA-X) m , organized at random or repetitive configuration, wherein A and B are oligomers, m is an integer of 1-30, and X is chain extender.  
     
     
         80 . The method according to  claim 79 , wherein said X is selected from the group consisiting of di, tri and poly isocyanates, di, tri and poly carboxylic acids, diacyl halides, triphosgene or any combination thereof.  
     
     
         81 . The method according to  claim 79 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         82 . The method according to  claim 79 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         83 . The method according to  claim 79 , wherein said multi block plymer of ABA is a polyurethane, polycarbonate, polyester or any combination thereof.  
     
     
         84 . The method according to  claim 73 , wherein said Temperature Sensitive Polymers are poly (N-substituted (meth)acrylamides).  
     
     
         85 . The method according to  claim 79 , wherein said poly (N-substituted (meth)acrylamides) is poly (N-isopropyl (meth)acrylamides).  
     
     
         86 . The method according to  claim 73 , wherein said Temperature Sensitive Polymer is a poly vinyl alcohol derivative, hydroxypropyl methylcellulose, Ethyl hydroxyethyl cellulose (EHEC) or any combination thereof.  
     
     
         87 . The method according to  claim 67 , wherein said surface-active agent is capable of reducing the surface tension of said composition to about 30 dyne/cm.  
     
     
         88 . The method according to  claim 67 , wherein said surface-active agent is silicon surface-active agent additive, a fluoro-base surface-active agent additive, or a combination thereof.  
     
     
         89 . The method according to  claim 67 , wherein said composition further comprises: 
 at least one photo-curable reactive component;    at least one photo-initiator; and    at least stabilizer;    whereby said method further comprises the step of curing said support composition, thereby increases the strength of said support composition.    
     
     
         90 . The method according to  claim 89 , wherein said photo curable reactive component is a (meth)acrylic component.  
     
     
         91 . The method according to  claim 89 , wherein said (meth)acrylic component is a (meth)acrylic monomer, a (meth)acrylic oligomer, or a combination thereof.  
     
     
         92 . The method according to  claim 90 , wherein said (meth)acrylic component is a polyethylene glycol mono or di (meth)acrylated, polyether triacryalate or any combination thereof.  
     
     
         93 . The method according to  claim 89 , wherein said reactive component is a water miscible component that is, after irradiation or curing, capable of dissolving or swelling upon exposure to water or to an alkaline or acidic water solution.  
     
     
         94 . The method according to  claim 93 , wherein said water miscible component is an acryloyl morpholine, a (meth)acrylated urethane oligomer derivative of polyethylene glycol, a partially (meth)acrylated polyol oligomer, an (meth)acrylated oligomer having hydrophilic substituents, or any combination thereof.  
     
     
         95 . The method according to  claim 94 , wherein said hydrophilic substituent is an acidic substituent, amino substituent, hydroxy substituent or any combination thereof.  
     
     
         96 . The method according to  claim 90 , wherein said (meth)acrylic component is beta-carboxyethyl acrylate.  
     
     
         97 . The method according to  claim 89 , wherein said reactive component is a molecule having one or more vinyl ether substituents.  
     
     
         98 . The method according to  claim 97 , wherein said vinyl ether substituent is hydroxy-butyl vinyl ether.  
     
     
         99 . The method according to  claim 89 , wherein said photo-initiator is a free radical photo-initiator, a cationic photo-initiator, or any combination thereof.  
     
     
         100 . The method according to  claim 99 , wherein said free radical photo-initiator is a benzophenone, an acylphosphine oxide, and alpha-amino ketone or any combination thereof.  
     
     
         101 . The method according to  claim 99 , wherein said cationic photo-initiator is selected from the group consisting of aryldiazonium salts, diaryliodonium salts, triarylsulphonium salts, triarylselnonium salts, triarylsolfonium hexafluoroantimonate salts.  
     
     
         102 . The method according to  claim 99 , wherein said photo-initiator further comprises a co-initiator component.  
     
     
         103 . The method according to  claim 102  wherein said co-initiator component is triethanol amine.  
     
     
         104 . The method according to  claim 89 , wherein said stabilizer is 4-methoxy phenol.  
     
     
         105 . A method for the preparation of a three-dimentional object by three-dimentional printing the step of: 
 dispensing a model composition from a first dispenser, said model composition comprising:    at least one reactive component;    at least one photo-initiator;    at least one surface-active agent; and    at least one stabilizer;    dispensing a support composition from a second dispenser, said support composition comprising:    at least one Temperature Sensitive Polymer;    at least one surface-active agent; and    combining said model composition and said support composition in pre-determined proportions to produce a multiplicity of construction layers for forming said three-dimentional object;    whereby said model composition is cured resulting in a solid form, and    whereby said support composition is gelated by increasing temperature to above the gelation temperatrure of said composition, thereby resulting in a gel form.    
     
     
         106 . The method according to  claim 105 , wherein said preparation od a three-dimentional object further comprising the step of removing said support composition after construction of said object by cooling said support composition to a temperature below the gelation temperature of said composition.  
     
     
         107 . The method according to  claim 105 , wherein said reactive component of said model composition is selected from the group consisting of an acrylic component, a molecule having one or more epoxy substituents, a molecule having one or more vonyl ether substituents, vinylpyrolidone, vinylcarpolactam, or any combination thereof.  
     
     
         108 . The method according to  claim 105 , wherein said reactive component of said model composition is comprised of at least one acrylic component.  
     
     
         109 . The method according to  claim 108 , wherein said acrylic component is an acrylic monomer, acrylic oligomer, an acrylic crooslinker, or any combination thereof.  
     
     
         110 . The method according to  claim 108 , wherein said reactive component of said model composition further comprises a molecule having one or more epoxy substituents, a molecule having one or more vinyl ether substituents, vinylcaprolactam, vinylpyrolidone, or any combination thereof.  
     
     
         111 . The method according to  claim 108 , wherein said reactive component of said model composition further comprises vinylcaprolactam.  
     
     
         112 . The method according to  claim 108 , wherein said reactive component of said model composition is a molecule having one or more vinyl ether substituents.  
     
     
         113 . The method according to  claim 105 , wherein said reactive component of said model composition is a molecule having one or more epoxy substituents.  
     
     
         114 . The method according to  claim 105 , wherein said photo-initiator of said model composition is a molecule having one or more epoxy substituents.  
     
     
         115 . The method according to  claim 105 , wherein said model composition further comprises at least one pigment and at least one dispersant.  
     
     
         116 . The method according to  claim 105 , wherein said pigment is a white pigment, an organic pigment, an inorganic pigment, a metal pigment or a combination thereof.  
     
     
         117 . The method according to  claim 105 , wherein said model composition further comprises a dye.  
     
     
         118 . The method according to  claim 105 , wherein said Temperature Sensitive Polymer is a water-soluble Temperature Sensitive Polymer.  
     
     
         119 . The method according to  claim 118 , wherein said water-soluble Temperature Sensitive is an ABA triblocks oligomer, wherein A and B are oligomers.  
     
     
         120 . The method according to  claim 119 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         121 . The method according to  claim 119 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         122 . The method according to  claim 119 , wherein A and B comprise aliphatic polyether and/or polyester units.  
     
     
         123 . The method according to  claim 119 , wherein A is poly(ethylene oxide) and B is poly(propylene oxide).  
     
     
         124 . The method according to  claim 118 , wherein said water-soluble Temperature Sensitive Polymer is a multi block polymer of (ABA-X) m , organized at random or repetitive configuration, wherein A and B are oligomers, m is an integer of 1-30, and X is a chain extender.  
     
     
         125 . The method according to  claim 124 , wherein said X is selected from the group consisting of di, tri and poly isocyanates, di, tri and poly carboxylic acids, duacil halides, triphosgene, or any combination thereof.  
     
     
         126 . The method according to  claim 124 , wherein A is a hydrophilic oligomer and B is a hydrophobic oligomer.  
     
     
         127 . The method according to  claim 124 , wherein A is a hydrophobic oligomer and B is a hydrophilic oligomer.  
     
     
         128 . The method according to  claim 124 , wherein said multi block polymer of ABA is a polyurethane, polycarbonate, polyester or anycombination thereof.  
     
     
         129 . The method according to  claim 118 , wherein said Temperature Sensitive Polymers are poly (N-substituted (meth)acrylamides).  
     
     
         130 . The method according to  claim 129 , wherein said poly (N-substituted (meth)acrylamides) is poly (n-isopropyl (meth)acrylomides).  
     
     
         131 . The method according to  claim 118 , wherein said Temperature Sensitive Polymer is a poly vinyl alcohol derivative, hydroxypropyl methylcellulose, Ethyl hydroxyethyl cellulose (EHEC) or any combination thereof.  
     
     
         132 . The method according to  claim 105 , wherein said surface-active agent is capable of reducing the surface tension of said composition to about 30 dyne/cm.  
     
     
         133 . The method according to  claim 105 , wherein said surface-active agent is a silicon surface-active agent additive, a fluoro-based surface-active agent additive, or a combination thereof.  
     
     
         134 . The method according to  claim 105 , wherein said Support composition further comprises: 
 at least one photo curable reactive component;    at least one photo-initiator; and    at least one stabilizer;    whereby said method further comprises the step of curing said support composition, thereby increases the strength of said composition.    
     
     
         135 . The method according to  claim 134 , whereinsaid photo curable reactive component is a (meth)acrylic component.  
     
     
         136 . The method according to  claim 135 , wherein said (meth)acrylic component is a (meth)acrylic monomer, (meth)acrylic oligomer, or a combination thereof.  
     
     
         137 . The method according to  claim 134 , wherein said (meth)acrylic component is a polyethylene glycol mono or di (meth)acrylated, polyether triacrylate or any combinatioin thereof.  
     
     
         138 . The method according to  claim 134 , wherein said reactive component is a water miscible component that is, after irradiation or curing, capable of dissolving or swelling upon exposure to water or to an alkaline or acidic water solution.  
     
     
         139 . The method according to  claim 138 , wherein said water miscible component is an acryloyl morpholine, a (meth)acrylated urethane oligomer derivative of polyethhylene glycol, a partially a (meth)acrylated polyol oligomer, an (meth)acrylated oligomer having hydrophilic substituents, or any combination thereof.  
     
     
         140 . The method according to  claim 139 , wherein said hydrophilic substituent is an acidic substituent, amino substituent, hydroxy substituent or any combination thereof.  
     
     
         141 . The method according to  claim 135 , wherein said (meth)acrylic component is beta-carboxyethyl acrylate.  
     
     
         142 . The method according to  claim 135 , wherein said reactive component is a molecule having one or more vinyl ether substituents.  
     
     
         143 . The method according to  claim 142 , wherein said vinyl ether substituent is hydroxy-butyl vinyl ether.  
     
     
         144 . The method according to  claim 134 , wherein said photo-initiator is a free radical photo-initiator, a cationic initiator, or any combination thereof.  
     
     
         145 . The method according to  claim 144 , wherein said free radical photo-initiator os abenzophenone, an acylphosphine oxide, an alpha-amino ketone or any combination thereof.  
     
     
         146 . The method according to  claim 144 , wherein said cationic pjoto-initiator is selected from the group consisting of aryldiazonium salts, diaryliodomium salts, triarylsulphomium salts, triarylselanonium salts, triarylsolfonium hexafluoroantimonate salts.  
     
     
         147 . The method according to  claim 144 , wherein said photo-initiator further comprises a co-initiator component.  
     
     
         148 . The method according to  claim 147 , wherein said co-initiator component is triethanol amine.  
     
     
         149 . The method according to  claim 105 , wherein said stabilizer is 4-methoxy phenol  
     
     
         150 . The method according to  claim 134 , wherein said stabilizer is 4-methoxy phenol.  
     
     
         151 . The method according to  claim 105 , further comprising the step of forming a multiplicity of supoprt layers for supporting sid object.  
     
     
         152 . A 3-dimentional object is prepared by the method according to  claim 34 .  
     
     
         153 . A 3-dimentional object is prepared by a method according to  claim 67 .  
     
     
         154 . A 3-dimentional object is prepared by a method according to  claim 105.