Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
  • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
  • C09D175/04—Polyurethanes
  • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
  • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y10/00—Processes of additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
  • B33Y80/00—Products made by additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation
  • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
  • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F220/00—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 a salt, anhydride ester, amide, imide or nitrile thereof
  • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
  • C08F220/52—Amides or imides
  • C08F220/54—Amides, e.g. N,N-dimethylacrylamide or N-isopropylacrylamide
  • C08F220/56—Acrylamide; Methacrylamide
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
  • C08F290/06—Polymers provided for in subclass C08G
  • C08F290/067—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
  • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
  • C08F290/14—Polymers provided for in subclass C08G
  • C08F290/147—Polyurethanes; Polyureas
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
  • C08G18/12—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step using two or more compounds having active hydrogen in the first polymerisation step
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/08—Processes
  • C08G18/16—Catalysts
  • C08G18/22—Catalysts containing metal compounds
  • C08G18/24—Catalysts containing metal compounds of tin
  • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
  • C08G18/246—Catalysts containing metal compounds of tin tin salts of carboxylic acids containing also tin-carbon bonds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/30—Low-molecular-weight compounds
  • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
  • C08G18/3203—Polyhydroxy compounds
  • C08G18/3206—Polyhydroxy compounds aliphatic
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/40—High-molecular-weight compounds
  • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
  • C08G18/4236—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups
  • C08G18/4238—Polycondensates having carboxylic or carbonic ester groups in the main chain containing only aliphatic groups derived from dicarboxylic acids and dialcohols
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
  • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
  • C08G18/6633—Compounds of group C08G18/42
  • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
  • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
  • C08G18/6644—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203 having at least three hydroxy groups
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
  • C08G18/67—Unsaturated compounds having active hydrogen
  • C08G18/671—Unsaturated compounds having only one group containing active hydrogen
  • C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
  • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
  • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
  • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
  • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G18/00—Polymeric products of isocyanates or isothiocyanates
  • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
  • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
  • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
  • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
  • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
  • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material

Definitions

• the present invention relates to photocurable compositions, comprising
• compositions, from which cured three-dimensional shaped articles having high toughness, high E modulus and impact strength can be made, are particularly suitable for the production of three-dimensional articles by stereolithography.
• JP63-117023A discloses a resin composition containing polyurethane (meth)acrylate and acryloylmorpholine.
• desirable polyurethane (meth)acrylates include polyether polyurethane acrylate, polyester polyurethane acrylate, etc.
• the amount of the polyurethane (meth)acrylate used is preferably 10-80wt percent based on the resin composition.
• Acryloylmorpholine is used is preferably in an amount of 5-60wt percent based on the resin composition.
• EP1337596B1 relates to a radiation curable ink jettable ink composition, comprising:
• a radiation curable alcohol comprising one or more radiation curable moieties, one or more hydroxyl moieties, and one or more polycaprolactone ester moieties;
• US7211368B2 is directed to a liquid stereolithography resin comprising
• the first urethane acrylate oligomer is an aliphatic polyester urethane diacrylate oligomer, wherein
• the first acrylate monomer is ethoxylated (3) trimethylolpropane acrylate
• the polymerization modifier is selected from the group consisting of isobornyl acrylate, ethoxylated (5) pentaerythritol tetraacrylate, an aliphatic urethane acrylate, tris-(2- hydroxyethy isocyanurate triacrylate, and mixtures thereof, wherein
• the resin includes 5-35 weight percent an aliphatic polyester urethane diacrylate oligomer and 0.5-25 weight percent ethoxylated (3) trimethylolpropane acrylate, wherein the resin includes 15-45 weight percent ethoxylated (5) pentaerythritol tetraacrylate.
• EP2636511 is directed to a modeling material for forming a photofabrication model in ink-jet three dimensional printing method, comprising
• curable resin component with a weighted average of SP value of 9.0 to 10.3, the curable resin component containing a monofunctional ethylen ical ly unsaturated monomer (A),
• a photopolymerization initiator (D) wherein the content of (A) is 50 to 90 %, the content of (B) is 3 to 25 %, the content of (C) is 5 to 35 %, and the content of (D) is 0.1 to 10 % on the basis of the weight of the modeling material.
• W015194487A1 is directed to an active-energy ray-curable resin composition which comprises (a) bifunctional urethane (meth)acrylate oligomer having polyester skeleton, (b) acrylamide and/or its derivative and (c) monofunctional (meth)acrylate monomer having heterocyclic group.
• the component c) may be cyclic trimethylolpropane formal monoacrylate, or tetrahydrofurfuryl acrylate.
• the amount of acrylamide and/or its derivative is preferably 3 to 40 % by weight, more preferably 5 to 20 % by weight.
• the amount of monofunctional (meth)acrylate monomer having heterocyclic group is preferably 35 to 55 % by weight. If the amount of component c) is below 35 % by weight, the hardness is low.
• EP1385055 relates to liquid radiation-curable compositions that comprise (A) at least one polymerizing organic substance comprising a mixture of (1) at least one alicyclic epoxide having at least two epoxy groups; and (2) at least one difunctional or higher functional glycidylether of a polyhydric compound; (B) at least one free-radical polymerizing organic substance comprising a mixture of (1) at least one aromatic di(meth)acrylate compound; and (2) optionally, at least one trifunctional or higher functional (meth)acrylate compound; and (C) at least one cationic polymerization initiator; (D) at least one free-radical polymerization initiator; (E) optionally at least one hydroxyl-functional aliphatic compound; and (F) at least one hydroxyl-functional aromatic compound; wherein the concentration of hydroxyl groups in the radiation- curable composition is at least about 1.1 equivalent OH groups per kilogram; wherein the concentration of epoxy groups in the radiation-curable composition is at least about 5.5 equivalent epoxy groups per kilogram
• W02012045660 discloses photocurable resin compositions comprising:
• MW average molecular weight
• PDI polydispersity
• the urethane acrylate or methacrylate component (A) is produced by reacting a polyalkylene glycol, preferably a polyethyleneglycol, with caprolactone,
• the resin composition comprises preferably
• (E) optionally 0.1 - 50 percent by weight of a difunctional acrylate or methacrylate component, or any mixture thereof, preferably a polyethylene glycol diacrylate or an ethoxylated bisphenol dimethacrylate, or a tricyclodecane dimethanol diacrylate, or any mixture thereof; based on the total weight of the composition.
• a difunctional acrylate or methacrylate component preferably a polyethylene glycol diacrylate or an ethoxylated bisphenol dimethacrylate, or a tricyclodecane dimethanol diacrylate, or any mixture thereof; based on the total weight of the composition.
• US20180046076 discloses a three-dimensional printing photocurable composition for a flexible material based object, the composition comprising:
• the urethane acrylate component including the capping reaction product of an acrylate and an isocyanate-terminated prepolymer, the isocyanate- terminated prepolymer being the reaction product of a polyisocyanate and at least one polyol having a molecular weight of at least 3000 g/mol;
• a multifunctional epoxide component that includes one or more multifunctional epoxides, based on the total weight of the composition
• a photoinitiator component from 1 wt % to 8 wt % of a photoinitiator component, based on the total weight of the composition and its use in a stereolithography based three-dimensional printing process.
• the present invention is directed to photocurable compositions, comprising
• (C) a photoinitiator (C), wherein the amount of component (A) is 30 to 60 % by weight, especially 45 to 55 % by weight and the amount of component (B) is 40 to 70 % by weight, especially 45 to 55 % by weight based on the amount of components (A) and (B), wherein the polyester urethane acrylate, or methacrylate (A) is obtained by reacting
• (A2) an aliphatic diisocyanate, an aliphatic polyisocyanate, a cycloaliphatic
• (A4) optionally a second polyol.
• the photocurable compositions of the present invention have viscosities in the range of from 100 to 600 mPas at 50 ° C.
• a three-dimensional article, which is a cured product of the photocurable composition of the present invention has optimized mechanical properties with desired balance of E modulus (1000-2000 M Pa) and impact strength (Izod, unnotched) 80-150 kJ/m 2 .
• the hydroxyalkylacrylate, or hydroxyalkylmethacrylate (Al) is preferably a compound of
• R 1 is a hydrogen atom, or a methyl group
• n is 2 to 6, especially 2 to 4.
• (Al) include 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl acrylate, 2- or 3- hydroxypropyl methacrylate, 4-hydroxybutyl methacrylate and 4-hydroxybutyl acrylate. 2-Hydroxyethyl acrylate is most preferred.
• diisocyanates and polyisocyanates and mixtures thereof can be used as component (A2).
• diisocyanates in particular aliphatic, cycloaliphatic and aromatic diisocyanates are preferred.
• prereacted prepolymers can be used as isocyanate components, in which a polyol is reacted with an isocyanate in an upstream reaction step.
• the obtained products have terminal isocyanate groups and can be used as component (A2).
• customary aliphatic and cycloaliphatic diisocyanates are tri -, tetra-, penta- , hexa-, hepta- and/or octamethylene diisocyanate, 2-methylpentamethylene 1,5- diisocyanate, 2-ethyltetramethylene 1,4-diisocyanate, hexamethylene 1,6-diisocyanate (H DI), pentamethylene 1,5-diisocyanate, butylene 1,4-diisocyanate,
• Preferred aliphatic and cycloaliphatic polyisocyanates are hexamethylene 1,6- diisocyanate (H DI), l-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, I PDI) and 4,4'-, 2,4'- and/or 2,2'-methylenedicyclohexyl diisocyanate (H 12M DI); particular preference is given to H 12M DI and I PDI or mixtures thereof.
• H DI hexamethylene 1,6- diisocyanate
• I PDI isophorone diisocyanate
• H 12M DI 4,4'-, 2,4'- and/or 2,2'-methylenedicyclohexyl diisocyanate
• Suitable aromatic diisocyanates include naphthylene 1.5- diisocyanate (N DI), tolylene 2,4- and/or 2,6-diisocyanate (TDI), diphenylmethane 2,2'-, 2,4'- and/or 4,4'- diisocyanate (M DI), 3,3‘-dimethyl-4,4‘-diisocyanato-diphenyl (TODI), p-phenylene diisocyanate (PDI), diphenylethan-4,4‘-diisoyanate (EDI), diphenylmethandiisocyanate, 3,3'-dimethyl-diphenyl-diisocyanate, 1,2-diphenylethandiisocyanate and/or phenylene diisocyanat.
• N DI naphthylene 1.5- diisocyanate
• TDI tolylene 2,4- and/or 2,6-diisocyanate
• M DI diphenylmethane 2,2'
• isocyanates of higher functionality may be used, such as, for example, triisocyanates, e.g. triphenylmethane 4,4', 4"-triisocyanate, and also the cyanurates of the above-mentioned diisocyanates, and also the oligomers obtainable via partial reaction of diisocyanates with water, e.g. the biurets of the above- mentioned diisocyanates, and also oligomers obtainable via controlled reaction of semicapped diisocyanates with polyols, where these have an average of more than 2 and preferably 3 or more hydroxy groups.
• triisocyanates e.g. triphenylmethane 4,4', 4"-triisocyanate
• oligomers obtainable via partial reaction of diisocyanates with water e.g. the biurets of the above- mentioned diisocyanates, and also oligomers obtainable via controlled reaction of semicapped diisocyanates with polyols, where these have
• the polyester polyols (A3) are preferably derived from dicarboxylic acids and diols.
• the polyester polyols (A3) do not contain polyether units.
• the polyester polyols (A3) have a number average molecular weight above 2000 g/mol.
• the polyester polyols (A3) in particular polyesterdiols, can by way of example be produced from dicarboxylic acids having from 2 to 12 carbon atoms, preferably from 4 to 10 carbon atoms, and from polyhydric alcohols.
• dicarboxylic acids that can be used are: aliphatic dicarboxylic acids, such as succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, and sebacic acid, or aromatic dicarboxylic acids, such as phthalic acid, isophthalic acid, and terephthalic acid.
• the dicarboxylic acids can be used individually or in the form of mixtures, for example in the form of a succinic, sebacic, and adipic acid mixture.
• the corresponding dicarboxylic acid derivatives such as carboxylic diesters having from 1 to 4 carbon atoms in the alcohol moiety, for example dimethyl terephthalate or dimethyl adipate, carboxylic anhydrides, such as succinic anhydride, glutaric anhydride, or phthalic anhydride, or acyl chloride.
• polyhydric alcohols are glycols having from 2 to 10 carbon atoms, preferably from 2 to 6 carbon atoms, e.g. ethylene glycol, diethylene glycol, 1,4- butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,10-decanediol, 2,2-dimethyl-l,3- propanediol, 1,3-propanediol, 2-methyl-l, 3-propanediol, 3-methyl-l,5-pentanediol, or dipropylene glycol.
• the polyhydric alcohols can be used individually or in the form of mixtures, for example in the form of a 1,4-butanediol mixture and/or 1,3-propanediol mixture.
• bifunctional starting compounds i.e. polymerdiol and diisocyanate.
• dimethyl esters of dicarboxylic acids are used in the production of the preferred polyester polyols, it is also possible that, as a consequence of incomplete transesterification, small amounts of unreacted terminal methyl ester groups reduce the functionality of the polyesters to less than 2.0, for example to 1.95 or else to 1.90.
• polyester polyols that are preferably used in accordance with the invention, particularly preferably polyesterdiols, for example by initially using temperatures of from 150 to 270 ° C at atmospheric pressure or slightly reduced pressure to remove the water of reaction and then slowly lowering the pressure, for example to from 5 to 20 mbar.
• a catalyst is in principle not necessary, but is preferably added. Examples of those that can be used for this purpose are tin (I I) salts, titanium(IV) compounds, bismuth (111) salts, and others.
• Polyester polyols (A3) derived from dicarboxylic acid and diols are preferred and, for example, described in US20160122465.
• the dicarboxylic acids used for making the polyester polyol include aliphatic, or cycloaliphatic dicarboxylic acids, or combinations thereof. Among them, aliphatic dicarboxylic acids are preferred. Suitable aliphatic dicarboxylic acids which can be used alone or in mixture typically contain from 4 to 12 carbon atoms and include: succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and the like. Adipic acid is preferred.
• the diols used for making the polyester polyol include aliphatic, or cycloaliphatic diols, or combinations thereof, preferably aliphatic diols containing 2 to 8 carbon atoms and more preferably 2 to 6 carbon atoms.
• aliphatic diols that can be used include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5- pentanediol, 1,6-hexanediol and the like.
• the polyester polyol is derived from adipic acid and ethylene glycol and 1,4-butanediol (poly(ethylene 1,4-butylene adipate) diol, PEBA).
• PEBA poly(ethylene 1,4-butylene adipate) diol
• the molar ratio of ethylene glycol to 1,4- butanediol is from 0.05: 1 to 10:1, preferably from 0.2: 1 to 5: 1, more preferably 0.5: 1 to 1.5: 1, most preferred from 0.75: 1 to 1.25: 1.
• the linear polyester polyol will typically have a number average molecular weight within the range of 4 xlO 2 to 7.0 x 10 3 , preferably 8 xlO 2 to 6.0 x 10 3 , more preferably lxlO 3 to 5.0 x 10 3 .
• the linear polyol is polyester polyol derived from one kind of aliphatic dicarboxylic acid and two kinds of aliphatic diols and has a number average molecular weight of from 2.0 x 10 3 to 4.0 x 10 3 .
• another preferred linear polyester polyol will typically have a number average molecular weight within the range of 4 xlO 2 to 7.0 x 10 3 , preferably 8 xlO 2 to 6.0 x 10 3 , more preferably lxlO 3 to 5.0 x 10 3 .
• the linear polyol is polyester polyol derived from one kind of aliphatic dicarboxylic acid and two kinds of aliphatic diols and has
• the linear polyol is polyester polyol derived from one kind of aliphatic dicarboxylic acid and one kind of aliphatic diol and has a number average molecular weight of from 1.5 x 10 3 to 4.0 x 10 3 , and more preferably from 1.8 x 10 3 to 3.5 x 10 3 . All molecular weights specified in this text have the unit of [g/mol] and refer, unless indicated otherwise, to the number average molecular weight (Mn).
• polyester urethane acrylates, or methacrylates (A) have viscosities in the range of from 2000 to 20000 mPas at 60 ° C.
• the high impact strength is mainly caused by polyester polyols (A3).
• no second polyol is used, as it may decrease the mechanical performance of the three-dimensional article.
• a second polyol such as, for example, glycerol, is used, to finetune the mechanical properties of the inventive urethane (meth)acrylates by introducing linear or branched structural elements.
• Examples of monofunctional acrylamide or methacrylamide components (B) include such as acryloylmorpholine, methacryloylmorpholine, N-(hydroxymethyl)acrylamide, N- hydroxyethyl acrylamide, N- isopropylacrylamide, N-isopropylmethacrylamide, N-tert- butylacrylamide, N,N'- methylenebisacrylamide, N-(isobutoxymethyl)acrylamide, N- (butoxy methyl) acrylamide, N- [3 -(dimethyl amino) propyl] methacrylamide, N,N- dimethylacrylamide, N,N-diethylacrylamide, N-(hydroxymethyl)methacrylamide, N- hydroxyethyl methacrylamide, N-isopropylmethacrylamide, N- isopropylmethmethacrylamide, N-tert-butylmethacrylamide, N,N'- methylenebismeth acrylamide, N-(isobutoxy
• the at present, most preferred acrylamide, or methacrylamide component (B) is acryloylmorpholine.
• composition can comprise additional compounds having
• photopolymerizable groups, diluents and oligomers in an amount of less than 10 % by weight, especially less than 5 % by weight based on the total amount of compounds having photopolymerizable groups.
• Suitable monofunctional acrylate, methacrylate, or vinylamide components are listed below (reactive diluent).
• Monofunctional refers to the fact that the molecule of the compound exhibits only one acrylate, methacrylate, or vinylamide functional group.
• monofunctional vinylamide components include such as N-vinyl- pyrrolidone, vinyl-imidazole, N-vinylcaprolactame, N-(hydroxymethyl)vinylamide, N- hydroxyethyl vinylamide, N-isopropylvinylamide, N-isopropylmethvinylamide, N-tert- butylvinylamide, N,N'-methylenebisvinylamide, N-(isobutoxymethyl)vinylamide, N- (butoxymethyl) vinylamide, N- [3 -(dimethyl amino) propyl] meth vinylamide, N,N- dimethylvinylamide, N,N-diethylvinylamide and N-methyl-N-
• cyclohexylmethacrylate lauryl methacrylate, stearyl methacrylate, octyl methacrylate, isodecyl methacrylate, tridecyl methacrylate, caprolactone methacrylate, nonyl phenol methacrylate, cyclic trimethylolpropane formal methacrylate, methoxy
• polyethyleneglycol methacrylates methoxy polypropyleneglycol methacrylates, hydroxyethyl methacrylate, hydroxypropyl methacrylate and glycidyl methacrylate.
• the photocurable composition may comprise difunctional, or tetrafunctional (meth)acrylates.
• aliphatic or cycloaliphatic diacrylates examples include tricyclodecane dimethanol diacrylate, dioxane glycerol diacrylate, 1,6-hexanediol diacrylate, 3-methyl-l,5- pentanediol diacrylate, tripropylene glycol diacrylate, neopentyl glycol diacrylate, dimethyloltricyclodecane diacrylate, 1,4- dihydroxymethylcyclohexane diacrylate, 2,2- bis(4-hydroxy-cyclohexyl)propane diacrylate and bis(4-hydroxycyclohexyl)methane diacrylate.
• aromatic diacrylates include bisphenol A polyethylene glycol diether diacrylate, 2, 2'-methyl enebis[p-phenylenepoly(oxyethylene)oxy] -diethyl diacrylate, hydroquinone diacrylate, 4, 4'-dihydroxybiphenyl diacrylate, bisphenol A diacrylate, bisphenol F diacrylate, bisphenol S diacrylate, ethoxylated or propoxylated bisphenol A diacrylate, ethoxylated or propoxylated bisphenol F diacrylate, ethoxylated or propoxylated bisphenol S diacrylate and bisphenol-A epoxy diacrylate.
• polyethylenglycol diacrylates examples include tetraethyleneglycol diacrylate, polyethyleneglycol(200) diacrylate and polyethyleneglycol(400) diacrylate.
• aromatic dimethacrylates examples include ethoxylated (2) bisphenol A
• dimethacrylate 4,4'- dihydroxybiphenyl dimethacrylate, bisphenol A dimethacrylate, bisphenol F dimethacrylate, bisphenol S dimethacrylate, ethoxylated or propoxylated bisphenol A dimethacrylate, ethoxylated or propoxylated bisphenol F dimethacrylate, and ethoxylated or propoxylated bisphenol S dimethacrylate.
• aliphatic or cycloaliphatic dimethacrylates include 1,4- dihydroxymethylcyclohexane
• dimethacrylate 2,2-bis(4-hydroxy-cyclohexyl)propane dimethacrylate and bis(4- hydroxycyclohexyl) methane.
• tetrafunctional (meth)acrylates are bistrimethylolpropane tetraacrylate, pentaerythritol tetracrylate, tetramethylolmethane tetramethacrylate, pentaerythritol tetramethacrylate, bistrimethylolpropane tetramethacrylate, ethoxylated pentaerythritol tetraacrylate, propoxylated pentaerythritol tetraacrylate, dipentaerythritol tetraacrylate, ethoxylated dipentaerythritol tetraacrylate, propoxylated dipentaerythritol tetraacrylate, aryl urethane tetraacrylates, aliphatic urethane tetraacrylates, melamine tetraacrylates, epoxy novolac tetraacrylates and polyester tetraacryl
• composition of the present invention does not comprise a tetrafunctional acrylate or methacrylate component.
• the present invention is directed to photocurable compositions, comprising
• (C) a photoinitiator (C), wherein the amount of component (A) is 30 to 60 % by weight, especially 45 to 55 % by weight and the amount of component (B) is 40 to 70 % by weight, especially 45 to 55 % by weight based on the amount of components (A) and (B), wherein the polyester urethane acrylate, or methacrylate (A) is obtained by reacting
• (A2) an aliphatic diisocyanate, an aliphatic polyisocyanate, a cycloaliphatic
• (A4) optionally a second polyol, which does not comprise a tetrafunctional acrylate or methacrylate component.
• Oligomers may include polyester acrylates, polyether acrylates, epoxy acrylates, and urethane acrylates.
• components (A) and (B) are the only
• compositions which comprise photopolymerizable groups.
• the photoinitiator (C) may be a single compound, or a mixture of compounds.
• photoinitiators (C) are known to the person skilled in the art and for example published by Kurt Dietliker in“A compilation of photoinitiators commercially available for UV today”, Sita Technology Textbook, Edinburgh, London, 2002.
• Suitable acylphosphine oxide compounds are of the formula XI I (XI I), wherein
• R 50 is unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl; or is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl substituted by one or more halogen, C 1 -C 12 alkyl , C j -C ⁇ alkoxy, C 1 -C 12 alkylth io or by N R 53 R 54 ;
• R 50 is unsubstituted C 1 -C 20 alkyl or is C 1 -C 20 alkyl which is substituted by one or more halogen, (VC ⁇ alkoxy, Ci-Ci 2 al kylth io, N R 53 R 54 or by -(C0)-0-C 1 -C 24 alkyl;
• R 51 is unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl; or is cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl substituted by one or more halogen, C ⁇ C ⁇ alkyl, C ⁇ C ⁇ alkoxy, C ⁇ C ⁇ alkylthio or by NR 53 R 54 ; or R 51 is -(CO) R’ 52 ; or R 51 is Ci-Ci 2 alkyl which is unsubstituted or substituted by one or more halogen, Ci-
• R 52 and R’ 52 independently of each other are unsubstituted cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl, or are cyclohexyl, cyclopentyl, phenyl, naphthyl or biphenylyl substituted by one or more halogen, C 1 -C 4 alkyl or C j - alkoxy; or R 52 is a 5- or 6-membered heterocyclic ring comprising an S atom or N atom;
• R 53 and R 54 independently of one another are hydrogen, unsubstituted C ⁇ C ⁇ alkyl or C 3 - C i2 a I ky I substituted by one or more OH or SH wherein the alkyl chain optionally is interrupted by one to four oxygen atoms; or R 53 and R 54 independently of one another are C 2 -C 12 -alkenyl, cyclopentyl, cyclohexyl, benzyl or phenyl;
• the photoinitiator (C) is a compound of the formula (XI I), such as, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester; (2,4,6-trimethylbenzoyl)-2,4-dipentoxyphenylphosphine oxide and bis(2,6-d imethoxy benzoyl) -2, 4, 4-tri methyl pentyl phosphine oxide.
• formula (XI I) such as, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide; 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester; (2,4,
• Examples are mixtures of bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide with 1-hydroxy-cyclohexyl-phenyl-ketone, of bis(2,4,6-trimethylbenzoyl)-phenyl- phosphine oxide with 2-hydroxy-2-methyl-l-phenyl-propan-l-one, of bis(2,4,6- trimethylbenzoyO-phenylphosphine oxide with ethyl (2,4,6 trimethylbenzoyl phenyl) phosphinic acid ester, etc.
• Suitable benzophenone compounds are compounds of the formula , wherein
• R 65 , R 66 and R 67 independently of one another are hydrogen, C 1 -C 4 alkyl, 0 4 -0 4 - halogenalkyl, C 1 -C 4 alkoxy, Cl or N(C 1 -C 4 alkyl) 2 ;
• R 68 is hydrogen, C 1 -C 4 alkyl, C 1 -C 4 halogenalkyl, phenyl, N(C 1 -C 4 alkyl) 2 , COOCH 3 ,
• Q is a residue of a polyhydroxy compound having 2 to 6 hydroxy groups
• x is a number greater than 1 but no greater than the number of available hydroxyl groups in Q;
• A is -[0(CH 2 ) b C0] y - or - [0(CH 2 ) b C0] (y-ir [0(CHR 69 CHR 69 , )J y - ;
• R 69 and R 69 independently of one another are hydrogen, methyl or ethyl; and if n (or a) is greater than 1 the radicals R 69 may be the same as or different from each other;
• a is a number from 1 to 2;
• b is a number from 4 to 5;
• y is a number from 1 to 10;
• n ;
• n is an integer 2-10.
• benzophenone Esacure TZT ® available from IGM, (a mixture of 2,4,6-trimethylbenzophenone and 4-methylbenzophenone), 4-phenylbenzophenone, 4- methoxybenzophenone, 4,4’-dimethoxybenzophenone, 4,4’-dimethylbenzophenone, 4,4’- dichlorobenzophenone, 4,4’-dimethylaminobenzophenone, 4,4’- diethylaminobenzophenone, 4-methylbenzophenone, 2,4,6-trimethylbenzophenone, 4- (4-methylthiophenyl) benzophenone, 3,3’-dimethyl-4-methoxy benzophenone, methyl -2- benzoylbenzoate, 4-(2-hydroxyethylthio)benzophenone, 4-(4-tolylthio)benzophenone, 4- benzoyl-N,N,N-trimethylbenzenemethanaminium chloride, 2-hydroxy-3-(4-
• R29 is hydrogen
• R30 is hydrogen, morpholino, S-Ci-Ci 8 alkyl, a group
• G 3 and G 2 independently of one another are end groups of the polymeric structure, preferably hydrogen or methyl;
• R 31 is hydroxy, Ci-Ci 6 alkoxy, morpholino, dimethylamino or -0(CH 2 CH 2 0) g -C 1 -C 16 alkyl; g is 1-20;
• R 32 and R 33 independently of one another are hydrogen, Ci-C 6 alkyl, Ci-Ci 6 alkoxy or -0(CH 2 CH 2 0) g -C 1 -C 16 alkyl; or are unsubstituted phenyl or benzyl; or phenyl or benzyl substituted by C j -C ⁇ -alkyl; or R 32 and R 33 together with the carbon atom to which they are attached form a cyclohexyl ring;
• R 35 is hydrogen, OR 36 or N R 37 R 38 ;
• R 36 is hydrogen, Ci-Ci 2 alkyl which optionally is interrupted by one or more non- consecutive O-atoms and which uninterrupted or interrupted Ci-Ci 2 alkyl optionally is substituted by one or more OH,
• R 37 and R 38 independently of each other are hydrogen or C ⁇ -C ⁇ alkyl which is unsubstituted or is substituted by one or more OH;
• R 39 is Ci-Ci 2 alkylene which optionally is interrupted by one or more non-consecutive
• R 31 , R 32 and R 33 not all together are C ⁇ C ⁇ alkoxy or -0(CH 2 CH 2 0) g -C 1 -C 16 alkyl.
• Suitable phenylglyoxylate compounds are of the formula
• R 55 , R 56 , R 57 , R 58 and R 59 independently of one another are hydrogen, unsubstituted C 4 - Ci 2 alkyl or C ⁇ C ⁇ alkyl substituted by one or more OH, C 1 -C 4 alkoxy, phenyl, naphthyl, halogen or by CN; wherein the alkyl chain optionally is interrupted by one or more oxygen atoms; or R 55 , R 56 , R 57 , R 58 and R 59 independently of one another are C 1 -C 4 alkoxy, C 4 - C 4 a I kyth io or N R 52 R 53 .
• R 52 and R 53 independently of one another are hydrogen, unsubstituted C 1 -C 12 alkyl or C 4 - C 12 a I kyl substituted by one or more OH or SH wherein the alkyl chain optionally is interrupted by one to four oxygen atoms; or R 52 and R 53 independently of one another are C 2 -C 12 -alkenyl, cyclopentyl, cyclohexyl, benzyl or phenyl; and
• Y 4 is C ⁇ C ⁇ alkylene optionally interrupted by one or more oxygen atoms.
• the compounds of the formula XIII are oxo-phenyl-acetic acid 2- [2-(2-oxo-2-phenyl-acetoxy)-ethoxy]-ethyl ester (lrgacure®754), methyl a-oxo benzeneacetate.
• Suitable oxime ester compounds are of the formula
• R 70 is hydrogen, C 3 -C 8 cycloalkyl; C 1 -C 12 alkyl which is unsubstituted or substituted by one or more halogen, phenyl or by CN; or R 70 is C 2 -C 5 alkenyl; phenyl which is unsubstituted or substituted by one or more C ! -C 6 a I ky I , halogen, CN, OR 73 , SR 74 or by NR 75 R 76 ; or R 70 is C j -C 8 alkoxy, benzyloxy; or phenoxy which is unsubstituted or substituted by one or more C j -C 8 alkyl or by halogen;
• R 71 is phenyl, naphthyl, benzoyl or naphthoyl, each of which is substituted by one or more halogen, C ⁇ C ⁇ alkyl, C 3 -C 8 cycloalkyl, benzyl, phenoxycarbonyl, C 2 -C 12 alkoxycar- bonyl, OR 73 , SR 74 , SOR 74 , S0 2 R 74 or by NR 75 R 76 , wherein the substituents OR 73 , SR 74 and NR 75 R 76 optionally form 5- or 6-membered rings via the radicals R 73 , R 74 , R 75 and/or R 76 with further substituents on the phenyl or naphthyl ring; or each of which is substituted by phenyl or by phenyl which is substituted by one or more OR 73 , SR 74 or by NR 75 R 66 ;
• R 72 is hydrogen; unsubstituted C 1 -C 20 alkyl or C 1 -C 20 alkyl which is substituted by one or more halogen, OR 73 , SR 74 , C 3 -C 8 cycloalkyl or by phenyl; or is C 3 -C 8 cycloalkyl; or is phenyl which is unsubstituted or substituted by one or more Ci-C 6 al kyl , phenyl, halogen, OR 73 , SR 74 or by NR 75 R 76 ; or is C 2 -C 20 alkanoyl or benzoyl which is unsubstituted or substituted by one or more Ci-C 6 al kyl , phenyl, OR 73 , SR 74 or by NR 75 R 76 ; or is C 2 -C 12 alkoxycarbonyl, phenoxycarbonyl, CN, CONR 75 R 76 , N0 2 , C 1
• Y 2 is a direct bondor no bond
• R 73 and R 74 independently of one another are hydrogen, C 1 -C 20 alkyl, C 2 -C 12 alkenyl, C 3 - C 8 cycloal kyl , C 3 -C 8 cycloalkyl which is interrupted by one or more, preferably 2, O, phenyl- C ! -C 3 al kyl; or are C !
• -C 6 al ky I halogen, OH, C 1 -C 4 alkoxy or by C 1 -C 4 alkylsulfanyl; or are phenyl or naphthyl, each of which is unsubstituted or substituted by halogen, C ⁇ C ⁇ alkyl, C 4 - C 12 alkoxy, phenyl-C ⁇ Cgalkyloxy, phenoxy, C ⁇ C ⁇ alkylsulfanyl, phenylsulfanyl, N (0 4 -
• R 75 and R 76 independently of each other are hydrogen, C 1 -C 20 alkyl, C 2 -C 4 hydroxyalkyl, C 2 - C 10 alkoxyalkyl, C 2 -C 5 alkenyl, C 3 -C 8 cycloalkyl, phenyl-C 1 -C 3 alkyl, C ⁇ C g alkanoyl, C 3 - C 12 alkenoyl, benzoyl; or are phenyl or naphthyl, each of which is unsubstituted or substituted by C j -C ⁇ alkyl, benzoyl or by C j -C ⁇ alkoxy; or R 75 and R 76 together are C 2 - C 6 alkylene optionally interrupted by O or N R 73 and optionally are substituted by hydroxyl, C 1 -C 4 alkoxy, C 2 -C 4 alkanoyloxy or by benzoyloxy;
• R 77 is C ! -C 12 alkyl, thienyl or phenyl which is unsubstituted or substituted by C 4 - C 12 a I ky I , OR 73 , morpholino or by N-carbazolyl.
• cationic photoinitiators such as benzoyl peroxide (other suitable peroxides are described in US 4 950 581, column 19, lines 17-25), or aromatic sulfonium, phosphonium or iodonium salts, such as are described, for example, in US 4 950 581, column 18, line 60 to column 19, line 10.
• Suitable sulfonium salt compounds are of formula
• R 80 , R 81 and R 82 are each independently of the others unsubstituted phenyl, or phenyl substituted by -S-phenyl,
• R 83 is a direct bond, S, O, CH 2 , (CH 2 ) 2 , CO or NR 89 ;
• R 84 , R 85 , R 86 and R 87 independently of one another are hydrogen, C 1 -C 20 alkyl, C 3 - C 8 cycloalkyl, Ci-C 20 alkoxy, C 2 -C 20 alkenyl, ON, OH, halogen, Ci-C 6 a I ky Ith io, phenyl, naphthyl, phenyl-C 1 -C 7 alkyl, naphtyl -Ci-C 3 alkyl , phenoxy, naphthyloxy, phenyl-C !
• R 89 is hydrogen, C ⁇ C ⁇ alkyl, C ⁇ C ⁇ hydroxyalkyl, phenyl, naphthyl or biphenylyl;
• R 90 , R 91I R 92 and R 93 independently of one another have one of the meanings as given for R 84 ; or R 90 and R 91 are joined to form a fused ring system with the benzene rings to which they are attached;
• R 95 is a direct bond, S, O or CH 2 ;
• R 96 is hydrogen, C 1 -C 20 alkyl; C 2 -C 20 alkyl interrupted by one or more O; or is -L-M-R 98 or -L-R 98 ;
• R 97 has one of the meanings as given for R 96 or is
• R 98 is a monovalent sensitizer or photoinitiator moiety
• Ar 4 and Ar 2 independently of one another are phenyl unsubstituted or substituted by C 4 - C 20 a I ky I , halogen or OR 99 ;
• OR 99 are -Ar 4 -A 1 -Ar 3 or
• Ar 3 is unsubstituted phenyl, naphthyl, anthryl, phenanthryl or biphenylyl; or is phenyl, naphthyl, anthryl, phenanthryl or biphenylyl substituted by C 1 -C 20 al kyl , OR 99 or benzoyl;
• Ar 4 is phenylene, naphthylene, anthrylene or phenanthrylene
• a 1 is a direct bond, S, 0 or C 1 -C 20 alkylene
• X is CO, C(0)0, OC(O), 0, S or NR 99 ;
• L is a direct bond, S, 0, C 1 -C 20 alkylene or C 2 -C 20 alkylene interrupted by one or more non-consecutive 0;
• M 2 is a direct bond, CH 2 , 0 or S;
• R 100 and R 101 independently of one another are hydrogen, halogen, C ⁇ Cgalkyl, C ⁇ Cgalkoxy or phenyl;
• R 102 is Ci-Cgoalkyl
• Suitable iodonium salt compounds are of formula (XVI), wherein
• R no and R m are each independently of the other hydrogen, C ⁇ Cgoalkyl, C ⁇ C ⁇ alkoxy, 0 H - substituted C ⁇ C ⁇ alkoxy, halogen, C 2 -C 12 alkenyl, C 3 -C 8 cycloalkyl, especially methyl, isopropyl or isobutyl; and
• E is an anion, especially PF 6 , SbF 6 , AsF 6 , BF 4 , (C 6 F 5 ) 4 B, Cl, Br, HS0 4 , CF 3 -S0 3 , F-S0 3 , H 3 C— L — so- , CH 3 -S0 3 , CI0 4 , P0 4 , N0 3 , S0 4 , CH 3 -S0 4 or H 3 C— ⁇ — so- .
• iodonium salt compounds are e.g. tolylcumyliodonium tetrakis(pentafluorophenyl) borate, 4- [(2-hydroxy-tetradecyloxy) phenyl] phenyliodonium hexafluoroantimonate or hexafluorophosphate, tolylcumyliodonium hexafluorophosphate, 4-isopropyl phenyl -4'-methyl phenyliodonium hexafluorophosphate, 4-isobutyl phenyl-4'-methylphenyliodonium hexafluorophosphate (Irgacure ® 250, BASF SE), 4-octyloxyphenyl-phenyliodonium hexafluorophosphate or hexafluoroantimonate, bis(dodecylphenyl)iodonium hexafluoroanti
• Acylphosphinoxides such as, for example, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (TPO) and ethyl phenyl (2,4,6- trimethylbenzoyOphosphinate, are preferred for curing with light sources having emission peak(s) in the UV-A range and (near) VIS range (Laser, LEDs, LCD) alpha- Elydroxy ketone type compounds, such as, for example, 1-hydroxy-cyclohexyl-phenyl- ketone, 2-hydroxy-2-methyl-l-phenyl-propan-l-one, 2-hydroxy-l- ⁇ 4-[4-(2-hydroxy-2- methyl-propionyl) -benzyl] -phenyl ⁇ -2-methyl -propan -1 -one, l-[4-(2-hydroxyethoxy)- phenyl] -2
• UV and visible range e.g. UV and visible range
• the absorption range of one photoinitiator might not cover the entire range.
• photoinitiators like titanocenes, such as, for example, bis (cyclopentadienyl) bis [2,6- difluoro- 3- (1 -pyrry I) phenyl titanium (Omnirad 784) are required.
• the photoinitiators are used typically in a proportion of from about 0.5 to 10 % by weight, especially 0.1 to 5.0% by weight based on the total weight of composition.
• Halogen is fluorine, chlorine, bromine and iodine.
• C 1 -C 24 alkyl (C 1 -C 20 alkyl , especially C 1 -C 12 al kyl) is typically linear or branched, where possible. Examples are methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.
• Cgalkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2- dimethyl-propyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl.
• C 1 -C 4 alkyl is typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec. -butyl, isobutyl, tert.-butyl.
• C 2 -C 12 alkenyl (C 2 -C 5 alkenyl) groups are straight-chain or branched alkenyl groups, such as e.g. vinyl, allyl, methallyl, isopropenyl, 2-butenyl, 3-butenyl, isobutenyl, n-penta-2,4- dienyl, 3-methyl-but-2-enyl, n-oct-2-enyl, or n-dodec-2-enyl.
• Ci-Ci 2 alkoxy groups are straight-chain or branched alkoxy groups, e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy and dodecyloxy.
• alkoxy groups e.g. methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, tert-butoxy, amyloxy, isoamyloxy or tert-amyloxy, heptyloxy, octyloxy, isooctyloxy, nonyloxy, decyloxy, undecyloxy and dodecyloxy.
• Ci-Ci 2 alkylthio groups are straight-chain or branched alkylthio groups and have the same preferences as the akoxy groups, except that oxygen is exchanged against sulfur.
• (VC ⁇ alkylene is bivalent C ⁇ C ⁇ alkyl, i.e. alkyl having two (instead of one) free valencies, e.g. trimethylene or tetramethylene.
• a cycloalkyl group is typically C 3 -C 8 cycloalkyl, such as, for example, cyclopentyl, cyclohexyl, cycloheptyl, or cyclooctyl, which may be unsubstituted or substituted.
• sensitizer compound in several cases it is advantageous to in addition to the photoinitiator employ a sensitizer compound.
• suitable sensitizer compounds are disclosed in WO 06/008251, page 36, line 30 to page 38, line 8, the disclosure of which is hereby incorporated by reference.
• sensitizer inter alia benzophenone compounds as described above can be employed.
• the photocurable composition comprises (A) a polyester urethane acrylate, or methacrylate (A),
• (C) a photoinitiator (C), which is a compound of formula (XI I), wherein the amount of component (A) is 30 to 60 % by weight, especially 45 to 55 % by weight and the amount of component (B) is 40 to 70 % by weight, especially 45 to 55 % by weight based on the amount of components (A) and B), wherein the polyester urethane acrylate, or methacrylate (A) is obtained by reacting
• A2 isophorone diisocyanates (I PDI), or tolylene 2,4- and/or 2,6-diisocyanate (TDI), and
• (A3) a polyester polyol, which is derived from adipic acid and ethylene glycol and 1,4- butanediol (poly(ethylene 1,4-butylene adipate) diol, PEBA), and optionally (A4) glycerol, with the proviso that components (A) and (B) are the only components of the composition which comprise photopolymerizable groups.
• the molar ratio of ethylene glycol to 1,4-butanediol in (poly(ethylene 1,4-butylene adipate) diol is from 0.05:1 to 10:1, preferably from 0.2: 1 to 5: 1, more preferably 0.5: 1 to 1.5:1, most preferred from 0.75: 1 to 1.25: 1.
• the polyester polyol has a number average molecular weight within the range of 4 xlO 2 to 7.0 x 10 3 , preferably 8 xlO 2 to 6.0 x 10 3 , more preferably lxlO 3 to 5.0 x 10 3 .
• the photocurable compositions may comprise further mixture constituents which are preferably selected from
• At least one component F which is in turn selected from light, heat and oxidation stabilizers;
• a certain additive may therefore be attributed to more than one of the grou ps (D.4) to (D.l l) described below.
• the defoamers of group (D.4) include silicon-free and silicon-containing polymers.
• the silicon-containing polymers are, for example, unmodified or modified
• the deaerating agents of group (D.4) include, for example, organic polymers, for instance polyethers and polyacrylates, d ial ky I polysil oxan es, especially
• dimethylpolysiloxanes organically modified polysiloxanes, for instance arylalkyl- modified polysiloxanes, or else fluorosilicones.
• defoamers act essentially in such a way that they promote the coalescence of finely distributed gas or air bubbles to larger bubbles in the medium to be deaerated, for example the inventive mixtures, and hence accelerate the escape of the gas (or of the air). Since defoamers can often also be used as deaerating agents and vice versa, these additives have been combined together under group (D.4).
• auxiliaries are, for example, obtainable commercially from Tego as TEGO ® Foamex 800, TEGO ®
• the auxil iaries of group (D.4) are typically used in a proportion of from about 0.05 to 3.0% by weight, preferably from about 0.5 to 2.0% by weight, based on the total weight of the composition.
• the group (D.5) of the lubricants and leveling agents includes, for example, silicon-free but also silicon-containing polymers, for example polyacrylates or modified low molecular weight polydialkylsiloxanes.
• the modification consists in replacing some of the alkyl groups with a wide variety of organic radicals. These organic radicals are, for example, polyethers, polyesters or else long-chain alkyl radicals, the former finding most frequent use.
• the polyether radicals of the correspondingly modified polysiloxanes are typically formed by means of ethylene oxide and/or propylene oxide units. The higher the proportion of these alkylene oxide units is in the modified polysiloxane, the more hydrophilic is generally the resulting product.
• auxiliaries are obtainable commercially, for example, from Tego as TEGO ® Glide 100, TEGO ® Glide ZG 400, TEGO ® Glide 406, TEGO ® Glide 410, TEGO ® Glide 411, TEGO ® Glide 415, TEGO ® Glide 420, TEGO ® Glide 435, TEGO ® Glide 440, TEGO ® Glide 450, TEGO ® Glide A 115, TEGO ® Glide B 1484 (also usable as a defoamer and deaerating agent), TEGO ® Flow ATF, TEGO ® Flow ATF2, TEGO ® Flow 300, TEGO ® Flow 460, TEGO ® Flow 425 and TEGO ® Flow ZFS 460.
• Tego TEGO ® Glide 100, TEGO ® Glide ZG 400,
• the radiation-curable lubricants and leveling agents used which additionally also serve to improve scratch resistance, can be the products TEGO ® Rad 2100, TEGO ® Rad 2200, TEGO ® Rad 2300, TEGO ® Rad 2500, TEGO ® Rad 2600, TEGO ® Rad 2700 and TEGO ® Twin 4000, likewise obtainable from Tego.
• auxiliaries are obtainable from BYK, for example as BYK ® -300, BYK ® - 306, BYK ® -307, BYK ® -310, BYK ® -320, BYK ® -322, BYK ® -331, BYK ® -333, BYK ® -337, BYK ® -341, Byk ® 354, Byk ® 361 N, BYK ® -378 and BYK ® -388.
• the auxiliaries of group (D.5) are typically used in a proportion of from about 0.005 to 1.0% by weight, preferably from about 0.01 to 0.2% by weight, based on the total weight of the composition .
• Group (D.6) includes, as radiation-curing auxiliaries, in particular polysiloxanes with terminal double bonds which are, for example, part of an acrylate group.
• auxiliaries can be made to crosslink by actinic or, for example, electron beam radiation.
• These auxiliaries generally combine several properties in one. In the uncrosslinked state, they can act as defoamers, deaerating agents, lubricants and leveling agents and/or substrate wetting aids; in the crosslinked state, they increase in particular the scratch resistance, for example of articles which can be produced with the inventive compositions.
• the improvement in the shine performance for example, articles can essentially be regarded as the effect of the action of these auxiliaries as defoamers, devolatilizers and/or lubricants and leveling agents (in the uncrosslinked state) .
• the radiation-curing auxiliaries which can be used are, for example, the products TEGO ® Rad 2100, TEGO ® Rad 2200, TEGO ® Rad 2500, TEGO ® Rad 2600 and TEGO ® Rad 2700 obtainable from Tego, and the product BYK ® -371 obtainable from BYK.
• Thermally curing auxiliaries of group (D.6) comprise, for example, primary OH groups which can react with isocyanate groups.
• the thermally curing auxiliaries used can, for example, be the products BYK ® -370, BYK ® -373 and BYK ® -375 obtainable from BYK.
• the auxiliaries of group (D.6) are typically used in a proportion of from about 0.1 to 5.0% by weight, preferably from about 0.1 to 3.0% by weight, based on the total weight of the composition.
• the auxiliaries of group (D.7) of the substrate wetting aids serve in particular to increase the wettability.
• the generally associated improvement in the lubricating and leveling performance of such printing compositions has an effect on the appearance of the finished (for example crosslinked) print or of the finished (for example crosslinked) layer.
• auxiliaries are commercially available, for example, from Tego as TEGO ® Wet KL 245, TEGO ® Wet 250, TEGO ® Wet 260 and TEGO ® Wet ZFS 453, and from BYK as BYK ® -306, BYK ® -307, BYK ® -310, BYK ® -333, BYK ® -344, BYK ® -345, BYK ® -346 and Byk ® -348.
• Tego TEGO ® Wet KL 245, TEGO ® Wet 250, TEGO ® Wet 260 and TEGO ® Wet ZFS 453, and from BYK as BYK ® -306, BYK ® -307, BYK ® -310, BYK ® -333, BYK ® -344, BYK ® -345, BYK ® -346 and Byk ® -348.
• Zonyl ® brand from Dupont, such as Zonyl ® FSA and Zonyl ® FSG. These are fluorinated surfactants/wetting agents.
• the auxiliaries of group (D.7) are typically used in a proportion of from about 0.01 to 3.0% by weight, preferably from about 0.01 to 1.5% by weight and especially from 0.03 to 1.5% by weight, based on the total weight of the composition .
• the auxil iaries of group (D.8) of the wetting and dispersing aids serve in particular to prevent the leaching and floating and also the settling of pigments, and are therefore useful , if necessary, in pigmented compositions in particular.
• auxiliaries stabilize pigment dispersions essentially by electrostatic repulsion and/or steric hindrance of the additized pigment particles, the interaction of the auxiliary with the surrounding medium (for example binder) playing a major role in the latter case. Since the use of such wetting and dispersing aids is common practice, for example, in the technical field of printing inks and paints, the selection of such a suitable auxiliary in the given case generally presents no difficulties to the person skilled in the art.
• Such wetting and dispersing aids are supplied commercially, for example, by Tego as TEGO ® Dispers 610, TEGO ® Dispers 610 S, TEGO ® Dispers 630, TEGO ® Dispers 700, TEGO ® Dispers 705, TEGO ® Dispers 710, TEGO ® Dispers 720 W, TEGO ® Dispers 725 W, TEGO ® Dispers 730 W, TEGO ® Dispers 735 W and TEGO ® Dispers 740 W, and by BYK as Disperbyk ® , Disperbyk ® -107, Disperbyk ® -108, Disperbyk ® -110, Disperbyk ® - 111, Disperbyk ® -115, Disperbyk ® -130, Disperbyk ® -160, Disperbyk ® -161, Disperbyk ® - 162, Disperbyk ® -163, Disperbyk ®
• the dosage of the auxiliaries of group (D.8) depends mainly upon the surface area of the pigments to be covered and upon the mean molar mass of the auxiliary.
• inorganic pigments and low molecular weight auxiliaries a content of the latter of from about 0.5 to 2.0% by weight based on the total weight of pigment and auxil iary is typically assumed.
• the content is increased to from about 1.0 to 30% by weight.
• the content of the latter is from about 1.0 to 5.0% by weight based on the total weight of pigment and auxiliary.
• th is content may be in the range from about 10.0 to 90% by weight.
• the hydrophobizing agents of group (D.9) can be used with a view, for example, to providing articles obtained with inventive compositions with water-repellent properties. This means that swelling resulting from water absorption and hence a change, for example, in the optical properties of such articles is no longer possible or at least greatly suppressed.
• the compositions when used, for example, as a printing ink in 3D printing, their absorption of water can be prevented or at least greatly inhibited.
• Such hydrophobizing agents are commercially available, for example, from Tego as Tego ® Phobe WF, Tego ® Phobe 1000, Tego ® Phobe 1000 S, Tego ® Phobe 1010, Tego ® Phobe 1030, Tego ® Phobe 1040, Tego ® Phobe 1050, Tego ® Phobe 1200, Tego ® Phobe 1300, Tego ® Phobe 1310 and Tego ® Phobe 1400.
• the auxiliaries of group (D.9) are used typically in a proportion of from about 0.05 to 5.0% by weight, preferably from about 0.1 to 3.0% by weight, based on the total weight of the composition .
• In-can stabilizers of group (D.10) provide increased storage stability from
• in-can stabilizers of group (D.10) are:
• Phosphites and phosphonites for example triphenyl phosphite, diphenylalkyl phosphites, phenyld ial kyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert- butylphenyl) phosphite, diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert- butyl phenyl) pentaerythritol di phosphite, bis(2,4-di-cu my I phenyl) pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylpheny
• R 21 and R 22 independently of each other are C ⁇ C ⁇ alkyl, C 5 -C 12 cycloalkyl, C 7 -C 15 - phenylalkyl, optionally substituted C 6 -C 10 aryl;
• R 23 and R 24 independently of each other are H, optionally substituted C 6 -C 10 -aryl, 2-, 3- ,4-pyridyl, 2-,3-furyl or thienyl, COOH, COOR 25 , CON H 2 , CON HR 25 , CON R 25 R 26 ,— CN,— COR 25 ,— OCOR 25 ,— OPO(OR 25 ) 2 , wherein R 25 and R 26 are independently of each other Ci-C 8 alkyl, or phenyl. Quinone methides are preferred, wherein R 21 and R 22 are tert- butyl;
• R 23 is H, and R 24 is optionally substituted phenyl, COOH, COOR 25 , CON H 2 , CON HR 25 , CON R 25 R 26 ,— CN,—COR 25 ,—OCOR 25 ,— OPO(OR 25 ) 2 , wherein R 25 and R 26 are C j - C 8 a I ky I , or phenyl.
• Examples of quinone methides are
• the quinone methides may be used in combination with highly sterically hindered nitroxyl radicals as described, for example, in US20110319535.
• In-can stabilizers of group (D.10) are used typically in a proportion of from about 0.01 to 0.3% by weight, preferably from about 0.04 to 0.15% by weight, based on the total weight of the composition .
• the group (D.ll) of the auxiliaries for improving scratch resistance includes, for example, the products TEGO ® Rad 2100, TEGO ® Rad 2200, TEGO ® Rad 2500, TEGO ® Rad 2600 and TEGO ® Rad 2700 which are obtainable from Tego and have already been mentioned above.
• useful amounts are likewise those mentioned in group (D.6), i.e.
• these additives are typically used in a proportion of from about 0.1 to 5.0% by weight, preferably from about 0.1 to 3.0% by weight, based on the total weight of the composition .
• the grou p (E.l) of the dyes incl udes for example, dyes from the class of the azo dyes, metal complex dyes, basic dyes such as d i- and triarylmethane dyes and salts thereof, azometh ine derivatives, polymethines, antraquinone dyes and the like.
• suitable dyes which can be used in the inventive mixture is given by the book by H. Zollinger, "Color Chemistry", Wiley-VCH, Weinheim, 3 rd edition 2003.
• thermochromic or luminescent dyes and dyes which have a combination of these properties.
• fluorescent dyes should also be understood to mean optical brighteners.
• Examples of the latter include the class of the bisstyrylbenzenes, especially of the cyanostyryl compounds, and correspond to the formula
• optical brighteners from the class of the stilbenes are, for example, those of the formulae
• Q 1 is in each case C 1- C 4- alkoxycarbonyl or cyano
• Q 2 is benzoxazol-2-yl, which may be mono- or disubstituted by C 1 - C 4- alkyl, especially methyl
• Q 3 is Ci-C 4- alkoxycarbonyl or 3 - (Ci -C 4- al kyl) - 1 ,2,4-oxad iazol -3-yl .
• optical brighteners from the class of the benzoxazoles obey, for example, the formulae
• Suitable optical brighteners from the class of the coumarins have, for example, the formula
• Q 5 is C 1- C 4- alkyl
• Q 6 is phenyl or 3-ha lopy razol - 1 -y I , especially 3-chloropyrazol-l-yl.
• optical brighteners from the class of the pyrenes correspond, for example, to the formula
• Q 7 is in each case C 1- C 4- alkoxy, especially methoxy.
• the abovementioned brighteners can be used either alone or in a mixture with one another.
• optical brighteners are generally commercially available products known per se. They are described, for example, in Ullmann ' s Encyclopedia of Industrial Chemistry, 5 th edition, volume A18, pages 156 to 161, or can be obtained by the methods described there.
• one or more optical brighteners from the class of the bisstyrylbenzenes is used, especially of the cyanostyrylbenzenes.
• the latter may be used as individual compounds, but also as a mixture of the isomeric compounds.
• Optical brighteners are sold, for example, commercially as Ultraphor ® SF 004,
• Ultraphor ® SF MO, Ultraphor ® SF M P and Ultraphor ® SF PO from BASF SE Ultraphor ® SF MO, Ultraphor ® SF M P and Ultraphor ® SF PO from BASF SE.
• Pigment Black 6 and Pigment Black 7 carbon black
• Pigment Black 11 iron oxide black, Fe 3 0 4
• Pigment White 4 zinc oxide, ZnO
• Pigment White 5 lithopone, ZnS/BaS0 4
• Pigment White 6 titanium oxide, Ti0 2
• Pigment White 7 zinc sulfide, ZnS
• inventive compositions magnetic, electrically conductive, photochromic, thermochromic or luminescent pigments, and also pigments which have a combination of these properties.
• organic pigments for example Lumogen ® Yellow 0795 (BASF SE)
• useful pigments having luminescent properties are also inorganic, doped or undoped compounds essentially based on alkaline earth metal oxides, alkaline earth
• metal/transition metal oxides alkaline earth metal/aluminum oxides, alkaline earth metal/silicon oxides or alkaline earth metal/phosphorus oxides, alkaline earth metal halides, Zn/silicon oxides, Zn/alkaline earth metal halides, rare earth metal oxides, rare earth metal/transition metal oxides, rare earth metal/aluminum oxides, rare earth metal/silicon oxides or rare earth metal/phosphorus oxides, rare earth metal oxide sulfides or oxide halides, zinc oxide, sulfide or selenide, cadmium oxide, sulfide or selenide or zinc/cadmium oxide, sulfide or selenide, the cadmium compounds being of lower importance owing to their toxicological and ecological relevance.
• the dopants used in these compounds are usually aluminum, tin, antimony, rare earth metals, such as cerium, europium or terbium, transition metals, such as manganese, copper, silver or zinc, or combinations of these elements.
• Luminescent pigments are specified below by way of example, the notation
• compound:element(s) being taken to mean to the relevant person skilled in the art that said compound has been doped with the corresponding element(s).
• the notation “(P,V)” denotes that the corresponding lattice positions in the solid structure of the pigment are randomly occupied by phosphorus and vanadium.
• Examples of such compounds which are capable of luminescence are MgW0 4 , CaW0 4 , Sr 4 Al 14 0 25 :Eu, BaMg 2 Al 10 O 2 7:Eu, MgAl n 0 19 :Ce,Tb, MgSi0 3 :M n, Ca 10 (PO 4 ) 6 (F,CI):Sb,Mn, (SrMg) 2 P 2 0 7 :Eu, SrMg 2 P 2 0 7 :Sn, BaFCL Eu, Zn 2 Si0 4 :Mn, (Zn,Mg) F 2 :Mn, Y 2 0 3 :Eu, YV0 4 :Eu, Y(P,V)0 4 : EU , Y 2 Si0 5 :Ce,Tb, Y 2 0 2 S:Eu, Y 2 0 2 S:Tb, La 2 0 2 S:Tb, Gd 2 0 2 S:Tb,
• component F examples include:
• alkylated monophenols such as 2,6-di-tert-butyl-4-methylphenol, 2-tert-butyl-4,6- dimethylphenol, 2 ,6-d i-tert-buty I -4-ethy I phen ol , 2,6-d i-tert-butyl -4-n-butylphenol, 2,6- di-tert-butyl -4-isobutyl phenol, 2, 6-dicyclopentyl -4-methyl phenol, 2-(a- methylcyclohexyl) -4,6-dimethyl phenol, 2,6-d ioctadecyl -4-methyl phenol, 2,4,6- tricyclohexylphenol, 2,6-di-tert-butyl-4-methoxymethylphenol, nonylphenols which have a linear or branched side chain, for example 2,6-dinonyl-4-methylphenol, 2,4-dimethyl- 6- (G-methylun de
• alkylthiomethylphenols such as 2,4-dioctylthiomethyl-6-tert-butylphenol, 2,4- dioctyl th iomethy I -6-methyl phenol , 2,4-dioctylthiomethyl-6-ethylphenol and 2,6- d id odecylth iomethy I -4-nonyl phenol,
• hydroquinones and alkylated hydroquinones such as 2,6-di-tert-butyl-4- methoxyphenol, 2,5-di-tert-butylhydroquinone, 2,5-di-tert-amylhydroquinone, 2,6- diphenyl -4-octadecyloxyphenol, 2,6-d i-tert-butyl hydroquin one, 2, 5-d i-tert-buty 1-4- hydroxyanisole, 3,5-di-tert- butyl -4-hydroxyanisole, 3,5-di-tert-butyl-4-hydroxyphenyl stearate and bis(3,5-di-tert-butyl-4-hydroxyphenyl)adipate,
• tocopherols such as a-tocopherol, b-tocopherol, g-tocopherol, d-tocopherol and mixtures of these compounds, and tocopherol derivatives, such as tocopheryl acetate, succinate, nicotinate and polyoxyethylenesuccinate ("tocofersolate”),
• hydroxylated diphenyl thioethers such as 2,2'-thiobis(6-tert-butyl-4-methylphenol),
• alkylidenebisphenols such as 2,2'-methylenebis(6-tert-butyl-4-methylphenol), 2,2'- methylenebis(6-tert-buty I -4-ethyl phenol), 2,2'-methylenebis[4-methyl-6-(a- methylcyclohexyl) phenol] , 2,2'-methylenebis(4-methyl -6-cyclohexyl phenol), 2,2'- methylenebis(6-nonyl -4-methyl phenol), 2,2'-methylenebis(4,6-d i-tert-butyl phenol), 2,2- ethyl id enebis (4, 6-d i-tert-buty I phenol), 2,2'-ethylidenebis(6-tert-butyl-4- isobuty I phenol), 2, 2'-methylenebis [6- (a-methyl benzyl) -4-nonyl phenol] , 2,2'- meth
• N-and S-benzyl compounds such as 3,5 ,3',5'-tetra-tert-butyl -4,4'-d ihyd roxyd i benzyl ether, octadecyl 4-hydroxy-3,5-dimethylbenzylmercaptoacetate, tridecyl 4-hydroxy-3,5- d i-tert-butyl benzyl mercaptoacetate, tris(3,5-di-tert-butyl-4-hydroxybenzyl)amine, bis (4-tert-buty I -3 -hydroxy-2, 6-dim ethyl benzyl) dithioterephthalate, bis(3,5-di-tert- butyl-4-hydroxybenzyl) sulfide and isooctyl -3,5 -d i -tert-bu tyl -4- hydroxybenzyl mercaptoacetate,
• aromatic hydroxybenzyl compounds such as 1 ,3,5-tris(3,5-d i -tert-butyl -4- hyd roxybenzy I) -2, 4, 6-tri methyl benzene, l,4-bis(3,5-di-tert-butyl-4-hydroxybenzyl)- 2,3,5,6-tetramethylbenzene and 2, 4, 6-tris(3,5-d i-tert-buty I -4-hyd roxybenzy I) phenol, triazine compounds, such as 2,4-bis(octylmercapto)-6-(3,5-di-tert-butyl-4- hyd roxyan ilino)-l,3,5-triazine, 2-octylmercapto-4,6-bis(3,5-di-tert-butyl-4- hyd roxyan II ino) -1,3,5-triazine, 2-octy
• benzylphosphonates such as dimethyl 2,5-di-tert-butyl-4-hydroxybenzylphosphonate, diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, dioctadecyl 3,5-di-tert-butyl-4- hydroxybenzylphosphonate and dioctadecyl 5-tert-butyl-4-hydroxy-3- methy I benzyl phosphonate,
• acylaminophenols such as 4-hydroxylauroylanilide, 4-hydroxystearoylanilide and octyl N -(3,5-d i-tert-buty I -4-hyd roxyphenyl) carbamate,
• propionic and acetic esters for example of monohydric or polyhydric alcohols, such as methanol, ethanol, n-octanol, isooctanol, octadecanol, 1,6-hexanediol, 1,9-nonanediol, ethylene glycol, 1,2-propanediol, neopentyl glycol, thiodiethylene glycol, diethylene glycol, triethylene glycol, pentaerythritol, tris(hydroxyethyl) isocyanurate, N,N'- bis(hydroxyethyl)oxamide, 3-thiaundecanol, 3-thiapentadecanol, trimethylhexanediol, trimethylol propane and 4-hydroxymethyl-l-phospha-2,6,7-trioxabicyclo [2.2.2] octane, propionamides based on amine derivatives, such as N,
• ascorbic acid Vitamin C
• ascorbic acid derivatives such as ascorbyl palmitate, laurate and stearate, and ascorbyl sulfate and phosphate, antioxidants based on amine compounds, such as N,N'-diisopropyl-p- phenylenediamine, N,N'-di -sec-butyl -p-phenylenedia mine, N,N'-bis(l,4- dimethyl pentyl) -p-phenylenedia mine, N,N'-bis(l -ethyl -3-methyl pentyl) -p- phenylenediamine, N,N '-bis (1 -methyl heptyl)-p-phenylenediam in e, N,N'-dicyclohexyl-p- phenylenediamine, N,N '-diphenyl -p-phenylenedia mine, N,N'-bis
• nonyldiphenylamine a mixture of mono- and dialkylated dodecyldiphenylamine, a mixture of mono- and dialkylated isopropyl/isohexyldiphenylamine, a mixture of mono- and dialkylated tert-butyldiphenylamine, 2,3-dihydro-3,3-dimethyl-4H-l,4- benzothiazine, phenothiazine, a mixture of mono- and dialkylated tert-butyl/tert- octylphenothiazine, a mixture of mono- and dialkylated tert-octylphenothiazine, N- ally I phenothiazine, N,N,N',N'-tetraphenyl-l,4-diaminobut-2-ene, N,N-bis(2,2,6,6- tetramethylpiperidin-4-yl)hexamethylene
• 2-(2'-hydroxyphenyl)benzotriazoles such as 2-(2'-hydroxy-5'- methy I phenyl) benzotriazole, 2-(3',5'-di-tert-butyl-2'-hydroxyphenyl)benzotriazole, 2-(5'- tert-butyl-2'-hydroxyphenyl)benzotriazole, 2 - (2'-hyd roxy-5'- (1 , 1,3,3- tetramethyl butyl) phenyl) benzotriazole, 2 - (3',5'-d i-tert-butyl -2'-hyd roxy ph eny I) -5 - chlorobenzotriazole, 2 - (3'-tert-bu ty I -2'-hyd roxy-5' -methyl phenyl) -5 -chlorobenzotriazole, 2-(3'-sec-butyl-5'-tert-buty
• sulfur-containing peroxide scavengers and sulfur-containing antioxidants such as esters of 3,3'-thiodipropionic acid, for example the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and the zinc salt of 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis( - dodecylmercapto) propionate,
• esters of 3,3'-thiodipropionic acid for example the lauryl, stearyl, myristyl and tridecyl esters, mercaptobenzimidazole and the zinc salt of 2-mercaptobenzimidazole, dibutylzinc dithiocarbamate, dioctadecyl disulfide and pentaerythritol tetrakis(
• 2-hydroxybenzophenones such as the 4-hydroxy, 4-methoxy, 4-octyloxy, 4-decycloxy, 4-dodecyloxy, 4-benzyloxy, 4,2',4'-trihydroxy and 2'-hydroxy-4,4'-dimethoxy derivatives, esters of unsubstituted and substituted benzoic acids, such as 4-tert-butylphenyl salicylate, phenyl salicylate, octylphenyl salicylate, dibenzoylresorcinol, bis(4-tert- butylbenzoyl)resorcinol, benzoylresorcinol, 2,4-di-tert-butylphenyl 3,5-di-tert-butyl-4- hydroxy benzoate, hexadecyl-3,5-di-tert-butyl-4-hydroxy benzoate, octadecyl-3,5-di-tert-butyl-4-
• acrylates such as ethyl a-cyano- , -diphenylacrylate, isooctyl a-cyano-b,b- diphenylacrylate, methyl a-methoxycarbonylcinnamate, methyl a-cyano ⁇ -methyl-p- methoxycinnamate, butyl-a-cyano ⁇ -methyl-p-methoxycinnamate and methyl-a- methoxycarbonyl-p-methoxycinnamate,
• sterically hindered amines such as bis(2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(2,2,6,6-tetramethylpiperidin-4-yl) succinate, bis(l,2,2,6,6-pentamethylpiperidin-4- yl) sebacate, bis(l-octyloxy-2,2,6,6-tetramethylpiperidin-4-yl) sebacate, bis(l, 2, 2, 6,6- pen tamethy I piperid in -4-yl) -n -butyl -3,5-di -tert-buty I -4-hydroxybenzylmalonate, the condensation product of l-(2-hydroxyethyl)-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, the condensation product of N,N'-bis(2,2,6,5-tetramethylpiperidin-4- yOhexamethylenediamine and 4-tert-octy
• oxamides such as 4,4'-dioctyloxyoxanilide, 2,2'-diethoxyoxanilide, 2,2'-dioctyloxy-5,5'- di-tert-butoxanilide, 2,2'-didodecyloxy-5,5'-d i-tert-butoxanilide, 2-ethoxy-2'- ethyloxan ilide, N,N'-bis(3-dimethylaminopropyl)oxamide, 2-ethoxy-5-tert-butyl-2'- ethoxanilide and its mixture with 2 -eth oxy-2'-ethy I -5 ,4'-d i -tert-butoxan ilide, and mixtures of ortho-, para-methoxy-disubstituted oxanilides and mixtures of ortho- and para-ethoxy-disubstituted oxanilides,
• the components G of the I R absorber used are compounds which exhibit one or more absorption bands in the infrared spectral region, i.e. from > 750 nm, e.g. from 751 nm, to 1 mm. Preference is given to compounds which exhibit one absorption band in the near infrared (N I R) spectral region, i.e. from > 750 (e.g. 751) to 2000 nm, and optionally additionally also in the visible spectral region, especially from 550 to 750 nm.
• N I R near infrared
• the compounds of component G When the compounds absorb both in the I R and in the visible spectral region, they preferably exhibit the greatest absorption maximum in the I R region and a smaller maximum (frequently in the form of a so-called absorption shoulder) in the visible region.
• the compounds of component G additionally also exhibit fluorescence. Fluorescence is the transition of a system excited by absorption of electromagnetic radiation (usually visible light, UV radiation, X-rays or electron beams) to a state of lower energy by spontaneous emission of radiation of the same wavelength (resonance fluorescence) or longer wavelength.
• Preferred compounds of component G exhibit, when they fluoresce, a fluorescence in the I R spectral region, preferably in the N IR.
• Such compounds are, for example, selected from naphthalenes, anthracenes, phenanthrenes, tetracenes, perylenes, terrylenes, quaterrylenes, pentarylenes, hexarylenes, anthraquinones, indanthrones, acridines, carbazoles, dibenzofuranes, dinaphthofuranes, benzimidazoles, benzthiazoles, phenazines, di-oxazines, quinacridones, metal phthalocyanines, metal naphthalocyanines, metal porphyrines, coumarines, dibenzofuranones, dinaphthofuranones, benzimidazolones, indigo compounds, thioindigo compounds, quinophthalones, naphthoquinophthalones and diketopyrrolopyrroles.
• Particularly preferred compounds of component G which absorb IR radiation and optionally fluoresce are selected from naphthalenes, anthracenes, phenanthrenes, tetracenes, perylenes, terrylenes, quaterrylenes, pentarylenes and hexarylenes, more preferably from perylenes, terrylenes and quaterrylenes and especially from terrylenes and quaterrylenes.
• the compound is especially a
• the present disclosure(s) also provides methods suitable for making 3-dimensional structures comprising a plurality of polymer layers and 3-dimensional patterns.
• the present invention is directed to the use of the photocurable composition of the present invention in a photopolymerization 3D printing process, especially a vat photopolymerization, or photopolymer jetting.
• a method for producing a three-dimensional article may comprise
• Some embodiments provide methods of patterning a polymeric image on a substrate, each method comprising;
• the method may comprise depositing a plurality of layers of a photocurable
• composition on a substrate before irradiation at least one of which is the photocurable composition of the present invention.
• the irradiated portion is patterned through use of a photomask, by a direct writing application of light, by interference, nanoimprint, or diffraction gradient lithography, by inkjet 3D printing, stereolithography, holography, LCD or digital light projection (DLP).
• a photomask by a direct writing application of light, by interference, nanoimprint, or diffraction gradient lithography, by inkjet 3D printing, stereolithography, holography, LCD or digital light projection (DLP).
• the photocurable compositions may be irradiated by any variety of methods known in the art. Patterning may be achieved by photolithography, using a positive or negative image photomask, by interference lithography (i.e., using a diffraction grating), by proximity field nanopatterning by diffraction gradient lithography, or by a direct laser writing application of light, such as by multi-photon lithography, by nanoimprint lithography, by inkjet 3D printing, stereolithography and the digital micromirror array variation of stereolithography (commonly referred to as digital light projection (DLP).
• the photocurable compositions are especially amenable to preparing structures using stereolithographic methods, for example including digital light projection (DLP).
• the photocurable compositions may be processed as bulk structures, for example using vat polymerization, wherein the photopolymer is cured directly onto a translated or rotated substrate, and the irradiation is patterned via stereolithography, holography, or digital light projection (DLP).
• vat polymerization wherein the photopolymer is cured directly onto a translated or rotated substrate, and the irradiation is patterned via stereolithography, holography, or digital light projection (DLP).
• DLP digital light projection
• Stereolithography is a form of three-dimensional (3D) printing technology used for creating models, prototypes, patterns and production parts in a layer by layer fashion (so-called “additive manufacturing”) using photo-polymerization, a process by which light causes chains of molecules to link, forming polymers. Those polymers then make up the body of a three-dimensional solid.
• additive manufacturing a process by which light causes chains of molecules to link, forming polymers.
• a manufacturing process uses a build platform having a build tray submerged in a liquid photosensitive material.
• a 3D model of the item to be manufactured is imported into an associated 3D printer software, which software slices the 3D model into 2D images that are then projected onto the build platform to expose the photopolymer.
• FIG. 3 of US4575330 depicts a known prior art "top-down" approach to printing.
• a container 21 is filled with a UV curable liquid 22 or the like, to provide a designated working surface 23.
• a programmable source of ultraviolet (UV) light 26 produces a spot of ultraviolet light 27 in the plane of surface 23.
• the spot 27 is movable across the surface 23 by the motion of mirrors or other optical or mechanical elements that are a part of light source 26.
• the position of the spot 27 on surface 23 is controlled by a computer 28.
• a movable elevator platform 29 inside container 21 is moved up and down selectively, the position of the platform being controlled by the computer 28.
• the elevator platform may be driven mechanically, pneumatically, hydraulically or electrically, and it typically uses optical or electronic feedback to precisely control its position.
• the device As the device operates, it produces a three-dimensional object 30 by step wise buildup of integrated laminate such as 30a, 30b, 30c.
• the surface of the UV curable liquid 22 is maintained at a constant level in the container 21, and the spot of UV light 27 is moved across the working surface 23 in a programmed manner.
• the elevator platform 29 that was initially just below surface 23 is moved down from the surface in a programmed manner by any suitable actuator. In this way, the solid material that was initially formed is taken below surface 23 and new liquid 22 flows across the surface 23. A portion of this new liquid is, in turn, converted to solid material by the programmed UV light spot 27, and the new material adhesively connects to the material below it. This process is continued until the entire three-dimensional object 30 is formed.
• a computer controlled pump (not shown) may be used to maintain a constant level of the liquid 22 at the working surface 23.
• Appropriate level detection system and feedback networks can be used to drive a fluid pump or a liquid displacement device to offset changes in fluid volume and maintain constant fluid level at the surface 23.
• the source 26 can be moved relative to the sensed level 23 and
• UV curable liquid 22 floats on a heavier UV transparent liquid 32 that is non-miscible and non-wetting with the curable liquid 22.
• ethylene glycol or heavy water are suitable for the intermediate liquid layer 32.
• the three-dimensional object 30 is pulled up from the liquid 22, rather than down and further into the liquid medium, as shown in the system of FIG. 3.
• the UV light source 26 in FIG. 4 focuses the spot 27 at the interface between the liquid 22 and the non-miscible intermediate liquid layer 32, the UV radiation passing through a suitable UV transparent window 33, of quartz or the like, supported at the bottom of the container 21.
• one or more layers of the item are printed from resin that is foamed (at the build surface 23).
• FIG. 3 of WO2018106977 depicts a representative implementation of an additive manufacturing method and apparatus wherein resin foam is the source material for the printer.
• the SLA apparatus comprises a radiation source 300 (e.g., DLP, laser, electron beam (EB), x-ray, etc. and scanner), a movement control mechanism 302 (e.g., a stepper motor) that moves a build platform 304 vertically up and down within a tank 305 that holds the photopolymer resin 306, and a sweeper 308 (also known as a "recoater" blade) that sweeps horizontally.
• a radiation source 300 e.g., DLP, laser, electron beam (EB), x-ray, etc. and scanner
• a movement control mechanism 302 e.g., a stepper motor
• a sweeper 308 also known as a "recoater" blade
• the SLA apparatus is augmented with a foam producing and dispensing mechanism to facilitate production of resin foam at the printer interface, namely, the layer being printed.
• the mechanism comprises a foaming or pressure vessel 312, an electromechanical valve 314, and a hose or tube 316.
• a manifold 318 is attached to the sweeper 308 to evenly distribute the foamed resin across the top layer of the build surface.
• the foaming vessel receives liquid resin and a suitable gas (e.g., C0 2 , N 2 0, etc.).
• Gas is dissolved in the liquid resin within the foaming vessel (e.g., by shaking, missing, agitation, etc.) and selectively delivered to the build plate/platform via the hose 316 when the valve 314 is actuated, e.g., by a solenoid or other electromechanical, pneumatic, optical or electronic control device.
• the mechanism is under program control using a computer, which may be the same computer used to control the printer.
• the mechanism includes a frother 320 (e.g., a mechanical agitator, an ultrasonic device, etc.) to shake or otherwise dissolve the gas within the liquid vessel if needed to produce foam.
• the gas spontaneously evolves out of the liquid mixture (due to the lower pressure) to produce a foam that is radiation-curable.
• the sweeper 308 spreads the foam evenly onto the plate, and the light engine is then activated to display the appropriate image to cure (solidify) the foam into a layer.
• the movement control mechanism moves the platform down so that the next layer of the item can be built; the process is then repeated, once again preferably using the foam layer at the print interface. While the preferred technique uses layer-wise additive manufacturing, other manufacturing processes may be used to process the foam to produce the build item, such as, for example, laser holography, wherein two lasers intersect in a tank of foamed resin and cure the resin at that spot.
• the photocurable composition of the present is preferably used in a vat
• the present invention relates to a method comprising a vat photopolymerization, wherein the photocurable composition of the present invention is cured directly onto a translated or rotated substrate, and the irradiation is patterned via stereolithography, holography, or digital light projection (DLP).
• DLP digital light projection
• the present invention relates to a method for manufacturing a three-dimensional article with photocurable composition of the present invention, comprising the steps of:
• the present invention is also directed to a three-dimensional article, which is obtainable according to the methods described above.
• the present invention is also directed to a three-dimensional article, which is a cured product of the photocurable composition of the present invention.
• Urethane (meth)acrylates were prepared filling the calculated amount of isocyanate (TDI, H DI, H12M DI, I PDI) in a suitable 3-neck round-bottom flask equipped with temperature element PT100, nitrogen flow, mechanic stirrer and heating hood. The material was heated to 50 ° C. In some experiments (compare recipes in Table 1), the catalyst 1 was added. Subsequently the polyol 1 was added. Any additional polyol 2, if used, was added afterwards. After addition of all components, the system was flushed with nitrogen and kept under nitrogen atmosphere during the reaction. The mixture was heated to 80 ° C and kept at this temperature for 2 h.
• isocyanate TDI, H DI, H12M DI, I PDI
• the mixture was allowed to cool down to 60 ° C and the NCO value of the prepolymer was determined.
• the amount of hydroxyalkyl(meth)acrylate needed to saturate all NCO groups was calculated and added under air at 60° C.
• the reaction mixture was stirred at this temperature for 1 h what typically led to a decrease in NCO to almost 0.
• the final urethane acrylate was kept at room temperature (RT) under air in a suitable vial. After 24 h, the viscosity was measured.
• NCO content was determined following DIN EN ISO 11909: primary and secondary amines react with free isocyanate groups to urea groups. This reaction is quantitative under excess of amine. After the complete reaction, the excess amine is determined by back titration with hydrochloric acid.
• Polyol viscosity was determined at 60 ° C in accordance with DIN EN ISO 3219 using a cone/plate Brookfield viscometer/ CAP 2000+ and a spindle with diameter of 9.53 mm and an angle of 1.8° at a shear rate of 100 s-1.
• Step 2 curing under a 365 nm UV-LED (Eloenle Powerline AC) placed over a conveyor belt (500 mJ/cm 2 per pass) at a total UV dose of 2500 mJ/cm 2 (tensile test, 2 mm specimen thickness) and 5000 mJ/cm 2 (Izod impact strength, 4 mm specimen thickness).
• the specimens were irradiated on both sides to ensure homogeneous curing.
• the viscosities of the photopolymers were determined at 50 ° C at 100 s 1 shear rate using a cone/plate (60 mm diameter, 2° cone angle) rheometer (H R-1 Discovery, TA Instruments).
• UV doses were measured with a UV-Control 3CT, UV-technik meyer gmbh.
• TDI is a mixture of 2,4-Toluene diisocyanate (2,4-TDI, 80%) and 2,6-TDI (20%) with a NCO content of 48%.
• BASF Lupranat T 80 A
• HDI is 1,6-Hexane diisocyanate with a NCO content of 50%.
• BASF is 1,6-Hexane diisocyanate with a NCO content of 50%.
• H12M DI is Dicyclohexylmethane-4,4’-diisocyanate with a NCO content of 32%.
• Trade name Evonik Vestanat H 12M DI
• IPI D is Isophorondiisocyanate with a NCO content of 38%.
• Trade name Evonik is
• BASF Lupraphen 6601/3
• Polyol 2 is Propane-1, 2, 3-triol from BASF.
• Catalyst 1 is a tin based catalyst. Trade name BASF: Fomrez UL 28.
• HEA is Hydroxyethylacrylate purchased from Sigma Aldrich (96%, contains 200- 650 ppm monomethyl ether hydroquinone as inhibitor)
• HEMA Hydroxyethylmethacrylate purchased from Sigma Aldrich (97%, contains

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