Classifications

• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
  • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
• • 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
• • 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
  • B29C64/20—Apparatus for additive manufacturing; Details thereof or accessories therefor
  • B29C64/264—Arrangements for irradiation
• • 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
  • C08F299/00—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers
  • C08F299/02—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates
  • C08F299/06—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes
  • C08F299/065—Macromolecular compounds obtained by interreacting polymers involving only carbon-to-carbon unsaturated bond reactions, in the absence of non-macromolecular monomers from unsaturated polycondensates from polyurethanes from polyurethanes with side or terminal unsaturations
• • 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
  • C08G18/67—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
  • C08G18/28—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
  • C08G18/6725—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen containing ester groups other than acrylate or alkylacrylate ester 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
  • C08G18/70—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
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7831—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing biuret 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/7806—Nitrogen containing -N-C=0 groups
  • C08G18/7818—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups
  • C08G18/7837—Nitrogen containing -N-C=0 groups containing ureum or ureum derivative groups containing allophanate 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/72—Polyisocyanates or polyisothiocyanates
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
• • 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
  • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
  • C08G18/78—Nitrogen
  • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
  • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate 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
  • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
  • C08G18/81—Unsaturated isocyanates or isothiocyanates
  • C08G18/8141—Unsaturated isocyanates or isothiocyanates masked
  • C08G18/815—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen
  • C08G18/8158—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen
  • C08G18/8175—Polyisocyanates or polyisothiocyanates masked with unsaturated compounds having active hydrogen with unsaturated compounds having only one group containing active hydrogen with esters of acrylic or alkylacrylic acid having only one group containing active hydrogen
• • 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

Definitions

• the present invention relates to a curable resin composition for stereolithography, a cured product, and a three-dimensional model.
• a curable resin composition is selectively polymerized and cured with an active energy beam such as an ultraviolet laser based on three-dimensional shape data designed by a three-dimensional design system such as three-dimensional CAD.
• an optical stereolithography method stereolithography method for producing a three-dimensional object is used.
• This optical three-dimensional modeling method can handle complicated shapes that are difficult to machine, and the production time is short, and it is easy to handle. is becoming widely used in
• a typical example of the optical stereolithography method is to irradiate a liquid photocurable resin in a container with a computer-controlled spot-shaped ultraviolet laser from above to harden one layer of a predetermined thickness, and then shape it.
• a three-dimensional object can be obtained by repeating this operation of supplying a liquid resin on the layer by lowering the object by one layer, and similarly irradiating and curing with ultraviolet laser light in the same manner as described above.
• a DMD digital micromirror device
• a light source other than a laser such as an LED
• Ultraviolet light is irradiated from below through a transparent container containing a photocurable resin through a so-called planar drawing mask to harden one layer of a predetermined cross-sectional pattern, and the modeled object is pulled up by one layer. Therefore, a surface exposure method is increasing in which the next layer is irradiated and cured in the same manner as described above and sequentially laminated to obtain a three-dimensional object.
• the properties required for the photocurable resin used in the optical stereolithography method include various properties such as low viscosity, ability to form a smooth liquid surface, and excellent curability.
• resin compositions based on radically polymerizable compounds are known (see, for example, Patent Documents 1 and 2). It did not satisfy the increasing required performance.
• An object of the present invention is to provide a curable resin composition for stereolithography that can form a cured product that has a low viscosity, a large elastic modulus, a large impact strength, little change over time, and excellent impact resistance.
• a specific urethane (meth)acrylate exhibiting a specific value for the content of acryloyl groups in the urethane (meth)acrylate is a curable resin for stereolithography.
• the inventors have found that the above-mentioned problems can be solved by including it in the composition, and have completed the present invention.
• a curable resin composition for stereolithography containing a urethane resin (A) having a (meth)acryloyl group and a photopolymerization initiator, A curable resin composition for stereolithography, wherein the content of (meth)acryloyl groups in the urethane resin (A) is 0.8 mmol/g or more and 2.2 mmol/g or less.
• the urethane resin (A) contains at least one polyisocyanate (a1) represented by any one of the following formulas (1), (2), and (3), a hydroxyl group, and a (meth)acryloyl group.
• R 1 , R 2 and R 3 each represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
• the urethane resin (A) is represented by at least one polyisocyanate (a1) represented by any one of the formulas (1), (2), and (3) and the following formula (4).
• the curable resin composition for stereolithography according to [2] or [3], which contains a compound (a2) having a hydroxyl group and a (meth)acryloyl group as an essential reaction raw material.
• R4 represents a hydrogen atom or a methyl group
• n represents an integer of 0 or more and 10 or less.
• the curable resin composition for stereolithography contains a monofunctional (meth)acrylic compound (B1) and/or a bifunctional (meth)acrylic compound (B2),
• the curability for stereolithography according to any one of [1] to [4], wherein the content of the urethane resin (A) in the curable resin composition for stereolithography is 1% by mass or more and 50% by mass or less.
• R 6 and R 7 each independently represent a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a ring structure. , a group in which a portion of the carbon atoms of the hydrocarbon group is substituted with an oxygen atom or a nitrogen atom, or a hydrogen atom, and R 6 and R 7 may be bonded to each other to form a ring ;
• the monovalent hydrocarbon group having 1 to 40 carbon atoms represented by may or may not contain an unsaturated double bond.
• a curable resin composition for stereolithography that can form a cured product that has a low viscosity, a large elastic modulus, a large impact strength, little change over time, and excellent impact resistance.
• (meth)acrylate means acrylate and/or methacrylate.
• (meth)acryloyl means acryloyl and/or methacryloyl.
• (meth)acryl means acryl and/or methacryl.
• the curable resin composition for stereolithography of the present invention contains a urethane resin (A) having a (meth)acryloyl group and a photopolymerization initiator.
• the content of the (meth)acryloyl group in the urethane resin (A) is It is 0.8 mmol/g or more and 2.2 mmol/g or less.
• the curable resin composition for stereolithography of the present invention comprises, in addition to a urethane resin (A) having a (meth)acryloyl group and a photopolymerization initiator, a monofunctional (meth)acrylic compound (B1) and/or a bifunctional A (meth)acrylic compound (B2) can be contained.
• the curable resin composition for stereolithography of the present invention includes a monofunctional (meth)acrylic compound (B1) and/or a bifunctional (meth)acrylic compound (B2) within a range that does not impair the effects of the present invention. It is also possible to contain other (meth)acrylic compounds having three or more functionalities other than the above. Furthermore, the curable resin composition for stereolithography of the present invention can also contain other additives such as photosensitizers, ultraviolet absorbers, polymerization inhibitors and inorganic fillers, if necessary.
• the urethane resin (A) used in the present invention has a (meth)acryloyl group content of 0.8 mmol/g or more and 2.2 mmol/g or less.
• the curable resin composition has a low viscosity, as shown in the following examples.
• a cured product having excellent elastic modulus and impact resistance can be formed.
• Urethane resin (A) can be obtained by reacting polyisocyanate (a1) with compound (a2) having a hydroxyl group and a (meth)acryloyl group.
• the polyisocyanate (a1) is not particularly limited as long as it can form a urethane resin (A) having a specific content of (meth)acryloyl groups used in the present invention, and can be appropriately selected depending on the purpose.
• aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4 trimethylhexamethylene diisocyanate, 2,4,4 trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated diphenylmethane
• Alicyclic diisocyanate compounds such as diisocyanate; aromatics such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5 naphthalene diisocyanate, 4,4' diisocyanato 3,3' dimethylbiphenyl, o tolidine diisocyanate group diisocyanate compounds; polymethylene polyphenyl polyisocyanates having a repeating structure represented by the following formula (6); (In
• the polyisocyanate (a1) is at least one polyisocyanate particularly represented by any of the following formulas (1), (2), and (3), the content of (meth)acryloyl groups is It is more preferable for forming a urethane resin (A) exhibiting a specific value defined in the invention.
• Preferred embodiments of the polyisocyanate (a1) include the following ⁇ first embodiment >>>.
• the polyisocyanate (a1) is at least one polyisocyanate represented by any one of the following formulas (1), (2) and (3).
• R 1 , R 2 and R 3 each represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
• the polyisocyanate (a1) it is more preferable to use a polyisocyanate having an isocyanurate structure, a burette structure, or an allophanate structure, as represented by the above formulas (1) to (3).
• each of R 1 , R 2 and R 3 is more preferably a linear alkyl group.
• the polyisocyanate (a1) described above can be used alone or in combination of two or more.
• Compound (a2) having a hydroxyl group and a (meth)acryloyl group is not particularly limited as long as the urethane resin (A) having a specific content of the (meth)acryloyl group used in the present invention can be formed. can be selected as appropriate.
• (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are added to the molecular structures of the compounds having various hydroxyl groups and (meth)acryloyl groups.
• Introduced (poly)oxyalkylene modified products, and lactone modified products obtained by introducing a (poly)lactone structure into the molecular structure of the above various compounds having a hydroxyl group and a (meth)acryloyl group can also be used.
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group is particularly a compound having a hydroxyl group and a (meth)acryloyl group represented by the following formula (4), the content of the (meth)acryloyl group is It is more preferable for forming the urethane resin (A) exhibiting the specific values specified in the present invention.
• Preferred embodiments of the compound (a2) having a hydroxyl group and a (meth)acryloyl group include the following ⁇ second embodiment >>>.
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group is more preferably a compound having a hydroxyl group and a (meth)acryloyl group represented by the following formula (4).
• R4 represents a hydrogen atom or a methyl group
• n represents an integer of 0 or more and 10 or less.
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group it is more preferable to use a caprolactone-modified hydroxyl group-containing (meth)acrylate as represented by the above formula (4).
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group described above can be used alone or in combination of two or more.
• the method for producing the urethane resin (A) is not particularly limited, and any method may be used.
• the polyisocyanate (a1) and the reaction raw materials containing the compound (a2) having a hydroxyl group and a (meth)acryloyl group may be reacted together, or the reaction raw materials may be divided and sequentially prepared. You may manufacture by the method to make it react.
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group has The equivalent ratio (OH/NCO) between the hydroxyl group (OH) and the isocyanate group (NCO) possessed by the polyisocyanate (a1) is in the range of 0.95/1.00 to 1.05/1.00. It is preferably 1/1 and more preferably 1/1.
• urethane resin (A) for example, dibutyltin laurate, dibutyltin acetate, or the like can be used as a catalyst, and the production can be carried out under the conditions of a normal urethanization reaction.
• a solvent such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, or xylene, or a radically polymerizable monomer that does not contain a site that reacts with isocyanate and that does not contain a hydroxyl group or an amino group. etc. can also be used as a solvent.
• the content of (meth)acryloyl groups in the urethane resin (A) is the amount per unit mass (mmol/g) of the urethane resin (A).
• the content of (meth)acryloyl groups in the urethane resin (A) is 0.8 mmol/g or more and 2.2 mmol/g or less. /g or more, more preferably 1.2 mmol/g or more, more preferably 2.0 mmol/g or less, and even more preferably 1.9 mmol/g or less.
• the content of (meth)acryloyl groups in the urethane resin (A) can be determined, for example, by assigning each peak of a measurement sample and an internal standard using a 1 H NMR spectrometer and determining the integral ratio, or by using an IR spectrometer. , a method of preparing a calibration curve from the ratio of the peak due to the acryloyl group and the specific peak of the standard substance, and quantifying it.
• the (meth)acryloyl group content of the urethane resin (A) was calculated based on the (meth)acryloyl group content (theoretical value) of the raw material.
• the curable resin composition for stereolithography of the present invention further contains a photopolymerization initiator.
• photopolymerization initiators include 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy -2-methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2′-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6 trimethoxybenzoyl)phosphine oxide, 2,4,6 trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one, 2 -benzyl-2-dimethylamino-1-(4-morpholinopheny
• the amount of the photopolymerization initiator to be added is preferably, for example, in the range of 120% by mass in the curable resin composition for stereolithography.
• (Meth)acrylic compounds may also include nitrogen-containing (meth)acrylic compounds.
• (meth)acrylic compounds include (meth)acrylic compounds such as (meth)acrylate compounds and (meth)acrylamides.
• Examples of the monofunctional (meth)acrylic compound (B1) include phenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, Cyclohexylethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dipropylene glycol mono(meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, isononyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, ethoxyethoxyethyl (meth) acrylate, 2-(meth) acryloyloxye
• Monofunctional (meth)acrylic compounds can be used alone or in combination of two or more.
• a curable resin composition having low viscosity and capable of forming a cured product having excellent mechanical properties can be obtained, so monofunctional (meth)acrylic compounds
• the glass transition temperature (hereinafter abbreviated as “Tg”) of the polymer of is preferably 50° C. or higher.
• a (meth)acrylic compound having a cyclic structure such as a condensed polycyclic structure or a heterocyclic structure is preferable, and isobornyl acrylate (Tg: 94°C), isobornyl methacrylate (Tg: 180°C), Dicyclopentenyl acrylate (Tg: 120°C), dicyclopentanyl acrylate (Tg: 120°C), and dicyclopentanyl methacrylate (Tg: 175°C) are preferred.
• the Tg of the copolymer of the two or more monofunctional (meth)acrylic compounds is preferably 50°C or higher.
• the (meth)acrylic compound (B1) may also include a nitrogen-containing (meth)acrylic compound. It is more preferable from the viewpoint of adhesion to.
• R5 represents a hydrogen atom or a methyl group.
• R 6 and R 7 each independently represent a monovalent hydrocarbon group having 1 to 40 carbon atoms which may have a ring structure, and part of the carbon atoms of the above hydrocarbon group is substituted with an oxygen atom or a nitrogen atom. or a hydrogen atom, R 6 and R 7 may be bonded to each other to form a ring, and the monovalent hydrocarbon group having 1 to 40 carbon atoms represented by R 6 and R 7 is an unsaturated group. It may or may not contain a saturated double bond.
• Examples of monofunctional (meth)acrylamide compounds represented by formula (5) include acryloylmorpholine, isopropylacrylamide, dimethylacrylamide, hydroxyethylacrylamide, and diethylacrylamide, and among them, condensed polycyclic structures and heterocyclic structures.
• Bifunctional (meth)acrylic compounds include, for example, bifunctional (meth)acrylate compounds. More specifically, the bifunctional (meth)acrylic compound (B2) includes, for example, 1,6-hexanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,3- butylene glycol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, ethylene oxide-modified 1,6-hexanediol di(meth)acrylate (Meth) acrylates, neopentyl glycol hydroxypivalate di(meth) acrylate, propylene oxide-modified neopentyl glycol di(meth) acrylate, tripropylene glycol di
• bifunctional (meth)acrylic compounds can be used alone or in combination of two or more.
• a curable resin composition having a low viscosity and capable of forming a cured product having excellent mechanical properties can be obtained.
• the Tg of the polymer of is preferably 40°C or higher.
• neopentyl glycol hydroxypivalate diacrylate Tg: 111°C are more preferable.
• the Tg of the copolymer of two or more bifunctional (meth)acrylic compounds is preferably 40°C or higher.
• a monofunctional (meth)acrylic compound (B1) and a bifunctional (meth)acrylic compound (B2) can be used together.
• the copolymer of the (meth)acrylic compound used in combination preferably has a Tg of 40° C. or higher.
• the curable resin composition for stereolithography of the present invention may contain the above monofunctional (meth)acrylic compound (B1) and/or the above bifunctional (meta )
• a trifunctional or higher (meth)acrylic compound can be used in combination.
• the Tg of the (meth)acrylic compound copolymer to be used in combination is preferably 40° C. or higher.
• Trifunctional or higher (meth)acrylic compounds include, for example, EO-modified glycerol acrylate, PO-modified glycerol triacrylate, pentaerythritol triacrylate, EO-modified phosphoric acid triacrylate, trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, Trifunctional (meth)acrylates such as acrylates, HPA-modified trimethylolpropane triacrylate, (EO)- or (PO)-modified trimethylolpropane triacrylate, alkyl-modified dipentaerythritol triacrylate, tris(acryloxyethyl) isocyanurate;
• tetrafunctional (meth)acrylates such as ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetraacrylate, and pentaerythritol tetraacrylate;
• Pentafunctional (meth)acrylates such as dipentaerythritol hydroxypentacrylate and alkyl-modified dipentaerythritol pentaacrylate;
• hexafunctional (meth)acrylates such as dipentaerythritol hexaacrylate.
• These trifunctional or higher (meth)acrylic compounds (more specifically, (meth)acrylates) can be used alone or in combination of two or more.
• the curable resin composition for stereolithography of the present invention may optionally contain a photosensitizer, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a silicon-based additive, a fluorine-based additive, and a silane cup.
• Various additives such as ring agents, phosphate ester compounds, organic beads, inorganic fine particles, organic fillers, inorganic fillers, rheology control agents, defoaming agents, and colorants may also be contained.
• the curable resin composition for stereolithography of the present invention can be further added with a photosensitizer to improve curability.
• photosensitizers include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, condensed polycyclic compounds such as anthraquinone derivatives, sodium diethyldithiophosphate, and s-benzylisothiuro.
• sulfur compounds such as nium-p-toluenesulfonate;
• UV absorbers include, for example, 2-[4- ⁇ (2-hydroxy-3-dodecyloxypropyl)oxy ⁇ -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5 triazine, 2-[4- ⁇ (2-hydroxy-3-tridecyloxypropyl)oxy ⁇ -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3, Triazine derivatives such as 5-triazine, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy 5'-methylphenyl)benzotriazole, 2-xanthenecarboxy -4-dodecyloxybenzophenone, 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone and the like. These ultraviolet absorbers can be used alone or in combination of two or more.
• antioxidants examples include hindered phenol-based antioxidants, hindered amine-based antioxidants, organic sulfur-based antioxidants, and phosphate-based antioxidants. These antioxidants can be used alone or in combination of two or more.
• polymerization inhibitors examples include hydroquinone, methoquinone, di-t-butylhydroquinone, p-methoxyphenol, butylhydroxytoluene, and nitrosamine salts.
• Silicon additives include, for example, dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethyl Polysiloxane copolymer, polyorganosiloxane having an alkyl group or a phenyl group such as an amino-modified dimethylpolysiloxane copolymer, polydimethylsiloxane having a polyether-modified acrylic group, polydimethylsiloxane having a polyester-modified acrylic group, and the like. be done. These silicon additives can be used alone or in combination of two or more.
• fluorine-based additives examples include the "Megaface” series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.
• Silane coupling agents include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3- glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- aminopropyl
• styrene-based silane coupling agent such as p-styryltrimethoxysilane
• (Meta) such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc. acryloxy-based silane coupling agent;
• ureido-based silane coupling agents such as 3-ureidopropyltriethoxysilane
• Chloropropyl-based silane coupling agents such as 3-chloropropyltrimethoxysilane
• mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoquinsilane;
• sulfide-based silane coupling agents such as bis(triethoxysilylpropyl) tetrasulfide
• silane coupling agents such as 3-isocyanatopropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.
• Examples of the phosphate ester compound include those having a (meth)acryloyl group in the molecular structure.
• Commercially available products include, for example, Nippon Kayaku Co., Ltd. "Kayamer PM-2", “Kayamer PM-21 ”, Kyoeisha Chemical Co., Ltd.
• organic beads examples include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylicstyrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyethylene fluoride resin beads, polyethylene resin beads, and the like. These organic beads can be used alone or in combination of two or more. Moreover, the average particle size of these organic beads is preferably in the range of 1 to 10 ⁇ m.
• inorganic fine particles examples include fine particles such as silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These inorganic fine particles can be used alone or in combination of two or more. In addition, the average particle size of these inorganic fine particles is preferably in the range of 95 to 250 nm, and more preferably in the range of 100 to 180 nm.
• a dispersing aid When inorganic fine particles are contained, a dispersing aid can be used.
• dispersion aids include phosphoric acid ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These dispersing aids can be used alone or in combination of two or more.
• examples of commercially available dispersion aids include "Kayamer PM-21” and “Kayamer PM-2” manufactured by Nippon Kayaku Co., Ltd., and “Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd., and the like.
• organic fillers examples include plant-derived solvent-insoluble substances such as cellulose, lignin, and cellulose nanofibers.
• inorganic fillers examples include glass (particles), silica (particles), alumina silicate, talc, mica, aluminum hydroxide, alumina, calcium carbonate, and carbon nanotubes.
• rheology control agents examples include amide waxes such as "Disparlon 6900” manufactured by Kusumoto Kasei Co., Ltd.; urea-based rheology control agents such as “BYK410” manufactured by Big Chemie; and “Disparlon 4200” manufactured by Kusumoto Kasei Co., Ltd. and cellulose acetate butyrate such as “CAB-381-2” and “CAB 32101” manufactured by Eastman Chemical Products.
• defoaming agents examples include oligomers containing fluorine or silicon atoms, or oligomers such as higher fatty acids and acrylic polymers.
• coloring agents include pigments and dyes.
• pigment known and commonly used inorganic pigments and organic pigments can be used.
• inorganic pigments examples include titanium oxide, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian blue, ultramarine blue, carbon black, and graphite.
• organic pigments examples include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, and quinophthalone pigments. pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments and the like. These pigments can be used alone or in combination of two or more.
• dyes examples include azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, and naphthoquinone dyes. , naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane dyes, and the like. These dyes can be used alone or in combination of two or more.
• the content of the urethane resin (A) in the curable resin composition for stereolithography of the present invention is 1% by mass or more and 50% by mass or less from the viewpoint of securing a practically effective viscosity range without excessively increasing the viscosity. It is preferably 3% by mass or more and 50% by mass or less.
• the cured product of the present invention can be obtained by irradiating the curable resin composition for stereolithography of the present invention with an active energy ray.
• active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• irradiation may be performed in an atmosphere of an inert gas such as nitrogen gas, or in an air atmosphere, in order to efficiently perform a curing reaction using ultraviolet rays.
• UV lamps are generally used as the source of UV light from the standpoint of practicality and economy. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.
• the integrated amount of active energy rays is not particularly limited, it is preferably 50 to 5,000 mJ/cm 2 , more preferably 300 to 1,000 mJ/cm 2 . It is preferable that the integrated amount of light is within the above range because the generation of uncured portions can be prevented or suppressed.
• the three-dimensional object of the present invention can be produced by a known optical stereolithography method.
• optical stereolithography methods examples include the stereolithography (SLA) method, the digital light processing (DLP) method, and the inkjet method.
• the stereolithography (SLA) method is a method in which a tank of a liquid curable resin composition is irradiated with active energy rays such as laser beams at points, and solidification is performed layer by layer while moving the modeling stage to create a three-dimensional model.
• the digital light processing (DLP) method is a method in which a tank of a liquid curable resin composition is irradiated with active energy rays such as LEDs on the surface, and three-dimensional modeling is performed by curing one layer at a time while moving the modeling stage. .
• the inkjet stereolithography method is a method in which fine droplets of a curable resin composition for stereolithography are ejected from a nozzle so as to draw a predetermined shape pattern, and then ultraviolet rays are irradiated to form a cured thin film.
• the DLP method is preferable because it enables high-speed modeling using surfaces.
• the DLP stereolithography method is not particularly limited as long as it is a method using a DLP stereolithography system.
• the pitch is in the range of 0.01 to 0.2 mm
• the irradiation wavelength is in the range of 350 to 410 nm
• the light intensity is in the range of 0.5 to 50 mW/cm 2
• the integrated light amount per layer is 1 to 1
• the range of 100 mJ/cm 2 is required, and above all, since the modeling accuracy of the three-dimensional model is further improved
• the lamination pitch of stereolithography is in the range of 0.02 to 0.1 mm
• the irradiation wavelength is in the range of 380 to 410 nm
• the light intensity is in the range of 5 to 15 mW/cm 2
• the integrated amount of light per layer is in the range of 5 to 15 mJ/cm 2 .
• the three-dimensional object of the present invention has a high elastic modulus and excellent impact resistance, it is used, for example, in automobile parts, aerospace-related parts, electrical and electronic parts, home appliances, building materials, interiors, jewelry, medical materials, etc. It can be used preferably.
• Sumidule N3300 isocyanurate-type hexamethylene diisocyanate represented by the following formula (a1-1)
• Duranate 24A-100 biuret-type hexamethylene diisocyanate represented by the following formula (a1-2)
• BasonatHA300 the following formula ( Allophanate-type hexamethylene diisocyanate represented by a1-3)
• ⁇ VESTANAT T1890 isocyanurate-type isophorone diisocyanate represented by the following formula (a1-4)
• ⁇ Isophorone diisocyanate diisocyanate represented by the following formula (a1-5)
• ⁇ Karenz AOI 2-acryloyloxyethyl isocyanate represented by the following formula (a1-6)
• ⁇ Placcel FA5 caprolactone 5 mol addition type 2-hydroxyethyl acrylate represented by the following formula (a2-1), hydroxyl value: 81.8 KOH mg / g, (meth) acryloyl group content (theoretical value): 1.46 mmol / g ⁇ Praxel FA4DT: 4 mol of caprolactone addition type 2-hydroxyethyl acrylate represented by the following formula (a2-2), hydroxyl value: 98.1 KOH mg / g, (meth) acryloyl group content (theoretical value): 1.76 mmol / g ⁇ Praxel FA2D: Caprolactone 2 mol addition type 2-hydroxyethyl acrylate represented by the following formula (a2-3), hydroxyl value: 163.1 KOH mg / g, (meth) acryloyl group content (theoretical value): 2.87 mmol / g Praxel FA10L: 10 mol addition type 2-hydroxyethy
• ACMO acryloylmorpholine represented by the following formula (b1-1) (manufactured by KJ Chemicals Co., Ltd.), Tg 145 ° C., number of functional groups 1 ⁇ NIPAM: isopropyl acrylamide (manufactured by KJ Chemicals Co., Ltd.) represented by the following formula (b1-2), Tg 134 ° C., number of functional groups 1 FA-513AS: dicyclopentanyl acrylate represented by the following formula (b1-3) (manufactured by Showa Denko Materials Co., Ltd.), Tg 120 ° C., number of functional groups 1 DMAA: dimethylacrylamide (manufactured by KJ Chemicals Co., Ltd.) represented by the following formula (b1-4), Tg 119 ° C., number of functional groups 1 - IBXA: isobornyl acrylate represented by the following formula (b1-5) (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Tg
• ⁇ MIRAMER M210 Neopentylglycol hydroxypivalate represented by the following formula (b2-1) (manufactured by MIWON), Tg 111 ° C., functional number 2 ⁇ MIRAMER M262: tricyclodecanedimethanol diacrylate represented by the following formula (b2-2) (manufactured by MIWON), Tg 110 ° C., number of functional groups 2 ⁇ MIRAMER M222: Dipropylene glycol diacrylate represented by the following formula (b2-3) (manufactured by MIWON), Tg 102 ° C., number of functional groups 2 ⁇ MIRAMER M240: Bisphenol A EO-modified diacrylate represented by the following formula (b2-3) (manufactured by MIWON), Tg 42 ° C., functional number 2
• urethane (meth)acrylate (A1) The content of (meth)acryloyl groups per 1 g of urethane (meth)acrylate (A1) calculated from the acryloyl group content (theoretical value) of the raw material was 1.14 mmol (described in Table 1 below.
• the (meth)acryloyl group content in each urethane (meth)acrylate obtained in Synthesis Examples is also shown in Table 1).
• Example 1 Preparation of curable resin composition (1)
• urethane (meth)acrylate (A1) obtained in Synthesis Example 1
• IGM Resins 2 parts by mass of Omnirad TPO manufactured by Co., Ltd. was added, and the mixture was stirred at 60° C. or lower until uniformly dissolved to obtain a curable resin composition (1).
• Examples 2 to 23 Preparation of curable resin compositions (2) to (23)
• a curable resin composition was prepared in the same manner as in Example 1, except that the urethane (meth)acrylate and (meth)acrylic compound were changed to the compositions and blending amounts shown in Table 1 or Table 2. Products (2) to (23) were obtained.
• dumbbells for tensile tests and test pieces for Izod impact tests were produced.
• the dumbbell for the tensile test was produced in a shape similar to ASTM D638 TYPE 1 with a total length of 55 mm.
• the dumbbell for the tensile test obtained by stereolithography and the test piece for the Izod impact test were washed with isopropyl alcohol, dried at room temperature for 1 hour, and then post-cured using "Multicure 180" manufactured by XYZ Printing. Both surfaces were irradiated with an LED having a wavelength of 385 nm for 10 minutes each to obtain test piece 1 (dumbbell for tensile test) and test piece 2 (test piece for Izod impact test).
• a tensile test was performed using a universal material testing machine "5965" manufactured by INSTRON to measure the elastic modulus. The test was carried out under the conditions of a load cell of 1 kN, a tensile speed of 1 mm/min, and a distance between tensile jigs of 38 mm.
• compositions and evaluation results of the curable resin compositions obtained in Examples 1 to 23 and Comparative Examples 1 to 3 are shown in Tables 1 to 3 below.
• the viscosity of the curable resin composition is 1,100 mPa ⁇ s or less, preferably 1,000 mPa ⁇ s or less, from the viewpoint of formability and load on the forming machine.
• the modulus of elasticity in the tensile test of the shaped article should be 0.5 ⁇ 10 9 Pa or more in terms of hardness, and the higher the better.
• the Izod impact strength is 18 J/m or more, preferably 20 J/m or more, and more preferably 30 J/m or more.
• the rate of change in Izod impact strength over time is less than 50%, the smaller the better.
• the curable resin composition of the present invention had a low viscosity. Moreover, it was confirmed that the curable resin composition of the present invention can form a cured product having an excellent elastic modulus. Furthermore, it was confirmed that the curable resin composition of the present invention can form a cured product having high impact strength, little change over time, and excellent impact resistance in an Izod impact strength test.
• the curable resin composition of the present invention can be effectively used for stereolithography.

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