US20180258297A1 - Resin composition for modeling material, light curing molding ink set, and method for manufacturing optically shaped article - Google Patents

Resin composition for modeling material, light curing molding ink set, and method for manufacturing optically shaped article Download PDF

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Publication number
US20180258297A1
US20180258297A1 US15/759,807 US201615759807A US2018258297A1 US 20180258297 A1 US20180258297 A1 US 20180258297A1 US 201615759807 A US201615759807 A US 201615759807A US 2018258297 A1 US2018258297 A1 US 2018258297A1
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Prior art keywords
resin composition
modeling material
weight
parts
supporting material
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Abandoned
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US15/759,807
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Inventor
Katsuyuki KITOU
Taeko IZUMO
Masakatsu Okawa
Kenta HONGO
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Mimaki Engineering Co Ltd
Maxell Ltd
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Maxell Holdings Ltd
Mimaki Engineering Co Ltd
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Assigned to MIMAKI ENGINEERING CO., LTD., MAXELL HOLDINGS, LTD. reassignment MIMAKI ENGINEERING CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: HONGO, Kenta, OKAWA, MASAKATSU, IZUMO, Taeko, KITOU, Katsuyuki
Publication of US20180258297A1 publication Critical patent/US20180258297A1/en
Assigned to MAXELL, LTD. reassignment MAXELL, LTD. CHANGE OF NAME (SEE DOCUMENT FOR DETAILS). Assignors: MAXELL HOLDINGS, LTD.
Abandoned legal-status Critical Current

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    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing
    • 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
    • B29C64/112—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using individual droplets, e.g. from jetting heads
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D 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 [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for 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
    • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
    • 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
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • 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
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/30—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety
    • C08F220/301—Esters containing oxygen in addition to the carboxy oxygen containing aromatic rings in the alcohol moiety and one oxygen in the alcohol moiety
    • 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
    • C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
    • C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
    • 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
    • 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
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C09D11/107—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds from unsaturated acids or derivatives thereof
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/32—Inkjet printing inks characterised by colouring agents
    • C09D11/322—Pigment inks
    • 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
    • C09D11/00—Inks
    • C09D11/30—Inkjet printing inks
    • C09D11/38—Inkjet printing inks characterised by non-macromolecular additives other than solvents, pigments or dyes
    • 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
    • B29C64/40—Structures for supporting 3D objects during manufacture and intended to be sacrificed after completion thereof
    • 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
    • B29K2105/00—Condition, form or state of moulded material or of the material to be shaped
    • B29K2105/0005—Condition, form or state of moulded material or of the material to be shaped containing compounding ingredients
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • 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
    • C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
    • C08F222/10—Esters
    • C08F222/1006—Esters of polyhydric alcohols or polyhydric phenols
    • C08F222/102—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate
    • C08F222/1025—Esters of polyhydric alcohols or polyhydric phenols of dialcohols, e.g. ethylene glycol di(meth)acrylate or 1,4-butanediol dimethacrylate of aromatic dialcohols

Definitions

  • a shaping method using a photocurable resin composition which cures by irradiating ultraviolet rays or the like has widely been known.
  • a cured layer having a predetermined shape is formed by irradiating the photocurable resin composition with ultraviolet rays or the like to cure it.
  • a new cured layer is formed by further feeding the photocurable resin composition on the cured layer to cure it.
  • a shaping apparatus can be miniaturized as compared with the conventional method.
  • the manufacturing method for light curing molding using an ink-jet scheme has been paid attention as a shaping method which is realized by a 3D printer that can freely make a stereoscopically shaped product, based on CAD (Computer Aided Design) data.
  • the modeling material and a supporting material are formed in combination (JP-A-2004-255839, JP-A-2010-155889 and JP-A-2012-111226).
  • the supporting material is made by irradiating the photocurable resin composition with ultraviolet rays or the like to cure it, like the modeling material. After the modeling material has been made, the supporting material can be removed by physically peeling the supporting material, or dissolving the supporting material in an organic solvent or water.
  • the cured layer is formed, for example, by the following method.
  • a roller is used to remove the extra resin composition for a modeling material and resin composition for a supporting material.
  • the resin compositions are cured. Thereby, a cured layer composed of the modeling material and the supporting material is formed.
  • the conventional light cured article which is obtained by using the resin composition for a modeling material and the resin composition for a supporting material had a problem that the dimensional accuracy is reduced.
  • the present invention was made in view of the above-mentioned present situation, and an object thereof is to provide a resin composition for a modeling material by which a light cured article having the good dimensional accuracy can be obtained, a light curing molding ink set comprising the resin composition for a modeling material, and a method for manufacturing a light cured article using the light curing molding ink set.
  • the present inventors intensively studied the cause for reduction in the dimensional accuracy of the light cured article.
  • the present inventors obtained the finding that in the light cured article having the reduced dimensional accuracy, by movement of one of the resin composition for a modeling material and the resin composition for a supporting material to the other side at an interface between the layer composed of the resin composition for a modeling material and the layer composed of the resin composition for a supporting material, blur (bleeding) is generated at the interface. That is, the present inventors obtained the finding that bleeding which is generated at the interface between the layer composed of the resin composition for a modeling material and the layer composed of the resin composition for a supporting material is one of the causes for reduction in the dimensional accuracy of the light cured article.
  • the present invention was made based on the above-mentioned finding, and the gist thereof is as follows:
  • a resin composition for a modeling material used for shaping a modeling material by a manufacturing method for light curing molding using an inkjet scheme, comprising (A) an ethylenic unsaturated monomer as a photocuring component, (B) a photopolymerization initiator, and (C) a surface adjusting agent, wherein the resin composition for a modeling material has surface tension Mt of 26.0 to 33.0 mN/m, and the resin composition for a modeling material has surface tension Mst represented by the following (i) expression of 33.0 mN/m or more.
  • a resin composition for a modeling material by which a light cured article having the good dimensional accuracy can be obtained by suppressing generation of bleeding at an interface between a layer composed of a resin composition for a modeling material and a layer composed of a resin composition for a supporting material, a light curing molding ink set comprising the resin composition for a modeling material, and a method for manufacturing a light cured article using the light curing molding ink set.
  • FIG. 1 is a view schematically showing a step (I) in the method for manufacturing a light cured article of the present embodiment.
  • FIG. 2 is a view schematically showing a step (II) in the method for manufacturing a light cured article of the present embodiment.
  • FIG. 3 is a view schematically showing a cured product 6 composed of a modeling material 4 and a supporting material 5 , which was obtained by repeatedly performing steps (I) and (II) in the method for manufacturing a light cured article of the present embodiment.
  • FIG. 4 is a view schematically showing a step (III) in the method for manufacturing a light cured article of the present embodiment.
  • FIG. 5 ( a ) is a top view of a cured product which is obtained using each resin composition for a modeling material and each resin composition for a supporting material shown in Table 1.
  • FIG. 5 ( b ) is a line A-A cross-sectional view of FIG. 5 ( a ) .
  • (meth)acrylate is a generic name of acrylate and methacrylate, and means one or both of acrylate and methacrylate. This also applies to “(meth)acryloyl” and “(meth)acryl”.
  • the resin composition for a modeling material of the present embodiment is a resin composition for a modeling material, used for shaping a modeling material by a manufacturing method for light curing molding using an ink-jet scheme, comprising (A) an ethylenic unsaturated monomer as a photocuring component, (B) a photopolymerization initiator, and (C) a surface adjusting agent, wherein the resin composition for a modeling material has surface tension Mt of 26.0 to 33.0 mN/m, and the resin composition for a modeling material has surface tension Mst represented by the following (i) expression of 33.0 mN/m or more.
  • the (A) component comprises 70 parts by weight or less of a monofunctional ethylenic unsaturated monomer, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the content of the monofunctional ethylenic unsaturated monomer is 5 to 70 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the (A) component comprises 70 parts by weight or less of a polyfunctional ethylenic unsaturated monomer, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the content of the polyfunctional ethylenic unsaturated monomer is 20 to 70 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the content of the (A) component is 80 to 99 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the resin composition for a modeling material further contains an oligomer as (D) a photocuring component.
  • the content of the (D) component is 10 to 45 parts by weight, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the resin composition for a modeling material has the surface tension Mst of 33.0 to 40.0 mN/m.
  • the light curing molding ink set of the present embodiment is a light curing molding ink set used for a manufacturing method for light curing molding using an ink-jet scheme, comprising a combination of the resin composition for a modeling material as defined in any one of [ 1 ] to [ 9 ], and a resin composition for a supporting material used for shaping the supporting material, wherein the resin composition for a supporting material contains (E) a water-soluble monofunctional ethylenic unsaturated monomer, (F) polyalkylene glycol comprising an oxyethylene group and/or an oxypropylene group, (B) a photopolymerization initiator, and (C) a surface adjusting agent.
  • E a water-soluble monofunctional ethylenic unsaturated monomer
  • F polyalkylene glycol comprising an oxyethylene group and/or an oxypropylene group
  • B a photopolymerization initiator
  • C a surface adjusting agent
  • the content of the (E) component is 20 to 50 parts by weight, based on 100 parts by weight of the whole resin composition for a supporting material.
  • the content of the (F) component is 20 to 49 parts by weight, based on 100 parts by weight of the whole resin composition for a supporting material.
  • a number average molecular weight Mn of the (F) component is 100 to 5,000.
  • surface tension St of the resin composition for a supporting material is 24.0 to 33.0 mN/m.
  • the method for manufacturing a light cured article of the present embodiment is a method for manufacturing a light cured article using the light curing molding ink set as defined in any one of [10] to [14] by a manufacturing method for light curing molding using an ink-jet scheme, comprising a step (I) of discharging a resin composition for a modeling material and a resin composition for a supporting material from an ink-jet head, so that a resin composition layer in which a layer composed of the resin composition for a modeling material and a layer composed of the resin composition for a supporting material are arranged contiguously, a step (II) of photocuring the resin composition for a modeling material and the resin composition for a supporting material constituting the resin composition layer, respectively, thereby, obtaining a modeling material and a supporting material, and a step (III) of removing the supporting material, thereby, obtaining a light cured article.
  • the resin composition for a modeling material contains (A) an ethylenic unsaturated monomer as a photocuring component, (B) a photopolymerization initiator, and (C) a surface adjusting agent.
  • the (A) ethylenic unsaturated monomer is a photocuring component having property that it cures by energy rays.
  • the (A) component comprises at least one of a monofunctional ethylenic unsaturated monomer having one ethylenic double bond in a molecule, and a polyfunctional ethylenic unsaturated monomer having two or more ethylenic double bonds in a molecule.
  • the monofunctional ethylenic unsaturated monomer comprises at least one of a water-insoluble monofunctional ethylenic unsaturated monomer, and a water-soluble monofunctional ethylenic unsaturated monomer.
  • water-insoluble monofunctional ethylenic unsaturated monomer examples include, for example, linear or branched alkyl (meth)acrylates having 4 to 30 carbon atoms [e.g. methyl (meth)acrylate, ethyl (meth)acrylate, isobutyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, t-butyl (meth)acrylate etc.], alicycle-containing (meth)acrylates having 6 to 20 carbon atoms [e.g.
  • cyclohexyl (meth)acrylate 4-t-cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, 4-t-butylcyclohexanol (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, phenoxyethyl (meth)acrylate etc.], heterocycle-containing (meth)acrylates having 5 to 20 carbon atoms [e.g.
  • tetrahydrofurfuryl (meth)acrylate 4-(meth)acryloyloxymethyl-2-methyl-2-ethyl-1,3-dioxolane, 4-(meth)acryloyloxymethyl-2-cyclohexyl-1,3-dioxolane, adamantyl (meth)acrylate, cyclic trimethylolpropaneformal (meth)acrylate etc.] and the like. These may be used alone, or two or more may be used concurrently.
  • the water-insoluble monofunctional ethylenic unsaturated monomer is preferably 4-t-butylcyclohexanol (meth)acrylate, 3,3,5-trimethylcyclohexanol (meth)acrylate, or phenoxyethyl (meth)acrylate.
  • water-soluble monofunctional ethylenic unsaturated monomer examples include, for example, hydoxy group-containing (meth)acrylates having 5 to 15 carbon atoms [e.g. hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate etc.], hydroxy group-containing (meth)acrylates having Mn of 200 to 1,000 [polyethylene glycol mono(meth)acrylate, monoalkoxy (having 1 to 4 carbon atoms) polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, monoalkoxy (having 1 to 4 carbon atoms) polypropylene glycol mono(meth)acrylate, mono(meth)acrylate of PEG-PPG block polymer etc.], (meth)acrylamide derivatives having 3 to 15 carbon atoms [(meth)acrylamide, N-methyl(meth)acrylamide, N-ethyl(meth)
  • the water-soluble monofunctional ethylenic unsaturated monomer is preferably (meth)acryloylmorpholine.
  • the total content of the water-insoluble monofunctional ethylenic unsaturated monomer and the water-soluble monofunctional ethylenic unsaturated monomer is preferably 5 parts by weight or more, more preferably 30 parts by weight or more, and particularly preferably 50 parts by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the content of the monofunctional ethylenic unsaturated monomer is preferably 70 parts by weight or less, and more preferably 69 parts by weight or less, based on 100 parts by weight of the whole resin composition for a modeling material.
  • the content is a total of the contents of respective monofunctional ethylenic unsaturated monomers.
  • polyfunctional ethylenic unsaturated monomer examples include, for example, Tinier or branched alkylene glycol di(meth)acrylates or alkylene glycol tri(meth)acrylates having 10 to 25 carbon atoms [e.g., Tinier or branched alkylene glycol di(meth)acrylates or alkylene glycol tri(meth)acrylates having 10 to 25 carbon atoms [e.g., Tinier or branched alkylene glycol di(meth)acrylates or alkylene glycol tri(meth)acrylates having 10 to 25 carbon atoms [e.g.
  • the polyfunctional ethylenic unsaturated monomer is preferably diethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, or modified bisphenol A di(meth)acrylate.
  • the content of the polyfunctional ethylenic unsaturated monomer is preferably 70 parts by weight or less, and more preferably 60 parts by weight or less, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the polyfunctional ethylenic unsaturated monomer is preferably 20 parts by weight or more, and more preferably 30 parts by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. In addition, when two or more of the polyfunctional ethylenic unsaturated monomers are contained, the content is a total of the contents of respective polyfunctional ethylenic unsaturated monomers.
  • the content of the (A) component is preferably 80 parts by weight or more, and more preferably 90 parts by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the (A) component is preferably 99 parts by weight or less, and more preferably 95 parts by weight or less. In addition, when two or more of the (A) components are contained, the content is a total of the contents of respective (A) components.
  • the photopolymerization initiator (B) is not particularly limited, as far as it is a compound which promotes a radical reaction when light of a wavelength in an ultraviolet ray, near ultraviolet ray or visible light region is irradiated.
  • the (B) component include, for example, benzoin compounds having 14 to 18 carbon atoms [e.g. benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, benzoin isobutyl ether etc.], acetophenone compounds having 8 to 18 carbon atoms [e.g.
  • acetophenone 2,2-diethoxy-2-phenylacetophenone, 2,2-diethoxy-2-phenylacetophenone, 1,1-dichloroacetophenone, 2-hydroxy-2-methyl-phenylpropane-1-one, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one etc.], anthraquinone compounds having 14 to 19 carbon atoms [e.g.
  • acylphosphine oxide compounds having 22 to 28 carbon atoms e.g. 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide], a mixture of these compounds and the like. These may be used alone, or two or more may be used concurrently.
  • the (B) component is preferably 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide.
  • examples of an acylphosphine oxide compound which is available in the market include, for example, DAROCURE TPO manufactured by BASF company and the like.
  • the content of the (B) component is preferably 1 part by weight or more, and more preferably 3 parts by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the (B) component is preferably 15 parts by weight or less, and more preferably 13 parts by weight or less. In addition, when two or more of the (B) components are contained, the content is a total of the contents of respective (B) components.
  • the surface adjusting agent (C) is a component which adjusts the surface tension of the resin composition at an appropriate range.
  • the (C) component include, for example, a silicone-based compound and the like.
  • the silicone-based compound include, for example, a silicone-based compound having a polydimethylsiloxane structure, and the like. Specifically, examples thereof include polyether-modified polydimethylsiloxane, polyester-modified polydimethylsiloxane, polyaralkyl-modified polydimethylsiloxane and the like.
  • the content of the (C) component is preferably 0.005 part by weight or more, and more preferably 0.01 part by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the (C) component is preferably 3.0 parts by weight or less, and more preferably 1.5 parts by weight or less. In addition, when two or more of the (C) components are contained, the content is a total of the contents of respective (C) components.
  • the resin composition for a modeling material of the present embodiment further contains (D) an oligomer.
  • the (D) component is a photocuring component having property that it cures by energy rays.
  • Examples of the (D) component include, for example, a urethane (meth)acrylate oligomer, an epoxy (meth)acrylate oligomer, a polyester (meth)acrylate oligomer, a polyether (meth)acrylate oligomer and the like. These may be used alone, or two or more may be used concurrently. Among them, from a view point that curability of the resin composition for a modeling material is improved, the (D) component is preferably a urethane (meth)acrylate oligomer.
  • the content of the (D) component is preferably 10 parts by weight or more, and more preferably 15 parts by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the (D) component is preferably 45 parts by weight or less, and more preferably 40 parts by weight or less. In addition, when two or more of the (D) components are contained, the content is a total of the contents of respective (D) components.
  • oligomer refers to one having a weight average molecular weight of 800 to 10,000.
  • a weight average molecular weight means a weight average molecular weight in terms of polystyrene, which is measured by GPC (Gel Permeation Chromatography).
  • the resin composition for a modeling material can contain, as necessary, other additives in such a range that the effect of the present invention is not impaired.
  • other additives include, for example, an antioxidant, a coloring agent, a pigment dispersant, a preservation stabilizer, an ultraviolet absorbing agent, a light stabilizer, a polymerization inhibitor, a chain transfer agent, a filler and the like.
  • the previously known coloring agents such as a diarylide-based coloring agent, a condensed azo-based coloring agent, a quinacridone-based coloring agent, a vat-based coloring agent, an isoindolinone-based coloring agent, a phthalocyanine-based coloring agent, an aniline-based coloring agent, titanium oxide, nickel titanium, yellow iron oxide, red iron oxide, ultramarine, cobalt blue, chromium oxide, iron black, chrome yellow, chrome orange, molybdenum red, a cadmium-based coloring agent, carbon black and the like can be used. These may be used alone, or two or more may be used concurrently.
  • the coloring agent is preferably, for example, carbon black, Nickel Azo which is a condensed azo-based coloring agent, Quinacridone which is a quinacridone-based coloring agent, copper phthalocyanine which is a phthalocyanine-based coloring agent, titanium oxide or the like.
  • the content of the coloring agent is preferably 0.01 part by weight or more, and more preferably 0.1 part by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the coloring agent is preferably 5.0 parts by weight or less, and more preferably 3.0 parts by weight or less.
  • the pigment dispersant may be contained in order to improve dispersibility of the pigment.
  • the pigment dispersant include, for example, an ionic or nonionic surfactant, an anionic, cationic or nonionic polymer compound and the like. These may be used alone, or two more may be used concurrently.
  • the pigment dispersant is preferably a polymer compound comprising a cationic group or an anionic group.
  • the pigment dispersant which is available in the market include Solsperse manufactured by Avecia company, DISPERBYK manufactured by BYK-Chemie company, EFKA manufactured by EFKA ADDITIVES B.V., and the like.
  • the content of the pigment dispersant is preferably 0.05 part by weight or more, based on 100 parts by weight of the whole resin composition for a modeling material. Additionally, the content of the pigment dispersant is preferably 5 parts by weight or less.
  • the preservation stabilizer may be contained in order to enhance preservation stability of the resin composition.
  • the preservation stabilizer include, for example, a hindered amine-based compound (HALS), a phenol-based antioxidant, a phosphorus-based antioxidant and the like.
  • HALS hindered amine-based compound
  • examples of the preservation stabilizer include specifically hydroquinone, methoquinone, benzoquinone, p-methoxyphenol, hydroquinone monomethyl ether, hydroquinone monobutyl ether, TEMPO, 4-hydroxy-TEMPO, TEMPOL, Cupherron AI, IRGASTAB UV-10, IRGASTAB UV-22, FIRSTCURE ST-1 (manufactured by ALBEMARLE company), t-butylcatechol, pyrogallol, TINUVIN 111 FDL, TINUVIN 144, TINUVIN 292, TINUVIN XP40, TINUVIN XP60, TINUVIN 400 manufactured by BASF company, and the like
  • the resin composition for a modeling material can be manufactured, for example, by uniformly mixing the (A) to (C) components, and as necessary (D) oligomer and other additives using a mixing and stirring device or the like, without particular limitation.
  • the thus manufactured resin composition for a modeling material has preferably the viscosity at 25° C. of 70 mPa ⁇ s or less, from a view point that dischargeability from an ink-jet head is improved.
  • measurement of the viscosity of the resin composition for a modeling material is performed using a R100-type viscometer in accordance with JIS Z 8803.
  • the resin composition for a modeling material has the surface tension Mt of 26.0 to 33.0 mN/m, from a view point that dischargeability from an ink-jet head is improved.
  • the surface tension refers to a value of the surface tension after 20 seconds from measurement initiation at 25° C. Measurement of the surface tension is performed, for example, using Full Automatic Equilibrium Electro Surface Tension Meter ESB-V (manufactured by Kyowa Interface Science Co., Ltd.).
  • the resin composition for a modeling material has surface tension (also referred to as equivalence surface tension) Mst represented by the (i) expression, of 33.0 mN/m or more.
  • surface tension Mst also referred to as equivalence surface tension
  • generation of bleeding at an interface between the layer composed of the resin composition for a modeling material and the layer composed of the resin composition for a supporting material can be suppressed. That is, by movement of the resin composition for a modeling material to a side of the resin composition for a supporting material, or by movement of the resin composition for a supporting material to a side of the resin composition for a modeling material, phenomenon of generation of blur becomes difficult to be generated.
  • a light cured article having the good dimensional accuracy can be obtained using a light curing molding ink set comprising a combination of such resin composition for a modeling material and resin composition for a supporting material.
  • the surface tension Mst is preferably 40.0 mN/m or less, and more preferably 39.0 mN/m or less.
  • the photocuring component in the expression is a component having property that it cures by energy rays.
  • the (A) ethylenic unsaturated monomer, and the (D) oligomer which is an optional component are the photocuring component.
  • the resin composition for a modeling material of the present embodiment may comprise other photocuring components.
  • the resin composition for a supporting material contains a water-soluble monofunctional ethylenic unsaturated monomer (E), polyalkylene glycol comprising an oxyethylene group and/or an oxypropylene group (F), a photopolymerization initiator (B), and a surface adjusting agent (C).
  • E water-soluble monofunctional ethylenic unsaturated monomer
  • F polyalkylene glycol comprising an oxyethylene group and/or an oxypropylene group
  • B photopolymerization initiator
  • C surface adjusting agent
  • the same components as those of the resin composition for a modeling material can be used.
  • the content of the (E) component is preferably 20 parts by weight or more, and more preferably 25 parts by weight or more, based on 100 parts by weight of the whole resin composition for a supporting material. Additionally, the content of the (E) component is preferably 50 parts by weight or less, and more preferably 45 parts by weight or less. In addition, when two or more of the (E) components are contained, the content is a total of the contents of respective (E) components.
  • the polyalkylene glycol comprising an oxyethylene group and/or an oxypropylene group (F) is such that at least ethylene oxide and/or propylene oxide are (is) added to an active hydrogen compound.
  • the (F) component include, for example, polyethylene glycol, polypropylene glycol and the like. These may be used alone, or two or more may be used concurrently.
  • the active hydrogen compound include monohydric to tetrahydric alcohols, amine compounds and the like. Among them, the active hydrogen compound is preferably a dihydric alcohol or water.
  • the content of the (F) component is preferably 20 parts by weight or more, and more preferably 25 parts by weight or more, based on 100 parts by weight of the whole resin composition for a supporting material. Additionally, the content of the (F) component is preferably 49 parts by weight or less, and more preferably 45 parts by weight or less. In addition, when two or more of the (F) components are contained, the content is a total of the contents of respective (F) components.
  • a number average molecular weight Mn of the (F) component is preferably 100 to 5,000.
  • Mn of the (F) component is in the range, the resin composition is compatible with the (F) component before photocuring, and is not compatible with the (F) component after photocuring.
  • Mn of the (F) component is more preferably 200 to 3,000, and further preferably 400 to 2,000.
  • the same components as those of the resin composition for a modeling material can be used at the same contents.
  • the resin composition for a supporting material can contain other additives, as necessary, in such a range that the effect of the present invention is not impaired.
  • other additives include, for example, a water-soluble organic solvent, an antioxidant, a coloring agent, a pigment dispersant, a preservation stabilizer, an ultraviolet absorbing agent, a light stabilizer, a polymerization inhibitor, a chain transfer agent, a filler and the like.
  • water-soluble organic solvent examples include, for example, ethylene glycol monoacetate, propylene glycol monoacetate, diethylene glycol monoacetate, dipropylene glycol monoacetate, triethylene glycol monoacetate, tripropylene glycol monoacetate, tetraethylene glycol monoacetate, tetrapropylene glycol monoacetate, ethylene glycol monomethyl ether, propylene glycol monomethyl ether, diethylene glycol monomethyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether, tetraethylene glycol monomethyl ether, tetrapropylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monoethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monoethyl ether, tripropylene glycol monoethyl ether, tetra
  • the water-soluble organic solvent is more preferably triethylene glycol monomethyl ether, or dipropylene glycol monomethyl ether acetate.
  • the content of the water-soluble organic solvent is preferably 5 parts by weight or more, and more preferably 10 parts by weight or more, based on 100 parts by weight of the whole resin composition for a supporting material. Additionally, the content of the water-soluble organic solvent is preferably 35 parts by weight or less, and more preferably 30 parts by weight or less. In addition, when two or more of the water-soluble organic solvents are contained, the content is a total of the contents of respective water-soluble organic solvents.
  • the same components as those of the resin-composition for a modeling material can be used at the same contents.
  • a method for manufacturing the resin composition for a supporting material is not particularly limited.
  • the resin composition for a supporting material can be manufactured, for example, by uniformly mixing the (B), (C), (E), and (F) components, and as necessary, other additives using a mixing and stirring device or the like.
  • the thus manufactured resin composition for a supporting material has preferably the viscosity at 25° C. of 70 mPa ⁇ s or less.
  • measurement of the viscosity of the resin composition for a supporting material is performed using a R100-type viscometer in accordance with JIS Z 8803.
  • the resin composition for a supporting material has preferably the surface tension of 24.0 to 33.0 mN/m.
  • the surface tension refers to a value of the surface tension after 20 seconds from measurement initiation at 25° C. Measurement of the surface tension is performed, for example, using Full Automatic Equilibrium Electro Surface Tension Meter ESB-V (manufactured by Kyowa Interface Science Co., Ltd.).
  • the light cured article is manufactured using the resin composition for a modeling material and the light curing molding ink set comprising the resin composition for a modeling material, of the present embodiment by a manufacturing method for light curing molding using an ink-jet scheme.
  • the light cured article is manufactured by passing through a step (I) of discharging a resin composition for a modeling material and a resin composition for a supporting material from an ink-jet head so that a resin composition layer in which a layer composed of the resin composition for a modeling material and a layer composed of the resin composition for a supporting material are arranged contiguously is formed, a step (II) of photocuring the resin composition for a modeling material and the resin composition for a supporting material constituting the resin composition layer, respectively, thereby, obtaining a modeling material and a supporting material, and a step (III) of removing the supporting material, thereby, obtaining a light cured article.
  • the steps (I) to (III) are not particularly limited, but are performed, for example, by
  • FIG. 1 is a view schematically showing a step (I) in the method for manufacturing a light cured article of the present embodiment.
  • a three-dimensional shaping apparatus 1 comprises an ink-jet head module 2 and a shaping table 3 .
  • the ink-jet head module 2 has a light curing molding ink unit 25 , a roller 23 , and a light source 24 .
  • the light curing molding ink unit 25 has an ink-jet head 21 for a modeling material, which is filled with a resin composition 4 a for a modeling material, and an ink-jet head 22 for a supporting material, which is filled with a resin composition 5 a for, a supporting material.
  • the light curing molding ink set 20 of the present embodiment is constructed of a combination of the resin composition 4 a for a modeling material and the resin composition 5 a for a supporting material.
  • the ink-jet head module 2 is made to perform scanning in an X direction and a Y direction, and at the same time, discharge the resin composition 4 a for a modeling material from the ink-jet head 21 for a modeling material, and discharge the resin composition 5 a for a supporting material from the ink-jet head 22 for a supporting material, relatively to the shaping table 3 in FIG. 1 .
  • a resin composition layer in which interfaces between a layer composed of the resin composition 4 a for a modeling material and a layer composed of the resin composition 5 a for a supporting material are arranged contiguously so as to come into contact with each other is formed on the shaping table 3 .
  • the extra resin composition 4 a for a modeling material and resin composition 5 a for a supporting material are removed using the roller 23 .
  • FIG. 2 is a view schematically showing a step (II) in the method for manufacturing a light cured article of the present embodiment.
  • a step (II) in the method for manufacturing a light cured article of the present embodiment.
  • a cured layer composed of a modeling material 4 and a supporting material 5 is formed.
  • FIG. 3 is a view schematically showing a cured product 6 composed of a modeling material 4 and a supporting material 5 , which has been obtained by repeatedly performing steps (I) and (II) in the method for manufacturing a light cured article of the present embodiment.
  • Examples of light which cures the resin composition include, for example, far infrared rays, infrared rays, visible rays, near ultraviolet rays, ultraviolet rays and the like. Among them, from a view point of easiness and the efficiency of curing work, near ultraviolet rays or ultraviolet rays are preferable.
  • the light source 24 examples include a mercury lamp, a metal halide lamp, an ultraviolet. LED, an ultraviolet laser and the like. Among them, from a view point of miniaturization of facilities and electric power saving, the light source 24 is preferably an ultraviolet LED. In addition, when the ultraviolet LED is used as the light source 24 , the integrated light quantity of ultraviolet rays is preferably around 500 mJ/cm 2 .
  • FIG. 4 is a view schematically showing a step (III) in the method for manufacturing a light cured article of the present embodiment.
  • the cured product 6 composed of the modeling material 4 and the supporting material 5 , which has been made in a step (III), is immersed in a solvent 8 contained in a container 7 .
  • the supporting material 5 can be removed by dissolving it in the solvent 8 .
  • the solvent 8 which dissolves the supporting material 5 examples include, for example, ion-exchanged water, distilled water, tap water, well water and the like. Among them, from a view point of relatively few impurities and availability at a low price, the solvent 8 is preferably ion-exchanged water.
  • a light cured article having the good dimensional accuracy can be obtained using the resin composition for a modeling material and the light curing molding ink set of the present embodiment.
  • each resin composition for a modeling material and each resin composition for a supporting material of test Nos. A1 to A4 shown in Table 1 a cured product was made. A shape and a target dimension of the cured product are shown in FIGS. 5 ( a ) and ( b ) .
  • a step of discharging each resin composition for a modeling material and each resin composition for a supporting material from an ink-jet head was performed so that the resolution became 600 ⁇ 600 dpi, and a thickness of one resin composition layer became 48 ⁇ m.
  • each resin composition for a modeling material and each resin composition for a supporting material, respectively was performed using a LED light source of a wavelength 385 nm, which had been installed on a rear side of an ink-jet head in a scanning direction, under the conditions of the illuminance of 580 mW/cm 2 , and the integrated light quantity per one resin composition layer of 600 mJ/cm 2 . Then, by immersing the cured product in ion-exchanged water, the supporting material was removed to obtain a light cured article. Thereafter, the resulting light cured article was allowed to stand in a desiccator for 24 hours, and was sufficiently dried.
  • each five of light cured articles of test Nos. A1 to A4 were manufactured.
  • Concerning the light cured articles after drying dimensions in an x direction and a y direction in FIG. 5 ( a ) were measured using a slide caliper, and a change rate from the target dimension was calculated.
  • For the dimensional accuracy an average of a dimensional change rate in respective light cured articles of test Nos. A1 to A4 was obtained, and assessment was performed using the average based on the following criteria. The assessment results are shown in Table 1.
  • An average dimensional change rate is less than ⁇ 1.0%.
  • An average dimensional change rate is ⁇ 1.0% or more.
  • each 0.02 mL of each resin composition for a modeling material and each resin composition for a supporting material shown in Table 1 were added dropwise on a film composed of polyethylene terephthalate (A4300, manufactured by TOYOBO CO., LTD., 100 mm ⁇ 150 mm ⁇ thickness 188 ⁇ m) using a micropipette.
  • a distance between central parts of respective liquid droplets was 10 mm, and respective liquid droplets were independent.
  • respective liquid droplets were gradually wettedly spread, and respective liquid droplets were unified after about 10 seconds.
  • the state of an interface of respective liquid droplets was observed visually from an upper side, and bleeding was assessed based on the following criteria.
  • the assessment results are shown in Table 1.
  • bleeding which is generated at an interface between the layer composed of the resin composition for a modeling material and the layer composed of the resin composition for a supporting material is one of the causes for reduction in the dimensional accuracy of the light cured article. Then, bleeding which is generated at an interface between the layer composed of the resin composition for a modeling material and the layer composed of the resin composition for a supporting material was assessed below.
  • TMCHA 3,3,5-Trimethylcyclohexanol acrylate [SR420 (ethylenic double bond/one molecule: one), manufactured by Arkema S.A.]
  • ACMO Acryloylmorpholine
  • PEA Phenoxyethyl acrylate [SR339 (ethylenic double bond/one molecule: one), manufactured by Arkema S.A.]
  • DEGDA Diethylene glycol diacrylate [SR230 (ethylenic double bond/one molecule: 2), manufactured by Arkema S.A.]
  • A-NPA Alkoxylated neopentyl glycol diacrylate [SR9003 (ethylenic double bond/one molecule: 2), manufactured by Arkema S.A.]
  • Ebe150 Modified bisphenol A diacrylate [Ebacryl150 (ethylenic double bond/one molecule: 2), manufactured by DAICEL-ALLNEX LTD.]
  • DAROCURE TPO 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide
  • IRGACURE907 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one [IRGACURE 907, manufactured by Ciba company]
  • CN996 Urethane acrylate oligomer [CN996 (ethylenic double bond/one molecule: 2), manufactured by Arkema S.A.]
  • MA-8 Acidic carbon black pigment [MA-8, manufactured by Mitsubishi Chemical Corporation]
  • RT355D Quinacridone pigment [CINQUASIA Magenda RT-355-D, manufactured by Ciba company]
  • BT-617-D Copper phthalocyanine pigment [HOSTAPERM BLUE BT-617-D, manufactured by Clariant company]
  • CR-60 Titanium oxide [CR-60, manufactured by ISHIHARA SANGYO KAISHA, LTD.]
  • ACMO Acryloylmorpholine
  • PPG-1000 Polypropylene glycol [UNIOL D1000 (molecular weight 1000), manufactured by NOF CORPORATION]
  • DAROCURE TPO 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [DEROCURE TPO, manufactured by BASF company]
  • IRGACURE907 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopro pane-1-one [IRGACURE 907, manufactured by Ciba company]
  • Chivacure ITX Isopropylthioxanthone [Chivacure ITX, manufactured by Double Bond Chemical Ind., Co., Ltd.]
  • BYK-307 Silicone-based compound having a polydimethylcyclohexane structure [BYK-307, manufactured by BYK-Chemie company]
  • MTG Triethylene glycol monomethyl ether [MPG, manufactured by NIPPON NYUKAZAI CO., LTD.]
  • each resin composition for a modeling material of M1 to M23 and each photocuring component contained in the resin composition for a modeling material shown in Table 2 as well as each resin composition for a supporting material of S1 to S6 and each photocuring component contained in the resin composition for a supporting material shown in Table 3, a value after 20 seconds from measurement initiation, at 25° C. was measured using Full Automatic Equilibrium Electro Surface Tension Meter ESB-V (manufactured by Kyowa Interface Science Co., Ltd.). The measurement results are shown in Table 2 and Table 3.
  • Discharge stability of each composition for a modeling material of M1 to M23 shown in Table 2 and each resin composition for a supporting material of S1 to S6 shown in Table 3 was assessed by calculating the ratio of generation of nozzle slip-out, and the ligament length.
  • nozzle slip-out refers to the state where an ink is not discharged due to clogging of a nozzle.
  • Discharge was performed under the conditions of a nozzle diameter: 20 ⁇ m, a flying speed: 7 m/sec. and a discharge frequency: 1 kHz, the time from passing of the head of liquid droplets until passing of the tail end of liquid droplets was measured at a position of 1 mm distance from the nozzle, and thereafter, the ligament length was calculated by integrating the time and the flying speed. And, the ligament length was assessed based on the following criteria. The assessment results are shown in Table 2 and Table 3. In addition, the ligament length refers to the length of a liquid droplet which is discharged from a nozzle. When the ligament length is great, ink mist becomes easy to be generated.
  • the resin composition in which assessment of the ratio of generation of nozzle slip-out was “O”, and assessment of the ligament length was “O” was determined to be excellent in discharge stability. Additionally, the resin composition having another assessment was determined to be inferior in discharge stability.
  • resin compositions for a modeling material of M3 to M7, and M11 to M21 in which the surface tension Mt is 26.0 to 33.0 mN/m are excellent in discharge stability. Additionally, as seen from Table 3, resin compositions for a supporting material of S3 to S5 in which the surface tension St is 24.0 to 33.0 mN/m are excellent in discharge stability.
  • the surface tension Mt of which does not satisfy the requirement of the present invention at an interface between the layer composed of the resin composition for a modeling material and the layer composed of the resin composition for a supporting material, slight blur was generated.
  • the method for manufacturing a light cured article of the above-mentioned embodiment may further comprise a step of discharging only a resin composition for a modeling material from an ink-jet head so that only a layer composed of the resin composition for a modeling material is formed, thereafter, photocuring the resin composition for a modeling material constituting the layer, thereby, obtaining a modeling material and/or a step of discharging only a resin composition for a supporting material from an ink-jet head so that only a layer composed of the resin composition for a supporting material is formed, thereafter, photocuring the resin composition for a supporting material constituting the layer, thereby, obtaining a supporting material.
  • the resin composition for a modeling material, and the light curing molding ink set comprising the resin composition for a modeling material of the present invention can afford a light cured article having the good dimensional accuracy.
  • the resin composition for a modeling material and the light curing molding ink set of the present invention can be suitably used in manufacturing a light cured article by a manufacturing method for light curing molding using an ink-jet scheme.

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US11306170B2 (en) 2016-12-15 2022-04-19 Clariant International Ltd. Water-soluble and/or water-swellable hybrid polymer
US11311473B2 (en) 2016-12-12 2022-04-26 Clariant International Ltd Use of a bio-based polymer in a cosmetic, dermatological or pharmaceutical composition
US11339241B2 (en) 2016-12-15 2022-05-24 Clariant International Ltd. Water-soluble and/or water-swellable hybrid polymer
US11384186B2 (en) 2016-12-12 2022-07-12 Clariant International Ltd Polymer comprising certain level of bio-based carbon
US11401362B2 (en) 2016-12-15 2022-08-02 Clariant International Ltd Water-soluble and/or water-swellable hybrid polymer
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