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WO2013151157A1 - Composition de résine pour moulage tridimensionnel optique comprenant des microcapsules thermiquement extensibles - Google Patents

Composition de résine pour moulage tridimensionnel optique comprenant des microcapsules thermiquement extensibles Download PDF

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Publication number
WO2013151157A1
WO2013151157A1 PCT/JP2013/060478 JP2013060478W WO2013151157A1 WO 2013151157 A1 WO2013151157 A1 WO 2013151157A1 JP 2013060478 W JP2013060478 W JP 2013060478W WO 2013151157 A1 WO2013151157 A1 WO 2013151157A1
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Prior art keywords
optical
resin composition
dimensional modeling
dimensional
compound
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PCT/JP2013/060478
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English (en)
Japanese (ja)
Inventor
勇哉 大長
信夫 大金
好一 大場
秀明 中西
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CMET Inc
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CMET Inc
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Priority to JP2014509221A priority Critical patent/JP6033850B2/ja
Publication of WO2013151157A1 publication Critical patent/WO2013151157A1/fr
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    • 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
    • B29C33/00—Moulds or cores; Details thereof or accessories therefor
    • B29C33/44—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles
    • B29C33/48—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles with means for collapsing or disassembling
    • B29C33/485—Moulds or cores; Details thereof or accessories therefor with means for, or specially constructed to facilitate, the removal of articles, e.g. of undercut articles with means for collapsing or disassembling cores or mandrels
    • 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
    • B29C64/129—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 characterised by the energy source therefor, e.g. by global irradiation combined with a mask
    • B29C64/135—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 characterised by the energy source therefor, e.g. by global irradiation combined with a mask the energy source being concentrated, e.g. scanning lasers or focused light sources
    • 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
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/22—Expandable microspheres, e.g. Expancel®
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2207/00—Foams characterised by their intended use
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2335/00—Characterised by the use of homopolymers or 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, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Derivatives of such polymers
    • C08J2335/02—Characterised by the use of homopolymers or copolymers of esters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2471/00—Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2471/02—Polyalkylene oxides

Definitions

  • the present invention relates to a resin composition for optical three-dimensional modeling containing thermally expandable microcapsules.
  • Patent Document 1 describes the production of a resin mold using a disappearing core.
  • the foamed polystyrene fine particles are mixed with the two-component reaction-curable soft urethane resin liquid, and the obtained mixture is cast into a mold for forming a core having a recess to be cured to obtain a urethane resin. Thereafter, the cured urethane resin is removed from the mold for forming the core, thereby producing the disappearing core.
  • the disappearing core is placed in a mold for resin mold production, and a two-component reaction rapid-curing urethane resin liquid is poured into the mold and cured, and then the cured urethane resin is used for resin mold production.
  • a resin mold is manufactured by removing the mold from the mold.
  • the disappearing core is removed by injecting an expanded polystyrene-soluble organic solvent into the disappearing core in the resin mold to dissolve the expanded polystyrene fine particles.
  • a resin mold is manufactured.
  • the disappearing core is manufactured by casting, even if the expanded polystyrene fine particles are used, it is not possible to manufacture the disappearing core having an extremely complicated shape, structure, or extremely small size. Have difficulty.
  • Patent Document 2 a thin-walled hollow body having a shape corresponding to the shape of the disappearance model is produced using an optical modeling technique, and an unfoamed foam material is put into the thin-walled hollow body and foamed. Describes filling the inside of a thin-walled hollow body with a foaming material, and removing the photocurable resin in a photocured state after the foaming material is cured to produce a disappeared model.
  • Patent Document 3 a hollow core manufactured by stereolithography is placed in an outer mold, and a liquid soft resin material is injected into a gap between the core and the outer mold to be solidified to form a soft resin molded body.
  • the core is deformed and made smaller by deforming the soft resin molded body by applying a force from the outside of the soft resin molded body and / or Alternatively, it has been proposed to produce a soft resin molded body by discharging a crushed and deformed core or a crushed core from the opening of the soft resin molded body to the outside.
  • the core is manufactured by stereolithography, it is possible to manufacture a core having a complicated shape, and when the core is taken out, the soft resin molded body obtained by molding is externally provided. Since the core contained in the resin molded body is reduced or crushed by applying force from the opening of the flexible resin molded body, it is not necessary to dissolve and disappear the core using an organic solvent. The removal of the core is easy.
  • the wall thickness of the hollow core is too thick, the core is less likely to be small when pressed from the outside of the soft resin molded body, and the core is less likely to be crushed. Since it becomes difficult to discharge the core from the body, it is necessary to reduce the wall thickness of the hollow core. When the wall thickness of the hollow core is reduced, when the core is placed in the outer mold and the soft resin material is injected, the core may be deformed or in some cases the core may be damaged. It becomes difficult to obtain a soft resin molded body having a shape and dimensions.
  • the object of the present invention is to satisfactorily manufacture even a core having a complicated shape or structure or other three-dimensional modeled object.
  • the three-dimensional modeled object can be used as a core or used for other purposes.
  • a resin material that can produce a three-dimensional model that is excellent in strength, shape retention and handling properties, is not damaged or deformed, and can be easily removed after use. That is.
  • a thermally expandable microcapsule is included in a resin composition for optical three-dimensional modeling. Accordingly, a resin composition for optical three-dimensional modeling containing a photopolymerizable compound, a photopolymerization initiator, and a heat-expandable microcapsule is manufactured, and the resin composition for optical three-dimensional modeling is used to produce a thermally expandable microcapsule.
  • a three-dimensional object was manufactured by performing optical three-dimensional modeling under conditions where expansion did not occur.
  • the three-dimensional object obtained by this method was excellent in strength, shape retention, and handleability even if it contained a heat-expandable microcapsule, but the heat-expandable microcapsule contained in the optical three-dimensional object When heated to a temperature at which the three-dimensional model is expanded, even if the entire three-dimensional model is foamed and collapses or does not collapse, the strength of the three-dimensional model is greatly reduced and easily collapses.
  • the present invention has been completed by finding that the product is extremely effective as a master model for producing a molded body or mold by a core or casting.
  • the present invention (1) A resin composition for optical three-dimensional modeling containing a photopolymerizable compound, a photopolymerization initiator, and a thermally expandable microcapsule.
  • the present invention also provides: (2) The resin composition for optical three-dimensional modeling according to (1), wherein the thermally expandable microcapsules do not expand during optical three-dimensional modeling; and (3) The resin composition for optical three-dimensional modeling of the above (1) or (2), which is for producing a three-dimensional modeled product containing the thermally expandable microcapsules in an unexpanded state; It is.
  • the thermally expandable microcapsule includes an outer shell made of a thermoplastic polymer and a volatile liquid expander encapsulated in the outer shell, and has an average particle diameter of 1 to 100 ⁇ m ( A resin composition for optical three-dimensional modeling according to any one of 1) to (3); and (5) The above (1) to (4), wherein the content of the thermally expandable microcapsule is 20 to 80 parts by mass with respect to 100 parts by mass of the total photopolymerizable compound contained in the resin composition for optical three-dimensional modeling. ) Any one of the resin compositions for optical three-dimensional modeling; It is. That is, the optical three-dimensional modeling resin composition includes 100 parts by mass of a photopolymerizable compound and 20 to 80 parts by mass of thermally expandable microcapsules.
  • the present invention provides (6) For optical three-dimensional modeling according to any one of the above (1) to (5), wherein the photopolymerizable compound is selected from one or more radically polymerizable compounds, one or more cationically polymerizable compounds, or both Resin composition; (7) The resin composition for optical three-dimensional modeling according to any one of (1) to (6), wherein the photopolymerizable compound is a radical polymerizable compound and the photopolymerization initiator is a photoradical polymerization initiator; (8) The resin composition for optical three-dimensional modeling according to (6) or (7), wherein the radical polymerizable compound is a di (meth) acrylate compound having two (meth) acryloyloxy groups; (9) For optical three-dimensional modeling of (8), wherein the di (meth) acrylate compound having two (meth) acryloyloxy groups is a di (meth) acrylate of a substituted or unsubstituted bisphenol.
  • Resin composition (10) The resin composition for optical three-dimensional modeling according to any one of (7) to (9), wherein the radical photopolymerization initiator is benzyl or a dialkyl acetal compound thereof; (11) The resin composition for optical three-dimensional modeling according to any one of (1) to (10), further containing a polyalkylene ether compound; It is.
  • optical three-dimensional modeling is performed under conditions where expansion of the heat-expandable microcapsule does not occur.
  • An optical three-dimensional model including the unexpanded state can be manufactured.
  • An optical three-dimensional modeled article containing thermally expandable microcapsules in an unexpanded state obtained by optical three-dimensional modeling using the resin composition for optical three-dimensional model modeling according to any one of (1) to (11) Is used as a core or the like, and the core or the like is heated to a temperature higher than the expansion start temperature of the thermally expandable microcapsule, whereby a hollow molded body or a mold can be produced.
  • optical three-dimensional modeling is performed using the resin composition for optical three-dimensional modeling of the present invention to produce a hollow molded body, and the hollow molded body is used as a master model, and an organic weight is formed inside the master model.
  • a hollow molded body (master model) formed from a resin composition for optical three-dimensional modeling on the outside after injecting or filling a solid body (for example, silicone rubber, silicone resin, other polymer) or other material to solidify.
  • a mold made of an organic polymer and other materials and a molded body that can be used for other applications can be produced.
  • a three-dimensional modeled object or a minute three-dimensional modeled object having a complicated shape or structure containing a thermally expandable microcapsule is also obtained. It can be manufactured easily and smoothly.
  • the three-dimensional model obtained by performing the optical three-dimensional model using the optical three-dimensional model resin composition of the present invention is included in the three-dimensional model by heating above the expansion start temperature of the thermally expandable microcapsule.
  • the thermally expandable microcapsule expands, the entire three-dimensional structure foams and collapses or easily collapses, so various hollow molded bodies, cores for producing hollow products, It can be effectively used as a core for producing a mold used for producing various molded articles (various products).
  • three-dimensional model foams and collapses in this specification means that the three-dimensional model foams and directly becomes a strip-like foam, or the three-dimensional model foams with a small external force. It means that it becomes a foam having no shape retaining property that easily collapses into a strip shape, or a foam that has no shape retaining property and can easily reduce its volume with a small external force.
  • FIG. 1 shows the production of a hollow molded body using a core (three-dimensional model) obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention containing thermally expandable microcapsules. It is the figure which showed an example of the case.
  • FIG. 2 is a drawing-substituting photograph showing a foamed state when the optical three-dimensional structure (bar-shaped test piece) obtained in Example 1 is heated at 150 ° C. for 10 minutes.
  • FIG. 3 is a drawing-substituting photograph showing a foamed state when the optical three-dimensional object (bar-shaped test piece) obtained in Example 2 is heated at 150 ° C. for 10 minutes.
  • FIG. 4 is a drawing-substituting photograph showing a state when the optical three-dimensional structure (bar-shaped test piece) obtained in Reference Example 1 is heated at 150 ° C. for 10 minutes.
  • molding of this invention contains a photopolymerizable compound, a photoinitiator, and a thermally expansible microcapsule.
  • photopolymerizable compound As a photopolymerizable compound, a three-dimensional model that foams when a three-dimensional model obtained by optical three-dimensional modeling (hereinafter sometimes referred to as “photo-modeling”) is heated to the expansion temperature of a thermally expandable microcapsule is manufactured.
  • photopolymerizable compound that can be used, one or more radically polymerizable compounds, one or more cationically polymerizable compounds, or both conventionally used in resin compositions for optical three-dimensional modeling are used. be able to.
  • radical polymerizable organic compound examples include a compound having a (meth) acrylate group, an unsaturated polyester compound, an allylurethane compound, and a polythiol compound.
  • a compound having at least one (meth) acryloyloxy group in one molecule is preferably used.
  • Specific examples of the compound having a (meth) acryloyloxy group include a reaction product of an epoxy compound and (meth) acrylic acid, a (meth) acrylic acid ester of an alcohol, a urethane (meth) acrylate, and a polyester (meth) acrylate. And polyether (meth) acrylate.
  • reaction product of the above-mentioned epoxy compound and (meth) acrylic acid it can be obtained by reaction of an aromatic epoxy compound, an alicyclic epoxy compound and / or an aliphatic epoxy compound with (meth) acrylic acid (meta) ) Acrylate reaction products.
  • this (meth) acrylate reaction product examples include bisphenol compounds such as bisphenol A and bisphenol S, substituted bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring has a substituent such as an alkoxy group, and their (Meth) acrylate, epoxy novolac resin obtained by further reacting glycidyl ether obtained by reacting an alkylene oxide adduct of a bisphenol compound or a substituted bisphenol compound with an epoxidizing agent such as epichlorohydrin, and (meth) acrylic acid And (meth) acrylate reaction products obtained by reacting (meth) acrylic acid.
  • bisphenol compounds such as bisphenol A and bisphenol S
  • substituted bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring has a substituent such as an alkoxy group
  • their (Meth) acrylate epoxy novolac resin obtained by further reacting glycidyl ether obtained by reacting an alkylene oxide adduct of
  • aromatic alcohols, aliphatic alcohols, alicyclic alcohols and / or their alkylene oxide adducts having at least one hydroxyl group in the molecule are: Mention may be made of (meth) acrylates obtained by reacting with (meth) acrylic acid.
  • bisphenol compounds such as bisphenol A and bisphenol S
  • di (meth) acrylates of substituted bisphenol compounds such as bisphenol A and bisphenol S in which the benzene ring has a substituent such as an alkoxy group, 2-ethylhexyl ( (Meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isooctyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl ( (Meth) acrylate, benzyl (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol (Meth) acrylate, triethylene glycol di (meth) acrylate,
  • (meth) acrylate of alcohols (meth) acrylate having two (meth) acryl groups in one molecule obtained by reacting a dihydric alcohol with (meth) acrylic acid is preferably used. It is done.
  • examples of the urethane (meth) acrylate described above include (meth) acrylate obtained by reacting a hydroxyl group-containing (meth) acrylic acid ester with an isocyanate compound.
  • the hydroxyl group-containing (meth) acrylic acid ester is preferably a hydroxyl group-containing (meth) acrylic acid ester obtained by an esterification reaction of an aliphatic dihydric alcohol and (meth) acrylic acid.
  • 2-hydroxy Examples thereof include ethyl (meth) acrylate.
  • the polyisocyanate compound which has a 2 or more isocyanate group in 1 molecule like tolylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate etc. is preferable.
  • polyester (meth) acrylate described above examples include polyester (meth) acrylate obtained by a reaction between a hydroxyl group-containing polyester and (meth) acrylic acid.
  • polyether (meth) acrylate the polyether acrylate obtained by reaction of a hydroxyl-containing polyether and acrylic acid can be mentioned.
  • the cationically polymerizable organic compound include (1) Epoxy compounds such as alicyclic epoxy resins, aliphatic epoxy resins, aromatic epoxy resins; (2) trimethylene oxide, 3,3-dimethyloxetane, 3,3-dichloromethyloxetane, 3-methyl-3-phenoxymethyloxetane, 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl]
  • Oxetane compounds such as benzene, oxolane compounds such as tetrahydrofuran and 2,3-dimethyltetrahydrofuran, cyclic ethers or cyclic acetal compounds such as trioxane, 1,3-dioxolane and 1,3,6-trioxane cyclooctane;
  • an epoxy compound is preferably used, and a polyepoxy compound having two or more epoxy groups in one molecule is more preferably used.
  • a cationically polymerizable organic compound an alicyclic polyepoxy compound having two or more epoxy groups in one molecule is contained, and the content of the alicyclic polyepoxy compound is 30 mass based on the total mass of the epoxy compound. %, Especially 50% by mass or more of an epoxy compound (a mixture of epoxy compounds) gives good cationic polymerization rate, thick film curability, resolution, active energy ray permeability, etc. when producing a three-dimensional model. Moreover, the viscosity of the resin composition for optical three-dimensional modeling becomes low and modeling is performed smoothly, and the volumetric shrinkage of the three-dimensional model obtained is further reduced.
  • alicyclic epoxy resins examples include polyglycidyl ethers of polyhydric alcohols having at least one alicyclic ring, or cyclohexene or cyclopentene ring-containing compounds with an appropriate oxidizing agent such as hydrogen peroxide or peracid.
  • an appropriate oxidizing agent such as hydrogen peroxide or peracid.
  • examples thereof include cyclohexene oxide or cyclopentene oxide-containing compounds obtained by conversion.
  • alicyclic epoxy resin for example, hydrogenated bisphenol A diglycidyl ether, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 2- (3,4-epoxycyclohexyl- 5,5-spiro-3,4-epoxy) cyclohexane-meta-dioxane, bis (3,4-epoxycyclohexylmethyl) adipate, vinylcyclohexene dioxide, 4-vinylepoxycyclohexane, bis (3,4-epoxy-6 -Methylcyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexyl-3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis (3,4-epoxycyclohexane), dicyclopentadiene diepoxide And di (3,4-epoxycyclohexane), m
  • aliphatic epoxy resins examples include polyglycidyl ethers of aliphatic polyhydric alcohols or alkylene oxide adducts thereof, polyglycidyl esters of aliphatic long-chain polybasic acids, homopolymers and copolymers of glycidyl acrylate and glycidyl methacrylate. And so on.
  • 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, sorbitol tetraglycidyl ether Obtained by adding one or more alkylene oxides to aliphatic polyhydric alcohols such as hexaglycidyl ether of dipentaerythritol, diglycidyl ether of polyethylene glycol, diglycidyl ether of polypropylene glycol, ethylene glycol, propylene glycol, glycerin
  • examples thereof include polyglycidyl ethers of polyether polyols and diglycidyl esters of aliphatic long-chain dibasic acids.
  • epoxy compounds for example, monoglycidyl ethers of higher aliphatic alcohols, glycidyl esters of higher fatty acids, epoxidized soybean oil, butyl epoxy stearate, octyl epoxy stearate, epoxidized linseed oil, epoxidized polybutadiene And so on.
  • aromatic epoxy resin examples include mono- or polyglycidyl ethers of mono- or polyhydric phenols having at least one aromatic nucleus or alkylene oxide adducts thereof. Glycidyl ether, epoxy novolac resin, phenol, cresol, butylphenol obtained by reaction of bisphenol A or bisphenol F or its alkylene oxide adduct with epichlorohydrin, or monoglycidyl ether of polyether alcohol obtained by adding alkylene oxide to these And so on.
  • the reaction rate of the cationically polymerizable compound is slow, and modeling takes time.
  • an oxetane compound is added, cationic polymerization is performed. The reaction is promoted.
  • an oxetane monoalcohol compound having one or more oxetane groups and one alcoholic hydroxyl group in one molecule is preferably used.
  • molding of this invention may contain the polyoxetane compound which has 2 or more of oxetane groups in 1 molecule, and does not have an alcoholic hydroxyl group as needed.
  • the polyoxetane compound is contained, the dimensional accuracy of the resulting three-dimensional structure is improved.
  • Examples of compounds having two or more oxetane groups in one molecule include 1,4-bis [(3-ethyl-3-oxetanylmethoxy) methyl] benzene, 1,4-bis (3-ethyl-3- And oxetanylmethoxy) butane.
  • a radical photopolymerization initiator is contained as a photoinitiator.
  • the photo radical polymerization initiator that can be used in the resin composition for optical three-dimensional modeling of the present invention include benzyl or its dialkyl acetal compound, acetophenone compound, benzoin or its alkyl ether compound, benzophenone compound, and thioxanthone. And the like.
  • examples of benzyl or a dialkyl acetal compound thereof include benzyl dimethyl ketal, benzyl- ⁇ -methoxyethyl acetal, 1-hydroxycyclohexyl phenyl ketone, and the like.
  • acetophenone compounds include diethoxyacetophenone, 2-hydroxymethyl-1-phenylpropan-1-one, 4′-isopropyl-2-hydroxy-2-methyl-propiophenone, 2-hydroxy-2 -Methyl-propiophenone, p-dimethylaminoacetophenone, p-tert-butyldichloroacetophenone, p-tert-butyltrichloroacetophenone, p-azidobenzalacetophenone and the like.
  • examples of the benzoin compound include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin normal butyl ether, and benzoin isobutyl ether.
  • benzophenone compound examples include benzophenone, methyl o-benzoylbenzoate, Michler's ketone, 4,4'-bisdiethylaminobenzophenone, 4,4'-dichlorobenzophenone, and the like.
  • thioxanthone compound examples include thioxanthone, 2-methylthioxanthone, 2-ethylthioxanthone, 2-chlorothioxanthone, and 2-isopropylthioxanthone.
  • photo radical polymerization initiators may be used alone or in combination of two or more.
  • a photocationic polymerization initiator is contained as a photoinitiator.
  • any polymerization initiator capable of initiating cationic polymerization of the cationic polymerizable compound can be used.
  • the cationic photopolymerization initiator include an onium salt that releases a Lewis acid when irradiated with light, such as an aromatic sulfonium salt of a Group VIIa element, an aromatic onium salt of a Group VIa element, and a Group Va element.
  • non-antimony aromatic sulfonium compounds having iodonium and fluorophosphoric acid as counter ions and one or more of these can be used.
  • a photosensitizer such as benzophenone, benzoin alkyl ether, thioxanthone, etc. may be used together with the cationic polymerization initiator as necessary.
  • the amount of the photo radical polymerization initiator used is preferably 0.5 to 10% by mass, particularly 1 to 5% by mass, based on the mass of the radical polymerizable compound.
  • the amount of the photocationic polymerization initiator used is preferably 0.5 to 10% by mass, particularly 1 to 5% by mass, based on the mass of the cationically polymerizable compound.
  • the photopolymerizable compound contains dimethacrylate of substituted bisphenol compounds such as ethoxylated bisphenol A dimethacrylate as the photopolymerizable compound, and benzyl (also known as diphenylethanedione) or its photopolymerization initiator (photo radical polymerization initiator)
  • benzyl also known as diphenylethanedione
  • photopolymerization initiator photo radical polymerization initiator
  • thermally expandable microcapsules contained in the resin composition for optical three-dimensional modeling of the present invention are also referred to as thermally expandable microspheres, thermally expandable fine particles, and the like.
  • Thermally expandable microcapsules are microcapsules in which a volatile liquid expansion agent such as liquefied hydrocarbon is encapsulated in an outer shell made of a thermoplastic polymer, and the expansion of the liquid expansion agent encapsulated in the microcapsule begins. By heating to a temperature higher than the temperature, it usually expands to a volume of about 10 to several tens of times, and sometimes 100 times.
  • thermoly expandable microcapsules many applications have been filed (eg, Patent Documents 4 to 6), and various types are commercially available (eg, Kureha microspheres, Matsumoto microspheres, dyes). Form V etc.).
  • the type of thermally expandable microcapsule to be contained in the optical three-dimensional modeling resin composition is not particularly limited, and the type of photopolymerizable compound contained in the optical three-dimensional modeling resin composition of the present invention, A suitable one can be used according to the component composition of the composition, the use of the three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention, the usage form, and the like.
  • the expansion start temperature is about 90 ° C., about 100 ° C., about 125 ° C., depending on the type of liquid expansion agent contained in the outer shell, etc.
  • Various products such as those of 140 ° C., about 180 ° C., about 190 ° C., and about 260 ° C. are already commercially available.
  • the temperature of the modeling bath is generally in the range of 10 to 40 ° C. when performing the optical three-dimensional modeling using the resin composition for optical three-dimensional modeling containing the photopolymerizable compound and the photopolymerization initiator, and the ambient temperature is Since the temperature is generally in the range of 20 to 50 ° C., any of thermally expandable microcapsules having an expansion start temperature (foaming start temperature) higher than 50 ° C. can be used in the present invention.
  • thermally expandable microcapsule having an expansion start temperature suitable for each situation.
  • the expansion start temperature of the thermally expandable microcapsule is too low, the expansion of the thermally expandable microcapsule occurs before the softening temperature (thermal deformation temperature) of the 3D object is reached.
  • the expansion start temperature of the thermally expandable microcapsule is too high, the three-dimensional object is thermally deteriorated before the expansion of the thermally expandable microcapsule is started.
  • thermal deterioration of the polymer used for the production of the molded product is likely to occur.
  • the particle size of the heat-expandable microcapsule is 1 to 100 ⁇ m in average particle size from the viewpoints of handling at the time of optical three-dimensional modeling, dimensional accuracy of the three-dimensional model to be obtained, and availability. Preferably, it is 10 to 50 ⁇ m.
  • the three-dimensional structure including the heat-expandable microcapsules will not foam sufficiently when heated above the expansion start temperature of the heat-expandable microcapsules.
  • the capsule particle size is too large, workability at the time of optical three-dimensional modeling decreases, the strength and heat resistance of the resulting three-dimensional model decreases, and dimensional accuracy decreases.
  • the average particle diameter of the thermally expandable microcapsule referred to in the present specification is a value measured by a laser diffraction scattering method.
  • content of a thermally expansible microcapsule is a kind of photopolymerizable compound contained in a photocurable resin composition, a composition of a photocurable resin composition, and optical modeling. It can adjust according to the use of the three-dimensional molded item obtained by using, a usage form, etc. Foaming (expansion) is sufficient when the three-dimensional structure obtained by stereolithography has good strength, heat resistance and dimensional accuracy, and the three-dimensional structure is heated above the expansion start temperature of the thermally expandable microcapsule contained therein.
  • the content of the thermally expandable microcapsule is 20 to 80 parts by mass with respect to 100 parts by mass of the total photopolymerizable compound contained in the resin composition for optical three-dimensional modeling.
  • the amount is preferably 35 to 75 parts by mass, more preferably 40 to 70 parts by mass, and still more preferably 45 to 65 parts by mass.
  • molding of this invention can contain a polyalkylene ether type compound depending on the case.
  • a polyalkylene ether compound When a polyalkylene ether compound is contained, physical properties such as impact resistance of the resulting three-dimensional structure are improved, and when the three-dimensional structure is heated to a temperature equal to or higher than the expansion start temperature of the thermally expandable microcapsule.
  • the three-dimensional structure is foamed well.
  • the polyalkylene ether compound those having a number average molecular weight in the range of 500 to 10,000, particularly 500 to 5,000 are preferably used.
  • polyalkylene ether compounds include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyethylene oxide-polypropylene oxide block copolymer, random copolymer of ethylene oxide and propylene oxide, formula: —CH 2 CH 2 CH (R 1 ) CH 2 O— (wherein R 1 is a lower alkyl group, preferably a methyl or ethyl group) and an oxytetramethylene unit having an alkyl substituent (having an alkyl substituent)
  • R 1 is a lower alkyl group, preferably a methyl or ethyl group
  • R 1 is a lower alkyl group having an alkyl substituent (having an alkyl substituent)
  • a polyether bonded with a tetramethylene ether unit an alkyl represented by the oxytetramethylene unit and the formula: —CH 2 CH 2 CH (R 1 ) CH 2 O— (wherein R 1 is a lower alkyl
  • R A polyether in which tetramethylene ether units having an alkyl substituent represented by 1 is a lower alkyl group is preferably used.
  • the hygroscopic property is low, and the dimensional stability and physical property stability are improved. It is possible to obtain a three-dimensional structure that is excellent and has excellent foamability.
  • the content of the polyalkylene ether compound in the resin composition for optical three-dimensional modeling of the present invention is preferably 0 to 30% by mass with respect to the total mass of the resin composition for optical three-dimensional modeling. More preferably, it is mass%. Moreover, you may contain the 2 or more types of polyalkylene ether type compound simultaneously in the range which does not exceed the said content.
  • optical modeling may become difficult, or the strength of the three-dimensional molded product obtained may be insufficient, and the toughness and rigidity of the three-dimensional molded product obtained are too high.
  • the three-dimensional model obtained by stereolithography is heated to a temperature equal to or higher than the expansion start temperature of the thermally expandable microcapsule, foaming of the three-dimensional model is difficult to occur, so the strength is not insufficient before heating and foaming.
  • the type of photopolymerizable compound constituting the resin composition for optical three-dimensional modeling, the type of photopolymerization catalyst, and the resin composition for optical three-dimensional modeling so as to obtain a three-dimensional modeled product that foams sufficiently when heated It is preferable to select the component composition, etc., and adjust the type, thermal expansion performance, content, and the like of the thermally expandable microcapsules.
  • molding of this invention is as needed as long as the effect of this invention is not impaired with a photopolymerizable compound, a photoinitiator, a thermally expansible microcapsule, and the polyalkylene ether type compound depending on the case.
  • Colorants such as pigments and dyes, antifoaming agents, leveling agents, thickeners, flame retardants, antioxidants, fillers (crosslinked polymer particles, silica, glass powder, ceramic powder, metal powder, etc.), modification
  • An appropriate amount of at least one kind of resin may be contained.
  • any conventionally known optical three-dimensional modeling method and apparatus can be used.
  • the active energy ray is selectively irradiated so that a cured layer having a desired pattern can be obtained in the liquid resin composition for optical three-dimensional modeling of the present invention.
  • a hardened layer is formed, and then an uncured liquid resin composition for optical three-dimensional modeling is supplied to the hardened layer.
  • the hardened layer continuous with the hardened layer is newly irradiated with active energy rays.
  • molding can be mentioned by repeating the lamination
  • ultraviolet rays As the active energy rays at that time, as described above, ultraviolet rays, electron beams, X-rays, radiation, high frequencies and the like can be mentioned. Among them, ultraviolet rays having a wavelength of 300 to 400 nm are preferably used from an economical viewpoint.
  • an ultraviolet laser for example, a semiconductor-excited solid laser, an Ar laser, a He—Cd laser
  • a high-pressure mercury lamp is used as a light source at that time.
  • Ultra high pressure mercury lamps, low pressure mercury lamps, xenon lamps, halogen lamps, metal halide lamps, ultraviolet LEDs (light emitting diodes), ultraviolet fluorescent lamps, and the like can be used.
  • a cured resin layer having a predetermined shape pattern by irradiating an active energy ray on a modeling surface made of a resin composition for optical three-dimensional modeling the active energy is reduced to a point such as a laser beam.
  • a planar drawing mask in which a hardened resin layer may be formed by a line drawing method using a line or a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter (DMD).
  • a modeling method may be employed in which a cured resin layer is formed by irradiating the modeling surface with active energy rays through the surface.
  • the heat-expandable microcapsules In performing optical modeling using the resin composition for optical three-dimensional modeling of the present invention containing the heat-expandable microcapsules, the heat-expandable microcapsules float and separate above the resin composition for optical three-dimensional modeling. If it is in the state, it becomes difficult to perform optical modeling smoothly, and it becomes difficult to obtain a three-dimensional modeled product in which thermally expandable microcapsules are uniformly dispersed, so the optical three-dimensional modeled resin composition is stirred. However, it is preferable to perform stereolithography. In addition, by adjusting the viscosity of the resin composition for optical three-dimensional modeling and adding anti-floating agents such as thickeners, floating separation of thermally expandable microcapsules in the resin composition for optical three-dimensional modeling Can be suppressed.
  • the optical three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention contains a thermally expandable microcapsule in an unexpanded state, and the expansion of the thermally expandable microcapsule.
  • the three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention is a core (disappearing core) to be removed after use, a master model for casting, etc. It can be effectively used for
  • the core three-dimensional modeled object obtained by performing optical modeling using the resin composition for optical three-dimensional model
  • the hollow molded body can be manufactured smoothly.
  • the resin composition for optical three-dimensional modeling of the present invention containing a thermally expandable microcapsule for example, the thermally expandable microcapsule 2 in an unexpanded state as shown in FIG.
  • the core 1 to be manufactured is manufactured.
  • the core 1 is disposed in the outer mold 3 with a molding space 4 disposed therein, and then, as shown in FIG. A polymerizable material that forms a coalescence or elastic polymer is introduced to form the elastic polymer layer 5 on the surface of the core 1.
  • the thermally expandable microcapsule contained in the core 1 is removed.
  • the thermally expandable microcapsule 2 By expanding the thermally expandable microcapsule 2 by heating to a temperature equal to or higher than the expansion start temperature, the core 1 is foamed and collapsed as shown in FIG. 6 or a foam 6 that easily disintegrates in strips.
  • the foamed / collapsed material 6 derived from the core is taken out of the hollow molded body made of an elastic polymer.
  • the hollow molded body 7 made of a soft elastic polymer shown in FIG. 1 (f) can be obtained.
  • the hollow molded body 7 is formed of an elastic polymer
  • the core 1 having the elastic polymer layer 5 formed on the surface is taken out from the outer mold 3, and then heat treatment is performed. Even if foaming / collapse is performed, the hollow molded body 7 made of an elastic polymer that swells during foaming can return to its original size due to its elasticity when the foam / collapse material derived from the core is removed.
  • heating and foaming of the core on which the surface of the hollow molded body production material layer is formed will depend on the outer mold It may be carried out after being taken out from the container or may be carried out while being put in the outer mold.
  • the shape of the core is hollow, but the shape is not limited thereto, and may be a solid core.
  • the core obtained by using the resin composition for optical three-dimensional modeling of the present invention containing the heat-expandable microcapsule is used for producing a hollow molded body by increasing the wall thickness even when making a hollow shape.
  • the strength can sufficiently withstand the molding operation and pressure.
  • FIG. 1 although illustrated about the case where a hollow molded object is manufactured using the core manufactured by performing optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of this invention, it is limited to it. It is not a thing, it performs optical three-dimensional modeling using the resin composition for optical three-dimensional modeling of the present invention to produce a hollow molded body for a master model, and various types using a master model composed of the hollow molded body. Molded bodies and products can be manufactured.
  • a molding material for example, silicone or other organic polymer, curable inorganic material, etc.
  • a molding material inside the hollow master model (hollow molded body) formed from the resin composition for optical three-dimensional modeling of the present invention.
  • the viscosity of the resin composition for optical modeling was performed as follows.
  • Viscosity of the resin composition for optical three-dimensional modeling After the resin composition for optical three-dimensional modeling is put in a thermostatic bath at 25 ° C. and the temperature of the resin composition for optical three-dimensional modeling is adjusted to 25 ° C., a B-type viscometer (manufactured by Toki Sangyo Co., Ltd.) is used. And measured at a rotational speed of 20 rpm.
  • a B-type viscometer manufactured by Toki Sangyo Co., Ltd.
  • Example 1 100 parts by mass of ethoxylated bisphenol A dimethacrylate (“BPE-200” manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts by mass of polytetramethylene glycol (“PTG-850SN” manufactured by Hodogaya Chemical Co., Ltd.), benzyldimethyl ketal 2.5 parts by mass (“Irgacure 651” manufactured by BASF) and 58 parts by mass of Kureha Microsphere “H850” (expansion start temperature 125 ° C., average particle size 35 ⁇ m) are mixed well at room temperature (25 ° C.) to obtain an optical A resin composition for three-dimensional modeling was manufactured. It was 4,500 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
  • BPE-200 ethoxylated bisphenol A dimethacrylate
  • PSG-850SN polytetramethylene glycol
  • Example 2 The photograph which image
  • Example 2 (1) 100 parts by mass of ethoxylated bisphenol A dimethacrylate (“BPE-200” manufactured by Shin-Nakamura Chemical Co., Ltd.), 2.5 parts by mass of benzyldimethyl ketal (“Irgacure 651” manufactured by BASF) and Kureha Microsphere “H850” 58 parts by mass (expansion start temperature 125 ° C., average particle size 35 ⁇ m) were mixed well at room temperature (25 ° C.) to produce a resin composition for optical three-dimensional modeling. It was 5,700 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method.
  • BPE-200 ethoxylated bisphenol A dimethacrylate
  • Irgacure 651 manufactured by
  • Example 3 The photograph which image
  • Example 3 100 parts by mass of ethoxylated bisphenol A dimethacrylate (“BPE-200” manufactured by Shin-Nakamura Chemical Co., Ltd.), 15 parts by mass of polytetramethylene glycol (“PTG-850SN” manufactured by Hodogaya Chemical Co., Ltd.), benzyldimethyl ketal 2.5 parts by mass (“Irgacure 651” manufactured by BASF) and 39 parts by mass of Kureha Microsphere “H850” (expansion start temperature 125 ° C., average particle size 35 ⁇ m) are mixed well at room temperature (25 ° C.), and optical A resin composition for three-dimensional modeling was manufactured. It was 1,870 mPa * s (25 degreeC) when the viscosity of this resin composition for optical three-dimensional modeling was measured by the above-mentioned method
  • the three-dimensional structure obtained by optical modeling using the resin composition for optical three-dimensional modeling of the present invention containing the thermally expandable microcapsule has sufficient strength that can be practically used before foaming by heating.
  • the thermally expandable microcapsule when heated above the expansion start temperature of the thermally expandable microcapsule, it foams greatly and becomes a foam that can be collapsed into strips or easily collapsed into strips. Therefore, it is useful as a core or a casting master model when manufacturing a hollow molded body.

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PCT/JP2013/060478 2012-04-07 2013-04-05 Composition de résine pour moulage tridimensionnel optique comprenant des microcapsules thermiquement extensibles Ceased WO2013151157A1 (fr)

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WO2016076209A1 (fr) * 2014-11-12 2016-05-19 株式会社スリーボンド Composition durcissable à deux composants
WO2020028232A1 (fr) * 2018-08-01 2020-02-06 Carbon, Inc. Production de produits de faible densité par fabrication additive
EP3800218A1 (fr) * 2019-10-04 2021-04-07 Nabtesco Corporation Composition de résine transparente pour le moulage et article moulé en 3d
US20230080581A1 (en) * 2021-09-13 2023-03-16 Intrepid Automation Expanding foams in additive manufacturing
US11684104B2 (en) 2019-05-21 2023-06-27 Bauer Hockey Llc Helmets comprising additively-manufactured components
US11779821B2 (en) 2014-05-13 2023-10-10 Bauer Hockey Llc Sporting goods including microlattice structures
WO2023248767A1 (fr) * 2022-06-20 2023-12-28 日本ゼオン株式会社 Mélange de résine pour la fabrication par imprimante 3d, matériau de fabrication par imprimante 3d, corps fabriqué et procédé de fabrication

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JP2024073880A (ja) 2022-11-18 2024-05-30 株式会社アシックス 樹脂発泡体の製造方法、樹脂発泡体、及び、樹脂発泡体を備えるシューズ

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US11844986B2 (en) 2014-05-13 2023-12-19 Bauer Hockey Llc Sporting goods including microlattice structures
US11794084B2 (en) 2014-05-13 2023-10-24 Bauer Hockey Llc Sporting goods including microlattice structures
US11779821B2 (en) 2014-05-13 2023-10-10 Bauer Hockey Llc Sporting goods including microlattice structures
WO2016076209A1 (fr) * 2014-11-12 2016-05-19 株式会社スリーボンド Composition durcissable à deux composants
JPWO2016076209A1 (ja) * 2014-11-12 2017-09-14 株式会社スリーボンド 二液型硬化性組成物
WO2020028232A1 (fr) * 2018-08-01 2020-02-06 Carbon, Inc. Production de produits de faible densité par fabrication additive
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US11292186B2 (en) 2018-08-01 2022-04-05 Carbon, Inc. Production of low density products by additive manufacturing
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US12369668B2 (en) 2019-05-21 2025-07-29 Bauer Hockey Llc Helmets comprising additively-manufactured components
EP3800218A1 (fr) * 2019-10-04 2021-04-07 Nabtesco Corporation Composition de résine transparente pour le moulage et article moulé en 3d
WO2023037263A1 (fr) * 2021-09-13 2023-03-16 Intrepid Automation Mousses expansives en fabrication additive
US20230080581A1 (en) * 2021-09-13 2023-03-16 Intrepid Automation Expanding foams in additive manufacturing
WO2023248767A1 (fr) * 2022-06-20 2023-12-28 日本ゼオン株式会社 Mélange de résine pour la fabrication par imprimante 3d, matériau de fabrication par imprimante 3d, corps fabriqué et procédé de fabrication

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