WO2020066047A1 - Composition pour stéréolithographie optique, objet stéréolithographique, et son procédé de production - Google Patents

Composition pour stéréolithographie optique, objet stéréolithographique, et son procédé de production Download PDF

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WO2020066047A1
WO2020066047A1 PCT/JP2019/001476 JP2019001476W WO2020066047A1 WO 2020066047 A1 WO2020066047 A1 WO 2020066047A1 JP 2019001476 W JP2019001476 W JP 2019001476W WO 2020066047 A1 WO2020066047 A1 WO 2020066047A1
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composition
optical
mass
meth
acrylate
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PCT/JP2019/001476
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博明 岡本
雅郎 中塚
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岡本化学工業株式会社
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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
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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
    • 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
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/44—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
    • C08F263/00—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00
    • C08F263/06—Macromolecular compounds obtained by polymerising monomers on to polymers of esters of unsaturated alcohols with saturated acids as defined in group C08F18/00 on to polymers of esters with polycarboxylic acids
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/08—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated side groups
    • C08F290/12—Polymers provided for in subclasses C08C or C08F

Definitions

  • the present invention relates to a composition for optical three-dimensional modeling, a three-dimensional molded article, and a method for producing the same.
  • optical three-dimensional modeling is also referred to as “stereo modeling”
  • stereo modeling a prototype can be easily and quickly manufactured without preparing a mold or a mold. The time and cost required from product development design to production can be reduced.
  • a photocurable resin capable of forming a resin For example, when a (meth) acrylate of a polyglycerin alkylene oxide adduct (addition mole number: 50 to 200) is contained as a raw material of a photocurable resin, a coating film is prepared by irradiation with active energy rays. It is described that a photocurable resin which does not cause warpage of a base film or cracks of a coating film was obtained (Patent Document 1).
  • ⁇ Manufactured objects manufactured by stereolithography often have complicated shapes, and must be adapted to applications in which force is applied, bent, or heated.
  • a three-dimensional object is produced by superimposing a plurality of thin cured film layers having a thickness of about 20 to 100 microns formed by scanning an optical molding composition with an ultraviolet laser.
  • the thin cured film layers do not adhere to each other, the strength of the three-dimensional structure may be affected.
  • the conventional stereolithography composition has a problem that a three-dimensional molded article may warp and be caught by an ultraviolet laser scanner during production.
  • Patent Literature 2 in order to improve the heat resistance of a three-dimensional molded object, it is general to further heat the composition at, for example, 60 to 250 ° C. after curing the composition by light irradiation. However, if the heat treatment is performed as described above, the number of steps is increased, and thus the work efficiency may be deteriorated.
  • the present invention completes optical shaping (light curing) in a shorter time, and performs an ultraviolet irradiation treatment after the optical shaping to provide excellent strength (for example, when it is subjected to an impact, it is dropped.
  • a three-dimensional structure having strength to prevent the occurrence of cracks and the like, strength to withstand repeated bending) is obtained, a composition for optical three-dimensional structure comprising a water-insoluble radically polymerizable component, the three-dimensional structure, And a method for producing a three-dimensional structure.
  • composition for optical stereolithography comprises (A) a diallylcycloalkane-based polymer or diallyl Including a combination of a cycloalkane-based polymer and a diallyl phthalate-based polymer, (B) a radical polymerizable compound having a methacryl group and / or an acryl group, (C) a radical polymerization initiator, and (D) a sensitizer.
  • the composition for optical stereolithography wherein the diallylcycloalkane-based polymer of (A) has a carbon number of 3 to 8 carbon atoms and has a methacrylic group and / or an acrylic group of (B).
  • the radical polymerizable compound (B1) a radical polymerizable compound of an epoxy (meth) acrylate having a methacryl group and / or an acrylic group, and / or (B2) at least a radical polymerizable compound of dioxane (meth) acrylate having a methacrylic group and / or an acrylic group, wherein the (A) diallylcycloalkane-based polymer or the diallylcycloalkane-based polymer and the diallylphthalate-based polymer The combination is 0.5 to 10% by mass, the total of the radical polymerizable compounds of (B1) and (B2) is 5 to 43% by mass, and the radical polymerizable compounds of (B) are (B1) and (B2). 20 to 95% by
  • composition for optical stereolithography according to the present invention may further contain (E) a compound having an allyl group which is not a diallyl phthalate-based polymer in an amount of 0.125 to 2.5% by mass.
  • the diallylcycloalkane-based polymer (A) may be a diallylcycloalkanedicarboxylate polymer. Further, the diallyl phthalate-based polymer (A) may be a diallyl orthophthalate polymer or a diallyl isophthalate polymer.
  • composition for optical three-dimensional modeling according to the present invention further comprises (F) the following general formula (1) (In the formula, n represents an integer of 2 to 20 and m represents an integer of 50 to 200.)
  • the polyoxyethylene polyglyceryl ether / acrylic acid adduct having a structure of 5 to 40% by mass may be contained.
  • the present invention relates to a method for producing a three-dimensional structure, which includes at least a step of irradiating the above-described composition for optical three-dimensional structure with an active energy ray to cure the composition.
  • the present invention relates to a three-dimensional structure, which is a cured product of the above-described composition for optical three-dimensional structure.
  • the present invention it is possible to shorten the photocuring time when producing a three-dimensional molded article, and to perform an ultraviolet irradiation treatment after photocuring, to have excellent strength (for example, when subjected to an impact, or It is possible to provide a composition for optical three-dimensional molding capable of producing a three-dimensional molded article having a strength of preventing the occurrence of cracks or the like when dropped, and a strength capable of withstanding repeated bending. .
  • the warp deformation is reduced because the cured layer films adhere to each other in the process of manufacturing the three-dimensional structure, and further, the adhesion between the layers is good, so that the strength (for example, bending) It is possible to obtain a three-dimensional structure having high strength, flexural modulus, and repeated bending strength.
  • composition for optical three-dimensional object according to the present invention the three-dimensional object, and a method for manufacturing a three-dimensional object will be described, but the scope of the present invention is not limited to this embodiment. Absent.
  • composition for optical stereolithography of the present embodiment contains at least components (A) to (D) described in detail below, and preferably further contains components (E) and / or (F), Other components are further contained as necessary.
  • Component (A) is a diallylcycloalkane-based polymer or a combination of a diallylcycloalkane-based polymer and a diallylphthalate-based polymer.
  • the carbon number of the carbon ring of the diallylcycloalkane-based polymer (also called diallylcycloalkane resin) is in the range of 3 to 8, preferably 5 to 6.
  • Examples of the diallylcycloalkane-based polymer include a diallyl-1,2-cycloalkane polymer and a diallyl-1,3-cycloalkane polymer.
  • a diallylcycloalkanedicarboxylate polymer is preferable, and examples thereof include diallyl-1,2-cycloalkanedicarboxylate polymer and diallyl-1,3-cycloalkanedicarboxylate polymer. . More specifically, examples thereof include diallyl-1,2-cyclohexanedicarboxylate polymer and diallyl-1,3-cyclohexanedicarboxylate polymer. Further, specific examples of the diallyl phthalate-based polymer (also referred to as diallyl phthalate resin) include, for example, a diallyl orthophthalate polymer and a diallyl isophthalate polymer.
  • the component (A) By adding the component (A) to the optical three-dimensional structure composition, it is possible to obtain sufficient mechanical strength and flexibility when the three-dimensional structure is formed, and furthermore, to obtain excellent strength (for example, impact resistance). When it is dropped, the strength for preventing the occurrence of cracks or the like is obtained. In addition, even if the diallyl phthalate-based polymer is used alone, the same effect as that of the diallyl cycloalkane-based polymer can be obtained.
  • the diallyl phthalate-based polymer will be described in more detail.
  • the diallyl orthophthalate polymer is obtained by a polymerization reaction using diallyl orthophthalate as a monomer, and has the following two kinds of structures, an ortho A structure and an ortho B structure. .
  • an ortho A structure and an ortho B structure.
  • two ester positions are close to each other, so that an ortho B structure is easily formed.
  • the diallyl metaphthalate polymer is obtained by a polymerization reaction using diallyl metaphthalate as a monomer, and has the following two types of structures, a meta A structure and a meta B structure.
  • a meta A structure Usually, in the meta-form, the meta-B structure is hardly formed because the two ester positions are separated from each other, and almost the meta-A structure is formed.
  • the diallylcycloalkane-based polymer will be described in more detail.
  • the diallyl-1,2-cyclohexanedicarboxylate polymer is obtained by a polymerization reaction using ortho-hydrogenated diallyl phthalate as a monomer. And an ortho-B structure.
  • ortho-B structure usually, in the ortho form, two ester positions are close to each other, so that an ortho B structure is easily formed.
  • the diallyl-1,3-cyclohexanedicarboxylate polymer is obtained by a polymerization reaction using meta-hydrogenated diallyl phthalate as a monomer, and has the following two types of structures, a meta-A structure and a meta-B structure. Have. Usually, in the meta form, two ester positions are separated from each other, so that a meta B structure is hardly formed.
  • diallylcycloalkane-based polymer and diallylphthalate-based polymer of the component (A) can be synthesized by a known method, or commercially available ones can be used.
  • diallylcycloalkane-based polymers include, for example, RADPAR @ AD-032 and RADPAR @ AD-044 manufactured by Osaka Soda Co., Ltd.
  • examples of the dialifphthalate-based polymer include, for example, Daisodap A, Daisodap K, Daisodap S, and Daiso Isodap manufactured by Osaka Soda Co., Ltd.
  • the content of the diallylcycloalkane-based polymer of the component (A) or the combination of the diallylcycloalkane-based polymer and the diallylphthalate-based polymer is 0.5 to 10% by mass based on the total amount of the composition for optical stereolithography. And preferably 1 to 8% by mass.
  • the content of the component (A) is less than 0.5% by mass, the effect of the diallylcycloalkane-based polymer or the diallylphthalate-based polymer does not appear in the composition for optical three-dimensional modeling, and the composition becomes hard and brittle.
  • the content exceeds 10% by mass the composition can be cured only on the surface portion, and becomes a soft and brittle composition as a whole.
  • the component (B) is a radically polymerizable compound having a methacryl group and / or an acryl group.
  • the radically polymerizable compound having a methacryl group and / or an acryl group of the component (B) the methacryl group of the component (B1) is used.
  • epoxy (meth) acrylate having a methacryl group and / or an acrylic group of the component (B1) include bisphenol A diglycidyl ether (meth) acrylic acid adduct and bisphenol A diglycidyl ether (meth) acrylic acid adduct , Ethylene glycol diglycidyl ether (meth) acrylic acid adduct, propylene glycol diglycidyl ether (meth) acrylic acid adduct, glycerin diglycidyl ether (meth) acrylic acid adduct, bisphenol A (PO2 mol) adduct diglycidyl ether ( (Meth) acrylic acid adduct, epoxidized soybean oil (meth) acrylic acid adduct, novolak epoxy resin (meth) acrylic acid adduct, and the like.
  • the epoxy (meth) acrylate having a methacryl group and / or an acryl group of the component (B1) can be synthesized by a known method, or a commercially available one can be used.
  • the content of the epoxy (meth) acrylate having a methacryl group and / or an acrylic group of the component (B1) is in the range of 5 to 43% by mass, preferably 10 to 43% by mass, based on the total amount of the composition for stereolithography. The range is 30% by mass.
  • the content of the component (B1) is less than 5% by mass, the toughness becomes insufficient when a three-dimensional structure is formed.
  • the content exceeds 43% by mass the sensitivity to the active energy ray irradiated to obtain a three-dimensional structure is reduced, and a desired three-dimensional structure cannot be obtained.
  • dioxane (meth) acrylate having a methacryl group and / or an acrylic group of the component (B2) include dioxane glycol di (meth) acrylate and methacrylic acid (2-oxo-1,3-dioxolan-4-yl) Methyl and the like.
  • the dioxane (meth) acrylate having a methacryl group and / or an acryl group as the component (B2) can be synthesized by a known method, or a commercially available dioxane (meth) acrylate can be used.
  • KAYARAD® R-604 manufactured by Nippon Kayaku Co., Ltd. and NK ester A-DOG manufactured by Shin-Nakamura Chemical Co., Ltd. may be mentioned.
  • the content of the dioxane (meth) acrylate having a methacrylic group and / or an acrylic group of the component (B2) is in the range of 5 to 43% by mass, preferably 10 to 30% by mass in the total amount of the composition for stereolithography. % By mass.
  • the content of the component (B2) is less than 5% by mass, the curing is slow and the product becomes brittle when formed into a three-dimensional structure. If the content is more than 43% by mass, the curing will be too fast, the mutual adhesion of the thin cured film layers will be poor, and the strength of the three-dimensional structure will be low.
  • the component (B1) and the component (2) may be contained at the same time, and the content in that case is the total of the component (B1) and the component (B2), and is included in the total amount of the composition for optical three-dimensional modeling.
  • the range is 5 to 43% by mass, preferably 10 to 30% by mass.
  • the radical polymerizable compound having a methacryl group and / or an acryl group of the component (B) may further contain a radical polymerizable compound other than the above-mentioned components (B1) and (B2) ( Hereinafter, it is referred to as “another radically polymerizable compound of the component (B)”.
  • the content of the other radically polymerizable compound of the component (B) is not particularly limited as long as the performance of the composition for optical three-dimensional modeling is not impaired. For example, in the total amount of the composition for optical three-dimensional modeling, It is preferably 20 to 95% by mass, more preferably 20 to 85% by mass.
  • monofunctional monomers of other radically polymerizable compounds of component (B) include, for example, (meth) acryloylmorpholine, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, polyethylene glycol mono (Meth) acrylate, glycerin (meth) acrylate, nonylphenol EO-modified (meth) acrylate, reaction product of 2-hydroxyethyl (meth) acrylate and phosphoric anhydride, hexalide addition polymer of 2-hydroxyethyl (meth) acrylate and anhydrous Reaction product of phosphoric acid, acrylamide, 7-amino-3,7-dimethyloctyl (meth) acrylate, isobutoxymethyl (meth) acrylamide, isobonyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, Seton (meth) acrylamide, dimethylamino
  • bifunctional monomer of another radical polymerizable compound of the component (B) include triethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol (400) di (meth) acrylate, Polyethylene glycol (600) di (meth) acrylate, polypropylene glycol (400) di (meth) acrylate, ethoxylated (4) bisphenol A di (meth) acrylate, ethoxylated (10) bisphenol A di (meth) acrylate, ethoxylated (30) bisphenol A di (meth) acrylate, ethoxylated (4) hydrogenated bisphenol A di (meth) acrylate, ethoxylated (30) hydrogenated bisphenol A di (meth) acrylate, EO modified (10) hydrogenated bisphenol A (Meth) acrylate, ethylene glycol di (meth) acrylate, tricyclodecanediyl dimethylene di (meth) acrylate,
  • polyfunctional monomer of another radical polymerizable compound of the component (B) examples include ethoxylated (9) glycerin tri (meth) acrylate, ethoxylated (20) glycerin tri (meth) acrylate, and polyether trifunctional.
  • the other radical polymerizable compound of the component (B) can be synthesized by a known method, or a commercially available compound can be used.
  • monofunctional monomers include Aronix M-111 manufactured by Toagosei Co., Ltd.
  • bifunctional monomers include Light Ester 4EG manufactured by Kyoeisha Chemical Co., Ltd., and KAYARAD series @ HX-220, HX-620 manufactured by Nippon Kayaku Co., Ltd.
  • Examples of the polyfunctional monomer include Aronix M-306 manufactured by Toagosei Co., Ltd.
  • Component (C) is a radical polymerization initiator, and is not particularly limited as long as it is a compound capable of generating a radical species upon irradiation with an active energy ray and initiating a radical reaction of the radical polymerizable compound.
  • the radical polymerization initiator of the component (C) can be synthesized by a known method, or a commercially available one can be used.
  • IRGACURE series manufactured by BASF DAROCUR series, LUCIRIN series, SB-PI series manufactured by Sort
  • ESACURE series manufactured by IGM-RESINS LUNACURE series manufactured by DKSH Japan
  • Adeka Optomer series manufactured by ADEKA Showa Denko Organic boron compound series manufactured by Hokuei Chemical Industry Co., Ltd. and the like.
  • the content of the radical polymerization initiator of the component (C) is in the range of 0.1 to 5.0% by mass, preferably 0.5 to 5.0% by mass, based on the total amount of the composition for optical stereolithography. % Range.
  • the amount is less than 0.1% by mass, the radical polymerization reaction of the composition for optical three-dimensional modeling becomes slow. If the content exceeds 5.0% by mass, the curing properties of the composition for optical three-dimensional modeling will be reduced.
  • the component (D) is a sensitizer and is not particularly limited as long as it is a compound (preferably a compound absorbing a wavelength of 300 to 500 nm) that can increase the photosensitivity of the composition for optical stereolithography. And a polyfunctional thiol compound.
  • polyfunctional thiol compound examples include 1,3,5-tris (3-mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 1,4-bis (3-mercaptobutyryloxy) butane, pentaerythritol tetrakis (3-mercaptobutyrate), trimethylolpropane tris (3-mercaptopropionate), tris [(3-mercaptopropionyloxy) -ethyl ] -Isocyanurate, pentaerythritol tetrakis (3-mercaptopropionate) and the like.
  • the polyfunctional thiol compound as the sensitizer of the component (D) can be synthesized by a known method, or a commercially available product can be used.
  • a commercially available product can be used.
  • QX40 manufactured by Mitsubishi Chemical Corporation and Adeka Hardener EH-317 manufactured by Adeka Corporation can be used.
  • the sensitizer other than the polythiol thiol compound include benzophenone.
  • acridine-based compounds 9-phenylacridine, 9- (P-methylphenyl) acridine, 9- (o-methylphenyl) acridine, 9- (o-chlorophenyl) acridine, 9- (o-fluorophenyl) acridine,
  • coumarin-based compounds include 7,7- (diethylamino) (3,3-carbonylbiscoumarin), 3-benzoyl-7-diethylaminocoumarin, and 7,7-bis (methoxy) (3,3-carbonylbiscoumarin).
  • anthracene-based compounds 9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 9,10-bis (octanoyl) anthracene, 2,4-diethylthioxanthone, 4- (dimethyl Examples thereof include ethyl amino) benzoate, curcumin, diphenyl (2,4,6-trimethylbenzoyl) phosphine oxide, 2-ethylanthraquinone, and 2-isopropylthioxanthone.
  • the content of the sensitizer of the component (D) is in the range of 0.1 to 5.0% by mass, preferably 3.0 to 5.0% by mass, based on the total amount of the composition for stereolithography. Range. When the amount is less than 0.1% by mass, photocuring is not performed or sensitivity is extremely lowered. When the content exceeds 5.0% by mass, the sensitivity is locally lowered, or only the surface is cured.
  • the component (D) By adding the component (D) to the composition for optical three-dimensional modeling, the photo-curing reaction is further promoted, and all the polymerizable components in the composition are cured (bonded) to form a three-dimensional molded article. It is possible to obtain high mechanical strength and heat resistance.
  • the optional component (E) is a compound having an allyl group that is not the diallyl phthalate-based polymer of the component (A) among the compounds having an allyl group.
  • Specific examples of the component (E) having an allyl group which is not a diallyl phthalate polymer include 2,2′-biphenyldicarboxylic acid diallyl ester, 2,3-naphthalenedicarboxylic acid diallyl ester, pentaerythritol triallyl ether Diallyl terephthalate, diallyl isophthalate, diallyl orthophthalate, diallyl malate, allyl acrylate, allyl methacrylate, allyl glycidyl ether, trimethylolpropane diallyl ether, glycerin monoallyl ether, and the like.
  • a compound having an allyl group which is not a diallyl phthalate polymer a commercially available compound can be used.
  • Daiso Isodap monomer manufactured by Osaka Soda Co. Daiso Isodap 100 monomer, Neoallyl series, Nissan Eclipse DAD and DAND manufactured by Techno Fine Chemical Co., Ltd. are exemplified.
  • the content of the compound having an allyl group which is not the diallyl phthalate-based polymer of the component (E) is preferably in the range of 0.125 to 2.5% by mass, based on the total amount of the composition for optical stereolithography. Preferably, it is in the range of 0.15 to 2% by mass.
  • the optional component (F) is represented by the following general formula (1) Is a polyoxyethylene polyglyceryl ether / acrylic acid adduct having the structure:
  • the average polymerization degree n of the polyglycerol of the polyoxyethylene polyglyceryl ether / acrylic acid adduct of the component (F) is in the range of 2 to 20, preferably in the range of 4 to 20.
  • the average degree of polymerization is 1, that is, glycerin, the curing speed becomes slow.
  • the average degree of polymerization is larger than 20, it becomes difficult to produce the radically polymerizable compound.
  • the polymerization degree (number of moles of addition) m of ethylene oxide of the polyoxyethylene polyglyceryl ether / acrylic acid adduct of the component (F) is in the range of 50 to 200 moles, preferably 60 moles, per mole of polyglycerin. In the range of 150150 mol. If the number of added moles is less than 50 moles, the cured product loses flexibility and hydrophilicity. When the number of added moles is larger than 200 moles, it becomes difficult to produce the radically polymerizable compound.
  • the polyoxyethylene polyglyceryl / acrylic acid adduct of the component (F) can be synthesized by a known method, or a commercially available product can be used.
  • the content of the polyoxyethylene polyglycerin / acrylic acid adduct of the component (F) is preferably in the range of 5 to 40% by mass, more preferably 10 to 30% by mass, based on the total amount of the composition for optical stereolithography. % Range.
  • the content of the component (F) is less than 5% by mass, the effect of improving the curing speed and curing shrinkage is not sufficiently exhibited.
  • the content exceeds 40% by mass the curing is too fast, the mutual adhesion between the thin cured film layers is deteriorated, the strength of the three-dimensional structure is reduced, and the water resistance of the three-dimensional structure is also reduced. .
  • the composition for optical three-dimensional modeling includes, as other components, a solvent for dissolving or dispersing the component (C), a curing accelerator, a polymerization inhibitor, an ultraviolet absorber, a fluorescent brightener, and a coloring agent (dye, organic Pigments, inorganic pigments), luminescent agents, phosphorescent particles, organic polymer particles, cellulosic particles, metal particles, conductive fillers, cationic photopolymerizable curing components, biodegradable plastics, biomass plastics, starch, etc. It can be contained in a range that does not adversely affect the properties of the composition for three-dimensional modeling.
  • the content of other components is not particularly limited, and can be appropriately adjusted by those skilled in the art.
  • the three-dimensional structure according to the present embodiment is a cured product of the above-described composition for optical three-dimensional structure.
  • the three-dimensional object can be applied to a wide range of fields. Specific examples of the use are not particularly limited, but precision parts, electric / electronic parts, building structures, automobile parts, molds, mother dies, medical fixtures such as casts, mouthpieces for fixing teeth, dentistry. Examples include a plastic molded article for medical use, a plastic medical instrument for medical use, and an automobile part.
  • the method of manufacturing a three-dimensional molded object according to the present embodiment includes at least a step of irradiating the above-described composition for optical three-dimensional molding with an active energy ray to cure the composition, and a conventional optical three-dimensional molding method and a conventional stereolithography apparatus Can be done using
  • the thickness of the single layer or the laminated cured layer can be, for example, 20 to 200 ⁇ m. The smaller the thickness of the hardened layer, the higher the shaping accuracy can be. However, the time and cost required for the production increase, so that the thickness can be appropriately adjusted in consideration of the balance between them.
  • the stereolithography apparatus used for the production of a three-dimensional object made of a cured product of the optical three-dimensional object composition is not particularly limited.
  • ATOMm-4000 manufactured by Seamet
  • DigitalWax® 020X sina
  • three-dimensional additive manufacturing apparatuses such as ACCULAS (registered trademark) BA-85S (manufactured by D-MEC).
  • the active energy ray for irradiating the composition for optical stereolithography is, for example, ultraviolet light, visible light, radiation, X-ray, or electron beam, and is preferably ultraviolet light or visible light.
  • the wavelength of ultraviolet light or visible light is preferably from 300 to 500 nm.
  • Ultraviolet or visible light sources include, but are not limited to, semiconductor-excited solid-state lasers, carbon arc lamps, mercury lamps, metal halide lamps, xenon lamps, chemical lamps, white LEDs, and the like. In particular, it is preferable to use a laser from the viewpoint of modeling accuracy and curability.
  • the three-dimensional structure is a three-dimensional structure including a cured product of the above-described optical three-dimensional structure composition, and is preferably a three-dimensional structure formed by laminating a cured layer formed by curing the optical three-dimensional structure composition. It is a model.
  • the three-dimensional structure is manufactured by, for example, the above-described method of manufacturing a three-dimensional structure.
  • the three-dimensional structure has a high degree of strength (for example, bending strength, flexural modulus, repetitive bending strength, etc.) because the cured layer films are in close contact with each other so that warpage is small, and the adhesion between layers is good. Can be obtained.
  • RADPAR AD-032 component ( A) diallylcycloalkane-based polymer, iodine value (g / 100 g) 55-70, viscosity 40-120 mPa ⁇ s / 30 ° C. (50% MEK viscosity), manufactured by Osaka Soda Co., Ltd.
  • EBECRYL 600 bisphenol of component (B1) A type epoxy diacrylate, viscosity 3000 (60 ° C) mPa.s, average molecular weight 500, acid value ⁇ 1, OH value 2 0 mg KOH / g, manufactured by Daicel Ornex Co., Ltd.-KAYARAD R-604: dioxane glycol diacrylate of component (B2), viscosity 200 to 400 mPas (25 ° C), acid value ⁇ 1.0, manufactured by Nippon Kayaku Co., Ltd.-Aronix M-306: Mixture of pentaerythritol tri and tetraacrylate (tri-body 65-70%) of another radical polymerizable compound of component (B), viscosity 400-650 mPa ⁇ s / 25 ° C., manufactured by Toagosei Co., Ltd.
  • Irgacure 907 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one of component (C), manufactured by BASF Corporation
  • Karenz MTNR1 1,3,5-tris (3) of component (D) -Mercaptobutyryloxyethyl) -1,3,5-triazine-2,4,6- (1H, 3H, 5H) -trione -Showa Denko Co., Ltd.-Daisodap 100 monomer: diallyl isophthalate of component (E), manufactured by Osaka Soda Co., Ltd.-SA-ZE6: polyoxyethylene polyglycerin ether of component (F).
  • evaluation sample A In order to evaluate the curing time of the optical three-dimensional structure forming composition, a sample was manufactured in the following procedure.
  • the composition for optical stereolithography of Example 1 was poured into a handmade polyethylene rectangular mold (approximately 10 mm wide ⁇ 100 mm long ⁇ 5 mm deep) so as to form a 1 mm liquid film, and 3 kw high pressure mercury or the like (wavelength 365 nm, Irradiation was performed for 5 seconds, 10 seconds, 15 seconds, 20 seconds, 25 seconds, and 30 seconds at a distance of 1 m) to obtain an evaluation sample A.
  • Evaluation samples A were obtained in the same manner for the optical stereolithography compositions of Examples 2 to 12 and Comparative Examples 1 to 4.
  • evaluation sample B In order to evaluate the curing time of the optical three-dimensional structure forming composition, a sample was manufactured in the following procedure.
  • the composition for optical stereolithography of Example 1 was poured into a handmade polyethylene rectangular mold (approximately 10 mm wide ⁇ 100 mm long ⁇ 5 mm deep) so as to form a 1 mm liquid film, and a 3 kw high-pressure mercury lamp (wavelength 365 nm, distance) 1 m) for 20 seconds, and this was repeated four times in total to produce a flat plate having a thickness of about 4 mm (width of about 10 mm ⁇ length of 100 mm). Further, the flat plate was re-irradiated for 30 minutes to obtain an evaluation sample B as an optical three-dimensional structure. Evaluation samples B were obtained in the same manner for the optical three-dimensional structure forming compositions of Examples 2 to 12 and Comparative Examples 1 to 4.
  • Three-Point Bending Test A three-point bending test of the flat plate of the evaluation sample B was performed under the following measurement conditions in accordance with ISO 527-1, and the bending strength and the bending elastic modulus were measured. The results are shown in Table 2.
  • Measuring device Instron 3366 universal testing machine Test condition: 3-point bending test jig Indenter radius: 5 mm Distance between supporting points 64mm Load speed (crosshead speed) 2 mm / min Measurement environment: temperature 25 ° C, humidity 45% RH
  • Table 2 shows the evaluation, observation, and test results of 1 to 7 described above.
  • Compositions for optical stereolithography of Reference Examples 1 to 12 using a diallyl phthalate-based polymer as the component (A) and Examples 1 to 3 using a diallylcycloalkane-based polymer which is a non-phthalate-type allyl resin are described in US Pat. Since the curing time is up to 10 seconds, it can be seen that the curing time is shorter than that of the comparative example, the sensitivity is high, and the curing speed is high. This indicates that the cured density is high.
  • the three-dimensional molded products obtained by laminating the cured layers of the optical three-dimensional molding compositions of Reference Examples 1 to 12 and Examples 1 to 3 are warped because the cured films are in close contact with each other. It was not observed, and was excellent in tensile strength, elongation, bending strength and flexural modulus, and repeated bending strength, and almost no drop crack was observed.

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  • Medicinal Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Polymers & Plastics (AREA)
  • Manufacturing & Machinery (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Optics & Photonics (AREA)
  • Polymerisation Methods In General (AREA)
  • Graft Or Block Polymers (AREA)
  • Macromonomer-Based Addition Polymer (AREA)

Abstract

La présente invention concerne une composition qui sert à la stéréolithographie optique et qui permet un achèvement plus rapide de la stéréolithographie optique (durcissement optique) pour fournir un objet stéréolithographique présentant une résistance supérieure (une résistance qui empêche l'apparition d'une fissure, etc., lorsque ledit objet reçoit un choc ou est laissé tomber, et une résistance qui résiste à la flexion répétitive). La composition pour stéréolithographie optique selon la présente invention comprend (A) un polymère de diallylcycloalcane ayant un cycle carbone comprenant de 3 à 8 atomes de carbone, (B) un composé polymérisable par voie radicalaire comprenant un groupe méthacryle et/ou un groupe acryle, (C) un initiateur de polymérisation radicalaire, et (D) un agent de sensibilisation, la composition contenant, comme (B), au moins (B1) un (méth)acrylate époxy comprenant un groupe méthacryle et/ou un groupe acryle, ou (B2) un (méth)acrylate de dioxane comprenant un groupe méthacryle et/ou un groupe acryle, et qui contient de 0,5 à 10 % en masse de (A), de 5 à 43 % en masse de (B1) et (B2), de 20 à 95 % en masse de (B) excluant (B1) et (B2), de 0,1 à 5 % en masse de (C), et de 0,1 à 5 % en masse de (D).
PCT/JP2019/001476 2018-09-26 2019-01-18 Composition pour stéréolithographie optique, objet stéréolithographique, et son procédé de production WO2020066047A1 (fr)

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JPH01131223A (ja) * 1987-08-14 1989-05-24 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性樹脂組成物並びに被覆組成物および印刷インキ組成物
JPH0673145A (ja) * 1992-08-26 1994-03-15 Showa Denko Kk 光学材料用組成物
JP2001310916A (ja) * 2000-04-27 2001-11-06 Nippon Shokubai Co Ltd 重合性樹脂組成物、その製造方法及びその硬化物
JP2003012782A (ja) * 2001-04-24 2003-01-15 Showa Denko Kk 新規（メタ）アリルエステル化合物、該化合物の製造方法、該化合物を用いたプラスチックレンズ用組成物、該組成物を硬化してなるプラスチックレンズ及び該プラスチックレンズの製造方法
JP2004109851A (ja) * 2002-09-20 2004-04-08 Fuji Photo Film Co Ltd 樹脂組成物
JP2008001795A (ja) * 2006-06-22 2008-01-10 San Nopco Ltd 放射線硬化性組成物
JP2010260917A (ja) * 2009-04-30 2010-11-18 Sakamoto Yakuhin Kogyo Co Ltd 活性エネルギー線硬化型樹脂組成物
WO2016125661A1 (fr) * 2015-02-03 2016-08-11 株式会社大阪ソーダ Composition de résine photodurcissable, encre et matériau de revêtement
WO2019039185A1 (fr) * 2017-08-24 2019-02-28 株式会社大阪ソーダ Composition de résine de polyester insaturé

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH01131223A (ja) * 1987-08-14 1989-05-24 Toyo Ink Mfg Co Ltd 活性エネルギー線硬化性樹脂組成物並びに被覆組成物および印刷インキ組成物
JPH0673145A (ja) * 1992-08-26 1994-03-15 Showa Denko Kk 光学材料用組成物
JP2001310916A (ja) * 2000-04-27 2001-11-06 Nippon Shokubai Co Ltd 重合性樹脂組成物、その製造方法及びその硬化物
JP2003012782A (ja) * 2001-04-24 2003-01-15 Showa Denko Kk 新規（メタ）アリルエステル化合物、該化合物の製造方法、該化合物を用いたプラスチックレンズ用組成物、該組成物を硬化してなるプラスチックレンズ及び該プラスチックレンズの製造方法
JP2004109851A (ja) * 2002-09-20 2004-04-08 Fuji Photo Film Co Ltd 樹脂組成物
JP2008001795A (ja) * 2006-06-22 2008-01-10 San Nopco Ltd 放射線硬化性組成物
JP2010260917A (ja) * 2009-04-30 2010-11-18 Sakamoto Yakuhin Kogyo Co Ltd 活性エネルギー線硬化型樹脂組成物
WO2016125661A1 (fr) * 2015-02-03 2016-08-11 株式会社大阪ソーダ Composition de résine photodurcissable, encre et matériau de revêtement
WO2019039185A1 (fr) * 2017-08-24 2019-02-28 株式会社大阪ソーダ Composition de résine de polyester insaturé

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