WO2020066047A1 - Composition for optical stereolithography, stereolithographic object, and production method therefor - Google Patents
Composition for optical stereolithography, stereolithographic object, and production method therefor Download PDFInfo
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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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- acrylate
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- VTLHIRNKQSFSJS-UHFFFAOYSA-N [3-(3-sulfanylbutanoyloxy)-2,2-bis(3-sulfanylbutanoyloxymethyl)propyl] 3-sulfanylbutanoate Chemical compound CC(S)CC(=O)OCC(COC(=O)CC(C)S)(COC(=O)CC(C)S)COC(=O)CC(C)S VTLHIRNKQSFSJS-UHFFFAOYSA-N 0.000 description 1
- YSVZGWAJIHWNQK-UHFFFAOYSA-N [3-(hydroxymethyl)-2-bicyclo[2.2.1]heptanyl]methanol Chemical compound C1CC2C(CO)C(CO)C1C2 YSVZGWAJIHWNQK-UHFFFAOYSA-N 0.000 description 1
- DBHQYYNDKZDVTN-UHFFFAOYSA-N [4-(4-methylphenyl)sulfanylphenyl]-phenylmethanone Chemical compound C1=CC(C)=CC=C1SC1=CC=C(C(=O)C=2C=CC=CC=2)C=C1 DBHQYYNDKZDVTN-UHFFFAOYSA-N 0.000 description 1
- MZVQCMJNVPIDEA-UHFFFAOYSA-N [CH2]CN(CC)CC Chemical group [CH2]CN(CC)CC MZVQCMJNVPIDEA-UHFFFAOYSA-N 0.000 description 1
- GUCYFKSBFREPBC-UHFFFAOYSA-N [phenyl-(2,4,6-trimethylbenzoyl)phosphoryl]-(2,4,6-trimethylphenyl)methanone Chemical compound CC1=CC(C)=CC(C)=C1C(=O)P(=O)(C=1C=CC=CC=1)C(=O)C1=C(C)C=C(C)C=C1C GUCYFKSBFREPBC-UHFFFAOYSA-N 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 1
- 229920000704 biodegradable plastic Polymers 0.000 description 1
- JQRRFDWXQOQICD-UHFFFAOYSA-N biphenylen-1-ylboronic acid Chemical compound C12=CC=CC=C2C2=C1C=CC=C2B(O)O JQRRFDWXQOQICD-UHFFFAOYSA-N 0.000 description 1
- YLTDNYQTDYMOBH-UHFFFAOYSA-N bis(prop-2-enyl) 2-hydroxybutanedioate Chemical compound C=CCOC(=O)C(O)CC(=O)OCC=C YLTDNYQTDYMOBH-UHFFFAOYSA-N 0.000 description 1
- ZDNFTNPFYCKVTB-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,4-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=C(C(=O)OCC=C)C=C1 ZDNFTNPFYCKVTB-UHFFFAOYSA-N 0.000 description 1
- VYHBFRJRBHMIQZ-UHFFFAOYSA-N bis[4-(diethylamino)phenyl]methanone Chemical compound C1=CC(N(CC)CC)=CC=C1C(=O)C1=CC=C(N(CC)CC)C=C1 VYHBFRJRBHMIQZ-UHFFFAOYSA-N 0.000 description 1
- 150000001639 boron compounds Chemical class 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 125000006226 butoxyethyl group Chemical group 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 238000010538 cationic polymerization reaction Methods 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 229940109262 curcumin Drugs 0.000 description 1
- 235000012754 curcumin Nutrition 0.000 description 1
- 239000004148 curcumin Substances 0.000 description 1
- 150000007973 cyanuric acids Chemical class 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000004386 diacrylate group Chemical group 0.000 description 1
- VFLDPWHFBUODDF-UHFFFAOYSA-N diferuloylmethane Natural products C1=C(O)C(OC)=CC(C=CC(=O)CC(=O)C=CC=2C=C(OC)C(O)=CC=2)=C1 VFLDPWHFBUODDF-UHFFFAOYSA-N 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical compound C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- UHESRSKEBRADOO-UHFFFAOYSA-N ethyl carbamate;prop-2-enoic acid Chemical compound OC(=O)C=C.CCOC(N)=O UHESRSKEBRADOO-UHFFFAOYSA-N 0.000 description 1
- 125000000031 ethylamino group Chemical group [H]C([H])([H])C([H])([H])N([H])[*] 0.000 description 1
- 230000006355 external stress Effects 0.000 description 1
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000000891 luminescent agent Substances 0.000 description 1
- 229910001507 metal halide Inorganic materials 0.000 description 1
- 150000005309 metal halides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- YLHXLHGIAMFFBU-UHFFFAOYSA-N methyl phenylglyoxalate Chemical compound COC(=O)C(=O)C1=CC=CC=C1 YLHXLHGIAMFFBU-UHFFFAOYSA-N 0.000 description 1
- 125000002757 morpholinyl group Chemical group 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 125000003566 oxetanyl group Chemical group 0.000 description 1
- 125000001037 p-tolyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)C([H])([H])[H] 0.000 description 1
- FZUGPQWGEGAKET-UHFFFAOYSA-N parbenate Chemical compound CCOC(=O)C1=CC=C(N(C)C)C=C1 FZUGPQWGEGAKET-UHFFFAOYSA-N 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 125000003356 phenylsulfanyl group Chemical group [*]SC1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 229920000223 polyglycerol Polymers 0.000 description 1
- 239000005076 polymer ester Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920006295 polythiol Polymers 0.000 description 1
- 238000011417 postcuring Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- FBCQUCJYYPMKRO-UHFFFAOYSA-N prop-2-enyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC=C FBCQUCJYYPMKRO-UHFFFAOYSA-N 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 238000007348 radical reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 235000012424 soybean oil Nutrition 0.000 description 1
- 239000003549 soybean oil Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 description 1
- UWHCKJMYHZGTIT-UHFFFAOYSA-N tetraethylene glycol Chemical compound OCCOCCOCCOCCO UWHCKJMYHZGTIT-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 229940042596 viscoat Drugs 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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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Abstract
Provided is a composition that is for optical stereolithography and that allows quicker completion of optical stereolithography (optical curing) to provide a stereolithographic object having a superior strength (e.g., a strength that prevents occurrence of a crack, etc., when impacted or dropped, and a strength that resists repetitive bending). The composition for optical stereolithography according to the present invention comprises (A) a diallylcycloalkane polymer having a carbon ring having 3-8 carbon atoms, (B) a radically polymerizable compound having a methacryl group and/or an acryl group, (C) a radical polymerization initiator, and (D) a sensitizer, wherein the composition contains, as (B), at least (B1) an epoxy (meth)acrylate having a methacryl group and/or an acryl group, or (B2) a dioxane (meth)acrylate having a methacryl group and/or an acryl group, and contains 0.5-10 mass% of (A), 5-43 mass% of (B1) and (B2), 20-95 mass% of (B) excluding (B1) and (B2), 0.1-5 mass% of (C), and 0.1-5 mass% of (D).
Description
本発明は、光学的立体造形用組成物、並びに立体造形物、及びその製造方法に関するものである。
The present invention relates to a composition for optical three-dimensional modeling, a three-dimensional molded article, and a method for producing the same.
近年、3次元CADデータに基づいて、光硬化性樹脂を紫外線レーザーの走査により硬化させて形成した硬化層を積層することによって、立体造形物を作製する光学的立体造形技術が着目されている。光学的立体造形技術(以下、「光学的立体造形」を「光造形」とも称する。)によれば、金型や鋳型を用意せずに、簡便に素早く試作品を作製することができるため、製品開発の設計から生産までに要する時間とコストを削減することができる。光造形技術は、3次元CADが急速に普及したことに伴い、自動車部品や、電気機器、医療機器など、多岐にわたる産業分野で採用されてきた。
In recent years, attention has been focused on an optical three-dimensional molding technique for producing a three-dimensional molded object by laminating a cured layer formed by curing a photocurable resin by scanning with an ultraviolet laser based on three-dimensional CAD data. According to the optical three-dimensional modeling technology (hereinafter, “optical three-dimensional modeling” is also referred to as “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. BACKGROUND ART With the rapid spread of three-dimensional CAD, stereolithography has been adopted in a wide variety of industrial fields such as automobile parts, electric equipment, and medical equipment.
光学的立体造形技術の適用分野の拡大により、光硬化性樹脂に要求される性能も高まっている。特に、硬化速度が速く、硬化時の寸法安定性や寸法精度に優れ、曲げなどの外部応力が加えられても破損しにくい、靱性や耐久性などの機械特性及び耐熱性に優れた立体造形物を形成できる光硬化性樹脂が求められている。例えば、光硬化性樹脂の原料として、ポリグリセリンアルキレンオキサイド付加物(付加モル数50~200)の(メタ)アクリレートを含有させることにより、活性エネルギー線を照射してコーティング塗膜を作成した際、基材フィルムの反りや塗膜のひび割れを発生させることのない光硬化性樹脂を得たことが記載されている(特許文献1)。
性能 With the expansion of the application field of the optical three-dimensional molding technology, the performance required for the photocurable resin is also increasing. In particular, a three-dimensional structure that has a high curing speed, excellent dimensional stability and dimensional accuracy during curing, is resistant to breakage even when subjected to external stress such as bending, and has excellent mechanical properties such as toughness and durability and heat resistance. There is a demand for 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).
また、立体造形技術の進展に伴い、例えばエンジン部分に用いられる立体造形物等の、より高い耐熱性を必要とする用途へ適用できる光硬化性樹脂が求められており、例えば、特定のカチオン重合性有機物質や、オキセタニル基を2個有する特定の化合物を配合した組成物が提案されている(特許文献2、特許文献3、特許文献4)。
In addition, with the development of three-dimensional molding technology, there is a demand for a photocurable resin that can be applied to applications requiring higher heat resistance, such as a three-dimensional molded product used for an engine part, for example, a specific cationic polymerization. There have been proposed compositions containing a volatile organic substance and a specific compound having two oxetanyl groups (Patent Documents 2, 3, and 4).
光造形で製造された商用造形物は、複雑な形状を有している場合が多く、力を加えたり、曲げたり、熱が加わったりする用途に適応しなければならない。しかしながら、一般に、立体造形物の製造においては、光造形用組成物に紫外線レーザーを走査して形成した厚さ約20~100ミクロン程度の薄い硬化膜層を何層も重ねて立体造形物を製造するが、このとき、薄い硬化膜層同士が相互に密着しないと立体造形物の強度に影響する場合がある。さらに、従来の光造形用組成物は、製造途中で立体造形物が反って紫外線レーザー走査機に引っかかる場合があるという問題があった。
商用 Manufactured objects manufactured by stereolithography often have complicated shapes, and must be adapted to applications in which force is applied, bent, or heated. However, in general, in the production of a three-dimensional object, 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. However, at this time, if the thin cured film layers do not adhere to each other, the strength of the three-dimensional structure may be affected. Further, 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.
また、特許文献2に記載されているように、立体造形物の耐熱性を向上させるために、組成物を光照射によって硬化させた後にさらに紫外線照射処理や加熱処理が一般的に施されているが、このような紫外線照射処理を行っても、まだ満足する強度(例えば、衝撃を受けたとき、落下したとき、割れ等の発生を防ぐ強度)は提供されていない。
Further, as described in Patent Document 2, in order to improve the heat resistance of a three-dimensional molded object, after the composition is cured by light irradiation, an ultraviolet irradiation treatment or a heat treatment is generally performed. However, even if such an ultraviolet irradiation treatment is performed, a satisfactory strength (for example, a strength for preventing occurrence of cracks or the like when subjected to an impact, when dropped, or the like) has not been provided yet.
さらに、特許文献2に記載されているように、立体造形物の耐熱性を向上させるために、組成物を光照射によって硬化させた後にさらに、例えば60~250℃で加熱させることが一般的に行われているが、このように加熱処理を行うと、工程が増えるため作業効率が悪くなるおそれがあった。
Further, as described in 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.
そこで本発明は、上記の課題に鑑み、より短時間で光造形(光硬化)が完了し、光造形後に紫外線照射処理を施すことで、優れた強度(例えば、衝撃を受けたとき、落下したとき、割れ等の発生を防ぐ強度、繰り返しの折り曲げに耐えられる強度)を有する立体造形物が得られる、非水溶性のラジカル重合性成分からなる光学的立体造形用組成物、その立体造形物、及び立体造形物の製造方法を提供することを目的とする。
In view of the above problems, 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. Sometimes, 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.
上記目的を達成するため、本発明は、その一態様によれば、光学的立体造形用組成物であって、この光学的立体造形用組成物は、(A)ジアリルシクロアルカン系ポリマー、又はジアリルシクロアルカン系ポリマーとジアリルフタレート系ポリマーとの組み合わせと、(B)メタクリル基及び/又はアクリル基を有するラジカル重合性化合物と、(C)ラジカル重合開始剤と、(D)増感剤とを含む光学的立体造形用組成物であって、前記(A)のジアリルシクロアルカン系ポリマーの炭素環の炭素数が3~8の範囲であり、前記(B)のメタクリル基及び/又はアクリル基を有するラジカル重合性化合物として、(B1)メタクリル基及び/若しくはアクリル基を有するエポキシ(メタ)アクリレートのラジカル重合性化合物、及び/又は(B2)メタクリル基及び/若しくはアクリル基を有するジオキサン(メタ)アクリレートのラジカル重合性化合物を少なくとも含み、前記(A)のジアリルシクロアルカン系ポリマー、又はジアリルシクロアルカン系ポリマーとジアリルフタレート系ポリマーとの組み合わせを0.5~10質量%、前記(B1)及び前記(B2)のラジカル重合性化合物を合計で5~43質量%、前記(B)のラジカル重合性化合物のうち、前記(B1)及び前記(B2)以外のラジカル重合性化合物を20~95質量%、前記(C)のラジカル重合開始剤を0.1~5質量%、及び、前記(D)の増感剤を0.1~5質量%を含有するものである。
In order to achieve the above object, according to one aspect of the present invention, there is provided a composition for optical stereolithography, wherein the 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). As 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 mass of the radical polymerizable compound other than (B2), 0.1 to 5% by mass of the radical polymerization initiator of (C), and 0.1 to 5% by mass of the sensitizer of (D). It contains 5% by mass.
本発明に係る光学的立体造形用組成物は、さらに、(E)ジアリルフタレート系ポリマーではないアリル基を有する化合物を0.125~2.5質量%含有してもよい。
The 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.
本発明に係る光学的立体造形用組成物において、前記(A)のジアリルシクロアルカン系ポリマーが、ジアリルシクロアルカンジカルボキシレートポリマーであってもよい。また、前記(A)のジアリルフタレート系ポリマーは、ジアリルオルソフタレートポリマー又はジアリルイソフタレートポリマーであってもよい。
に お い て In the composition for optical stereolithography according to the present invention, 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.
本発明に係る光学的立体造形用組成物は、さらに、(F)下記一般式(1)
(式中、nは2~20の整数、及びmは50~200の整数を表す。)の構造を有するポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物を5~40質量%含有してもよい。 The 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.
(式中、nは2~20の整数、及びmは50~200の整数を表す。)の構造を有するポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物を5~40質量%含有してもよい。 The 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.
本発明は、また別の態様として、立体造形物の製造方法であって、上述した光学的立体造形用組成物に、活性エネルギー線を照射して硬化させる工程を少なくとも含む。
As another aspect, 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.
本発明は、更に別の態様として、立体造形物であって、上述した光学的立体造形用組成物の硬化物からなるものである。
As another aspect, the present invention relates to a three-dimensional structure, which is a cured product of the above-described composition for optical three-dimensional structure.
本発明によれば、立体造形物を製造する際の光硬化時間を短縮することができ、また、光硬化後に紫外線照射処理を施すことで、優れた強度(例えば、衝撃を受けたとき、若しくは落下したとき、割れ等の発生を防ぐ強度、及び繰り返しの折り曲げに耐えられる柔軟性がある強度)の立体造形物を製造することが可能な、光学的立体造形用組成物を提供することができる。また、この光学的立体造形用組成物を用いれば、立体造形物の製造過程において硬化層膜が相互に密着するために反り変形が小さくなり、さらに、層間の接着が良いので強度(例えば、曲げ強度、曲げ弾性率、繰り返し曲げ強度等)が高い立体造形物を得ることが可能となる。
According to 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. . In addition, when the optical three-dimensional structure forming composition is used, 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.
以下、本発明に係る光学的立体造形用組成物、その立体造形物、及び立体造形物の製造方法の一実施の形態について説明するが、本発明の範囲は、この形態に限定されるものではない。
Hereinafter, an embodiment of the 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.
本実施の形態の光学的立体造形用組成物は、以下に詳細を後述する成分(A)~(D)を少なくとも含有し、好ましくは成分(E)及び/又は(F)をさらに含有し、必要に応じてその他の成分をさらに含有する。
The 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.
成分(A)は、ジアリルシクロアルカン系ポリマー、又はジアリルシクロアルカン系ポリマーとジアリルフタレート系ポリマーとの組み合わせである。ジアリルシクロアルカン系ポリマー(ジアリルシクロアルカン樹脂とも呼ばれる)の炭素環の炭素数は3~8の範囲であり、好ましくは5~6の範囲である。ジアリルシクロアルカン系ポリマーとしては、例えば、ジアリル-1,2-シクロアルカンポリマー、ジアリル-1,3-シクロアルカンポリマーが挙げられる。また、ジアリルシクロアルカン系ポリマーとしては、ジアリルシクロアルカンジカルボキシレートポリマーが好ましく、例えば、ジアリル-1,2-シクロアルカンジカルボキシレートポリマー、ジアリル-1,3-シクロアルカンジカルボキシレートポリマーが挙げられる。より具体的には、例えば、ジアリル-1,2-シクロヘキサンジカルボキシレートポリマー、ジアリル-1,3-シクロヘキサンジカルボキシレートポリマーが挙げられる。また、ジアリルフタレート系ポリマー(ジアリルフタレート樹脂とも呼ばれる)の具体例としては、例えば、ジアリルオルソフタレートポリマー、ジアリルイソフタレートポリマーが挙げられる。光学的立体造形物組成物に成分(A)を加えることにより、立体造形物とした際に十分な機械的強度及び柔軟性を得ることが可能となり、加えて優れた強度(例えば、衝撃を受けたとき、落下したとき、割れ等の発生を防ぐ強度)が得られる。なお、ジアリルフタレート系ポリマー単独であっても、ジアリルシクロアルカン系ポリマーと同等の効果を得ることができる。
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. As the diallylcycloalkane-based 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. 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.
ジアリルフタレート系ポリマーについて更に詳細に説明すると、ジアリルオルソフタレートポリマーは、オルソフタル酸ジアリルエステルをモノマーとして用いる重合反応によって得られるものであり、以下のオルソA構造とオルソB構造の2種類の構造を有する。通常、オルソ体は、二つのエステル位置が近いため、オルソB構造も形成されやすい。
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. . Usually, in the ortho form, two ester positions are close to each other, so that an ortho B structure is easily formed.
また、ジアリルメタフタレートポリマーは、メタフタル酸ジアリルエステルをモノマーとして用いる重合反応によって得られるものであり、以下のメタA構造とメタB構造の2種類の構造を有する。通常、メタ体は、二つのエステル位置が離れているため、メタB構造は形成されにくく、ほとんど、メタA構造が形成される。
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. 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.
ジアリルシクロアルカン系ポリマーについて更に詳細に説明すると、ジアリル-1,2-シクロヘキサンジカルボキシレートポリマーは、オルソ水素添加フタル酸ジアリルエステルをモノマーとして用いる重合反応によって得られるものであり、以下のオルソA構造とオルソB構造の2種類の構造を有する。通常、オルソ体は、二つのエステル位置が近いため、オルソB構造も形成しやすい。
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. Usually, in the ortho form, two ester positions are close to each other, so that an ortho B structure is easily formed.
また、ジアリル-1,3-シクロヘキサンジカルボキシレートポリマーは、メタ水素添加フタル酸ジアリルエステルをモノマーとして用いる重合反応によって得られるものであり、以下のメタA構造とメタB構造の2種類の構造を有する。通常、メタ体は、二つのエステル位置が離れているため、メタB構造は形成されにくい。
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.
成分(A)のジアリルシクロアルカン系ポリマーやジアリルフタレート系ポリマーは、公知の方法で合成できるほか、市販のものを用いることができる。例えば、ジアリルシクロアルカン系ポリマーでは、例えば、大阪ソーダ社製のRADPAR AD-032や、RADPAR AD-044等がある。また、ジアリフフタレート系ポリマーでは、例えば、大阪ソーダ社製のダイソーダップA、ダイソーダップK、ダイソーダップS、ダイソーイソダップ等がある。
(4) The 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. For example, diallylcycloalkane-based polymers include, for example, RADPAR @ AD-032 and RADPAR @ AD-044 manufactured by Osaka Soda Co., Ltd. In addition, examples of the dialifphthalate-based polymer include, for example, Daisodap A, Daisodap K, Daisodap S, and Daiso Isodap manufactured by Osaka Soda Co., Ltd.
成分(A)のジアリルシクロアルカン系ポリマー、又はジアリルシクロアルカン系ポリマーとジアリルフタレート系ポリマーとの組み合わせの含有量は、光学的立体造形用組成物の総量中に、0.5~10質量%の範囲であり、好ましくは1~8質量%である。成分(A)の含有量が0.5質量%未満の場合は、ジアリルシクロアルカン系ポリマーやジアリルフタレート系ポリマーの影響が光学的立体造形用組成物に現れず、硬くて脆い組成物となる。含有量が10質量%を超える場合は、表面の部分でしか硬化できず、全体として柔らかくて脆い組成物となる。
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. When 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. When 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.
成分(B)は、メタクリル基及び/又はアクリル基を有するラジカル重合性化合物であり、この成分(B)のメタクリル基及び/又はアクリル基を有するラジカル重合性化合物として、成分(B1)のメタクリル基及び/若しくはアクリル基を有するエポキシ(メタ)アクリレート、又は成分(B2)のメタクリル基及び/若しくはアクリル基を有するジオキサン(メタ)アクリレートを少なくとも含む。光学的立体造形用組成物に成分(B1)又は成分(B2)のラジカル重合性化合物を加えることによって、機械的強度及び柔軟性を付与することができ、破断しにくい硬化物が得られる。
The component (B) is a radically polymerizable compound having a methacryl group and / or an acryl group. As 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. And / or epoxy (meth) acrylate having an acrylic group, or dioxane (meth) acrylate having a methacryl group and / or an acrylic group of component (B2). By adding the radically polymerizable compound of the component (B1) or the component (B2) to the composition for optical three-dimensional modeling, mechanical strength and flexibility can be imparted, and a cured product that is hard to break can be obtained.
成分(B1)のメタクリル基及び/又はアクリル基を有するエポキシ(メタ)アクリレートの具体例としては、ビスフェノールAジグリシジルエーテル(メタ)アクリル酸付加物、ビスフェノールAジグリシジルエーテル(メタ)アクリル酸付加物、エチレングリコールジグリシジルエーテル(メタ)アクリル酸付加物、プロピレングリコールジグリシジルエーテル(メタ)アクリル酸付加物、グリセリンジグリシジルエーテル(メタ)アクリル酸付加物、ビスフェノールA(PO2mol)付加物ジグリシジルエーテル(メタ)アクリル酸付加物、エポキシ化大豆油(メタ)アクリル酸付加物、ノボラック系エポキシ樹脂(メタ)アクリル酸付加物等が挙げられる。
Specific examples of the 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.
成分(B1)のメタクリル基及び/若しくはアクリル基を有するエポキシ(メタ)アクリレートは、公知の方法で合成できるほか、市販のものを用いることができる。例えば、共栄社化学社製のエポキシエステルシリーズ40EM、70PA、200PA、80MFA、3002M(N)、3002A(N)、3000MK、3000A、ダイセル・オルネックス社製のEBECRYLシリーズ600、605、645、648、860、3500、3603、3608、3700、3701、3702、3703、3708、日本火薬社製のKAYARADシリーズR-115F、R-130、R-381、EAM-2160、ZFA-266H、大阪有機化学工業社製のビスコートシリーズ#540、米国サートマー社製のCNシリーズ104、111、115、116、118、120、120A60、等が挙げられる。
エ ポ キ シ 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. For example, epoxy ester series 40EM, 70PA, 200PA, 80MFA, 3002M (N), 3002A (N), 3000MK, 3000A manufactured by Kyoeisha Chemical Co., Ltd., EBECRYL series 600, 605, 645, 648, 860 manufactured by Daicel Ornex, Inc. 3500, 3603, 3608, 3700, 3701, 3702, 3703, 3708, KAYARAD series R-115F, R-130, R-381, EAM-2160, ZFA-266H, manufactured by Nippon Kayaku Co., Ltd. Viscoat series # 540, CN series 104, 111, 115, 116, 118, 120, 120A60 manufactured by Sartomer, USA, and the like.
成分(B1)のメタクリル基及び/若しくはアクリル基を有するエポキシ(メタ)アクリレートの含有量は、光学的立体造形用組成物の総量中に、5~43質量%の範囲であり、好ましくは10~30質量%の範囲である。成分(B1)の含有量が5質量%未満の場合は、立体造形物とした際に靭性が不十分となる。含有量が43質量%を超える場合は、立体造形物を得るために照射する活性エネルギー線に対する感度が低下し、所望の立体造形物を得られなくなる。
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. When the content of the component (B1) is less than 5% by mass, the toughness becomes insufficient when a three-dimensional structure is formed. When 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.
成分(B2)のメタクリル基及び/若しくはアクリル基を有するジオキサン(メタ)アクリレートの具体例としては、ジオキサングリコールジ(メタ)アクリレート、メタクリル酸(2-オキソ-1,3-ジオキソラン-4-イル)メチル等が挙げられる。
Specific examples of the 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.
成分(B2)のメタクリル基及び/若しくはアクリル基を有するジオキサン(メタ)アクリレートは、公知の方法で合成できるほか、市販のものを用いることができる。例えば、日本化薬社製のKAYARAD R-604、新中村化学工業社製のNKエステルA-DOGが挙げられる。
ジ オ 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. For example, KAYARAD® R-604 manufactured by Nippon Kayaku Co., Ltd., and NK ester A-DOG manufactured by Shin-Nakamura Chemical Co., Ltd. may be mentioned.
成分(B2)のメタクリル基及び/又はアクリル基を有するジオキサン(メタ)アクリレートの含有量は、光学的立体造形用組成物の総量中に5~43質量%の範囲であり、好ましくは10~30質量%の範囲である。成分(B2)の含有量が5質量%未満の場合は、硬化が遅くなり、立体造形物とした際に脆くなる。含有量が43質量%を超える場合は、硬化が速くなりすぎて、薄い硬化膜層同士の相互の密着が悪くなり立体造形物の強度が低くなる。なお、成分(B1)と成分(2)は同時に含有してもよく、その場合の含有量は、成分(B1)と成分(B2)の合計で、光学的立体造形用組成物の総量中に5~43質量%の範囲とし、好ましくは10~30質量%の範囲とする。
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. When 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. In addition, 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.
また、成分(B)のメタクリル基及び/又はアクリル基を有するラジカル重合性化合物としては、上述した成分(B1)及び成分(B2)以外の他のラジカル重合性化合物をさらに含有することができる(以下、「成分(B)の他のラジカル重合性化合物」と呼ぶ)。この成分(B)の他のラジカル重合性化合物の含有量は、光学的立体造形用組成物の性能を損なわない程度であれば特に限定されず、例えば、光学的立体造形用組成物の総量中に20~95質量%とするのが好ましく、20~85質量%とするのがより好ましい。
Further, 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.
成分(B)の他のラジカル重合性化合物の単官能モノマーの具体例としては、例えば、(メタ)アクリロイルモルホリン、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシルプロピル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)クリレート、グリセリン(メタ)アクリレート、ノニルフェノールEO変性(メタ)アクリレート、2-ヒドロキシルエチル(メタ)アクリレートと無水リン酸の反応物、2-ヒドロキシルエチル(メタ)アクリレートのヘキサリド付加重合物と無水リン酸の反応生成物、アクリルアミド、7-アミノ-3,7-ジメチルオクチル(メタ)アクリレート、イソブトキシメチル(メタ)アクリルアミド、イソボニル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ジアセトン(メタ)アクリルアミド、ジメチルアミノエチル(メタ)アクリレート、ジエチルアミノエチル(メタ)アクリレート、ラウリル(メタ)アクリレート、ジシクロペンテニルオキシエチル(メタ)アクリレート、ジシクロペンテニル(メタ)アクリレート、N,N-ジメチル(メタ)アクリルアミド、テトラヒドロフルフリル(メタ)アクリレート、ビニルカプロラクタム、N-ビニルピロリドン、フェノキシエチル(メタ)アクリレート、ブトキシエチル(メタ)アクリレート、ペンタクロロフェニル(メタ)アクリレート、ペンタブロモフェニル(メタ)アクリレート、ポリエチレングリコールモノ(メタ)アクリレート、イソボニル(メタ)アクリレート等を挙げる
ことができる。 Specific examples of 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, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (Meth) acrylamide, tetrahydrofurfuryl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, Examples include polyethylene glycol mono (meth) acrylate and isobonyl (meth) acrylate.
ことができる。 Specific examples of 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, dimethylaminoethyl (meth) acrylate, diethylaminoethyl (meth) acrylate, lauryl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, N, N-dimethyl (Meth) acrylamide, tetrahydrofurfuryl (meth) acrylate, vinylcaprolactam, N-vinylpyrrolidone, phenoxyethyl (meth) acrylate, butoxyethyl (meth) acrylate, pentachlorophenyl (meth) acrylate, pentabromophenyl (meth) acrylate, Examples include polyethylene glycol mono (meth) acrylate and isobonyl (meth) acrylate.
成分(B)の他のラジカル重合性化合物の2官能モノマーの具体例としては、トリエチレングリコールジ(メタ)アクリレート、テトラエチレングリコールジ(メタ)アクリレート、ポリエチレングリコール(400)ジ(メタ)アクリレート、ポリエチレングリコール(600)ジ(メタ)アクリレート、ポリプロピレングリコール(400)ジ(メタ)アクリレート、エトキシ化(4)ビスフェノールAジ(メタ)アクリレート、エトキシ化(10)ビスフェノールAジ(メタ)アクリレート、エトキシ化(30)ビスフェノールAジ(メタ)アクリレート、エトキシ化(4)水添ビスフェノールAジ(メタ)アクリレート、エトキシ化(30)水添ビスフェノールAジ(メタ)アクリレート、EO変性(10)水添ビスフェノールAジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、トリシクロデカンジイルジメチレンジ(メタ)アクリレート、トリプロピレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、ヒドロキシピバリン酸ネオペンチルグリコール(メタ)アクリル酸付加物、カプロラクトン変性ヒドロキシピバリン酸ネオペンチルグリコールエステルジ(メタ)アクリレート、ポリエステルジ(メタ)アクリレート、ポリエステル系ウレタン2官能(メタ)アクリレート、脂肪族ウレタンアクリレート、3ーヒドロキシー2,2ージメチルプロピルー3ーヒドロキシー2,2ージメチルプロピオナートの6ーヘキサノリド付加重合物(重合度1~7)と(メタ)アクリル酸のエステル化合物等を挙げることができる。
Specific examples of the 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, tripropylene glycol di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,4-butanediol di ( (Meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol hydroxypivalate (meth) acrylic acid adduct, caprolactone-modified neopentyl glycol hydroxypivalate ester di (meth) acrylate, polyester di (meth) Acrylate, polyester urethane bifunctional (meth) acrylate, aliphatic urethane acrylate, 3-hydroxy-2,2-dimethylpropyl-3-hydroxy-2,2-dimethylpropionate And the like 6 Hekisanorido addition polymer ester compound (polymerization degree 1-7) and (meth) acrylic acid.
成分(B)の他のラジカル重合性化合物の多官能モノマーの具体例としては、エトキシ化(9)グリセリントリ(メタ)アクリレート、エトキシ化(20)グリセリントリ(メタ)アクリレート、ポリエーテル系3官能(メタ)アクリレート、トリス(アクリロイルオキシエチル)イソシアヌレート、トリメチロールプロパントリ(メタ)アクリレート、EO変性トリメチロールプロパントリ(メタ)アクリレート、PO変性トリメチロールプロパントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ジペンタエリスリトールヘキサ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート、ジトリメチロールプロパンテトラ(メタ)アクリレート、ジペンタエリスリトールモノヒドロキシペンタ(メタ)アクリレート、ε-カプロラクトン変性ジペンタエリスリトールの(メタ)アクリレート、ポリエーテル系ウレタン3官能(メタ)アクリレート、エトキシ化イソシアヌル酸トリ(メタ)アクリレート、脂肪族ウレタンアクリレートを挙げることができる。
Specific examples of the polyfunctional monomer of another radical polymerizable compound of the component (B) include ethoxylated (9) glycerin tri (meth) acrylate, ethoxylated (20) glycerin tri (meth) acrylate, and polyether trifunctional. (Meth) acrylate, tris (acryloyloxyethyl) isocyanurate, trimethylolpropanetri (meth) acrylate, EO-modified trimethylolpropanetri (meth) acrylate, PO-modified trimethylolpropanetri (meth) acrylate, pentaerythritol tri (meth) ) Acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol monohydroxy Pointer (meth) acrylate, .epsilon.-caprolactone-modified dipentaerythritol (meth) acrylate, polyether urethane trifunctional (meth) acrylate, ethoxylated isocyanuric acid tri (meth) acrylate, and aliphatic urethane acrylates.
成分(B)の他のラジカル重合性化合物は、公知の方法で合成できるほか、市販のものを用いることができる。例えば、単官能モノマーは東亜合成社製のアロニックスM-111等が挙げられ、2官能モノマーは共栄社化学社製のライトエステル4EG、日本化薬社製のKAYARADシリーズ HX-220、HX-620等が挙げられ、多官能モノマーは東亜合成社製のアロニックスM-306等が挙げられる。
ラ ジ カ ル The other radical polymerizable compound of the component (B) can be synthesized by a known method, or a commercially available compound can be used. For example, monofunctional monomers include Aronix M-111 manufactured by Toagosei Co., Ltd., and 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.
成分(C)は、ラジカル重合開始剤であり、活性エネルギー線の照射によってラジカル種を発生させ、ラジカル重合性化合物のラジカル反応を開始できる化合物であれば特に限定しない。ラジカル重合開始剤の具体例としては、2,2-ジメトキシ-1,2-ジフェニルエタン-1-オン、1-ヒドロキシ-シクロヘキシル=フェニル=ケトン、4-(4-メチルフェニルチオ)ベンゾフェノン、2-ヒドロキシ-2-メチル-1-フェニル-プロパン-1-オン、1-[4-(2-ヒドロキシエトキシ)-フェニル]-2-ヒドロキシ-2-メチル-1-プロパン-1-オン、2-ヒドロキシ-1-[4-[4-(2-ヒドロキシ-2-メチル-プロピオニル)-ベンジル]フェニル-2-メチル-プロパン-1-オン、2-ヒドロキシ-1-[4-(2-ヒドロキシエトキシ)フェニル]-2-メチル-1-プロパノン、フェニルグリオキシリックアシドメチルエステル、2-メチル-1-(4-メチルチオフェニル)-2-モルホリノプロパン-1-オン、2-ベンジル-ジメチルアミノ-1-(4-モルホリノフェニル)ブタン-1、2-(ジメチルアミノ)-2-[(4-メチルフェニル)メチル]-1-[4-(モルホリニル)フェニル]-1-ブタン、2,4,6-トリメチルベンゾイルージフェニルーホスフィンオキサイド、ビス(2,4,6-トリメチルベンゾイル)-フェニルホスフィンオキサイド、2,4,6-トリメチルベンゾイルフェニルエトキシホスフィンオキサイド、2-イソプロピルチオキサントン、2-エチル-9,10アンスラキノン、ビス(η5-2,4-シクロペンタジエン-1-イル)-ビス(2,6-ジフルオロ-3-(1H-ピロール-1-イル)-フェニル)チタニウム、1,2-オクタンジオン-1-[4-(フェニルチオ)-2-(o-ベンゾイルオキシム)]、エタノン,1-[9-エチル-6-(2-メチルベンゾイル)-9H-カルバゾール-3-イル]-1-(o-アセチルオキシム)、カンファーキノン、ベンゾフェノン、2,4-ジエチルチオキサントン-9-オン、2-ヒドロキシ-2-メチル-1-フェニル-1-プロパン、4,4-ビス(ジエチルアミノ)ベンゾフェノン、エチル=4-(ジメチルアミノ)-ベンゾエート、[4-(メチルフェニルチオ)フェニル]-フェニルメタン、エチルヘキシル-4-ジメチルアミノベンゾエート、メチル=o-ベンゾイルベンゾエート、4-メチルベンゾフェノン、カンファーキノン、テトラブチルアンモニウム=ブチルトリフェニルボラート、テトラブチルアンモニウムブチルトリナフチルボレート、2-エチル-4-メチルイミダゾリウムテトラフェニルボレート、1,5-ディアザビシクロ[4,3,0]ノンエン-5-テトラフェニルボレート等を挙げることができる。ラジカル重合開始剤は、1種単独、又は2種類以上を組み合わせて用いることができる。
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. Specific examples of the radical polymerization initiator include 2,2-dimethoxy-1,2-diphenylethan-1-one, 1-hydroxy-cyclohexyl phenyl = ketone, 4- (4-methylphenylthio) benzophenone, Hydroxy-2-methyl-1-phenyl-propan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, 2-hydroxy -1- [4- [4- (2-hydroxy-2-methyl-propionyl) -benzyl] phenyl-2-methyl-propan-1-one, 2-hydroxy-1- [4- (2-hydroxyethoxy) Phenyl] -2-methyl-1-propanone, phenylglyoxylic acid methyl ester, 2-methyl-1- (4-methylthiophenyl) -2-morpholy Nopropan-1-one, 2-benzyl-dimethylamino-1- (4-morpholinophenyl) butane-1,2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- ( Morpholinyl) phenyl] -1-butane, 2,4,6-trimethylbenzoyldiphenyl-phosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, 2,4,6-trimethylbenzoylphenylethoxy Phosphine oxide, 2-isopropylthioxanthone, 2-ethyl-9,10 anthraquinone, bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrole-1) -Yl) -phenyl) titanium, 1,2-octanedione-1- [4- (phenylthio) -2- (O-benzoyloxime)], ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl] -1- (o-acetyloxime), camphorquinone, benzophenone, , 4-Diethylthioxanthon-9-one, 2-hydroxy-2-methyl-1-phenyl-1-propane, 4,4-bis (diethylamino) benzophenone, ethyl 4- (dimethylamino) -benzoate, [4- (Methylphenylthio) phenyl] -phenylmethane, ethylhexyl-4-dimethylaminobenzoate, methyl = o-benzoylbenzoate, 4-methylbenzophenone, camphorquinone, tetrabutylammonium = butyltriphenylborate, tetrabutylammoniumbutyltrinaphthyl Borate, 2-d -4-methylimidazolium tetraphenylborate, 1,5 Deer triazabicyclo [4,3,0] can be exemplified Non'en 5 tetraphenylborate and the like. The radical polymerization initiator can be used alone or in combination of two or more.
成分(C)のラジカル重合開始剤は、公知の方法で合成できるほか、市販のものを用いることができる。例えば、BASF社製IRGACUREシリーズ、DAROCURシリーズ、LUCIRINシリーズ、ソート社製のSB-PIシリーズ、IGM-RESINS社製のESACUREシリーズ、DKSHジャパン社製のLUNACUREシリーズ、ADEKA社製アデカオプトマーシリーズ、昭和電工社製有機ホウ素化合物シリーズ、北興化学工業社製有機ホウ素化合物シリーズ等がある。
ラ ジ カ ル The radical polymerization initiator of the component (C) can be synthesized by a known method, or a commercially available one can be used. For example, 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.
成分(C)のラジカル重合開始剤の含有量は、光学的立体造形用組成物の総量中に、0.1~5.0質量%の範囲であり、好ましくは0.5~5.0質量%の範囲である。0.1質量%未満の場合は、光学的立体造形用組成物のラジカル重合反応が遅くなる。含有量が5.0質量%を超える場合は、光学的立体造形用組成物の硬化特性が低下する。
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. When 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.
成分(D)は、増感剤であり、光学的立体造形用組成物の光感度を増大させることができる化合物(好ましくは300~500nmの波長を吸収する化合物)であれば、特に限定されないが、多官能チオール化合物が好ましい。
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.
多官能チオール化合物の具体例としては、1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6(1H,3H,5H)-トリオン、1,4-ビス(3-メルカプトブチリルオキシ)ブタン、ペンタエリスリトールテトラキス(3-メルカプトブチレート)、トリメチロールプロパントリス(3-メルカプトプロピオネート)、トリス[(3-メルカプトプロピオニルオキシ)-エチル]-イソシアヌレート、ペンタエリスリトールテトラキス(3-メルカプトプロピオネート)等が挙げられる。
Specific examples of the polyfunctional thiol compound 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.
成分(D)の増感剤の多官能チオール化合物は、公知の方法で合成できるほか、市販のものを用いることができ、例えば、三菱化学社製のQX40、アデカ社製のアデカハードナーEH-317、SC有機化学社製のPEMP、TBMPIC、TMPMP、昭和電工社製のカレンズMTシリーズ等が挙げられる。
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. For example, QX40 manufactured by Mitsubishi Chemical Corporation and Adeka Hardener EH-317 manufactured by Adeka Corporation can be used. And PEMP, TMBPIC and TMPMP manufactured by SC Organic Chemical Co., Ltd., Karenz MT series manufactured by Showa Denko KK, and the like.
多官チオール化合物以外の増感剤の具体例としては、ベンゾフェノン等が挙げられる。また、アクリジン系として、9-フェニルアクリジン、9-(P-メチルフェニル)アクリジン、9-(o-メチルフェニル)アクリジン、9-(o-クロロフェニル)アクリジン、9-(o-フロロフェニル)アクリジン、又はクマリン系として、7,7-(ジエチルアミノ)(3,3-カルボニルビスクマリン)、3-ベンゾイル-7-ジエチルアミノクマリン、7,7-ビス(メトキシ)(3,3-カルボニルビスクマリン)等が挙げられる。また、アントラセン系として、9,10-ジメトキシアントラセン、9,10-ジエトキシアントラセン、9,10-ジブトキシアントラセン、9,10-ビス(オクタノイル)アントラセン、2,4-ジエチルチオキサントン、4-(ジメチルアミノ)安息香酸エチル、クルクミン、ジフェニル(2,4,6-トリメチルベンゾイル)ホスフィンオキサイド、2-エチルアンスラキノン、2-イソプロピルチオキサントン等が挙げられる。
具体 Specific examples of the sensitizer other than the polythiol thiol compound include benzophenone. As acridine-based compounds, 9-phenylacridine, 9- (P-methylphenyl) acridine, 9- (o-methylphenyl) acridine, 9- (o-chlorophenyl) acridine, 9- (o-fluorophenyl) acridine, Alternatively, coumarin-based compounds include 7,7- (diethylamino) (3,3-carbonylbiscoumarin), 3-benzoyl-7-diethylaminocoumarin, and 7,7-bis (methoxy) (3,3-carbonylbiscoumarin). No. As 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.
成分(D)の増感剤の含有量は、光学的立体造形用組成物の総量中に、0.1~5.0質量%の範囲であり、好ましくは3.0~5.0質量%の範囲である。0.1質量%未満の場合は、光硬化しなかったり、極端に感度が低くなったりする。含有量が5.0質量%を超える場合は、局所的に感度が低下したり、表面の部分でしか硬化しなかったりする。光学的立体造形用組成物に成分(D)を加えることで、光硬化の反応をより促進し、組成物中の全ての重合成分を硬化(結合)させて、立体造形物とした際に十分な機械的強度及び耐熱性を得ることが可能となる。
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. 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.
任意の成分(E)は、アリル基を有する化合物のうち、上述した成分(A)のジアリルフタレート系ポリマーではないアリル基を有する化合物である。この成分(E)のジアリルフタレート系ポリマーではないアリル基を有する化合部の具体例としては、2,2´-ビフェニルジカルボン酸ジアリルエステル、2,3-ナフタレンジカルボン酸ジアリルエステル、ペンタエリスリトールトリアリルエーテル、テレフタル酸ジアリル、イソフタル酸ジアリル、オルソフタル酸ジアリル、ジアリルマレート、アクリル酸アリル、メタクリル酸アリル、アリルグリシジルエーテル、トリメチロールプロパンジアリルエーテル、グリセリンモノアリルエーテル等が挙げられる。
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.
成分(E)のジアリルフタレート系ポリマーではないアリル基を有する化合物は、市販のものを用いることができ、例えば、大阪ソーダ社製のダイソーイソダップモノマー、ダイソーイソダップ100モノマー、ネオアリルシリーズ、日蝕テクノファインケミカル社製のDAD、DAND等が挙げられる。
As the component (E), a compound having an allyl group which is not a diallyl phthalate polymer, a commercially available compound can be used. For example, 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.
成分(E)のジアリルフタレート系ポリマーではないアリル基を有する化合物の含有量は、光学的立体造形用組成物の総量中に、好ましくは0.125~2.5質量%の範囲であり、より好ましくは0.15~2質量%の範囲である。光学的立体造形用組成物に成分(E)を加えることで、光硬化の反応をより促進し、組成物中の全ての重合成分を硬化(結合)させて、立体造形物とした際に十分な機械的強度及び柔軟性を得ることが可能となる。
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. By adding the component (E) to the composition for optical three-dimensional modeling, the photocuring 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 flexibility.
任意の成分(F)は、下記一般式(1)
の構造を有するポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物である。この成分(F)のラジカル重合性化合物を光学的立体造形用組成物に加えることで、硬化の速さと、硬化収縮性がより改善される。 The optional component (F) is represented by the following general formula (1)
Is a polyoxyethylene polyglyceryl ether / acrylic acid adduct having the structure: By adding the radical polymerizable compound of the component (F) to the composition for optical stereolithography, the curing speed and the curing shrinkage are further improved.
の構造を有するポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物である。この成分(F)のラジカル重合性化合物を光学的立体造形用組成物に加えることで、硬化の速さと、硬化収縮性がより改善される。 The optional component (F) is represented by the following general formula (1)
Is a polyoxyethylene polyglyceryl ether / acrylic acid adduct having the structure: By adding the radical polymerizable compound of the component (F) to the composition for optical stereolithography, the curing speed and the curing shrinkage are further improved.
成分(F)のポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物のポリグリセリンの平均重合度nは、2~20の範囲であり、好ましくは平均重合度4~20の範囲である。平均重合度が1すなわちグリセリンの場合は硬化速度が遅くなる。平均重合度が20より大きい場合は、当該ラジカル重合性化合物の製造が難しくなる。
平均 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. When the average degree of polymerization is 1, that is, glycerin, the curing speed becomes slow. When the average degree of polymerization is larger than 20, it becomes difficult to produce the radically polymerizable compound.
成分(F)のポリオキシエチレンポリグリセリリルエーテル・アクリル酸付加物のエチレンオキサイドの重合度(付加モル数)mは、ポリグリセリン1モルに対して50~200モルの範囲であり、好ましくは60~150モルの範囲である。付加モル数が50モルより少ない場合は、硬化物の柔軟性と親水性がなくなる。付加モル数が200モルより大きい場合は、当該ラジカル重合性化合物の製造が難しくなる。
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.
成分(F)のポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物のアクリル酸の反応率は、ポリグリセリン1分子のエチレンオキサイド付加物の水酸基のうち、3つ以上反応させることが好ましい。
は As for the conversion of acrylic acid of the polyoxyethylene polyglyceryl ether / acrylic acid adduct of the component (F), it is preferable to react three or more of the hydroxyl groups of the ethylene oxide adduct of one molecule of polyglycerin.
成分(F)のポリオキシエチレンポリグリセリル・アクリル酸付加物は公知の方法で合成できるほか、市販のものを用いることができ、例えば、坂本薬品工業社製のポリグリセリン系アクリレートシリーズのSA-TE6、SA-TE60、SA-ZE12等が挙げられる。
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. For example, SA-TE6 of the polyglycerin acrylate series manufactured by Sakamoto Pharmaceutical Co., Ltd. SA-TE60, SA-ZE12, and the like.
成分(F)のポリオキシエチレンポリグリセリン・アクリル酸付加物の含有量は、光学的立体造形用組成物の総量中に好ましくは5~40質量%の範囲であり、より好ましくは10~30質量%の範囲である。成分(F)の含有量が5質量%未満の場合は、硬化の速さ及び硬化収縮性の改善効果が十分に発揮されない。含有量が40質量%を超える場合は、硬化が速くなりすぎて、薄い硬化膜層同士の相互の密着が悪くなり立体造形物の強度が低くなり、また、立体造形物の耐水性も低下する。
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. When 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. When 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. .
光学的立体造形用組成物は、その他の成分として、成分(C)を溶解又は分散させるための溶剤、硬化促進剤、重合禁止剤、紫外線吸収剤、蛍光増白剤、着色剤(染料、有機顔料、無機顔料)、発光剤、蓄光剤粒子、有機系ポリマー粒子、セルロース系粒子、金属粒子、導電性フィラー、光カチオン重合性硬化成分、生分解性プラスチック、バイオマスプラスチック、デンプン等を、光学的立体造形用組成物の特性に悪影響を与えない範囲内において含有することができる。その他の成分の含有量は、特に限定されず、当業者が適宜調整することができる。
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.
本実施の形態の立体造形物は、上述した光学的立体造形用組成物の、硬化物からなるものである。立体造形物は、幅広い分野に応用することができる。用途の具体例としては、特に限定されないが、精密部品、電気・電子部品、建築構造物、自動車用部品、金型、母型、ギブスなど医療用固定具、歯を固定するマウスピ-ス、歯科医療用プラスチック造形物、医療用プラスチック器具、自動車部品等を挙げることができる。
立体 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.
本実施の形態の立体造形物を製造する方法は、上述した光学的立体造形用組成物に、活性エネルギー線を照射して硬化させる工程を少なくとも含み、従来の光学的立体造形方法及び光造形装置を使用して行うことができる。
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
例えば、(a)3次元CADで入力された形状データを幾層もの薄い断面体にスライスして作成された等高線データに基づき、光学的立体造形用組成物の表面に活性エネルギー線を選択的に照射して硬化層を形成する工程、(b)硬化層上に光学的立体造形用組成物をさらに供給する工程、(c)前記工程(a)と同様に活性エネルギー線を選択的に照射して前述の硬化層と連続した硬化層を新たに形成する積層操作を行う工程、及び(d)この積層操作を繰り返し行う工程を含むことにより、目的とする立体造形物を提供することができる。単層または積層された硬化層の厚さは、例えば20~200μmとすることができる。硬化層の厚さは、小さくするほど造形精度を高められるが、製造に必要な時間及びコストは増えるため、これらのバランスを考慮して適宜調整することができる。
For example, (a) based on contour data created by slicing shape data input by three-dimensional CAD into several thin cross-sections, selectively apply active energy rays to the surface of the composition for optical three-dimensional modeling. Irradiating to form a cured layer, (b) further supplying a composition for optical three-dimensional modeling onto the cured layer, and (c) selectively irradiating active energy rays as in the step (a). And (d) a step of repeatedly performing the lamination operation to newly form a cured layer continuous with the above-described cured layer, thereby providing a target three-dimensional structure. The thickness of the single layer or the laminated cured layer can be, for example, 20 to 200 μm. 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.
光学的立体造形用組成物の硬化物からなる立体造形物の製造に使用する光造形装置としては、特に限定されないが、例えば、ATOMm-4000(シーメット社製)、DigitalWaX(登録商標)020X(シーフォース社製)及びACCULAS(登録商標)BA-85S(ディーメック社製)等の三次元積層造形装置を挙げることができる。
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. For example, ATOMm-4000 (manufactured by Seamet), DigitalWax® 020X (sea) And three-dimensional additive manufacturing apparatuses such as ACCULAS (registered trademark) BA-85S (manufactured by D-MEC).
光学的立体造形用組成物に照射する活性エネルギー線は、例えば紫外線、可視光線、放射線、X線、又は電子線等であり、好ましくは紫外線又は可視光線である。紫外線又は可視光線の波長は、好ましくは300~500nmである。紫外線又は可視光線の光源としては、半導体励起固体レーザー、カーボンアーク灯、水銀灯、メタルハライドランプ、キセノンランプ、ケミカルランプ、白色LED等が挙げられるが、これらに限定されない。
特に、造形精度及び硬化性等の観点からレーザーを使用することが好ましい。 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.
特に、造形精度及び硬化性等の観点からレーザーを使用することが好ましい。 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.
積層操作の終了後に、得られた立体造形物及び光造形装置に付着した未硬化の光学的立体造形用組成物を除去するため、立体造形物及び光造形装置を洗浄することが好ましい。洗浄には、水、又は水に界面活性剤、殺菌剤、防腐剤及び/又はアルコール等を混合したものを使用することができる。洗浄後には、必要に応じて紫外線又は可視光線等の活性エネルギー線の照射又は加熱によりポストキュアを行うことができる。
(4) After the stacking operation is completed, it is preferable to wash the three-dimensional structure and the three-dimensional object in order to remove the uncured optical three-dimensional structure composition adhered to the obtained three-dimensional object and the three-dimensional object. For washing, water or a mixture of water and a surfactant, a bactericide, a preservative, and / or an alcohol can be used. After the washing, post-curing can be performed by irradiation with active energy rays such as ultraviolet rays or visible rays or heating, if necessary.
立体造形物は、上述の光学的立体造形用組成物の硬化物を含む立体造形物であり、好ましくは、光学的立体造形用組成物を硬化して形成される硬化層を積層してなる立体造形物である。立体造形物は、例えば、上述の立体造形物の製造方法により製造される。立体造形物は、硬化層膜が相互に密着するために反り変形が小さくなり、さらに、層間の接着が良いので強度(例えば、曲げ強度、曲げ弾性率、繰り返し曲げ強度等)が高い立体造形物を得ることが可能となる。
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.
以下に実施例、参考例および比較例を挙げて、
本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Examples, reference examples and comparative examples below,
The present invention will be specifically described, but the present invention is not limited to the following examples.
本発明を具体的に説明するが、本発明は以下の実施例に限定されるものではない。 Examples, reference examples and comparative examples below,
The present invention will be specifically described, but the present invention is not limited to the following examples.
[参考例1~12、実施例1~3及び比較例1~4]光学的立体造形用組成物の調整
参考例1~12、実施例1~3及び比較例1~4の光学的立体造形用組成物を、以下の手順で調整した。表1に示す組成の重量比に従って全ての成分を、撹拌容器に仕込み、20~40℃で2時間撹拌して液体組成物を得た。この液体組成物を、10ミクロンフイルターバッグ(PO-10-PO3A-503、Xinxiang D.King industry社製)でろ過して異物を除去し、一晩放置後に脱気して透明な液体組成物を得た。なお、調整した光学的立体造形用組成物の各々を数ml取って台の上に配置し、イソプロピルアルコールをかけると、いずれも容易に洗い流すことができた。 [Reference Examples 1 to 12, Examples 1 to 3 and Comparative Examples 1 to 4] Preparation of Composition for Optical Three-dimensional Modeling Optical three-dimensional modeling of Reference Examples 1 to 12, Examples 1 to 3, and Comparative Examples 1 to 4 The composition for use was prepared by the following procedure. According to the weight ratio of the compositions shown in Table 1, all the components were charged into a stirring vessel and stirred at 20 to 40 ° C. for 2 hours to obtain a liquid composition. This liquid composition was filtered through a 10-micron filter bag (PO-10-PO3A-503, manufactured by Xinxiang D. King industry) to remove foreign substances, left overnight, and then deaerated to form a transparent liquid composition. Obtained. In addition, when several ml of each of the adjusted compositions for optical three-dimensional modeling was placed on a table, and isopropyl alcohol was applied, all of them could be easily washed away.
参考例1~12、実施例1~3及び比較例1~4の光学的立体造形用組成物を、以下の手順で調整した。表1に示す組成の重量比に従って全ての成分を、撹拌容器に仕込み、20~40℃で2時間撹拌して液体組成物を得た。この液体組成物を、10ミクロンフイルターバッグ(PO-10-PO3A-503、Xinxiang D.King industry社製)でろ過して異物を除去し、一晩放置後に脱気して透明な液体組成物を得た。なお、調整した光学的立体造形用組成物の各々を数ml取って台の上に配置し、イソプロピルアルコールをかけると、いずれも容易に洗い流すことができた。 [Reference Examples 1 to 12, Examples 1 to 3 and Comparative Examples 1 to 4] Preparation of Composition for Optical Three-dimensional Modeling Optical three-dimensional modeling of Reference Examples 1 to 12, Examples 1 to 3, and Comparative Examples 1 to 4 The composition for use was prepared by the following procedure. According to the weight ratio of the compositions shown in Table 1, all the components were charged into a stirring vessel and stirred at 20 to 40 ° C. for 2 hours to obtain a liquid composition. This liquid composition was filtered through a 10-micron filter bag (PO-10-PO3A-503, manufactured by Xinxiang D. King industry) to remove foreign substances, left overnight, and then deaerated to form a transparent liquid composition. Obtained. In addition, when several ml of each of the adjusted compositions for optical three-dimensional modeling was placed on a table, and isopropyl alcohol was applied, all of them could be easily washed away.
また、表中の各成分の詳細を以下に示す。
・ダイソーダップA:成分(A)のジアリルフタレート系ポリマー、ヨウ素価(g/100g)50~60、粘度70~110mPa・s/30℃(50%MEK粘度)、大阪ソーダ社製
・ダイソーダップK:成分(A)のジアリルフタレート系ポリマー、ヨウ素価(g/100g)50~60、粘度30~50mPa・s/30℃(50%MEK粘度)、大阪ソーダ社製
・RADPAR AD-032:成分(A)のジアリルシクロアルカン系ポリマー、ヨウ素価(g/100g)55~70、粘度40~120mPa・s/30℃(50%MEK粘度)、大阪ソーダ社製
・EBECRYL 600:成分(B1)のビスフェノールA系エポキシジアクリレート、粘度3000(60℃)mPa.s、平均分子量500、酸価<1、OH価220mgKOH/g、ダイセル・オルネックス社製
・KAYARAD R-604:成分(B2)のジオキサングリコールジアクリレート、粘度200~400mPa・s(25℃)、酸価<1.0、日本化薬社製
・アロニックスM-306:成分(B)の他のラジカル重合性化合物のペンタエリスリトールトリ及びテトラアクリレートの混合物(トリ体65~70%)、粘度400~650mPa・s/25℃、東亜合成社製
・イルガキュアー907:成分(C)の2-メチル-1-(4-メチルチオフェニル)-2-モルホリノプロパン-1-オン、BASF社製
・カレンズMTNR1:成分(D)の1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6-(1H,3H,5H)-トリオン、昭和電工社製
・ダイソーダップ100モノマー:成分(E)のイソフタル酸ジアリル、大阪ソーダ社製
・SA-ZE6:成分(F)のポリオキシエチレンポリグリセリンエーテル・(6)アクリル酸付加物、硬化収縮率8.7%、鉛筆硬度H、粘度600/25℃mPa・s、溶解性;水×、メタノール〇、アセトン◎(◎:透明溶解、〇:くすみあり、△:一部分散・沈降、×:不溶)、坂本薬品工業社製
・SA-ZE12:成分(F)のポリオキシエチレンポリグリセリンエーテル・(12)アクリル酸付加物、硬化収縮率7.4%、鉛筆硬度F、粘度1700/25℃mPa・s、溶解性;水△、メタノール◎、アセトン◎(◎:透明溶解、〇:くすみあり、△:一部分散・沈降、×:不溶)、坂本薬品工業社製 Details of each component in the table are shown below.
・ Die sodap A: diallyl phthalate polymer of component (A), iodine value (g / 100 g) 50-60, viscosity 70-110 mPa · s / 30 ° C. (50% MEK viscosity), manufactured by Osaka Soda Co., Ltd. : Diallyl phthalate polymer of component (A), iodine value (g / 100 g) 50 to 60, viscosity 30 to 50 mPa · s / 30 ° C. (50% MEK viscosity), manufactured by Osaka Soda Co., Ltd. ・ 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). (6) Acrylic acid adduct, curing shrinkage Rate: 8.7%, pencil hardness H, viscosity: 600/25 ° C. mPa · s, solubility: water ×, methanol 〇, acetone ((◎: transparent dissolution, 〇: dullness, △: partial dispersion / sedimentation, ×: Insoluble), manufactured by Sakamoto Pharmaceutical Co., Ltd. • SA-ZE12: polyoxyethylene polyglycerin ether of component (F). (12) Acrylic acid adduct, curing shrinkage 7.4%, pencil hardness F, viscosity 1700/25 ° C. mPa · s, solubility; water △, methanol 、, acetone ((◎: transparent dissolution, 〇: dullness, △: partially dispersed / sedimented, ×: insoluble), manufactured by Sakamoto Pharmaceutical Co., Ltd.
・ダイソーダップA:成分(A)のジアリルフタレート系ポリマー、ヨウ素価(g/100g)50~60、粘度70~110mPa・s/30℃(50%MEK粘度)、大阪ソーダ社製
・ダイソーダップK:成分(A)のジアリルフタレート系ポリマー、ヨウ素価(g/100g)50~60、粘度30~50mPa・s/30℃(50%MEK粘度)、大阪ソーダ社製
・RADPAR AD-032:成分(A)のジアリルシクロアルカン系ポリマー、ヨウ素価(g/100g)55~70、粘度40~120mPa・s/30℃(50%MEK粘度)、大阪ソーダ社製
・EBECRYL 600:成分(B1)のビスフェノールA系エポキシジアクリレート、粘度3000(60℃)mPa.s、平均分子量500、酸価<1、OH価220mgKOH/g、ダイセル・オルネックス社製
・KAYARAD R-604:成分(B2)のジオキサングリコールジアクリレート、粘度200~400mPa・s(25℃)、酸価<1.0、日本化薬社製
・アロニックスM-306:成分(B)の他のラジカル重合性化合物のペンタエリスリトールトリ及びテトラアクリレートの混合物(トリ体65~70%)、粘度400~650mPa・s/25℃、東亜合成社製
・イルガキュアー907:成分(C)の2-メチル-1-(4-メチルチオフェニル)-2-モルホリノプロパン-1-オン、BASF社製
・カレンズMTNR1:成分(D)の1,3,5-トリス(3-メルカプトブチリルオキシエチル)-1,3,5-トリアジン-2,4,6-(1H,3H,5H)-トリオン、昭和電工社製
・ダイソーダップ100モノマー:成分(E)のイソフタル酸ジアリル、大阪ソーダ社製
・SA-ZE6:成分(F)のポリオキシエチレンポリグリセリンエーテル・(6)アクリル酸付加物、硬化収縮率8.7%、鉛筆硬度H、粘度600/25℃mPa・s、溶解性;水×、メタノール〇、アセトン◎(◎:透明溶解、〇:くすみあり、△:一部分散・沈降、×:不溶)、坂本薬品工業社製
・SA-ZE12:成分(F)のポリオキシエチレンポリグリセリンエーテル・(12)アクリル酸付加物、硬化収縮率7.4%、鉛筆硬度F、粘度1700/25℃mPa・s、溶解性;水△、メタノール◎、アセトン◎(◎:透明溶解、〇:くすみあり、△:一部分散・沈降、×:不溶)、坂本薬品工業社製 Details of each component in the table are shown below.
・ Die sodap A: diallyl phthalate polymer of component (A), iodine value (g / 100 g) 50-60, viscosity 70-110 mPa · s / 30 ° C. (50% MEK viscosity), manufactured by Osaka Soda Co., Ltd. : Diallyl phthalate polymer of component (A), iodine value (g / 100 g) 50 to 60, viscosity 30 to 50 mPa · s / 30 ° C. (50% MEK viscosity), manufactured by Osaka Soda Co., Ltd. ・ 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). (6) Acrylic acid adduct, curing shrinkage Rate: 8.7%, pencil hardness H, viscosity: 600/25 ° C. mPa · s, solubility: water ×, methanol 〇, acetone ((◎: transparent dissolution, 〇: dullness, △: partial dispersion / sedimentation, ×: Insoluble), manufactured by Sakamoto Pharmaceutical Co., Ltd. • SA-ZE12: polyoxyethylene polyglycerin ether of component (F). (12) Acrylic acid adduct, curing shrinkage 7.4%, pencil hardness F, viscosity 1700/25 ° C. mPa · s, solubility; water △, methanol 、, acetone ((◎: transparent dissolution, 〇: dullness, △: partially dispersed / sedimented, ×: insoluble), manufactured by Sakamoto Pharmaceutical Co., Ltd.
[評価サンプルAの製作]
光学的立体造形用組成物の硬化時間を評価するために、以下の手順でサンプルを製作した。実施例1の光学的立体造形用組成物を手製のポリエチレン製長方形型(幅約10mm×長さ100mm×、深さ5mm)に1mm液膜になるように流し込み、3kw高圧水銀等(波長365nm、距離1m)で、5秒間、10秒間、15秒間、20秒間、25秒間、30秒間、各々照射し、評価サンプルAを得た。実施例2~12及び比較例1~4の光学的立体造形用組成物についても、同様にして評価サンプルAを得た。 [Production of 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.
光学的立体造形用組成物の硬化時間を評価するために、以下の手順でサンプルを製作した。実施例1の光学的立体造形用組成物を手製のポリエチレン製長方形型(幅約10mm×長さ100mm×、深さ5mm)に1mm液膜になるように流し込み、3kw高圧水銀等(波長365nm、距離1m)で、5秒間、10秒間、15秒間、20秒間、25秒間、30秒間、各々照射し、評価サンプルAを得た。実施例2~12及び比較例1~4の光学的立体造形用組成物についても、同様にして評価サンプルAを得た。 [Production of 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.
[評価サンプルBの製作]
光学的立体造形用組成物の硬化時間を評価するために、以下の手順でサンプルを製作した。実施例1の光学的立体造形用組成物を手製のポリエチレン製長方形型(幅約10mm×長さ100mm×、深さ5mm)に1mm液膜になるように流し込み、3kw高圧水銀灯(波長365nm、距離1m)で20秒間照射し、これを合計4回繰り返して厚さ約4mmの平面板(幅約10mm×長さ100mm)を作成した。さらに平面板を30分間再照射し、光学的立体造形物である評価サンプルBを得た。実施例2~12及び比較例1~4の光学的立体造形用組成物についても、同様にして評価サンプルBを得た。 [Production of 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.
光学的立体造形用組成物の硬化時間を評価するために、以下の手順でサンプルを製作した。実施例1の光学的立体造形用組成物を手製のポリエチレン製長方形型(幅約10mm×長さ100mm×、深さ5mm)に1mm液膜になるように流し込み、3kw高圧水銀灯(波長365nm、距離1m)で20秒間照射し、これを合計4回繰り返して厚さ約4mmの平面板(幅約10mm×長さ100mm)を作成した。さらに平面板を30分間再照射し、光学的立体造形物である評価サンプルBを得た。実施例2~12及び比較例1~4の光学的立体造形用組成物についても、同様にして評価サンプルBを得た。 [Production of 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.
[評価方法]
1.光学的立体造形用組成物の硬化時間の評価
評価サンプルAを用いて、照謝時間の短いサンプルからその表面状態を観察し、表面のタックが無い評価サンプルAに係る照射時間を硬化時間とした。なお、「表面のタックの有無」は、評価サンプルAをオーブンに入れて35℃で30分間処理し、室温(25℃)まで冷却した後、評価サンプルAの表面にポリエステルフイルムを手で押し当て、ポリエステルフイルムが簡単に剥がれなければタック有りとし、剥がれればタック無しとして判断した。評価サンプルAの硬化時間を表2に示した。 [Evaluation methods]
1. Evaluation of Curing Time of Optical Stereolithography Composition Using Evaluation Sample A, the surface state was observed from a sample having a short irradiation time, and the irradiation time of Evaluation Sample A having no tack on the surface was defined as the curing time. . In addition, "the presence or absence of tackiness on the surface" was determined by placing the evaluation sample A in an oven at 35 ° C. for 30 minutes, cooling to room temperature (25 ° C.), and then pressing the polyester film against the surface of the evaluation sample A by hand. If the polyester film was not easily peeled, it was judged that there was a tack, and if it was peeled, it was judged that there was no tack. Table 2 shows the curing time of Evaluation Sample A.
1.光学的立体造形用組成物の硬化時間の評価
評価サンプルAを用いて、照謝時間の短いサンプルからその表面状態を観察し、表面のタックが無い評価サンプルAに係る照射時間を硬化時間とした。なお、「表面のタックの有無」は、評価サンプルAをオーブンに入れて35℃で30分間処理し、室温(25℃)まで冷却した後、評価サンプルAの表面にポリエステルフイルムを手で押し当て、ポリエステルフイルムが簡単に剥がれなければタック有りとし、剥がれればタック無しとして判断した。評価サンプルAの硬化時間を表2に示した。 [Evaluation methods]
1. Evaluation of Curing Time of Optical Stereolithography Composition Using Evaluation Sample A, the surface state was observed from a sample having a short irradiation time, and the irradiation time of Evaluation Sample A having no tack on the surface was defined as the curing time. . In addition, "the presence or absence of tackiness on the surface" was determined by placing the evaluation sample A in an oven at 35 ° C. for 30 minutes, cooling to room temperature (25 ° C.), and then pressing the polyester film against the surface of the evaluation sample A by hand. If the polyester film was not easily peeled, it was judged that there was a tack, and if it was peeled, it was judged that there was no tack. Table 2 shows the curing time of Evaluation Sample A.
2.光学的立体造形物の層(側面)観察
評価サンプルBを用いて、平面板の層(側面)を日本電子JSM-5600型走査電子顕微鏡(加速電圧7kv、倍率200倍)で観察した。評価の基準は、層間の隙間が存在する場合は(「×」)、層間の隙間がない場合は(「〇」)、とした。結果を表2に示した。 2. Observation of Layer (Side) of Optical Three-dimensional Object Using Evaluation Sample B, the layer (side) of the flat plate was observed with a JEOL JSM-5600 scanning electron microscope (acceleration voltage: 7 kv, magnification: 200 ×). The evaluation criteria were as follows: when there was a gap between the layers (“x”), and when there was no gap between the layers (“Δ”). The results are shown in Table 2.
評価サンプルBを用いて、平面板の層(側面)を日本電子JSM-5600型走査電子顕微鏡(加速電圧7kv、倍率200倍)で観察した。評価の基準は、層間の隙間が存在する場合は(「×」)、層間の隙間がない場合は(「〇」)、とした。結果を表2に示した。 2. Observation of Layer (Side) of Optical Three-dimensional Object Using Evaluation Sample B, the layer (side) of the flat plate was observed with a JEOL JSM-5600 scanning electron microscope (acceleration voltage: 7 kv, magnification: 200 ×). The evaluation criteria were as follows: when there was a gap between the layers (“x”), and when there was no gap between the layers (“Δ”). The results are shown in Table 2.
3.光学的立体造形物の反り変形観察
評価サンプルBの平面板を平台に置いて、その端部が平台から浮いた距離を測定する。判定の基準は、浮いた距離2mm以上の場合は(「×」)、浮いた距離2mm以下で浮いている場合は(「△」)、浮いた距離0mmつまり浮いていない場合は(「〇」)、とした。結果を表2に示した。 3. Observation of warpage of optical three-dimensional object The flat plate of the evaluation sample B is placed on a flat base, and the distance at which the end of the flat plate floats from the flat base is measured. The criterion for the determination is that when the floating distance is 2 mm or more (“×”), when the floating distance is 2 mm or less (“△”), the floating distance is 0 mm, that is, when the floating distance is not (“〇”). ). The results are shown in Table 2.
評価サンプルBの平面板を平台に置いて、その端部が平台から浮いた距離を測定する。判定の基準は、浮いた距離2mm以上の場合は(「×」)、浮いた距離2mm以下で浮いている場合は(「△」)、浮いた距離0mmつまり浮いていない場合は(「〇」)、とした。結果を表2に示した。 3. Observation of warpage of optical three-dimensional object The flat plate of the evaluation sample B is placed on a flat base, and the distance at which the end of the flat plate floats from the flat base is measured. The criterion for the determination is that when the floating distance is 2 mm or more (“×”), when the floating distance is 2 mm or less (“△”), the floating distance is 0 mm, that is, when the floating distance is not (“〇”). ). The results are shown in Table 2.
4.引張試験
評価サンプルBの平面板について、ISO527-1に準拠して、以下の測定条件で引張り強度及び伸度を測定した。伸度は、破断時の最大の伸び率として測定した。結果を表2に示した。
測定装置 : インストロン社製3366型万能試験機
引張速度(クロスヘッド速度) : 5mm/分
測定環境 : 温度25℃、湿度45%RH
標点間距離 : 80mm 4. Tensile Test The tensile strength and elongation of the flat plate of the evaluation sample B were measured under the following measurement conditions in accordance with ISO 527-1. The elongation was measured as the maximum elongation at break. The results are shown in Table 2.
Measuring device: Instron 3366 universal tester Tensile speed (crosshead speed): 5 mm / min Measurement environment: Temperature 25 ° C., Humidity 45% RH
Gauge distance: 80mm
評価サンプルBの平面板について、ISO527-1に準拠して、以下の測定条件で引張り強度及び伸度を測定した。伸度は、破断時の最大の伸び率として測定した。結果を表2に示した。
測定装置 : インストロン社製3366型万能試験機
引張速度(クロスヘッド速度) : 5mm/分
測定環境 : 温度25℃、湿度45%RH
標点間距離 : 80mm 4. Tensile Test The tensile strength and elongation of the flat plate of the evaluation sample B were measured under the following measurement conditions in accordance with ISO 527-1. The elongation was measured as the maximum elongation at break. The results are shown in Table 2.
Measuring device: Instron 3366 universal tester Tensile speed (crosshead speed): 5 mm / min Measurement environment: Temperature 25 ° C., Humidity 45% RH
Gauge distance: 80mm
5.3点曲げ試験
評価サンプルBの平面板の3点曲げ試験を、ISO527-1に準拠して、以下の測定条件で行い、曲げ強度及び曲げ弾性率を測定した。結果を表2に示した。
測定装置 : インストロン社製3366型万能試験機
試験条件 : 3点曲げ試験治具 圧子半径5mm
支点間距離 64mm
負荷速度(クロスヘッド速度)2mm/分
測定環境 : 温度25℃、湿度45%RH 5.3 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
評価サンプルBの平面板の3点曲げ試験を、ISO527-1に準拠して、以下の測定条件で行い、曲げ強度及び曲げ弾性率を測定した。結果を表2に示した。
測定装置 : インストロン社製3366型万能試験機
試験条件 : 3点曲げ試験治具 圧子半径5mm
支点間距離 64mm
負荷速度(クロスヘッド速度)2mm/分
測定環境 : 温度25℃、湿度45%RH 5.3 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
6.裸落下試験
評価サンプルBについて、以下の測定条件で裸落下試験を行い、割れの有無を目視で観察し、落下割れ観察をした。結果を表2に示した。
落下床面 : 大理石床タイル
落下高さ : 3m
サンプルの重さ : 14.5g
サンプルの落下角度 : 大理石床タイル面に対して60度
判定の基準は、サンプル5つを落下させて、ヒビを含めた割れサンプル個数を記録した。 6. Naked Drop Test The evaluation sample B was subjected to a naked drop test under the following measurement conditions, and the presence or absence of cracks was visually observed, and drop cracks were observed. The results are shown in Table 2.
Falling floor: Marble floor tile Falling height: 3m
Sample weight: 14.5g
Sample drop angle: 60 degrees with respect to the marble floor tile surface As a criterion, five samples were dropped and the number of cracked samples including cracks was recorded.
評価サンプルBについて、以下の測定条件で裸落下試験を行い、割れの有無を目視で観察し、落下割れ観察をした。結果を表2に示した。
落下床面 : 大理石床タイル
落下高さ : 3m
サンプルの重さ : 14.5g
サンプルの落下角度 : 大理石床タイル面に対して60度
判定の基準は、サンプル5つを落下させて、ヒビを含めた割れサンプル個数を記録した。 6. Naked Drop Test The evaluation sample B was subjected to a naked drop test under the following measurement conditions, and the presence or absence of cracks was visually observed, and drop cracks were observed. The results are shown in Table 2.
Falling floor: Marble floor tile Falling height: 3m
Sample weight: 14.5g
Sample drop angle: 60 degrees with respect to the marble floor tile surface As a criterion, five samples were dropped and the number of cracked samples including cracks was recorded.
7.繰り返し折り曲げ試験
評価サンプルBの端部10mmを万力で挟んで固定した。評価サンプルBの片方の端部をペンチで挟み、往復10回左右に折り曲げた。試験後、折り曲げた部位の外観を目視で観察する。判定の基準は、〇:変化なし、△:白く変色、▲:ひび割れ、×:割れた、とした。 7. Repeat bending test The end portion of the evaluation sample B was fixed at 10 mm with a vice. One end of the evaluation sample B was sandwiched between pliers and bent right and left 10 times. After the test, the appearance of the bent portion is visually observed. The criterion for judgment was Δ: no change, Δ: white discoloration, ▲: cracked, ×: broken.
評価サンプルBの端部10mmを万力で挟んで固定した。評価サンプルBの片方の端部をペンチで挟み、往復10回左右に折り曲げた。試験後、折り曲げた部位の外観を目視で観察する。判定の基準は、〇:変化なし、△:白く変色、▲:ひび割れ、×:割れた、とした。 7. Repeat bending test The end portion of the evaluation sample B was fixed at 10 mm with a vice. One end of the evaluation sample B was sandwiched between pliers and bent right and left 10 times. After the test, the appearance of the bent portion is visually observed. The criterion for judgment was Δ: no change, Δ: white discoloration, ▲: cracked, ×: broken.
上述した1~7の評価、観察、及び試験結果を表2に示した。成分(A)としてジアリルフタレート系ポリマーを用いた参考例1~12及びノンフタレート型のアリル樹脂であるジアリルシクロアルカン系ポリマーを用いた実施例1~3の光学的立体造形用組成物は、4~10秒の硬化時間であることから、比較例よりも硬化時間が短く、高感度であり硬化速度が速いことが分かる。これは硬化密度が高いことを示している。また、参考例1~12及び実施例1~3の光学的立体造形用組成物の硬化層を積層して得られた立体造形物は、硬化膜が相互に密着しているため、反り変形が観察されず、引張り強度、伸度、曲げ強度及び曲げ弾性率、そして繰り返し曲げ強度に優れ、落下割れがほとんど観察されなかった。
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. In addition, 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.
Claims (6)
- (A)ジアリルシクロアルカン系ポリマー、又はジアリルシクロアルカン系ポリマーとジアリルフタレート系ポリマーとの組み合わせと、
(B)メタクリル基及び/又はアクリル基を有するラジカル重合性化合物と、
(C)ラジカル重合開始剤と、
(D)増感剤とを含む光学的立体造形用組成物であって、
前記(A)のジアリルシクロアルカン系ポリマーの炭素環の炭素数が3~8の範囲であり、
前記(B)のメタクリル基及び/又はアクリル基を有するラジカル重合性化合物として、
(B1)メタクリル基及び/若しくはアクリル基を有するエポキシ(メタ)アクリレートのラジカル重合性化合物、及び/又は
(B2)メタクリル基及び/若しくはアクリル基を有するジオキサン(メタ)アクリレートのラジカル重合性化合物を少なくとも含み、
前記(A)のジアリルシクロアルカン系ポリマー、又はジアリルシクロアルカン系ポリマーとジアリルフタレート系ポリマーとの組み合わせを0.5~10質量%、
前記(B1)及び前記(B2)のラジカル重合性化合物を合計で5~43質量%、
前記(B)のラジカル重合性化合物のうち、前記(B1)及び前記(B2)以外のラジカル重合性化合物を20~95質量%、
前記(C)のラジカル重合開始剤を0.1~5質量%、及び、
前記(D)の増感剤を0.1~5質量%を含有する、光学的立体造形用組成物。 (A) a diallylcycloalkane-based polymer, or a combination of a diallylcycloalkane-based polymer and a diallylphthalate-based polymer,
(B) a radical polymerizable compound having a methacryl group and / or an acryl group;
(C) a radical polymerization initiator;
(D) a composition for optical three-dimensional modeling including a sensitizer,
The diallylcycloalkane-based polymer (A) has a carbon ring in the range of 3 to 8;
As the radical polymerizable compound having a methacryl group and / or an acryl group of (B),
(B1) at least a radical polymerizable compound of an epoxy (meth) acrylate having a methacryl group and / or an acrylic group, and / or (B2) a radical polymerizable compound of dioxane (meth) acrylate having a methacryl group and / or an acrylic group Including
0.5 to 10% by mass of the diallylcycloalkane-based polymer (A) or the combination of the diallylcycloalkane-based polymer and the diallylphthalate-based polymer,
5 to 43% by mass in total of the radical polymerizable compound of (B1) and (B2),
Among the radically polymerizable compounds of the above (B), the radical polymerizable compounds other than the above (B1) and (B2) are 20 to 95% by mass,
0.1 to 5% by mass of the radical polymerization initiator (C), and
An optical three-dimensional structure composition comprising 0.1 to 5% by mass of the sensitizer of (D). - さらに、(E)ジアリルフタレート系ポリマーではないアリル基を有する化合物を0.125~2.5質量%含有する、請求項1に記載の光学的立体造形用組成物。 The composition for optical stereolithography according to claim 1, further comprising (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.
- 前記(A)のジアリルシクロアルカン系ポリマーが、ジアリルシクロアルカンジカルボキシレートポリマーである、請求項1又は2に記載の光学的立体造形用組成物。 The optical stereolithography composition according to claim 1 or 2, wherein the diallylcycloalkane-based polymer (A) is a diallylcycloalkanedicarboxylate polymer.
- さらに、(F)下記一般式(1)
(式中、nは2~20の整数、及びmは50~200の整数を表す。)の構造を有するポリオキシエチレンポリグリセリルエーテル・アクリル酸付加物を5~40質量%含有する、請求項1~3のいずれか一項に記載の光学的立体造形用組成物。 Further, (F) the following general formula (1)
(5) The polyoxyethylene polyglyceryl ether / acrylic acid adduct having a structure of the formula (1) wherein n represents an integer of 2 to 20 and m represents an integer of 50 to 200. 4. The composition for optical three-dimensional modeling according to any one of items 3 to 3. - 請求項1~4のいずれか一項に記載の光学的立体造形用組成物に、活性エネルギー線を照射して硬化させる工程を含む、光学的立体造形物の製造方法。 (5) A method for producing an optical three-dimensional object, comprising a step of irradiating the composition for optical three-dimensional object according to any one of (1) to (4) with an active energy ray to cure the composition.
- 請求項1~4のいずれか一項に記載の光学的立体造形用組成物の硬化物を含む光学的立体造形物。 光学 An optical three-dimensional molded article comprising a cured product of the composition for optical three-dimensional modeling according to any one of claims 1 to 4.
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