WO2018159493A1 - Composition photodurcissable pour moulage solide, procédé de préparation d'un article solide l'utilisant, et résine - Google Patents

Composition photodurcissable pour moulage solide, procédé de préparation d'un article solide l'utilisant, et résine Download PDF

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WO2018159493A1
WO2018159493A1 PCT/JP2018/006708 JP2018006708W WO2018159493A1 WO 2018159493 A1 WO2018159493 A1 WO 2018159493A1 JP 2018006708 W JP2018006708 W JP 2018006708W WO 2018159493 A1 WO2018159493 A1 WO 2018159493A1
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group
photocurable composition
formula
meth
dimensional modeling
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PCT/JP2018/006708
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English (en)
Japanese (ja)
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岡田　誠司
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キヤノン株式会社
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Priority claimed from JP2017140151A external-priority patent/JP6946095B2/ja
Application filed by キヤノン株式会社 filed Critical キヤノン株式会社
Priority to CN201880015562.XA priority Critical patent/CN110382573A/zh
Publication of WO2018159493A1 publication Critical patent/WO2018159493A1/fr
Priority to US16/554,453 priority patent/US10961380B2/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • 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
    • C08F290/14—Polymers provided for in subclass C08G

Definitions

  • the present invention relates to a photocurable composition for three-dimensional modeling, a method for producing a three-dimensional object using the same, and a resin.
  • An optical three-dimensional modeling method for producing a desired three-dimensional object by curing a liquid photocurable composition for each layer with light such as ultraviolet rays and sequentially laminating them has been intensively studied.
  • the use of stereolithography is not limited to prototype modeling for rapid shape confirmation (rapid prototyping), but has expanded to include modeling of working models for functional verification and modeling of models (rapid tooling).
  • the use of stereolithography is spreading to real product modeling (rapid manufacturing).
  • Patent Document 1 modeling (photocuring) is performed by an optical modeling method using a photocurable composition containing an acrylic group-containing blocked isocyanate and a chain extender, and the obtained photocured product is further heat treated. Describes a method of modeling a three-dimensional object by applying the above. Thereby, it is possible to model a three-dimensional object having higher strength and rigidity than the conventional photocurable composition, and it is possible to model a three-dimensional object having an excellent balance of strength, rigidity, and toughness.
  • Patent Document 1 the photocured material is heat-treated to reduce the crosslink density and to improve the toughness by generating polyurethane and polyurea.
  • the toughness of the obtained cured product was not sufficiently large.
  • the present invention has an object to provide a photocurable composition for three-dimensional modeling that can form a three-dimensional object having higher toughness than before.
  • the photocurable composition for three-dimensional modeling as one aspect of the present invention includes a (meth) acrylic compound having a (meth) acryloyl group and a photoradical generator. And a polyrotaxane having a plurality of cyclic molecules having at least one of a (meth) acryloyl group and a hydroxyl group.
  • the photocurable composition for three-dimensional modeling as one aspect of the present invention, it is possible to provide a photocurable composition for three-dimensional modeling that can model a three-dimensional object having higher toughness than before.
  • the photocurable composition for three-dimensional modeling according to the present embodiment includes a (meth) acrylic compound (a) that is a polymerizable compound, and a photoradical.
  • a generator (b) and a polyrotaxane (c) are contained.
  • the meta (acrylic) compound (a) is a compound having at least one (meth) acryloyl group, and undergoes a polymerization reaction with radicals generated by the photoradical generator (b) described later.
  • (meth) acryloyl group means an acryloyl group or a methacryloyl group
  • (meth) acrylic compound means an acrylic compound or a methacrylic compound
  • the (meth) acrylic compound (a) may be composed of only one type of (meth) acrylic compound or may be composed of a plurality of types of (meth) acrylic compounds.
  • the number of (meth) acryloyl groups that the (meth) acrylic compound (a) has is not particularly limited.
  • the (meth) acrylic compound (a) include a monofunctional (meth) acrylic compound having one (meth) acryloyl group in the molecule and a bifunctional (meth) having one (meth) acryloyl group in the molecule.
  • examples include acrylic compounds, trifunctional (meth) acrylic compounds having three (meth) acryloyl groups in the molecule, and tetrafunctional or more (meth) acrylic compounds having four or more (meth) acryloyl groups in the molecule. However, it is not limited to these.
  • the (meth) acrylic compound (a) may be a urethane (meth) acrylic compound having a urethane structure in the molecular structure or a polyester (meth) acrylic compound having a polyester structure in the molecular structure.
  • (meth) acrylic compound (a) examples include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, (meth) acrylic.
  • N-butyl acid isobutyl (meth) acrylate, tert-butyl (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic N-heptyl acid, n-octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, isononyl (meth) acrylate, decyl (meth) acrylate , Isodecyl (meth) acrylate, dodecyl (meth) acrylate, lauryl (meth) acrylate, ( T) Stearyl acrylate, (meth) acrylic acid tridecyl, (meth) acrylic acid tridecyl, (meth)
  • urethane (meth) acrylic compound examples include polycarbonate urethane (meth) acrylate, polyester urethane (meth) acrylate, polyether urethane (meth) acrylate, caprolactone urethane (meth) acrylate, and the like. However, it is not limited to these.
  • urethane (meth) acrylic compounds can be obtained by reacting an isocyanate compound obtained by reacting a polyol with a diisocyanate and a (meth) acrylate monomer having a hydroxyl group.
  • specific examples of the polyol include polycarbonate polyol, polyester polyol, polyether polyol, and polycaprolactone polyol.
  • the photo radical generator (b) include benzoin, benzoin monomethyl ether, benzoin isopropyl ether, acetoin, benzyl, benzophenone, p-methoxybenzophenone, diethoxyacetophenone, benzyldimethylketal, Carbonyl such as 2,2-diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, methylphenylglyoxylate, ethylphenylglyoxylate, 2-hydroxy-2-methyl-1-phenylpropan-1-one Compounds, sulfur compounds such as tetramethylthiuram monosulfide and tetramethylthiuram disulfide, and acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide. To but are not limited to.
  • Examples of commercially available photo radical generators include IRGACURE series such as IRGACURE (registered trademark) 184 and IRGACURE 819, DAROCUR series such as DAROCUR (registered trademark) 1173 and DAROCUR TPO (above, manufactured by BASF), KAYACURE (registered trademark) ) Examples include, but are not limited to, KAYACURE series (manufactured by Nippon Kayaku Co., Ltd.) such as DETX-S and KAYACURE CTX.
  • the addition amount of the photoradical generator (b) is preferably 0.05% by mass or more and 20% by mass or less, and more preferably 0.1% by mass or more when the entire photocurable composition is 100% by mass. More preferably, it is 5 mass% or less.
  • the addition amount is less than 0.05% by mass, the radicals to be generated are insufficient, and the polymerization conversion rate of the photocurable composition is reduced. As a result, the photocurable composition is obtained by photocuring and then heat-treating. The strength of the three-dimensional object is insufficient.
  • the added amount exceeds 30% by mass, most of the light irradiated to the photocurable composition is absorbed by the excessive photoradical generator (b), and light does not reach the inside of the curable composition. Sometimes. Therefore, there exists a possibility that the polymerization conversion rate of the photocurable composition inside a photocurable composition may fall.
  • the polyrotaxane (c) includes a plurality of cyclic molecules having at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, a linear molecule penetrating through the plurality of cyclic molecules, A supramolecule having a blocking group disposed at both ends of a linear molecule and preventing elimination of the cyclic molecule.
  • the cyclic molecule can move freely along the linear molecular chain like a pulley.
  • the cyclic molecule is blocked by a blocking group at the end of the linear molecule, and thus has a structure that cannot escape from the linear molecule.
  • the polyrotaxane cyclic molecule has at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, can include a linear molecule, and is free along the linear molecular chain like a pulley. If it can move to, it will not be specifically limited.
  • the cyclic molecule does not necessarily have to be a completely closed ring, and may be, for example, approximately “C”.
  • polyrotaxane cyclic molecule examples include cyclodextrins such as ⁇ -cyclodextrin, ⁇ -cyclodextrin and ⁇ -cyclodextrin, crown ethers, benzocrowns, dibenzocrowns, dicyclohexanocrowns, etc. However, it is not limited to these. Of these, cyclodextrins are preferred because they are readily available and it is easy to select an appropriate ring diameter. In particular, ⁇ -cyclodextrin is more preferably used as the cyclic molecule of polyrotaxane.
  • the polyrotaxane (c) may contain two or more different types of cyclic molecules in one molecule of the polyrotaxane.
  • the polyrotaxane cyclic molecule has at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, and has two or more (meth) acryloyl groups or a hydroxyl group alone or simultaneously. You may do it.
  • the polyrotaxane (c) contains two or more different types of cyclic molecules in one molecule of the polyrotaxane, at least one type of cyclic molecule has at least one (meth) acryloyl group or hydroxyl group. It only has to have.
  • the polyrotaxane linear molecule is a molecule or substance that is included in a cyclic molecule and can be integrated without a covalent bond, and is not particularly limited as long as it is linear.
  • linear in the present specification means substantially “linear”. That is, as long as the cyclic molecule can slide or move on the linear molecule, the linear molecule may have a branched chain. Further, as long as the cyclic molecule can slide or move on the linear molecule, it may be bent or spiral. Further, the length of the “straight chain” is not particularly limited as long as the cyclic molecule can slide or move on the linear molecule.
  • polyrotaxane linear molecules include polyalkylenes, polyesters such as polycaprolactone, polyethers such as polyalkylene glycols such as polyethylene glycol and polypropylene glycol, polyamides, polyacryls, and benzene rings.
  • the linear molecule etc. which have are mentioned, However, It is not limited to these.
  • polyethers are preferable from the viewpoint of easy inclusion of molecules and flexibility, and among these, polyethylene glycol is more preferable.
  • the number average molecular weight of the linear molecule of the polyrotaxane is preferably 1,000 or more and 1,000,000 or less, and more preferably 5,000 or more and 50,000 or less.
  • the molecular weight of the linear molecule is less than 1,000, the pulley effect due to the cyclic molecule cannot be sufficiently obtained, and the sufficient impact improvement effect cannot be obtained.
  • the molecular weight exceeds 1,000,000, the viscosity becomes too high, and there is a possibility that the photo-curable resin composition for optical three-dimensional modeling of the present invention cannot be modeled by the optical modeling apparatus.
  • the blocking group is arranged at the end (both ends) of the polyrotaxane linear molecule, and has a role of preventing the cyclic molecule from being detached from the linear molecule.
  • the blocking group is not particularly limited as long as it has a role of a stopper for preventing the cyclic molecule from leaving. Examples of the method for preventing elimination include a method for physically preventing the use of a bulky group and a method for electrically preventing the use of an ionic group.
  • the blocking group include adamantane groups, dinitrophenyl groups, cyclodextrins, trityl groups, fluoresceins, pyrenes, and derivatives or modified products thereof. There is no limitation.
  • Examples of commercially available polyrotaxanes that can be used as the polyrotaxane (c) having a (meth) acryloyl group according to the present embodiment include, for example, SeRM SM3405P, SeRM SA3405P, SeRM SM3400C, SeRM SA3400C, SeRM SA2400C (all of these are advanced Soft Materials Co., Ltd.).
  • a commercial item of the polyrotaxane (c) which has a hydroxyl group SeRM SH3400P, SeRM SH2400P, SeRM SH1300P (all are the product made from Advanced Soft Materials Co., Ltd.) is mentioned, for example.
  • the blending ratio of the polyrotaxane (c) is not particularly limited as long as the effect of the present invention is not impaired.
  • the blending ratio is, for example, preferably 1% by mass or more and 50% by mass or more preferably 5% by mass or more and 30% by mass or less when the entire photocurable composition is 100% by mass.
  • the blending ratio is less than 1% by mass, the toughness of a cured product obtained by curing the photocurable composition may be lowered.
  • the said mixture ratio exceeds 50 mass%, there exists a possibility that the elasticity modulus and intensity
  • the photocurable composition according to this embodiment may further contain a radical polymerizable compound other than the (meth) acrylic compound.
  • radically polymerizable compounds include styrene monomers, styrene oligomers, acrylonitrile compounds, vinyl ester monomers, vinyl ester oligomers, N-vinyl pyrrolidone, acrylamide monomers, acrylamide oligomers, conjugated diene monomers.
  • Conjugated diene oligomers vinyl ketone monomers, vinyl ketone oligomers, vinyl halide monomers, vinyl halide oligomers, vinylidene halide monomers, vinylidene halide oligomers, etc. Absent.
  • the photocurable composition according to the present embodiment may further contain a cationic polymerizable compound.
  • the cationic polymerizable compound undergoes a polymerization reaction with an acid generated by a photoacid generator described later.
  • Examples of the cationic polymerizable compound include, but are not limited to, epoxy monomers, epoxy oligomers, oxetane monomers, oxetane oligomers, vinyl ether monomers, vinyl ether oligomers, and the like.
  • the photocurable composition according to this embodiment may further contain a photoacid generator when it contains the above-described cationic polymerizable compound.
  • the photoacid generator is a compound that initiates a polymerization reaction by generating an acid as a polymerization factor by receiving active energy rays such as light of a predetermined wavelength.
  • the photoacid generator examples include trichloromethyl-s-triazines, sulfonium salts and iodonium salts, quaternary ammonium salts, diazomethane compounds, imide sulfonate compounds, and oxime sulfonate compounds. These are not limited.
  • the addition amount of the photoacid generator is preferably 0.05% by mass or more and 20% by mass or less when the entire photocurable composition is 100% by mass. More preferably, the content is 1% by mass or more and 5% by mass or less.
  • the addition amount is less than 0.05% by mass, the acid generated is insufficient, and the polymerization conversion rate of the photocurable composition is decreased.
  • the photocurable composition is heat-treated after being photocured. The strength of the three-dimensional object is insufficient.
  • the added amount exceeds 30% by mass, most of the light irradiated to the photocurable composition is absorbed by the excessive photoacid generator, and the light may not reach the inside of the curable composition. . Therefore, there exists a possibility that the polymerization conversion rate of the photocurable composition inside a photocurable composition may fall.
  • reaction accelerators (e) may be used alone or in combination of two or more.
  • the amount of the reaction accelerator (e) used is preferably 0.001% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of polyol.
  • the photocurable composition according to the present embodiment is a reactive diluent, a colorant such as a pigment or a dye, an antifoaming agent, a leveling agent, a thickener, as necessary, unless the effects of the present invention are impaired.
  • Additives such as flame retardants, antioxidants, inorganic fillers (crosslinked polymer particles, silica, glass powder, ceramics powder, metal powders, etc.), modifying resins (thermoplastic resins, thermoplastic resin particles, rubber particles, etc.) 1 type or 2 types or more may be contained appropriately.
  • the photocurable composition according to the present embodiment can appropriately use a photoinitiator or a sensitizer in addition to the photoradical generator (b) as necessary.
  • the photoinitiation assistant or sensitizer include benzoin compounds, acetophenone compounds, anthraquinone compounds, thioxanthone compounds, ketal compounds, benzophenone compounds, tertiary amine compounds, and xanthone compounds.
  • the photocurable composition for three-dimensional modeling containing a (meth) acrylic compound (a) and a photoradical generator (b) can be cured by irradiation with light to form a cured product (three-dimensional object).
  • radical polymerization reaction of the (meth) acrylic compound (a) is started by radicals generated by the photoradical generator (b), and curing of the photocurable composition proceeds.
  • the crosslink density in the cured product (three-dimensional object) is high.
  • the crosslinking point in the cured product does not move. Therefore, if the crosslinking density is increased too much, the toughness is lowered and becomes brittle.
  • the photo-curable composition for three-dimensional modeling according to the present embodiment contains the polyrotaxane (c) described above.
  • the cyclic molecule in the polyrotaxane (c) contains at least one functional group selected from a (meth) acryloyl group and a hydroxyl group.
  • the cyclic molecule in the polyrotaxane (c) according to this embodiment contains a (meth) acryloyl group
  • the photocurable composition according to this embodiment is irradiated with light
  • the (meth) acrylic compound (a) The polymerization reaction between them proceeds.
  • a polymerization reaction between the (meth) acrylic compound (a) and the polyrotaxane (c) and a polymerization reaction between the polyrotaxanes (c) also proceed.
  • a cured product (three-dimensional product) having a structure as schematically shown in FIG.
  • the photocurable composition according to the present embodiment contains a hydroxyl group
  • polymerization of the (meth) acrylic compounds (a) is performed.
  • the reaction proceeds.
  • a cured product in which the (meth) acryloyl group in the molded article obtained and the hydroxyl group in the polyrotaxane (c) are bonded by hydrogen bonds is obtained.
  • the internal stress generated during the curing by the post-treatment by heat is eliminated by the movement of the crosslinking point in the cured product and the optimal arrangement of the (meth) acryloyl group and the polyrotaxane (c).
  • the photocurable composition which concerns on this embodiment can be used suitably for the manufacturing method of the solid thing by the optical three-dimensional modeling method (optical modeling method).
  • optical modeling method optical modeling method
  • a conventionally known method can be used as the stereolithography. That is, in the method for producing a three-dimensional object according to this embodiment, the photocurable composition according to this embodiment is selectively irradiated with active energy rays such as light to cure the photocurable composition one by one. This is a method for producing a three-dimensional object by repeating this process.
  • active energy rays are selectively irradiated to the photocurable composition based on slice data of the three-dimensional object to be created.
  • the active energy ray applied to the photocurable composition is not particularly limited as long as it is an active energy ray that can cure the photocurable composition according to the present embodiment.
  • Specific examples of the active energy rays include electromagnetic waves such as ultraviolet rays, visible rays, infrared rays, X rays, gamma rays and laser rays, and particle rays such as alpha rays, beta rays and electron rays.
  • ultraviolet rays are most preferable from the viewpoint of the absorption wavelength of the photoradical generator (c) to be used and the cost of equipment installation.
  • the exposure amount is not particularly limited, preferably not 0.001J / cm 2 or more 10J / cm 2 or less. If it is less than 0.001 J / cm 2 , the photocurable composition may not be sufficiently cured, and if it exceeds 10 J / cm 2 , the irradiation time becomes longer and the productivity is lowered.
  • the method of irradiating the photocurable composition with active energy rays is not particularly limited.
  • the following method can be employed.
  • As a first method there is a method of using two-dimensionally scanning light with respect to the photocurable composition using light condensed in a spot shape like laser light.
  • the two-dimensional scanning may be a point drawing method or a line drawing method.
  • As the second method there is a surface exposure method in which light is applied to the shape of the cross-sectional data using a projector or the like.
  • the active energy rays may be irradiated in a planar manner through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter.
  • the surface of the obtained shaped object may be washed with a cleaning agent such as an organic solvent. Moreover, you may perform the postcure which hardens the unreacted residual component which may remain
  • a cleaning agent such as an organic solvent.
  • the photocurable composition which concerns on this embodiment contains the block isocyanate (a1) which has the (meth) acryloyl group mentioned later as the polymeric compound (a) in 1st Embodiment. That is, when the polyrotaxane (c) has a (meth) acryloyl group, the photocurable composition according to the second embodiment includes a blocked isocyanate (a1) having a (meth) acryloyl group and a photo radical generator (b ), And a chain extender (d), and when the polyrotaxane (c) has a hydroxyl group, a blocked isocyanate (a1) having a (meth) acryloyl group, a photo radical generator (b), And a reaction accelerator (e).
  • the block isocyanate (a1) which has the (meth) acryloyl group mentioned later as the polymeric compound (a) in 1st Embodiment. That is, when the polyrotaxane (c) has a (
  • the blocked isocyanate (a1) is represented by the following general formula (1).
  • ABC (1) In formula (1), A and C each independently represent a group represented by the following formula (2), and B represents a group represented by the following formula (3).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms
  • L 1 represents a substituent.
  • R 3 and R 4 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, and a is an integer of 1 to 100. . )
  • the substituent when any of L 1 , R 2 , R 3 and R 4 has a substituent, the substituent may be a substituent containing a carbon atom. However, in that case, the atom to which the substituent is bonded to each of L 1 , R 2 , R 3 and R 4 is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”. Moreover, the said substituent may contain the hetero atom.
  • Block isocyanate (a1) is a (meth) acrylic compound containing at least two (meth) acryloyl groups as described above.
  • R 2 is preferably a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. This is preferable because the temperature (deblocking temperature) when the photocurable composition is photocured and then subjected to a heat treatment for deblocking can be reduced. Further, by adopting any one group of the R 2, it is possible to facilitate the synthesis of blocked isocyanate (a1). Further, by adopting any one group of the R 2, to obtain the synthesis of blocked isocyanate (a1) a low cost.
  • L 1 is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.
  • R 3 has at least one divalent linking group selected from the group consisting of the following formulas (A-1) to (A-4) from the viewpoint of easy availability and synthesis. Is preferred.
  • c is an integer of 1 to 10
  • d is an integer of 1 to 10.
  • R 3 is preferably has a group represented by the above formula (A-4). Thereby, the elasticity modulus of the hardened
  • a and C are preferably the same. That is, the blocked isocyanate (a1) is preferably represented by the following general formula (4). Thereby, the synthesis
  • ABA ... (4) In formula (4), A represents a group represented by the above formula (2), and B represents a group represented by the above formula (3).
  • blocked isocyanate (a1) examples include the following structures.
  • the blocked isocyanate (a1) contained in the photocurable composition may be one type of compound or a plurality of types of compounds.
  • the blending ratio of the blocked isocyanate (a1) in the photocurable composition is calculated based on the total mass of the plurality of types of compounds.
  • the blending ratio of the blocked isocyanate (a1) in the photocurable composition is preferably 10% by mass or more and 90% by mass or less, and 30% by mass or more and 70% by mass, when the entire photocurable composition is 100% by mass. It is more preferable that the amount is not more than mass%.
  • the blending ratio is less than 10% by mass, the toughness of the cured product obtained by curing the photocurable composition becomes low, and when the blending ratio exceeds 80% by mass, the viscosity of the photocurable composition is high. It becomes difficult to handle.
  • the blocked isocyanate (a1) includes the following step (I) and step (II).
  • This step is a step of reacting polyol and diisocyanate. Thereby, a polyisocyanate having a polyol skeleton is obtained.
  • polystyrene resin examples include polyether polyol, polyester polyol, polycarbonate polyol, polyalkylene polyol, and polyacetal, but are not limited thereto. Two or more of these polyols may be mixed and used.
  • diisocyanates used in this step include aliphatic diisocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 3- Cycloaliphatic diisocyanates such as isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylene bis (cyclohexyl isocyanate) or dicyclohexylmethane diisocyanate, bis (isocyanate methyl) cyclohexane, norbornane diisocyanate, phenylene diisocyanate, Li diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalen
  • the polyol and the diisocyanate are preferably reacted in a solvent.
  • the said solvent will not be specifically limited if a polyol and diisocyanate melt
  • dialkyl ethers such as diethyl ether and dipropyl ether, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisopropyl ketone and isobutyl methyl ketone, methyl acetate and ethyl acetate
  • esters such as butyl acetate
  • hydrocarbons such as toluene, xylene and ethylbenzene
  • halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane and chlorobenzene, and nitriles such as
  • the ratio of the number of moles of diisocyanate to the number of moles of polyol to be reacted in this step is preferably 1 or more and 20 or less, and more preferably 3 or more and 10 or less.
  • the ratio is less than 1, the ratio of the unwanted side formation of polyurethane by the polyaddition reaction of diisocyanate and polyol, which is a side reaction, increases, and the yield of diisocyanate having the target polyol skeleton decreases. If the ratio is greater than 20, unreacted diisocyanate remains excessively after the reaction, and it may be difficult to remove the unreacted diisocyanate.
  • This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, and more preferably performed at 30 ° C. or higher and 100 ° C. or lower. Moreover, you may perform this process under recirculation
  • an inert atmosphere such as nitrogen, helium or argon.
  • this step may be performed in the presence of a catalyst.
  • the catalyst include, for example, organic tin compounds such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate and 2-ethylhexanetin, naphthenic acid metal salts such as copper naphthenate, zinc naphthenate and cobalt naphthenate, triethylamine, benzyl And tertiary amines such as dimethylamine, pyridine, N, N-dimethylpiperazine, and triethylenediamine.
  • the amount of the catalyst used is preferably 0.001% by mass to 10% by mass with respect to 100% by mass of the total amount of polyol.
  • the diisocyanate having a polyol skeleton obtained in this step can be separated and purified by a conventional separation method, for example, separation means such as reprecipitation with a poor solvent, concentration and filtration, or a separation means combining these.
  • Step (II) a step of reacting a blocking agent with a diisocyanate having a polyol skeleton obtained in step (I)
  • This step is a step of reacting the blocking agent with the polyisocyanate having the polyol skeleton obtained in step (I).
  • the blocked isocyanate which concerns on this embodiment is obtained.
  • the blocking agent is a compound capable of protecting an active isocyanate group by reacting with an isocyanate group (—NCO) of diisocyanate.
  • Isocyanate groups protected by a blocking agent are called blocked isocyanate groups or blocked isocyanate groups. Since the blocked isocyanate group is protected by the blocking agent, it can be kept stable in a normal state.
  • the blocking agent is dissociated (deblocked) from the blocked isocyanate group, and the original isocyanate group can be regenerated.
  • the blocking agent used in this step is not particularly limited as long as it is a (meth) acrylic compound having an amino group, but tert-butylaminoethyl (meth) acrylate, tert-pentylaminoethyl (meth) acrylate, tert-hexylamino A compound selected from ethyl (meth) acrylate and tert-butylaminopropyl (meth) acrylate is preferable. Thereby, the deblocking temperature of blocked isocyanate can be lowered.
  • this step it is preferable to react a blocking agent and a diisocyanate having a polyol skeleton in a solvent.
  • the solvent is not particularly limited as long as the blocking agent and the polyisocyanate having a polyol skeleton are dissolved, and specifically, those described in the step (I) can be used.
  • This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, more preferably 30 ° C. or higher and 80 ° C. or lower. Moreover, you may perform this process under recirculation
  • an inert atmosphere such as nitrogen, helium or argon.
  • this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, more preferably 30 ° C. or higher and 80 ° C. or lower.
  • reflux
  • this step may be performed in the presence of a catalyst.
  • a catalyst those described in the step (I) can be used.
  • a polymerization inhibitor may be used for the purpose of suppressing polymerization of the (meth) acryloyl group of the blocking agent.
  • a polymerization inhibitor may be used for the purpose of suppressing polymerization of the (meth) acryloyl group of the blocking agent.
  • Specific examples include benzoquinone, hydroquinone, catechol, diphenylbenzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylcresol, dibutylhydroxytoluene and phenothiazine.
  • the blocked isocyanate obtained in this step can be separated and purified by the same method as in step (I).
  • the chain extender (d) is a compound having at least two active hydrogens that react with an isocyanate group formed by deblocking a blocked isocyanate group of the blocked isocyanate (a1) or the blocked isocyanate (a3) described later.
  • the chain extender (d) preferably contains a compound having at least two of the same or different functional groups selected from the group consisting of a hydroxyl group, an amino group, and a thiol group in one molecule.
  • the chain extender (d) is at least selected from the group consisting of a polyol having at least two hydroxyl groups, a polyamine having at least two amino groups, and a polythiol having at least two thiol groups. It is more preferable to contain one.
  • the reaction accelerator (e) described later is preferably used from the viewpoint of reactivity.
  • chain extender (d) examples include ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, Linear diols such as 1,9-nonanediol and 1,10-decanediol; 2-methyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol, 2,2-diethyl- 1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2,4-heptanediol, 1,4-dimethylolhexane, 2-ethyl-1,3-hexanediol, 2, 2,4-trimethyl-1,3-pentanediol, 2-methyl-1,8-octanediol, 2-butyl
  • the balance of the physical properties of a cured product obtained by heat-curing the photocurable composition after photocuring as described later is preferable, and it is industrially inexpensive and available in large quantities.
  • the ratio of the number of moles of chain extender (d) to the number of moles of blocked isocyanate (a1) is 0.1 or more and 5 or less. It is preferably 0.5 or more and 3 or less.
  • the ratio is less than 0.1, the efficiency of the reaction between the isocyanate group and the chain extender (d) is low, and the mechanical properties of the three-dimensional product finally obtained by heat treatment after photocuring Tend to decrease.
  • the ratio is larger than 5, unreacted excess chain extender (d) remains inside the three-dimensional object, and the mechanical properties of the three-dimensional object finally obtained by heat treatment after photocuring deteriorates. There is a tendency.
  • reaction accelerator (e) In the present embodiment, as described above, the polyrotaxane having at least one functional group selected from a (meth) acryloyl group and a hydroxyl group is contained.
  • the reaction accelerator (e) removes the blocked isocyanate group of the blocked isocyanate (a1). It is a compound characterized by accelerating the reaction between an isocyanate group formed by blocking and a hydroxyl group.
  • the reaction accelerator include tin compounds such as dibutyltin dilaurate, dioctyltin dilaurate, and dibutyltin dioctanoate.
  • reaction accelerators (e) may be used alone or in combination of two or more.
  • the amount of the reaction accelerator (e) used is preferably 0.001% by mass or more and 10% by mass or less with respect to 100% by mass of the total amount of polyol.
  • the photocurable composition for three-dimensional modeling contains a polyrotaxane (c) having at least one functional group selected from a (meth) acryloyl group and a hydroxyl group, the first embodiment.
  • a cured product (three-dimensional product) with higher toughness than before can be obtained.
  • the photocurable composition for three-dimensional modeling according to the present embodiment can be further improved in toughness by being cured by being irradiated with light (photocuring) and then subjected to heat treatment.
  • This reaction scheme will be described with reference to FIG.
  • FIG. 2 is a diagram schematically showing a reaction scheme when the photocurable composition according to this embodiment is cured by irradiating light and then subjected to heat treatment.
  • a photo radical generator in the photocurable composition is obtained by irradiating the photocurable composition according to the present embodiment with light of a predetermined wavelength (for example, ultraviolet rays).
  • (B) generates radicals.
  • the (meth) acryloyl group possessed by the blocked isocyanate (a1) undergoes a polymerization reaction and solidifies.
  • the polymerization reaction between the polyrotaxane (c) having a (meth) acryloyl group and the blocked isocyanate (a1) also proceeds.
  • the photocurable composition further contains a reactive diluent such as another radical polymerizable compound
  • a reactive diluent such as another radical polymerizable compound
  • the three components of blocked isocyanate (a1), polyrotaxane (c) and reactive diluent are appropriately combined.
  • the polymerization reaction proceeds. Thereby, a photocured material as schematically shown in FIG. 2B is generated. Since this photocured product can move a cross-linking point as in the first embodiment, the photocured composition has higher toughness than the case where the photocurable composition does not contain polyrotaxane (c).
  • a photocurable composition according to this embodiment when the photocurable composition according to this embodiment is irradiated with light having a predetermined wavelength (for example, ultraviolet rays), a photo radical generator (b) in the photocurable composition (b) ) Generates radicals. Then, the (meth) acryloyl group possessed by the blocked isocyanate (a1) undergoes a polymerization reaction and solidifies.
  • a photocurable composition further contains a reactive diluent such as another radical polymerizable compound
  • a polymerization reaction proceeds by appropriately combining the two components of the blocked isocyanate (a1) and the reactive diluent. To do. As a result, a photocured product as schematically shown in FIG. 3B is generated.
  • the crosslink density is reduced more than after photocuring due to deblocking as described above. be able to.
  • a urethane bond or a urea bond produces
  • the toughness can be further improved.
  • the degree to which the toughness of a cured product obtained by curing the curable composition by adding a toughness improving component to the curable composition is affected by the crosslink density of the cured product. . That is, the effect of improving toughness due to the toughness improving component is reduced in a cured product having a high crosslinking density, and conversely, the effect of improvement is increased in a cured product having a low crosslinking density.
  • a photocured product is obtained by a deblocking reaction by performing a heat treatment after photocuring. The bond inside can be broken.
  • the crosslink density of the cured product can be lowered. Therefore, according to the present embodiment, since the crosslinking density can be reduced by performing heat treatment as compared with a general photocured product, the toughness improving effect by the polyrotaxane (c), which is a toughness improving component, is exhibited more greatly. can do.
  • the photo-thermoset (resin) according to the present embodiment includes a repeating structural unit represented by the following general formula (8), a repeating structural unit represented by the following general formula (9), and a polyrotaxane structure. contains.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms
  • L 1 represents a substituent.
  • R 3 , R 4 and R 5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
  • X 1 and X 2 are each Independently, one of O (oxygen atom), S (sulfur atom), and NH (imino group) is represented.
  • a is an integer of 1 or more and 100 or less.
  • the substituent when any of L 1 , R 2 , R 3 , R 4 and R 5 has a substituent, the substituent is a substituent containing a carbon atom, Also good. However, in that case, the atom to which the substituent is bonded to each of L 1 , R 2 , R 3 , R 4 and R 5 is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”. Moreover, the said substituent may contain the hetero atom.
  • R 2 is a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group because the deblocking temperature can be lowered as described above. Is preferred.
  • R 2 by adopting any of the above groups as R 2 , the synthesis of the photo-thermosetting product can be facilitated at low cost.
  • L 1 is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.
  • R 3 has at least one divalent linking group selected from the group consisting of the following formulas (A-1) to (A-4) from the viewpoint of easy availability and synthesis. Is preferred.
  • c is an integer of 1 to 10
  • d is an integer of 1 to 10.
  • R 3 preferably has a group represented by Formula (A-4). Thereby, the elastic modulus of the photo-thermosetting product can be increased.
  • the “polyrotaxane structure” means a plurality of cyclic molecules, a linear molecule penetrating the plurality of cyclic molecules in a skewered manner, and the elimination of the cyclic molecules arranged at both ends of the linear molecule. And a blocking group that prevents the above.
  • the cyclic molecule, linear molecule, and blocking group are as described above.
  • the repeating structural unit represented by the general formula (8) is bonded to the cyclic molecule in the polyrotaxane structure.
  • the cyclic molecule in the polyrotaxane structure can freely move along the linear molecule in the polyrotaxane structure. Therefore, when an external stress is applied, the cross-linking point in the cured product can move in accordance with the stress. As a result, the tension between the polymers becomes uniform with respect to the stress. -Thermosets show high toughness.
  • the photocurable composition which concerns on this embodiment can be used suitably for the manufacturing method of the solid thing by the optical three-dimensional modeling method (optical modeling method).
  • optical modeling method optical modeling method
  • the manufacturing method of the three-dimensional object which concerns on this embodiment has the process of modeling a modeling object by the optical modeling method, and the process of heat-processing the said modeling object.
  • This step includes a step of selectively irradiating the photocurable composition with active energy rays based on slice data of a three-dimensional object to be created to cure the photocurable composition layer by layer.
  • the exposure amount is not particularly limited, preferably not 0.001J / cm 2 or more 10J / cm 2 or less. If it is less than 0.001 J / cm 2 , the photocurable composition may not be sufficiently cured, and if it exceeds 10 J / cm 2 , the irradiation time becomes longer and the productivity is lowered.
  • the method of irradiating the photocurable composition with active energy rays is not particularly limited.
  • the following method can be employed.
  • As a first method there is a method of using two-dimensionally scanning light with respect to the photocurable composition using light condensed in a spot shape like laser light.
  • the two-dimensional scanning may be a point drawing method or a line drawing method.
  • As the second method there is a surface exposure method in which light is applied to the shape of the cross-sectional data using a projector or the like.
  • the active energy rays may be irradiated in a planar manner through a planar drawing mask formed by arranging a plurality of micro light shutters such as a liquid crystal shutter or a digital micromirror shutter.
  • the surface of the obtained shaped object may be washed with a cleaning agent such as an organic solvent.
  • a cleaning agent such as an organic solvent.
  • heat treatment is performed on a modeled object obtained by the optical modeling method to advance deblocking as described above to reduce the crosslinking density and to generate polyurethane or polyurea. Thereby, a three-dimensional object with higher toughness can be formed.
  • the heat treatment time in this step is not particularly limited as long as the deblocking of the block part in the shaped article proceeds sufficiently, but is preferably 0.5 hours or more and 10 hours or less. If it is shorter than 0.5 hour, deblocking does not proceed, and the effect of improving toughness may not be sufficiently obtained. If it is longer than 10 hours, it is disadvantageous from the viewpoints of reduction in various mechanical properties of the three-dimensional object due to deterioration of the resin and productivity.
  • the photocurable composition which concerns on this embodiment contains the blocked isocyanate (a2) which has the (meth) acryloyl group mentioned later as the blocked isocyanate (a1) in 2nd Embodiment. That is, in the photocurable composition according to the third embodiment, when the polyrotaxane has a (meth) acryloyl group, the blocked isocyanate (a3), the photoradical generator (b), the polyrotaxane (c), and the chain And an extender (d). On the other hand, when the polyrotaxane has a hydroxyl group, it contains a blocked isocyanate (a3), a photo radical generator (b), a polyrotaxane (c), and a reaction accelerator (e).
  • the blocked isocyanate (a2) is represented by the following general formula (5).
  • A-D-C (5) (In formula (5), A and C each independently represent a group represented by the following formula (2), and D represents a group represented by the following formula (6).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms
  • L 1 represents a substituent.
  • R 11 , R 12 and R 13 each independently represent a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • E and f are integers satisfying 1 ⁇ e + f ⁇ 50, either one of which may be 0. )
  • the substituent when any of L 1 , R 2 , R 11 , R 12 and R 13 has a substituent, the substituent is a substituent containing a carbon atom, Also good. However, in that case, the atom to which the substituent is bonded to each of L 1 , R 2 , R 11 , R 12 and R 13 is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.
  • L 1 is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.
  • R 11 and R 12 are preferably each independently any one of the following formulas (B-1) to (B-9).
  • g is an integer of 1 to 10
  • h or i may be 0, and is an integer satisfying 1 ⁇ h + i ⁇ 10 is there.
  • either j or k may be 0, and is an integer that satisfies 1 ⁇ j + k ⁇ 10.
  • a and C are preferably the same. That is, the blocked isocyanate (a2) is preferably represented by the following general formula (7). Thereby, the synthesis
  • AD-A ... (7) (In the formula (7), A represents a group represented by the above formula (2), and D represents a group represented by the above formula (6).)
  • blocked isocyanate (a2) examples include the following structures.
  • the method for synthesizing the blocked isocyanate (a3) includes the following step (I) ′ and step (II).
  • Step (I) ′ Step of reacting polycarbonate diol and diisocyanate
  • Step (II) Step of reacting the blocking agent with the diisocyanate having the polycarbonate skeleton obtained in step (I)
  • step (I) ′ is the same as in step (I) of the second embodiment except that polycarbonate diol is used instead of polyol, description of portions overlapping with those of the second embodiment will be omitted.
  • the polycarbonate diol used in this step can be synthesized by, for example, a transesterification reaction between a carbonate compound and a diol.
  • diol used for synthesizing the polycarbonate diol examples include ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol, 1,3-butanediol, 1,5-pentanediol, neopentyl glycol, 3-methyl-1 , 5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanedimethanol, 2-methyl-1,8-octanediol, 1,9-nonanediol and other aliphatic diols, cyclohexanediol, hydrogenated bisphenol -A, hydrogenated bisphenol-F, hydrogenated xylylene cholole, and other alicyclic diols, bisphenol-A, bisphenol-F, 4,4'-biphenol, xylylene glycol, and other aromatic diols, etc. But only It is not. Two or more of these dio
  • the number average molecular weight M n of the polycarbonate diol is preferably 100 or more and 5000 or less.
  • the number average molecular weight Mn of the polycarbonate diol is less than 100, the molecular weight of the finally obtained blocked isocyanate is reduced, and the elastic modulus and strength of the three-dimensional product obtained by curing the photocurable composition are reduced. There is.
  • the number average molecular weight Mn of polycarbonate diol exceeds 5000, the molecular weight of the finally obtained blocked isocyanate will become large, the viscosity of a photocurable composition may become high, and workability
  • chain extender (d) When the photocurable composition which concerns on this embodiment has a (meth) acryloyl group on a polyrotaxane (c) similarly to the photocurable composition which concerns on 2nd Embodiment, chain extender (d) is used. contains. The description about the chain extender (d) according to this embodiment is the same except that the blocked isocyanate (a1) is replaced with the blocked isocyanate (a3) in the description of the chain extender (d) according to the second embodiment. Therefore, the description is omitted.
  • reaction accelerator (e) Similar to the reaction accelerator according to the second embodiment, the reaction accelerator according to this embodiment is added as necessary. That is, when the chain extender (d) has a hydroxyl group, a polyrotaxane is contained when (c) has a hydroxyl group.
  • the explanation about the reaction accelerator (e) according to this embodiment is the same except that the blocked isocyanate (a1) is replaced with the blocked isocyanate (23) in the description of the chain extender (d) according to the second embodiment. Therefore, the description is omitted.
  • the photo-thermoset (resin) according to the present embodiment includes a repeating structural unit represented by the following general formula (8), a repeating structural unit represented by the following general formula (10), and a polyrotaxane structure. contains.
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms
  • L 1 represents a substituent.
  • R 11 , R 12 , R 13 and R 14 each independently represents a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent
  • 3 and X 4 each independently represent one of O (oxygen atom), S (sulfur atom), and NH (imino group), and either e or f may be 0, 1 ⁇ e + f ⁇ An integer satisfying 50.
  • the substituent when any of L 1 , R 2 , R 11 , R 12 , R 13 and R 14 has a substituent, the substituent is a substituent containing a carbon atom. It may be. However, in that case, the atom to which the substituent is bonded to each of L 1 , R 2 , R 11 , R 12 , R 13 and R 14 is an atom other than a carbon atom. In that case, the number of carbon atoms contained in the substituent is not included in the number of carbon atoms of the “hydrocarbon group”.
  • R 2 is a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group because the deblocking temperature can be lowered as described above. Is preferred.
  • R 2 by adopting any of the above groups as R 2 , the synthesis of the photo-thermosetting product can be facilitated at low cost.
  • L 1 is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.
  • R 11 and R 12 are preferably each independently any one of the following formulas (B-1) to (B-9). Thereby, the elastic modulus and strength of the photo-thermoset can be further increased.
  • g is an integer of 1 to 10
  • h or i may be 0, and is an integer satisfying 1 ⁇ h + i ⁇ 10 is there.
  • either j or k may be 0, and is an integer that satisfies 1 ⁇ j + k ⁇ 10.
  • the “polyrotaxane structure” means a plurality of cyclic molecules, a linear molecule penetrating the plurality of cyclic molecules in a skewered manner, and the elimination of the cyclic molecules arranged at both ends of the linear molecule. And a blocking group that prevents the above.
  • the cyclic molecule, linear molecule, and blocking group are as described above.
  • the repeating structural unit represented by the general formula (8) is bonded to a cyclic molecule in the polyrotaxane structure.
  • the cyclic molecule in the polyrotaxane structure can freely move along the linear molecule in the polyrotaxane structure. Therefore, when an external stress is applied, the cross-linking point in the cured product can move in accordance with the stress. As a result, the tension between the polymers becomes uniform with respect to the stress. -Thermosets show high toughness.
  • the photocurable composition according to the present embodiment contains a hydroxyl group
  • polymerization of the (meth) acrylic compounds (a) is performed.
  • the reaction proceeds. Curing by reacting the isocyanate group formed by deblocking the blocked isocyanate group of the blocked isocyanate (a2) described later and the hydroxyl group in the polyrotaxane (c) by subjecting the resulting molded article to a heat treatment. A thing is obtained. Due to the effect of the polyrotaxane, a cured product having higher toughness than the conventional photocurable composition can be obtained.
  • the photocurable composition according to this embodiment contains a blocked isocyanate (a3) having a branched chain structure as the polymerizable compound (a) in the first embodiment. That is, the photocurable composition according to this embodiment comprises a blocked isocyanate (a3) having a branched chain structure, a photo radical generator (b), a polyrotaxane (c), and a chain extender (d). contains.
  • the blocked isocyanate having a branched chain structure is a (meth) acrylic compound containing at least three (meth) acryloyl groups.
  • Specific examples of the blocked isocyanate having a branched chain structure include a blocked isocyanate represented by the following general formula (A).
  • a 1 to A 4 are each independently a structure represented by the following general formula (12), and B is a structure represented by the following general formula (13).
  • R 1 represents a hydrogen atom or a methyl group
  • R 2 represents an optionally substituted hydrocarbon group having 1 to 10 carbon atoms
  • L 1 has a substituent.
  • R 3a , R 3b , R 4 , R 5 , R 6 and R 7 are each independently a divalent divalent having 1 to 20 carbon atoms which may have a substituent.
  • Y 1 represents a divalent linking group
  • a represents an integer of 1 to 99. It said R 4 is same as R 4 in the formula (3).
  • R 2 is preferably a group selected from a tert-butyl group, a tert-pentyl group, and a tert-hexyl group. This is preferable because the temperature (deblocking temperature) when the photocurable composition is photocured and then subjected to a heat treatment for deblocking can be reduced. Further, by adopting any one group of the R 2, it is possible to facilitate the synthesis of blocked isocyanate. Further, by adopting any one group of the R 2, to obtain the synthesis of blocked isocyanate at a low cost.
  • L 1 is preferably an ethylene group or a propylene group from the viewpoint of availability and ease of synthesis.
  • Y 1 is preferably at least one divalent linking group selected from the group consisting of the following formulas (C1) to (C3) from the viewpoint of easy availability and synthesis.
  • a 1 to A 4 are preferably the same. That is, the blocked isocyanate is preferably represented by the following general formula (6). Thereby, the synthesis
  • A represents a group represented by general formula (12)
  • B represents a group represented by general formula (13).
  • the blending ratio of the blocked isocyanate (a3) having a branched chain structure in the photocurable composition is preferably 0 part by mass or more and 90% by mass or less when the entire photocurable composition is 100%. More preferably, it is at least part% and no more than 70% by mass. When the said mixture ratio exceeds 80%, the viscosity of a photocurable composition will become high and handling will become difficult.
  • blocked isocyanate examples include blocked isocyanates represented by the following formulas (I-1) to (I-20).
  • This step is a step of reacting polyol and diisocyanate. Thereby, a polyisocyanate having a polyol skeleton is obtained.
  • polystyrene resin examples include polyether polyol, polyester polyol, polycarbonate polyol, polyalkylene polyol, and polyacetal, but are not limited thereto. Two or more of these polyols may be mixed and used.
  • diisocyanates used in this step include aliphatic diisocyanates such as trimethylene diisocyanate, 1,2-propylene diisocyanate, butylene diisocyanate, hexamethylene diisocyanate, pentamethylene diisocyanate, trimethylhexamethylene diisocyanate, cyclohexane diisocyanate, methylcyclohexane diisocyanate, 3- Cycloaliphatic diisocyanates such as isocyanate methyl-3,5,5-trimethylcyclohexyl isocyanate (isophorodiisocyanate), methylenebis (cyclohexyl isocyanate) or dicyclohexylmethane diisocyanate, bis (isocyanatomethyl) cyclohexane, norbornane diisocyanate, phenylene diisocyanate, Li diisocyanate, 4,4'-diphenyl diisocyanate, 1,5-naphthalen
  • the polyol and the diisocyanate are preferably reacted in a solvent.
  • the said solvent will not be specifically limited if a polyol and diisocyanate melt
  • dialkyl ethers such as diethyl ether and dipropyl ether, cyclic ethers such as 1,4-dioxane and tetrahydrofuran, ketones such as acetone, methyl ethyl ketone, diisopropyl ketone and isobutyl methyl ketone, methyl acetate and ethyl acetate
  • esters such as butyl acetate
  • hydrocarbons such as toluene, xylene and ethylbenzene
  • halogen solvents such as methylene chloride, chloroform, carbon tetrachloride, tetrachloroethane, trichloroethane and chlorobenzene, and nitriles such as
  • the ratio of the number of moles of diisocyanate to the number of moles of polyol to be reacted in this step is preferably 1 or more and 20 or less, and more preferably 3 or more and 10 or less.
  • the ratio is less than 1, the ratio of the unwanted addition of polyurethane by the polyaddition reaction of diisocyanate and polyol, which is a side reaction, increases, and the yield of polyisocyanate having the target polyol skeleton decreases. If the ratio is greater than 20, unreacted diisocyanate remains excessively after the reaction, and it may be difficult to remove the unreacted diisocyanate.
  • This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, and more preferably performed at 30 ° C. or higher and 100 ° C. or lower. Moreover, you may perform this process under recirculation
  • an inert atmosphere such as nitrogen, helium or argon.
  • this step may be performed in the presence of a catalyst.
  • the catalyst include, for example, organic tin compounds such as tin octylate, dibutyltin diacetate, dibutyltin dilaurate and 2-ethylhexanetin, naphthenic acid metal salts such as copper naphthenate, zinc naphthenate and cobalt naphthenate, triethylamine, benzyl And tertiary amines such as dimethylamine, pyridine, N, N-dimethylpiperazine, and triethylenediamine.
  • These catalysts may be used alone or in combination of two or more.
  • the amount of the catalyst used may be 0.001% by mass or more and 1% by mass or less with respect to 100% by mass of the total amount of polyol.
  • the diisocyanate having a polyol skeleton obtained in this step can be separated and purified by a conventional separation method, for example, separation means such as reprecipitation with a poor solvent, concentration and filtration, or a separation means combining these.
  • Step (II) a step of reacting a blocking agent with a polyisocyanate having a polyol skeleton obtained in step (I)
  • This step is a step of reacting the blocking agent with the polyisocyanate having the polyol skeleton obtained in step (I).
  • the blocked isocyanate (a3) having a branched structure according to the present embodiment is obtained.
  • the blocking agent is a compound capable of protecting an active isocyanate group by reacting with an isocyanate group (—NCO) of diisocyanate.
  • Isocyanate groups protected by a blocking agent are called blocked isocyanate groups or blocked isocyanate groups. Since the blocked isocyanate group is protected by the blocking agent, it can be kept stable in a normal state.
  • the blocking agent is dissociated (deblocked) from the blocked isocyanate group, and the original isocyanate group can be regenerated.
  • the blocking agent used in this step is not particularly limited as long as it is a (meth) acrylic compound having an amino group, but tert-butylaminoethyl (meth) acrylate, tert-pentylaminoethyl (meth) acrylate, tert-hexyl.
  • a compound selected from aminoethyl (meth) acrylate and tert-butylaminopropyl (meth) acrylate is preferred. Thereby, the deblocking temperature of blocked isocyanate can be lowered.
  • this step it is preferable to react a blocking agent and a diisocyanate having a polyol skeleton in a solvent.
  • the solvent is not particularly limited as long as the blocking agent and the polyisocyanate having a polyol skeleton are dissolved. Specifically, those described in the description of the step (I) can be used.
  • This step is preferably performed in an inert atmosphere such as nitrogen, helium or argon. Further, this step is preferably performed at 0 ° C. or higher and 150 ° C. or lower, and more preferably performed at 30 ° C. or higher and 120 ° C. or lower.
  • this step is carried out at a reaction temperature of less than 0 ° C., the reaction is difficult to proceed.
  • this process is performed at reaction temperature higher than 150 degreeC, there exists a possibility that block agents may superpose
  • this step may be performed in the presence of a catalyst.
  • a catalyst those described in the description of the step (I) can be used.
  • a polymerization inhibitor may be used for the purpose of suppressing the polymerization reaction of the (meth) acryloyl group of the blocking agent.
  • Specific examples include benzoquinone, hydroquinone, catechol, diphenylbenzoquinone, hydroquinone monomethyl ether, naphthoquinone, t-butylcatechol, t-butylphenol, dimethyl-t-butylphenol, t-butylcresol, dibutylhydroxytoluene and phenothiazine.
  • the blocked isocyanate obtained in this step can be separated and purified by the same method as in step (I).
  • the three-dimensional product produced using the photocurable composition according to the present embodiment can move the cross-linking point according to the stress even when an external stress is applied due to the effect of the polyrotaxane.
  • the tension between the polymers becomes uniform with respect to the stress, and as a result, a cured product having higher toughness than the conventional photocurable composition can be obtained.
  • the photocurable composition which concerns on this embodiment contains block isocyanate (a3).
  • the blocked isocyanate (a3) may have a polycarbonate structure containing a plurality of carbonate groups (—O— (C ⁇ O) —O—) in the molecular structure as represented by the above formula (3).
  • the cured product obtained by heat-curing the photocurable composition according to the present embodiment also includes the above-described polycarbonate structure therein, according to the photocurable composition according to the present embodiment, A three-dimensional object having high tensile strength and elastic modulus can be formed by stereolithography.
  • the use of the photocurable composition for three-dimensional modeling according to the first to third embodiments and the cured product thereof is not particularly limited.
  • it can be used for various applications such as resin for stereolithography 3D printers, sports equipment, medical / nursing care equipment, industrial machinery / equipment, precision equipment, electrical / electronic equipment, electrical / electronic parts, building materials. is there.
  • blocked isocyanate 1 was synthesized.
  • hexamethylene diisocyanate (207 g, 1.23 mol, 1.0 eq.) Were added to a 500 mL reactor at room temperature in an argon atmosphere and stirred. .
  • the resulting polytetrahydrofuran diisocyanate 1 was added with 300 mL of dichloromethane and cooled with ice while stirring. Hydroquinone (10 mg) and 2- (t-butylamino) ethyl methacrylate (142 g, 769 mmol, 5.0 eq.) Were slowly added thereto, and the mixture was stirred at room temperature for 12 hours. This solution was analyzed by infrared spectroscopy, and it was confirmed by the above method that there was no isocyanate-derived absorption peak.
  • blocked isocyanate 2 was synthesized.
  • 4,4′-methylenebis (cyclohexyl diisocyanate) 323 g, 1.23 mol, at room temperature in a 500 mL reactor at room temperature.
  • 1.0 eq. was added and stirred.
  • 2-ethylhexane tin (II) 80 ⁇ L, cat.
  • the solution was heated to 50 ° C. and stirred at the same temperature for 5 hours.
  • the solution was allowed to cool to room temperature and then added to vigorously stirred hexane (4 L).
  • the resulting polytetrahydrofuran diisocyanate 2 was added with 300 mL of dichloromethane and cooled with ice while stirring. Hydroquinone (10 mg) and 2- (t-butylamino) ethyl methacrylate (114 g, 615 mmol, 5.0 eq.) Were slowly added thereto and stirred at room temperature for 1.5 days. This solution was analyzed by infrared spectroscopy, and it was confirmed by the above method that there was no isocyanate-derived absorption peak.
  • blocked isocyanate 4 was synthesized. First, polytetrahydrofuran (100 g, 154 mmol, 1.0 eq.) And hexamethylene diisocyanate (207 g, 1.23 mol, 8.0 eq.) Having a number average molecular weight Mn of 650 at room temperature in an argon atmosphere in a 500 mL reactor. Added and stirred. To this solution was added tin (II) 2-ethylhexanoate (80 ⁇ L, cat.). The solution was heated to 80 ° C. and stirred at the same temperature for 8 hours. The solution was allowed to cool to room temperature and then added to vigorously stirred hexane (4 L).
  • photocurable composition A was prepared according to the following prescription.
  • Comparative Example 1 A photocurable composition 2 for three-dimensional modeling of Comparative Example 1 was prepared in the same manner as in Example 1 except that the polyrotaxane (c) was not used in Example 1. That is, the composition of the photocurable composition 2 for three-dimensional modeling of Comparative Example 1 is the same as the composition of the photocurable composition A in Example 1.
  • the photocurable composition B was prepared according to the following prescription.
  • Photocurable composition 3 for three-dimensional modeling of Example 2 was prepared.
  • Photocurable composition B 90% by mass Polyrotaxane (c): ⁇ C-1> SeRM SA2400C (manufactured by Advanced Soft Materials Co., Ltd.) 10.0% by mass
  • Comparative Example 2 A photocurable composition 4 for three-dimensional modeling of Comparative Example 2 was prepared in the same manner as in Example 2 except that the polyrotaxane (c) was not used in Example 2. That is, the composition of the photocurable composition 4 for three-dimensional modeling in Comparative Example 2 is the same as the composition of the photocurable composition B in Example 2.
  • a photocurable resin C was prepared according to the following formulation.
  • Example 3 the photocurable composition 6 for three-dimensional modeling of the comparative example 3 was prepared like Example 3 except not using a polyrotaxane (c). That is, the composition of the photocurable composition 6 for three-dimensional modeling in Comparative Example 3 is the same as the composition of the photocurable composition C in Example 3.
  • Example 4 First, according to the following prescription, the photocurable resin D was prepared.
  • Comparative Example 4 A photocurable composition 8 for three-dimensional modeling of Comparative Example 4 was prepared in the same manner as in Example 4 except that no reaction accelerator was used in Example 4. That is, the composition of the three-dimensional photocurable composition 8 of Comparative Example 4 is the same as the composition of the photocurable composition C in Example 4.
  • the photocurable resin E was prepared.
  • the obtained photo-thermoset having a thickness of about 300 ⁇ m was punched out into a No. 8 type dumbbell to prepare a test piece.
  • This test piece was measured according to JIS K 7127 using a tensile tester (trade name “Strograph EII” manufactured by Toyo Seiki Seisakusho) at a test temperature of 23 ° C. and a tensile speed of 10 mm / min. Maximum point strength and elongation were measured.
  • the breaking energy was determined from the area surrounded by the stress-strain curve obtained in this tensile test.
  • the tensile modulus can be used as an index of rigidity
  • the maximum point strength can be used as an index of strength
  • the breaking energy can be used as an index of toughness.
  • Table 1 summarizes each composition of the photo-curable composition for three-dimensional modeling and the mechanical properties of the light-thermosetting material produced using the composition.
  • Example 5 as compared with Comparative Example 1, polyrotaxane was added to a blocked isocyanate having a branched chain structure, but the toughness (breaking energy) could be improved while maintaining a high elastic modulus. .

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
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Abstract

Cette invention concerne une composition photodurcissable pour moulage solide qui contient : un composé de (méth)acryle ayant un groupe (méth)acryloyle ; et un générateur de photo-radicaux, où la composition photodurcissable est caractérisée en ce qu'elle contient un polyrotaxane comportant une pluralité de molécules cycliques ayant chacune au moins un groupe (méth)acryloyle et un groupe hydroxyle.
PCT/JP2018/006708 2017-03-03 2018-02-23 Composition photodurcissable pour moulage solide, procédé de préparation d'un article solide l'utilisant, et résine WO2018159493A1 (fr)

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US16/554,453 US10961380B2 (en) 2017-03-03 2019-08-28 Three-dimensional-forming photo-curable composition, method for producing three-dimensional article from the photo-curable composition, and resin

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JP2017140151A JP6946095B2 (ja) 2017-03-03 2017-07-19 立体造形用の光硬化性組成物、それを用いた立体物の製造方法、および樹脂
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015200201A1 (fr) * 2014-06-23 2015-12-30 Carbon3D, Inc. Résines de polyuréthane présentant de multiples mécanismes de durcissement destinées à être utilisées dans la production d'objets tridimensionnels
WO2016071811A1 (fr) * 2014-11-04 2016-05-12 Dws S.R.L. Procédé et composition de stréréolithographie
JP2017048288A (ja) * 2015-09-01 2017-03-09 Ｋｊケミカルズ株式会社 モデル材用活性エネルギー線硬化性樹脂組成物
WO2017154335A1 (fr) * 2016-03-07 2017-09-14 住友ゴム工業株式会社 Composition de caoutchouc pour impression tridimensionnelle
JP2018039962A (ja) * 2016-09-09 2018-03-15 Ｋｊケミカルズ株式会社 （メタ）アクリルアミド変性ポリロタキサン

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015200201A1 (fr) * 2014-06-23 2015-12-30 Carbon3D, Inc. Résines de polyuréthane présentant de multiples mécanismes de durcissement destinées à être utilisées dans la production d'objets tridimensionnels
WO2016071811A1 (fr) * 2014-11-04 2016-05-12 Dws S.R.L. Procédé et composition de stréréolithographie
JP2017048288A (ja) * 2015-09-01 2017-03-09 Ｋｊケミカルズ株式会社 モデル材用活性エネルギー線硬化性樹脂組成物
WO2017154335A1 (fr) * 2016-03-07 2017-09-14 住友ゴム工業株式会社 Composition de caoutchouc pour impression tridimensionnelle
JP2018039962A (ja) * 2016-09-09 2018-03-15 Ｋｊケミカルズ株式会社 （メタ）アクリルアミド変性ポリロタキサン

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