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
  • B29C64/30—Auxiliary operations or equipment
  • B29C64/307—Handling of material to be used in additive manufacturing
  • B29C64/314—Preparation
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B33—ADDITIVE MANUFACTURING TECHNOLOGY
  • B33Y—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
  • 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 [3D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3D 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
  • 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

Definitions

• the present invention relates to a curable resin composition, a cured product, and a three-dimensional structure.
• a method for manufacturing resin molded products has been to selectively polymerize and harden curable resin compositions using active energy rays such as ultraviolet lasers, based on three-dimensional shape data designed using three-dimensional design systems such as three-dimensional CAD. Accordingly, optical stereolithography (stereolithography) is used to create three-dimensional objects.
• This optical three-dimensional modeling method can handle complex shapes that are difficult to produce by cutting, and because it takes a short manufacturing time and is easy to handle, it can be used to manufacture prototype models of industrial products as well as resin molded products. It is becoming widely used.
• a typical example of optical stereolithography is to irradiate a computer-controlled spot-shaped ultraviolet laser from above onto a liquid photocurable resin placed in a container to harden a single layer of a predetermined thickness, and then create a model.
• An example of this method is to lower the object by one layer, supply a liquid resin onto the layer, cure it with ultraviolet laser light in the same manner as described above, and laminate the layers.By repeating this operation, a three-dimensional object can be obtained.
• DMD digital micromirror device
• DMD digital micromirror device
• UV light is irradiated from below through a transparent container containing a photocurable resin to harden one layer of a predetermined cross-sectional pattern, and the model is lifted up by one layer. Therefore, the surface exposure method, in which the next layer is irradiated and cured in the same way as described above, and three-dimensional objects are obtained by sequentially laminating layers, is increasing.
• the characteristics required for the photocurable resin used in the optical three-dimensional modeling method include various properties such as low viscosity, the ability to form a smooth liquid surface, and excellent curability.
• resin compositions mainly containing radically polymerizable compounds are known (see, for example, Patent Documents 1 and 2). The rate was not measured, and these required characteristics were not fully satisfied. Therefore, it has been difficult to realize a composition that can form a cured product that has a soft feel but has excellent tear strength and restoring force.
• the problem to be solved by the present invention is to provide a curable resin composition, a cured product, and a three-dimensional molded product that has a soft feel and has excellent tear strength and restoring force.
• the present inventors discovered that the monofunctional (meth)acrylic compound containing a specific urethane resin, a monofunctional (meth)acrylic compound, and a photopolymerization initiator, The inventors have discovered that the above-mentioned problems can be solved by using a curable resin composition for stereolithography in which the content of compound (B) exhibits a specific value, and the present invention has been completed.
• the present invention includes the following aspects.
• [1] Contains a urethane resin (A), a monofunctional (meth)acrylic compound (B), and a photopolymerization initiator, and the urethane resin (A) has at least two (meth)acryloyl groups in its molecule.
• the content of the monofunctional (meth)acrylic compound (B) is in the range of 50 to 85 parts by mass based on 100 parts by mass of the resin solid content.
• Curable resin composition [2] The curable resin composition for stereolithography according to [1], which does not contain a polyfunctional (meth)acrylic compound other than the urethane resin (A).
• the monofunctional (meth)acrylic compound (B) contains at least a monofunctional (meth)acrylic compound (B-1), and the glass transition temperature of the polymer of the compound (B-1) is The curable resin composition for stereolithography according to [1] or [2], which has a temperature of less than 10°C.
• the monofunctional (meth)acrylic compound (B) contains at least a monofunctional (meth)acrylic compound (B-2), and the glass transition temperature of the polymer of the compound (B-2) is The curable resin composition for stereolithography according to any one of [1] to [3], which has a temperature of 10°C or more and less than 50°C.
• the monofunctional (meth)acrylic compound (B) contains at least a monofunctional (meth)acrylic compound (B-3), and the glass transition temperature of the polymer of the compound (B-3) is
• [7] The curable resin composition for stereolithography according to any one of [1] to [6], wherein the urethane resin (A) has a concentration of acryloyl groups in the range of 0.5 to 2 mmol/g.
• [8] Contains a urethane resin (A), a monofunctional (meth)acrylic compound (B), and a photopolymerization initiator, and the content of the monofunctional (meth)acrylic compound (B) is based on the resin solid content.
• the amount is in the range of 50 to 85 parts by mass per 100 parts by mass, and the monofunctional (meth)acrylic compound (B) contains at least two types of monofunctional (meth)acrylic compounds having mutually different structures; Among the two types of monofunctional (meth)acrylic compounds, the glass transition temperature of the polymer of one monofunctional (meth)acrylic compound is less than 10°C, and the polymer of the other monofunctional (meth)acrylic compound is A curable resin composition for stereolithography, in which a polymer has a glass transition temperature of 10°C or higher. [9] A cured product that is a curing reaction product of the curable resin composition for stereolithography according to any one of [1] to [8].
• the curable resin composition of the present invention can provide a curable resin composition for stereolithography that can form a cured product that has a soft feel and has excellent tear strength and restoring force.
• (meth)acrylate means acrylate and/or methacrylate.
• (meth)acryloyl means acryloyl and/or methacryloyl.
• (meth)acrylic means acrylic and/or methacrylic.
• the curable resin composition for stereolithography of the present invention contains a urethane resin (A), a monofunctional (meth)acrylic compound (B), and a photopolymerization initiator.
• the urethane resin (A) has at least two (meth)acryloyl groups in the molecule, and the monofunctional (meth)acrylic compound (B) has an amount of 50 to 85 parts by mass based on 100 parts by mass of the resin solid content. Contained within the range of 50%. By setting the content of the monofunctional (meth)acrylic compound within this numerical range, it is possible to form a cured product that has a soft feel and has excellent tear strength and restoring force.
• the resin solid content in the present invention refers to the entire compound having a polymerizable double bond contained in the curable resin composition.
• the resin solid content is the sum of the solid content of the urethane resin (A) and the solid content of the monofunctional (meth)acrylic compound (B), or if the curable resin composition is composed of other resins (polymers).
• it contains an acrylic compound it is the total of the solid content of (A), the solid content of (B), and the solid content of other resins or acrylic compounds.
• the curable resin composition for stereolithography of the present invention may contain a difunctional or higher functional compound other than the urethane resin (A) and/or the monofunctional (meth)acrylic compound (B) within a range that does not impede the effects of the present invention. It can also contain other (meth)acrylic compounds.
• the curable resin composition for stereolithography of the present invention can also contain other additives such as a photosensitizer, an ultraviolet absorber, a polymerization inhibitor, and an inorganic filler, if necessary.
• the urethane resin (A) used in the present invention may be any compound as long as it has at least two (meth)acryloyl groups and one or more urethane bonds in the molecule.
• Urethane resin (A) can be obtained, for example, by reacting polyisocyanate (a1) with a compound (a2) having a hydroxyl group and a (meth)acryloyl group.
• a compound (a3) having a hydroxyl group other than the compound (a2) may be further used as a reaction raw material.
• the polyisocyanate (a1) is not particularly limited as long as it can form a urethane resin (A) having a specific content of (meth)acryloyl groups used in the present invention, and can be appropriately selected depending on the purpose.
• aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate; norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, water Alicyclic diisocyanate compounds such as added diphenylmethane diisocyanate; tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, 1,5-naphthalene diisocyanate, 4,4'-diisocyanato-3,3'-dimethylbiphenyl, Aromatic diisocyanate compounds such as o-tolidine diisocyanate; examples thereof include isocyanurate-modified products, biuret-modified products,
• the polyisocyanate (a1) is especially isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or an isocyanurate modified product of hexamethylene diisocyanate. It is more preferable if it is present in order to form a cured product that has a soft feel and has excellent tear strength and restoring force.
• the above-mentioned polyisocyanate (a1) can be used alone or in combination of two or more types.
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group is not particularly limited as long as it can form a urethane resin (A) having at least one (meth)acryloyl group in the molecule, and may be selected as appropriate depending on the purpose. I can do it.
• (poly)oxyalkylene chains such as (poly)oxyethylene chains, (poly)oxypropylene chains, and (poly)oxytetramethylene chains are added to the molecular structures of the compounds having various hydroxyl groups and (meth)acryloyl groups. It is also possible to use (poly)oxyalkylene modified products introduced therein, and lactone modified products in which a (poly)lactone structure is introduced into the molecular structure of the above-mentioned compounds having various hydroxyl groups and (meth)acryloyl groups.
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group is particularly hydroxyethyl (meth)acrylate or its lactone modified product, a cured product having a soft feel and excellent tear strength and restoring force can be obtained. It is more preferable in terms of formation.
• the above-mentioned compound (a2) having a hydroxyl group and a (meth)acryloyl group can be used alone or in combination of two or more.
• the compound (a3) having a hydroxyl group is not particularly limited as long as it does not have a (meth)acryloyl group in the molecule and has a hydroxyl group, and can be appropriately selected depending on the purpose.
• Polyhydric alcohols with a linear alkyl structure such as decanediol; 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octane
• Polyhydric alcohols having a branched alkyl structure such as diols
• polycarbonate polyols synthesized by transesterification of these polyhydric alcohols and carbonate esters polyester polyols synthesized by dehydration condensation reaction of the above polyhydric alcohols and dibasic acids
• Polyalkylene glycols such as tetramethylene ether glyco
• the compound (a3) having a hydroxyl group is polypropylene glycol or polytetramethylene ether glycol
• a curable resin composition capable of forming a cured product having a soft feel and excellent tear strength and restoring force can be obtained.
• the number average molecular weight of polypropylene glycol and polytetramethylene ether glycol is preferably in the range of 200 to 5,000, more preferably in the range of 400 to 3,500, and particularly preferably in the range of 500 to 3,000.
• the method for producing the urethane resin (A) is not particularly limited, and any method may be used.
• the reaction raw materials containing the polyisocyanate (a1) and the compound (a2) having a hydroxyl group and a (meth)acryloyl group may be reacted all at once, or the reaction raw materials may be divided and produced sequentially. It may be manufactured by a reaction method. Further, the compound (a3) having a hydroxyl group may or may not be used as a reaction raw material.
• the hydroxyl group contained in the compound (a2) having a hydroxyl group and a (meth)acryloyl group can be obtained.
• the equivalent ratio (OH/NCO) between (OH) and the isocyanate group (NCO) possessed by polyisocyanate (a1) is preferably in the range of 0.95/1.00 to 1.05/1.00. , more preferably 1/1.
• the urethane resin (A) for example, dibutyltin laurate, dibutyltin acetate, etc. can be used as a catalyst, and the resin can be produced under commonly used urethanization reaction conditions.
• solvents such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, etc., or radically polymerizable monomers that do not contain a site that reacts with isocyanate, but do not contain hydroxyl or amino groups. etc. can also be used as a solvent.
• the content of (meth)acryloyl groups in the urethane resin (A) is the amount per unit mass of the urethane resin (A) (mmol/g).
• the content of (meth)acryloyl groups in the urethane resin (A) is preferably in the range of 0.5 mmol/g or more and 2 mmol/g or less, and preferably 0.6 mmol/g or more and 1.8 mmol/g or less. More preferably, it is in the range of 0.7 mmol/g or more and 1.3 mmol/g or less.
• the curable resin composition has a soft feel, as shown in the examples below. However, it is possible to form a cured product with excellent tear strength and restoring force.
• the content of (meth)acryloyl groups in the urethane resin (A) can be determined, for example, by using a 1H NMR analyzer to attribute each peak of the measurement sample and the internal standard and determining the integral ratio, or by using an IR analyzer. It can be determined by creating a calibration curve from the ratio of the peak due to the acryloyl group and a specific peak of the standard substance and quantifying it. In this application, the (meth)acryloyl group content of the urethane resin (A) was calculated based on the (meth)acryloyl group content (theoretical value) of the raw material.
• the curable resin composition for stereolithography of the present invention further contains a photopolymerization initiator.
• the photopolymerization initiator include 1-hydroxycyclohexylphenylketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-[4-(2-hydroxyethoxy)phenyl]-2-hydroxy -2-Methyl-1-propan-1-one, thioxanthone and thioxanthone derivatives, 2,2'-dimethoxy-1,2-diphenylethan-1-one, diphenyl(2,4,6-trimethoxybenzoyl)phosphine oxide , 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one , 2-benzyl-2-dimethylamino-1-(
• photopolymerization initiators include, for example, "Omnirad-1173", “Omnirad-184", “Omnirad-127", “Omnirad-369", “Omnirad-379”, “Omnirad-907”, “Omnirad-4265”, “Omnirad-1000”, “Omnirad-651”, “Omnirad-TPO”, “Omnirad-819”, “Omnirad-2022”, “Omnirad-2100”, “Omnirad-2959”, “Omnirad rad -754'', ⁇ Omnirad-784'', ⁇ Omnirad-500'', ⁇ Omnirad-81'', ⁇ Omnirad TPO-L'', ⁇ Omnipol TP'' (manufactured by IGM), ⁇ Kayacure-DETX'', ⁇ Kayacure-MB
• the amount of the photopolymerization initiator added is preferably in the range of 0.1 to 20% by mass, for example, in the curable resin composition for stereolithography.
• the (meth)acrylic compound may also include a nitrogen-containing (meth)acrylic compound.
• (meth)acrylic compounds include (meth)acrylic compounds such as (meth)acrylate compounds and (meth)acrylamides.
• Examples of the monofunctional (meth)acrylic compound (B) include phenoxyethyl (meth)acrylate, phenoxybenzyl (meth)acrylate, cyclohexyl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, cyclohexylmethyl (meth)acrylate, Cyclohexylethyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dipropylene glycol mono(meth)acrylate, isobornyl (meth)acrylate, norbornyl (meth)acrylate, isononyl (meth)acrylate, benzyl (meth)acrylate, phenylbenzyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, ethoxyethoxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinate
• Preferred embodiments of the monofunctional (meth)acrylic compound (B) include the following ⁇ First to Fourth Embodiments>>>.
• the monofunctional (meth)acrylic compound (B) contains a monofunctional (meth)acrylic compound (B-1).
• the monofunctional (meth)acrylic compound (B-1) is a monofunctional (meth)acrylic compound whose polymer has a glass transition temperature (hereinafter abbreviated as "Tg") of less than 10°C. .
• a polymer of a monofunctional (meth)acrylic compound (B-1) is obtained by mixing a monofunctional (meth)acrylic compound (B-1) and a photopolymerization initiator and irradiating the mixture with active energy rays.
• Tg in this specification refers to Tg measured by a general method such as differential scanning calorimetry (DSC) method or dynamic mechanical analysis (DMA) method.
• DSC differential scanning calorimetry
• DMA dynamic mechanical analysis
• the Tg of the polymer of the monofunctional (meth)acrylic compound (B-1) is The temperature is preferably -100°C or more and less than 10°C, more preferably -60°C or more and 5°C or less, and particularly preferably -30°C or more and 0°C or less.
• Examples of the monofunctional (meth)acrylic compound (B-1) include tetrahydrofurfuryl acrylate (Tg: -15°C), lauryl acrylate (Tg: -30°C), lauryl methacrylate (Tg: -65°C), isodecyl 8 mol ethylene oxide adduct of acrylate (Tg: -60°C), isooctyl acrylate (Tg: -54°C), tridecyl acrylate (Tg: -55°C), tridecyl methacrylate (Tg: -40°C), nonylphenol acrylate (Tg: -45°C), 4 mol ethylene oxide adduct of nonylphenol acrylate (Tg: -28°C), 2 mol caprolactone adduct of hydroxyethyl acrylate (Tg: -40°C), 4 mol caprolactone adduct of hydroxyethyl acrylate (T
• a curable resin composition capable of forming a cured product having excellent mechanical properties 8 mol of ethylene oxide adduct of nonylphenol acrylate, 4 mol of ethylene oxide adduct of nonylphenol acrylate, and 2 mol of caprolactone of hydroxyethyl acrylate are used. It is preferable to use adducts, such as an adduct of hydroxyethyl acrylate with 4 mol of caprolactone, an adduct of hydroxyethyl acrylate with 10 mol of caprolactone, and phenoxybenzyl acrylate. These monofunctional (meth)acrylic compounds can be used alone or in combination of two or more.
• the monofunctional (meth)acrylic compound (B) contains a monofunctional (meth)acrylic compound (B-2).
• the monofunctional (meth)acrylic compound (B-2) is a monofunctional (meth)acrylic compound whose polymer has a Tg of 10°C or more and less than 50°C.
• Examples of the monofunctional (meth)acrylic compound (B-2) include benzyl acrylate (Tg: 11°C), trimethylcyclohexyl acrylate (Tg: 43°C), stearyl acrylate (Tg: 46°C), and cyclic trimethylolpropane formal acrylate. (Tg: 27°C), o-phenylphenoxyethyl (meth)acrylate (Tg: 33°C), and the like.
• cyclic trimethylolpropane formal acrylate o-phenylphenoxyethyl (meth)acrylate, etc.
• a curable resin composition capable of forming a cured product having excellent mechanical properties can be obtained.
• monofunctional (meth)acrylic compounds can be used alone or in combination of two or more.
• the monofunctional (meth)acrylic compound (B) contains a monofunctional (meth)acrylic compound (B-3).
• the monofunctional (meth)acrylic compound (B-3) is a monofunctional (meth)acrylic compound whose polymer has a Tg of 50° C. or higher.
• the Tg of the polymer of the monofunctional (meth)acrylic compound (B-3) is The temperature is preferably 50°C or more and 200°C or less, more preferably 80°C or more and 170°C or less, and particularly preferably 100°C or more and 150°C or less.
• Examples of the monofunctional (meth)acrylic compound (B-3) include 3,3,5-trimethylcyclohexyl acrylate (Tg: 52°C), 4-tert-butylcyclohexyl acrylate (Tg: 65°C), acryloylmorpholine (Tg : 145°C), isobornyl acrylate (Tg: 94°C), isobornyl methacrylate (Tg: 180°C), dicyclopentenyl acrylate (Tg: 120°C), dicyclopentanyl acrylate (Tg: 120°C), Dicyclopentanyl methacrylate (Tg: 175°C) is mentioned.
• the monofunctional (meth)acrylic compound (B) contains two types of monofunctional (meth)acrylic compounds having mutually different structures, one of the two types has a polymer Tg of less than 10°C, and the other It is more preferable that the Tg of the polymer is 10° C. or higher. By doing so, a curable resin composition can be obtained that can form a cured product that has a soft feel and has excellent tear strength and restoring force.
• the Tg of the polymer of the above-mentioned monofunctional (meth)acrylic compound (B-1) is less than 10°C
• the monofunctional (meth)acrylic compound (B-1) in combination with the monofunctional (meth)acrylic compound (B-1).
• the ratio of the amount Y of the monofunctional (meth)acrylic compound whose polymer Tg is 10° C. or higher to the amount X of the monofunctional (meth)acrylic compound whose polymer Tg is less than 10° C. [(X )/(Y)] is preferably in the range of 5/65 to 65/5, more preferably in the range of 10/60 to 50/20, and more preferably in the range of 10/60 to 30/40. It is particularly preferable. Within these ranges, it becomes easy to form a cured product that has a soft feel and has excellent tear strength and restoring force.
• the monofunctional (meth)acrylic compound (B) is the monofunctional (meth)acrylic compound (B-1), the monofunctional (meth)acrylic compound (B-2), and the monofunctional (meth)acrylic compound described above. It is more preferable to contain all of the compound (B-3). By doing so, a curable resin composition can be obtained that can form a cured product that has a soft feel and has excellent tear strength and restoring force.
• the content of the monofunctional (meth)acrylic compound (B-1) is preferably 10% by mass or more and 80% by mass or less, and 20% by mass or less in the monofunctional (meth)acrylic compound (B). % or more and 70% by mass or less, and particularly preferably 30% by mass or more and 60% by mass or less.
• the content of the monofunctional (meth)acrylic compound (B-2) is preferably 10% by mass or more and 80% by mass or less, and 20% by mass or more and 70% by mass or less. It is more preferably at most 30% by mass and at most 60% by mass.
• the content of the monofunctional (meth)acrylic compound (B-3) is preferably 1% by mass or more and 80% by mass or less, and 5% by mass or more and 70% by mass or less in the monofunctional (meth)acrylic compound (B). It is more preferably at most 10% by mass and at most 60% by mass.
• the curable resin composition for stereolithography of the present invention may contain, if necessary, within a range that does not impede the effects of the present invention. , a difunctional or more functional (meth)acrylic compound can also be contained in combination.
• Tetrafunctional (meth)acrylates such as ditrimethylolpropane tetraacrylate, pentaerythritol ethoxytetraacrylate, and pentaerythritol tetraacrylate;
• Pentafunctional (meth)acrylates such as dipentaerythritol hydroxypentaacrylate and alkyl-modified dipentaerythritol pentaacrylate;
• hexafunctional (meth)acrylates such as dipentaerythritol hexaacrylate. These compounds can be used alone or in combination of two or more.
• the curable resin composition for stereolithography of the present invention may optionally contain a photosensitizer, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a silicone additive, a fluorine additive, and a silane cup.
• a photosensitizer such as a ring agent, a phosphoric acid ester compound, an organic bead, an inorganic fine particle, an organic filler, an inorganic filler, a rheology control agent, a defoaming agent, a coloring agent, etc.
• a ring agent such as a phosphoric acid ester compound, an organic bead, an inorganic fine particle, an organic filler, an inorganic filler, a rheology control agent, a defoaming agent, a coloring agent, etc.
• the curable resin composition for stereolithography of the present invention can further have a photosensitizer added thereto to improve its curability, if necessary.
• photosensitizers include amine compounds such as aliphatic amines and aromatic amines, urea compounds such as o-tolylthiourea, condensed polycyclic compounds such as anthraquinone derivatives, sodium diethyldithiophosphate, and s-benzylisothiourea.
• sulfur compounds such as nium-p-toluenesulfonate.
• Examples of the ultraviolet absorber include 2-[4- ⁇ (2-hydroxy-3-dodecyloxypropyl)oxy ⁇ -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1, 3,5-triazine, 2-[4- ⁇ (2-hydroxy-3-tridecyloxypropyl)oxy ⁇ -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3 , 5-triazine and other triazine derivatives, 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2- Examples include xanthenecarboxy-4-dodecyloxybenzophenone and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These ultraviolet absorbers can be used alone or in combination of two or more.
• antioxidants examples include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, phosphate ester antioxidants, and the like. These antioxidants can be used alone or in combination of two or more.
• polymerization inhibitor examples include hydroquinone, methoquinone, di-t-butylhydroquinone, P-methoxyphenol, butylated hydroxytoluene, and nitrosamine salts.
• silicone additives include dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, and fluorine-modified dimethyl Polysiloxane copolymers, polyorganosiloxanes with alkyl groups or phenyl groups such as amino-modified dimethylpolysiloxane copolymers, polydimethylsiloxanes with polyether-modified acrylic groups, polydimethylsiloxanes with polyester-modified acrylic groups, etc. It will be done. These silicon-based additives can be used alone or in combination of two or more.
• fluorine-based additives examples include the "Megaface” series manufactured by DIC Corporation. These fluorine-based additives can be used alone or in combination of two or more.
• silane coupling agent examples include vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, Glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyl Diethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(amino
• Styrenic silane coupling agent such as p-styryltrimethoxysilane
• (Meta) such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
• Acryloxy-based silane coupling agent such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, etc.
• Ureido-based silane coupling agent such as 3-ureidopropyltriethoxysilane
• Chloropropyl-based silane coupling agent such as 3-chloropropyltrimethoxysilane
• Mercapto-based silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane;
• Sulfide-based silane coupling agents such as bis(triethoxysilylpropyl)tetrasulfide
• silane coupling agents such as 3-isocyanatepropyltriethoxysilane. These silane coupling agents can be used alone or in combination of two or more.
• Examples of phosphoric acid ester compounds include those having a (meth)acryloyl group in the molecular structure, and commercially available products include, for example, "Kayamar PM-2" and “Kayamar PM-21” manufactured by Nippon Kayaku Co., Ltd.
• organic beads examples include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacryl styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, and polyester beads.
• examples include resin beads, polyamide resin beads, polyimide resin beads, polyfluoroethylene resin beads, and polyethylene resin beads. These organic beads can be used alone or in combination of two or more. Further, the average particle size of these organic beads is preferably in the range of 1 to 10 ⁇ m.
• inorganic fine particles include fine particles of silica, alumina, zirconia, titania, barium titanate, antimony trioxide, and the like. These inorganic fine particles can be used alone or in combination of two or more types. Further, the average particle size of these inorganic fine particles is preferably in the range of 95 to 250 nm, particularly preferably in the range of 100 to 180 nm.
• a dispersion aid When containing inorganic fine particles, a dispersion aid can be used.
• the dispersion aid include phosphoric acid ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphoric acid dimethacrylate. These dispersion aids can be used alone or in combination of two or more.
• Commercially available dispersion aids include, for example, "Kayamar PM-21” and “Kayamar PM-2” manufactured by Nippon Kayaku Co., Ltd., and "Light Ester P-2M” manufactured by Kyoeisha Chemical Co., Ltd.
• organic fillers examples include plant-derived solvent-insoluble substances such as cellulose, lignin, and cellulose nanofibers.
• inorganic filler examples include glass (particles), silica (particles), alumina silicate, talc, mica, aluminum hydroxide, alumina, calcium carbonate, carbon nanotubes, and the like.
• amide waxes such as "Disparon 6900” manufactured by Kusumoto Kasei Co., Ltd.; urea-based rheology control agents such as “BYK410” manufactured by Big Chemie; "Disparon 4200” manufactured by Kusumoto Kasei Co., Ltd. and cellulose acetate butyrate such as “CAB-381-2" and “CAB 32101” manufactured by Eastman Chemical Products.
• defoamers examples include oligomers containing fluorine or silicon atoms, oligomers such as higher fatty acids, and acrylic polymers.
• Examples of the colorant include pigments, dyes, and the like.
• pigment known and commonly used inorganic pigments and organic pigments can be used.
• inorganic pigments examples include titanium oxide, antimony red, red red, cadmium red, cadmium yellow, cobalt blue, navy blue, ultramarine blue, carbon black, and graphite.
• organic pigments examples include quinacridone pigments, quinacridonequinone pigments, dioxazine pigments, phthalocyanine pigments, anthrapyrimidine pigments, anthanthrone pigments, indanthrone pigments, flavanthrone pigments, perylene pigments, diketopyrrolopyrrole pigments, perinone pigments, and quinophthalones. pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, azo pigments and the like. These pigments can be used alone or in combination of two or more.
• dyes examples include azo dyes such as monoazo and disazo, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, and naphthoquinone dyes. , naphthalimide dyes, perinone dyes, phthalocyanine dyes, triallylmethane dyes, and the like. These dyes can be used alone or in combination of two or more.
• the content of the urethane resin (A) in the curable resin composition for stereolithography of the present invention is 1% by mass from the viewpoint that it is possible to form a cured product that has a soft feel and has excellent tear strength and restoring force. It is preferably 50% by mass or less, and more preferably 3% by mass or more and 50% by mass or less.
• the curable resin composition for stereolithography of the present invention is a curable resin composition other than urethane resin (A) from the viewpoint of obtaining a curable resin composition that can form a cured product that has a soft feel and has excellent tear strength and restoring force. It is more preferable not to contain a (meth)acrylic compound having two or more functionalities.
• the concentration of (meth)acryloyl groups in the resin solid content is 2 to 4 mmol/g. It is preferably in the range of 2.5 to 3.5 mmol/g, more preferably in the range of 3 to 3.3 mmol/g.
• the cured product of the present invention can be obtained by irradiating the curable resin composition for stereolithography of the present invention with active energy rays.
• active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• the irradiation may be performed in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere.
• an ultraviolet lamp As a source of ultraviolet light, an ultraviolet lamp is generally used from the standpoint of practicality and economy. Specifically, low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, LEDs, etc. can be mentioned.
• the cumulative amount of active energy rays is not particularly limited, but is preferably 50 to 5,000 mJ/cm 2 , more preferably 300 to 1,000 mJ/cm 2 . It is preferable that the cumulative light amount is within the above range because it is possible to prevent or suppress the occurrence of uncured portions.
• the three-dimensional object of the present invention can be produced by a known optical three-dimensional modeling method.
• optical stereolithography method examples include a stereolithography (SLA) method, a digital light processing (DLP) method, and an inkjet method.
• SLA stereolithography
• DLP digital light processing
• inkjet method examples include a stereolithography (SLA) method, a digital light processing (DLP) method, and an inkjet method.
• the stereolithography (SLA) method is a method in which a tank of liquid curable resin composition is irradiated with active energy rays such as laser beams at points, and the molding stage is moved while curing layer by layer to perform three-dimensional modeling.
• the digital light processing (DLP) method is a method in which a tank of liquid curable resin composition is irradiated with active energy rays from LEDs, etc., and is cured layer by layer while moving the modeling stage to create three-dimensional modeling. .
• the inkjet stereolithography method is a method in which micro droplets of a curable resin composition for stereolithography are ejected from a nozzle so as to draw a predetermined shape pattern, and then ultraviolet rays are irradiated to form a cured thin film.
• the DLP method is preferable because it enables high-speed modeling using surfaces.
• the DLP stereolithography method is not particularly limited as long as it uses a DLP stereolithography system, but the modeling conditions include the following:
• the pitch is in the range of 0.01 to 0.2 mm
• the irradiation wavelength is in the range of 350 to 410 nm
• the light intensity is in the range of 0.5 to 50 mW/cm 2
• the cumulative light amount per layer is 1 to 4.
• 100 mJ/cm 2 and in particular, the lamination pitch of stereolithography is in the range of 0.02 to 0.1 mm, since the modeling accuracy of the three-dimensional model is even better.
• the irradiation wavelength is in the range of 365 to 410 nm
• the light intensity is in the range of 5 to 15 mW/cm 2
• the cumulative amount of light per layer is in the range of 5 to 15 mJ/cm 2 .
• the final three-dimensional object may be obtained by irradiating the three-dimensional object obtained by stereolithography with active energy rays from multiple directions. This irradiation process is called post-curing.
• the cured product and three-dimensional molded product of the present invention have a soft feel.
• the Shore-A hardness of the cured product and the three-dimensional molded product based on JIS K 6253; 2012 becomes low.
• the Shore-A hardness of the three-dimensional structure that has not been post-cured is too low, the shape may be distorted during the stereolithography process and may not be the desired shape.
• the Shore A hardness must not be too low without post-curing, and the Shore A hardness must not increase significantly even after post-curing ( It is preferable that the Shore-A hardness can be maintained at a low level. From this, the Shore-A hardness without post-curing is preferably 30 or more, and the Shore-A hardness after post-curing is preferably 99 or less, and preferably 75 or less. More preferably, it is particularly preferably 60 or less.
• the tensile strength of the cured product and the three-dimensional molded product based on ASTM D412-06a becomes low.
• it is preferably 10 MPa or less, more preferably 8 MPa or less, and particularly preferably 3 MPa or less.
• the cured product and three-dimensional molded product of the present invention have excellent tear strength.
• the tear strength according to ASTM D624-00 is preferably 1 kN/m or more and 40 kN/m or less, more preferably 3 kN/m or more and 30 kN/m or less, and 10 kN/m or more and 20 kN/m or less. It is particularly preferable that
• the cured products and three-dimensional molded products of the present invention have excellent restoring force after shape changes due to external forces.
• the compression set rate according to ASTM D395-03 will be low. It is more preferably 50 or less, particularly preferably 15 or less, and most preferably 3 or less.
• the three-dimensional structure of the present invention has a soft feel and excellent tear strength and restoring force, it can be used, for example, in shoe sole members, nursing care products, helmet interiors, protectors, cushioning materials for vehicles, flooring materials, sports equipment, etc. It can be suitably used in applications that require shock absorption, resilience, durability, bending resistance, etc., such as cosmetic tools.
• IPDI Isophorone diisocyanate, product name “VESTANAT IPDI” (manufactured by Evonik)
• ⁇ Sumidur N3300 Isocyanurate type hexamethylene diisocyanate (manufactured by Sumika Covestrourethane Co., Ltd.)
• ⁇ HEA 2-hydroxyethyl acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.)
• ⁇ Plaxel FA2D Caprolactone 2 mol addition type 2-hydroxyethyl acrylate (manufactured by Daicel Corporation), hydroxyl value: 163.1 KOHmg/g, (meth)acryloyl group content (theoretical value): 2.87 mmol/g ⁇ Plaxel FA4DT: 4 mol caprolactone addition type 2-hydroxyethyl acrylate (manufactured by Daicel Corporation), hydroxyl value: 98.1 KOHmg/g, (meth)acryloyl group content (theoretical value): 1.76 mmol/g ⁇ Plaxel FA10L: 10 mol caprolactone addition type 2-hydroxyethyl acrylate (solid content 70%) (manufactured by Daicel Corporation), hydroxyl value: 31 KOHmg/g, (meth)acryl
• ⁇ PPG1000 Polypropylene glycol, product name "Sannix PP-1000" (manufactured by Sanyo Chemical Industries, Ltd.), number average molecular weight 1000 ⁇ PTG650SN: Polytetramethylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.), number average molecular weight 650 ⁇ PTG850SN: Polytetramethylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.), number average molecular weight 850 ⁇ PTG1000SN: Polytetramethylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.), number average molecular weight 1000 ⁇ PTG2000SN: Polytetramethylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.), number average molecular weight 2000 ⁇ PTG2900SN: Polytetramethylene glycol (manufactured by Hodogaya Chemical Industry Co., Ltd.), number average
• ⁇ MIRAMER M170 Ethoxyethoxyethyl acrylate (manufactured by MIWON), Tg: -56°C ⁇ MIRAMER M166: 8 mol ethylene oxide addition type nonylphenol acrylate (manufactured by MIWON), Tg: -45°C ⁇ MIRAMER M164: 4 mol ethylene oxide addition type nonylphenol acrylate (manufactured by MIWON), Tg: -28°C ⁇ MIRAMER M1122: Phenoxybenzyl acrylate (manufactured by MIWON), Tg: 6°C ⁇ MIRAMER M140: Phenoxyethyl acrylate (manufactured by MIWON), Tg: 7°C ⁇ Viscoat #200: Cyclic trimethylolpropane formal acrylate (manufactured by Osaka Organic Chemical Industry Co., Ltd.), Tg: 27°C ⁇ MIRAMER M1142: o-phen
• ⁇ MIRAMER M210 Hydroxypivalic acid neopentyl glycol diacrylate (manufactured by MIWON)
• M2100 10 mol ethylene oxide addition type bisphenol A diacrylate (manufactured by MIWON)
• ⁇ Omnirad819 Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (manufactured by IGM Resins)
• urethane resin (A1) having an acryloyl group.
• the content of (meth)acryloyl groups per 1 g of urethane resin (A1) calculated from the acryloyl group content (theoretical value) of the raw material was 1.18 mmol (listed in Tables 1 to 3 below.
• the content of (meth)acryloyl groups in each urethane resin obtained in the examples is also listed in Tables 1 to 3).
• Example 1 Preparation of curable resin composition (1)
• urethane resin (A5) obtained in Synthesis Example 5
• 1.2 parts by mass of was added and stirred at 60° C. or lower until uniformly dissolved to obtain a curable resin composition (1).
• the content of (meth)acryloyl groups per 1 g of resin solid content in the curable resin composition calculated from the acryloyl group content (theoretical value) of each component contained in the curable resin composition is 2.83 mmol. (described in Tables 1 to 3 below; the content of (meth)acryloyl groups in the resin solids obtained in the following synthesis examples is also listed in Tables 1 to 3).
• Example 2 to 21 Preparation of curable resin compositions (2) to (22)
• a curable resin composition (2) was prepared in the same manner as in Example 1, except that the composition and blending amount of the urethane resin and (meth)acrylic compound were changed to those shown in Tables 1 to 3. ⁇ (22) was obtained.
• the tensile strength [Mpa] was measured using a universal material testing machine "5965" manufactured by INSTRON under the conditions of room temperature, a distance between chucks of 85 mm, and a tensile speed of 500 mm/min. Incidentally, five identical samples were prepared and each sample was measured, and the average values are shown in Tables 1 to 3. The lower the value, the softer the feel, and a score of 10 or less was considered acceptable.
• the tensile strength [Mpa] was measured using a precision universal testing machine "AGS-1KNX” manufactured by Shimadzu Corporation under the conditions of room temperature, a distance between chucks of 58 mm, and a tensile speed of 500 mm/min.
• AGS-1KNX precision universal testing machine
• five identical samples were prepared and each sample was measured, and the average values are shown in Tables 1 to 3. The larger this value is, the higher the tear strength is, and if it is too high, there will be no soft feel, so a value of 1 or more and 40 or less is considered to be a pass.
• Compression set rate CS [%] (t 0 - t 1 ) x 100/(t 0 - t 2 ) CS: Compression set rate t 0 : Thickness of sample before measurement t 1 : Thickness of sample 30 minutes after release from pressure t 2 : Thickness of spacer
• compositions and evaluation results of the curable resin compositions obtained in Examples 1 to 22 and Comparative Examples 1 to 2 are shown in Tables 1 to 3 below.
• the curable resin composition of the present invention can form a cured product that has a soft feel and has excellent tear strength and restoring force.
• the curable resin compositions of Comparative Examples 1 and 2 in which the blending amount of the monofunctional (meth)acrylic compound was less than 50 parts by mass based on 100 parts by mass of resin solids, had a hard texture. It was confirmed that a cured product with reduced restoring force was formed.

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