Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
  • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
  • B29C64/10—Processes of additive manufacturing
  • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
  • B29C64/124—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using layers of liquid which are selectively solidified
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/36—Silica
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/49—Phosphorus-containing compounds
  • C08K5/51—Phosphorus bound to oxygen
  • C08K5/52—Phosphorus bound to oxygen only
  • C08K5/521—Esters of phosphoric acids, e.g. of H3PO4
  • C08K5/523—Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds

Definitions

• the present invention relates to a curable resin composition for stereolithography, a cured product of the composition, and a three-dimensional object made from the cured product.
• optical 3D modeling (stereolithography) has become popular as a method for producing resin molded products.
• This method uses 3D shape data designed using a 3D design system such as 3D CAD to selectively polymerize and harden a curable resin composition using active energy rays such as an ultraviolet laser to create a 3D object.
• This optical 3D modeling method can handle complex shapes that are difficult to create using cutting, has a short manufacturing time, and is easy to handle. As a result, it has come to be widely used not only for resin molded products, but also for the production of prototype models for industrial products. Accordingly, various curable resin compositions containing polymerizable monomers used in optical 3D modeling have also been developed.
• the curable resin compositions used in such optical three-dimensional modeling methods are required not only to be capable of three-dimensional modeling, particularly for electrical and electronic components, automobile parts, furniture, and home appliance parts, but also to provide heat resistance and flame retardancy in the three-dimensionally modeled objects.
• One known method for imparting such heat resistance and flame retardancy is disclosed in Patent Document 1 below, which uses a polymerizable composition containing a liquid photopolymerizable compound, a flame retardant, and a flame retardant protective agent.
• Patent Document 1 The inventors of the present invention have studied the above-mentioned Patent Document 1 and found that there is a problem in that the concentration of reactive functional groups in the polymerizable composition is low, and sufficient heat resistance cannot be achieved in the presence of a flame retardant. They also found that the inclusion of a flame retardant protecting agent causes problems, such as lowering the molecular weight of the polymer by inhibiting UV curing, and the protecting agent itself acting as a plasticizer, resulting in a decrease in the heat resistance of the three-dimensionally shaped object.
• the problem that the present invention aims to solve is to provide a curable resin composition that can be used to create three-dimensional objects with excellent heat resistance and flame retardancy, a cured product of the composition, and a three-dimensional object made from the cured product.
• a curable resin composition for stereolithography comprising a polymerizable monomer including a photopolymerizable monomer (A) having two or more photopolymerizable functional groups, a phosphorus-based flame retardant (B), and a photopolymerization initiator.
• a curable resin composition for stereolithography comprising a polymerizable monomer including a photopolymerizable monomer (A) having two or more photopolymerizable functional groups, a phosphorus-based flame retardant (B), and a photopolymerization initiator.
• Tg glass transition temperature
• the curable resin composition for stereolithography of the present invention is capable of producing three-dimensional objects that possess excellent heat resistance, strength, and flame retardancy. Furthermore, by increasing the concentration of reactive functional groups in the composition, the curable resin composition for stereolithography of the present invention can produce three-dimensional objects at low light intensity, making it possible to suppress the decomposition of flame retardants without the need for flame retardant protectors. Furthermore, while the inclusion of non-reactive flame retardants such as metal hydroxides and antimony oxides can reduce heat resistance, the combination of a bifunctional or higher photopolymerizable monomer with a phosphorus-based flame retardant provides excellent heat resistance while achieving high flame retardancy with a small amount of flame retardant. In this way, three-dimensional objects can be obtained that exhibit both excellent flame retardancy and heat resistance that is useful in practical situations.
• (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 polymerizable monomer including a photopolymerizable monomer (A) having two or more photopolymerizable functional groups, a phosphorus-based flame retardant (B), and a photopolymerization initiator.
• the composition of the present invention may also contain a urethane oligomer (C) as the polymerizable monomer, other polymerizable monomers other than the photopolymerizable monomer (A) and the urethane oligomer (C), additives, etc.
• the photopolymerizable monomer (A) having two or more photopolymerizable functional groups is a central component that can increase the concentration of reactive functional groups in the polymerizable monomer, and the photopolymerizable functional group preferably has a (meth)acryloyl group or a vinyl group from the viewpoint of photoreactivity.
• the photopolymerizable monomer (A) preferably has a glass transition point (Tg) of 100°C or higher when made into a homopolymer from the viewpoint of heat resistance of the three-dimensionally shaped object.
• the Tg is preferably 110°C or higher, more preferably 120°C or higher.
• the photopolymerizable monomer (A) can be used alone or in combination of two or more types.
• Examples of monomers having two photopolymerizable functional groups include tricyclodecane dimethanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, hexanediol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, hexanediol EO-modified di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, neopentyl glycol PO-modified di(meth)acrylate, tripropylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, glycerin di(meth)acrylate, 2-[2-(vinyl alcohol)] [oxy)ethoxy]ethyl (meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,4-butaned
• Examples of monomers having three photopolymerizable functional groups include trimethylolpropane tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, glycerol propoxy tri(meth)acrylate, pentaerythritol tri(meth)acrylate, EO-modified glycerol acrylate, PO-modified glycerol triacrylate, pentaerythritol triacrylate, EO-modified phosphate triacrylate, trimethylolpropane triacrylate, caprolactone-modified trimethylolpropane triacrylate, HPA-modified trimethylolpropane triacrylate, (EO)- or (PO)-modified trimethylolpropane triacrylate, and alkyl-modified dipentaerythritol triacrylate.
• Examples of monomers having four or more photopolymerizable functional groups include pentaerythritol tetra(meth)acrylate, pentaerythritol EO-modified tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol ethoxy tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, and dipentaerythritol hexa(meth)acrylate.
• the photopolymerizable monomer (A) preferably has an isocyanuric acid skeleton, as the flame retardancy is improved by the synergistic effect of the nitrogen atom derived from the isocyanuric acid skeleton and the phosphorus atom derived from the phosphorus-based flame retardant (B).
• monomers having an isocyanuric acid skeleton include tris(2-acryloyloxyethyl) isocyanurate and triallyl isocyanurate.
• the content of photopolymerizable monomer (A) is, for example, 30% by weight or more, preferably 50% by weight or more, and more preferably 70% by weight or more, of the total amount of polymerizable monomers contained in the composition.
• the phosphorus-based flame retardant (B) is preferably liquid at 23° C. (room temperature) from the viewpoint of compatibility with polymerizable monomers such as the photopolymerizable monomer (A).
• the phosphorus-based flame retardant (B) can be used alone or in combination of two or more.
• Examples of phosphorus-based flame retardants (B) include ammonium polyphosphate, metal phosphinate, phosphazene, bisphenol A, phenyl, and aromatic condensed phosphate ester flame retardants.
• aromatic phosphate ester flame retardants are particularly preferred due to their improved compatibility.
• Examples of aromatic phosphate ester flame retardant compounds include cresyl diphenyl phosphate, tricresyl phosphate, triphenyl phosphate, trixylenyl phosphate, 2-ethylhexyl diphenyl phosphate, 2-naphthyl diphenyl phosphate, and cresyl di-2,6-xylenyl phosphate.
• phosphorus-based flame retardants include, for example, ammonium polyphosphate-based EXOLIT® AP422, AP423, and AP462 (manufactured by Clariant Chemicals), metal phosphinate-based EXOLIT® OP1230, OP1240, OP1312, and OP1400 (manufactured by Clariant Chemicals), phosphazene-based LAVITOL® FP-110 and FP-100 (manufactured by Mitsui Fine Chemicals), bisphenol A-based Adeka STAB FP-600 (manufactured by ADEKA), biphenyl-based Adeka STAB FP900L (manufactured by ADEKA), and phenyl-based aromatic condensed phosphate ester-based CR-733S and CR-741 (manufactured by Daihachi Chemical Industry Co., Ltd.).
• the content of the phosphorus-based flame retardant (B) is preferably 15 to 45 parts by weight per 100 parts by weight of the polymerizable monomer, from the viewpoint of achieving both flame retardancy and heat resistance.
• Polymerizable monomers include photopolymerizable monomers (A), urethane oligomers (C), and other polymerizable monomers.
• photopolymerization initiator examples include 1-hydroxycyclohexyl phenyl ketone, 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-(4-morpholinophenyl)-1-butanone, ethyl phenyl(2,4,6-tri
• 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-754", “Omnirad-784", “Omnirad-500”, “Omnirad-819", and “Om Examples include “nirad TPO-L,” “Omnipol TP” (manufactured by IGM), “Kayacure-DETX,” “Kayacure-MBP,” “Kayacure-DMBI,” “Kay
• the content of the photopolymerization initiator is preferably in the range of 0.1 to 10 parts by weight per 100 parts by weight of the polymerizable monomer.
• the composition of the present invention may further contain a urethane oligomer (C) as an optional polymerizable monomer.
• a urethane oligomer (C) is a compound having at least one (meth)acryloyl group and one or more urethane bonds in the molecule, but preferably has two or more (meth)acryloyl groups and two or more urethane bonds.
• the urethane oligomer (C) can be used alone or in combination of two or more.
• the number average molecular weight (Mn) of the urethane oligomer (C) is, for example, 300 to 10,000, preferably 400 to 9,000, and more preferably 500 to 8,000. Having a molecular weight within this range allows for the production of a three-dimensional object with excellent heat resistance and strength.
• urethane oligomer (C) As the urethane oligomer (C), it is preferable to use a polyfunctional urethane acrylate such as diurethane dimethacrylate, etc. Also, compounds represented by the following chemical formulas (C1) to (C6) are preferred. Commercially available products may also be used from the viewpoint of availability, and examples thereof include those manufactured by Daicel Allnex Co., Ltd.
• the urethane oligomer (C) preferably has an isocyanuric acid skeleton.
• the photopolymerizable monomer (A) or the urethane oligomer (C), or both have an isocyanuric acid skeleton.
• the composition of the present invention which combines a trifunctional or higher urethane oligomer (C), a compound having an isocyanuric acid skeleton, and a phosphorus-based flame retardant (B), enables the production of three-dimensional objects with particularly excellent heat resistance and flame retardancy.
• the trifunctional or higher urethane oligomer (C) exhibits particularly excellent heat resistance due to improved crosslink density and rigidification of the resin structure.
• the synergistic effect of the nitrogen atom derived from the isocyanuric acid skeleton and the phosphorus atom derived from the phosphorus-based flame retardant (B) significantly improves flame retardancy.
• its content is preferably 10 to 40 parts by weight, more preferably 15 to 30 parts by weight, per 100 parts by weight of polymerizable monomer.
• Examples of compounds having an isocyanuric acid skeleton include compounds represented by the following chemical formulas (C7) and (C8). (C7) (C8)
• the urethane oligomer (C) 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 also be used as a reaction raw material.
• polyisocyanate (a1) there are no particular restrictions on the polyisocyanate (a1) as long as it can form the urethane resin (A) used in the present invention having a specific content of (meth)acryloyl groups, and it can be selected appropriately depending on the purpose.
• examples include aliphatic diisocyanate compounds such as butane diisocyanate, hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, and 2,4,4-trimethylhexamethylene diisocyanate; alicyclic diisocyanate compounds such as norbornane diisocyanate, isophorone diisocyanate, hydrogenated xylylene diisocyanate, and hydrogenated diphenylmethane diisocyanate; aromatic diisocyanate compounds such as tolylene diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diiso
• polyisocyanate (a1) is particularly isophorone diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, hydrogenated diphenylmethane diisocyanate, or an isocyanurate-modified hexamethylene diisocyanate, it is more preferable in order to form a cured product that combines high heat resistance and flame retardancy.
• 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 can be selected appropriately depending on the purpose.
• Examples thereof include hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, trimethylolpropane (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol (meth)acrylate, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol (meth)acrylate, dipentaerythritol di(meth)acrylate, dipentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, ditrimethylolpropane (meth)acrylate, ditrimethylolpropane di(meth)acrylate, and ditrimethylolpropane tri(meth)acryl
• (poly)oxyalkylene modified compounds in which a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain has been introduced into the molecular structure of the above-mentioned various compounds having a hydroxyl group and a (meth)acryloyl group, and lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various compounds having a hydroxyl group and a (meth)acryloyl group, can also be used.
• a (poly)oxyalkylene chain such as a (poly)oxyethylene chain, a (poly)oxypropylene chain, or a (poly)oxytetramethylene chain
• lactone modified compounds in which a (poly)lactone structure has been introduced into the molecular structure of the above-mentioned various compounds having a hydroxyl group
• the compound (a2) having a hydroxyl group and a (meth)acryloyl group is, in particular, pentaerythritol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate (for example, various "ARONIX” (registered trademark) products manufactured by Toagosei Co., Ltd. (M-306, M-305, M-303, M-452, M-450, etc.)), or dipentaerythritol penta(meth)acrylate (for example, various "ARONIX” (registered trademark) products manufactured by Toagosei Co., Ltd. (M-400, M-403, M-404, M-405, M-406, MT-3545, etc.)), it is more preferable to form a cured product that combines high heat resistance and flame retardancy.
• the compound (a3) having a hydroxyl group there are no particular restrictions on the compound (a3) having a hydroxyl group, as long as it is a compound that does not have a (meth)acryloyl group in the molecule but has a hydroxyl group, and it can be selected appropriately depending on the purpose.
• polyhydric alcohols having a linear alkyl structure such as ethylene glycol, 1,3-propylene glycol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, and 1,10-decanediol; polyhydric alcohols having a branched alkyl structure such as 3-methyl-1,5-pentanediol, neopentyl glycol, 2-ethyl-1,3-hexanediol, and 2-methyl-1,8-octanediol; polycarbonate polyols synthesized by the transesterification reaction of these polyhydric alcohols with carbonate esters; polyester polyols synthesized by the dehydration condensation reaction of the above polyhydric alcohols with dibasic acids; and polyalkylene glycols such as polytetramethylene
• the method for producing the urethane oligomer (C) is not particularly limited, and any method may be used.
• it may be produced by reacting reactive raw materials containing the polyisocyanate (a1) and the compound (a2) having a hydroxyl group and a (meth)acryloyl group all at once, or by dividing the reactive raw materials and reacting them sequentially.
• the compound (a3) having a hydroxyl group may or may not be used as a reactive raw material.
• urethane oligomer (C) for example, dibutyltin laurate, dibutyltin acetate, etc. can be used as a catalyst, and production can be carried out under conditions typically used for urethane formation reactions.
• solvents such as ethyl acetate, butyl acetate, methyl isobutyl ketone, toluene, xylene, etc., or radical polymerizable monomers that do not contain a site reactive with isocyanate and that do not contain a hydroxyl group or an amino group, can also be used as solvents.
• the content of urethane oligomer (C) is, for example, 10 to 55% by weight, and preferably 15 to 50% by weight, based on the total amount of polymerizable monomers including the above-mentioned photopolymerizable monomer (A) and urethane oligomer (C).
• the content of urethane oligomer (C) is within the above range, the bending strength of the cured product can be further improved.
• composition of the present invention may contain, as a polymerizable monomer, a polymerizable monomer other than the photopolymerizable monomer (A) and the urethane oligomer (C).
• a polymerizable monomer other than the photopolymerizable monomer (A) and the urethane oligomer (C) examples include monofunctional (meth)acrylic compounds.
• Examples of monofunctional (meth)acrylic compounds 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, methyl
• composition of the present invention may also contain various additives, such as a photosensitizer, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a silicon-based additive, a fluorine-based additive, a silane coupling agent, organic beads, inorganic fine particles, an organic filler, an inorganic filler, a rheology control agent, a defoaming agent, and a colorant, as necessary.
• additives such as a photosensitizer, an ultraviolet absorber, an antioxidant, a polymerization inhibitor, a silicon-based additive, a fluorine-based additive, a silane coupling agent, organic beads, inorganic fine particles, an organic filler, an inorganic filler, a rheology control agent, a defoaming agent, and a colorant, as 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, and sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate.
• amine compounds such as aliphatic amines and aromatic amines
• urea compounds such as o-tolylthiourea
• condensed polycyclic compounds such as anthraquinone derivatives
• sulfur compounds such as sodium diethyldithiophosphate and s-benzylisothiuronium-p-toluenesulfonate.
• UV absorbers include triazine derivatives such as 2-[4- ⁇ (2-hydroxy-3-dodecyloxypropyl)oxy ⁇ -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-[4- ⁇ (2-hydroxy-3-tridecyloxypropyl)oxy ⁇ -2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, as well as 2-(2'-xanthenecarboxy-5'-methylphenyl)benzotriazole, 2-(2'-o-nitrobenzyloxy-5'-methylphenyl)benzotriazole, 2-xanthenecarboxy-4-dodecyloxybenzophenone, and 2-o-nitrobenzyloxy-4-dodecyloxybenzophenone. These UV absorbers can be used alone or in combination of two or more.
• antioxidants examples include hindered phenol antioxidants, hindered amine antioxidants, organic sulfur antioxidants, and phosphate ester antioxidants. These antioxidants can be used alone or in combination of two or more.
• polymerization inhibitors examples include hydroquinone, methoquinone, di-t-butylhydroquinone, p-methoxyphenol, butylhydroxytoluene, and nitrosamine salts.
• silicone additives include polyorganosiloxanes having alkyl or phenyl groups, such as dimethylpolysiloxane, methylphenylpolysiloxane, cyclic dimethylpolysiloxane, methylhydrogenpolysiloxane, polyether-modified dimethylpolysiloxane copolymer, polyester-modified dimethylpolysiloxane copolymer, fluorine-modified dimethylpolysiloxane copolymer, and amino-modified dimethylpolysiloxane copolymer, as well as polydimethylsiloxanes having polyether-modified acrylic groups and polydimethylsiloxanes having polyester-modified acrylic groups. These silicone 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 types.
• Silane coupling agents include, for example, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropy
• epoxy-based silane coupling agents such as diethoxy(glycidyloxypropyl)methylsilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as p-styryltrimethoxysilane; (meth)acryloxy-based silane coupling agents such as 3-methacryloxypropylmethyldimethoxysilane, 3-acryloxypropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, and 3-methacryloxypropyltriethoxysilane; N-2(aminoethyl)3-aminopropylmethyldimethoxy
• organic beads examples include polymethyl methacrylate beads, polycarbonate beads, polystyrene beads, polyacrylic styrene beads, silicone beads, glass beads, acrylic beads, benzoguanamine resin beads, melamine resin beads, polyolefin resin beads, polyester resin beads, polyamide resin beads, polyimide resin beads, polyethylene fluoride resin beads, and polyethylene resin beads. These organic beads can be used alone or in combination of two or more types. Furthermore, the average particle size of these organic beads is preferably in the range of 1 to 10 ⁇ m.
• inorganic fine particles examples include silica, alumina, zirconia, titania, barium titanate, and antimony trioxide. These inorganic fine particles can be used alone or in combination of two or more.
• the average particle size of these inorganic fine particles is preferably in the range of 0.05 to 3 ⁇ m, and more preferably in the range of 0.1 to 1 ⁇ m.
• the silica is not limited, and known silica fine particles such as powdered silica and colloidal silica can be used.
• powdered silica fine particles include, for example, the "Aerosil (registered trademark)” series (50, 200, etc.) manufactured by Nippon Aerosil Co., Ltd., the “Sildex” series (H31, H32, H51, H52, H121, H122, etc.) manufactured by AGC, the "E220A” or “E220” manufactured by Tosoh Silica Corporation, the “SYLYSIA (registered trademark) 470” manufactured by Fuji Silysia Chemical Ltd., and the "Sildex” series (H31, H32, H51, H52, H121, H122, etc.) manufactured by Nippon Sheet Glass Co., Ltd.
• Examples of such products include those manufactured by Admatechs Co., Ltd. under the trade name "SG Flake,” those manufactured by Adma Fine series (SC1500-SMJ, SC2500-SMJ, SC4500-SMJ, etc.) and those manufactured by Admanano series (YC100, etc.), those manufactured by Tokuyama Corporation under the trade names "Reoloseal,””Silfil,” and “Sunseal,” and those manufactured by Nippon Shokubai Co., Ltd. under the product name "Seahoster” series (S10, S30, S50, S100, etc.).
• colloidal silica can be used by removing the solvent from products such as "Methanol Silica Sol,””IPA-ST,””MEK-ST,””PGM-ST,”"NBA-ST,””XBA-ST,””DMAC-ST,””ST-UP,””ST-OUP,””ST-20,””ST-40,””ST-C,”"ST-N,””ST-O,””ST-50,””ST-OL,””MIBK-SD,””MIBK-SD-L,””MIBK-AC-2140Z,” and “MEK-AC-2140Z,” manufactured by Nissan Chemical Industries, Ltd.
• a dispersion aid When inorganic fine particles are contained, a dispersion aid can be used.
• dispersing aids include phosphate ester compounds such as isopropyl acid phosphate, triisodecyl phosphite, and ethylene oxide-modified phosphate dimethacrylate. These dispersing aids can be used alone or in combination of two or more.
• Commercially available dispersing aids include "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 include plant-derived solvent-insoluble substances such as cellulose, lignin, and cellulose nanofibers.
• inorganic fillers include glass (particles), silica (particles), alumina silicate, talc, mica, aluminum hydroxide, alumina, calcium carbonate, and carbon nanotubes.
• Rheology control agents include, for example, amide waxes such as "Disparlon 6900” manufactured by Kusumoto Chemicals Co., Ltd.; urea-based rheology control agents such as "BYK410” manufactured by BYK-Chemie; polyethylene waxes such as “Disparlon 4200” manufactured by Kusumoto Chemicals Co., Ltd.; and cellulose acetate butyrates such as "CAB-381-2" and "CAB 32101” manufactured by Eastman Chemical Products Co., Ltd.
• defoaming agents include oligomers containing fluorine or silicon atoms, or oligomers of higher fatty acids, acrylic polymers, etc.
• colorants include pigments and dyes.
• Known and commonly used inorganic and organic pigments can be used as pigments.
• examples of inorganic pigments include titanium oxide, antimony red, red iron oxide, cadmium red, cadmium yellow, cobalt blue, Prussian 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, quinophthalone pigments, anthraquinone pigments, thioindigo pigments, benzimidazolone pigments, and azo pigments. These pigments can be used alone or in combination of two or more.
• dyes examples include azo dyes such as monoazo and disazo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, perinone dyes, phthalocyanine dyes, and triarylmethane dyes. These dyes can be used alone or in combination of two or more.
• azo dyes such as monoazo and disazo dyes, metal complex dyes, naphthol dyes, anthraquinone dyes, indigo dyes, carbonium dyes, quinoimine dyes, cyanine dyes, quinoline dyes, nitro dyes, nitroso dyes, benzoquinone dyes, naphthoquinone dyes, naphthalimide dyes, per
• the cured product of the present invention is obtained by photocuring the composition of the present invention by irradiating it with active energy rays or the like.
• active energy rays include ionizing radiation such as ultraviolet rays, electron beams, ⁇ rays, ⁇ rays, and ⁇ rays.
• irradiation may be carried out in an inert gas atmosphere such as nitrogen gas, or in an air atmosphere, in order to efficiently carry out the curing reaction by ultraviolet rays.
• ultraviolet lamps are commonly used due to their practicality and economical efficiency. Specific examples include low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, xenon lamps, gallium lamps, metal halide lamps, sunlight, and LEDs.
• the cumulative light amount of the active energy rays is not particularly limited, but is preferably 50 to 5,000 mJ/cm 2 , and more preferably 300 to 1,000 mJ/cm 2. When the cumulative light amount is within the above range, it is possible to prevent or suppress the occurrence of uncured portions, which is preferable.
• the three-dimensional object of the present invention is made of the cured product and can be produced by a known optical three-dimensional modeling method using a 3D printer or the like.
• optical three-dimensional modeling methods include stereolithography (SLA), digital light processing (DLP), and inkjet.
• SLA stereolithography
• DLP digital light processing
• inkjet inkjet
• DLP digital light processing
• the stereolithography (SLA) method is a method in which a vat of liquid curable resin composition is irradiated with active energy rays such as laser beams at points, and the modeling stage is moved while the composition is cured layer by layer to create a three-dimensional object.
• the digital light processing (DLP) method is a method in which a vat of liquid curable resin composition is irradiated with active energy rays such as LEDs at surfaces, and the composition is cured layer by layer while the modeling stage is moved to create a three-dimensional object.
• the inkjet stereolithography method is a method in which tiny droplets of stereolithography curable resin composition are ejected from a nozzle to form a predetermined pattern, and then ultraviolet light is applied to form a cured thin film.
• the DLP three-dimensional modeling method is not particularly limited as long as it is a method using a DLP stereolithography system, but the modeling conditions are such that the modeling accuracy of the three-dimensional object is good, the layer pitch of the stereolithography 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 , and the integrated light amount per layer is in the range of 1 to 100 mJ / cm 2.
• the layer pitch of the stereolithography is in the range of 0.02 to 0.1 mm
• 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 integrated light amount per layer is preferably in the range of 5 to 15 mJ / cm 2.
• the three-dimensional object obtained by stereolithography may also be irradiated with active energy rays from multiple directions to form the final three-dimensional object. This irradiation step is called post-curing.
• the three-dimensional object of the present invention is both heat-resistant and flame-retardant, making it suitable for use in applications requiring both heat resistance and flame-retardance, such as electrical and electronic components, automobile parts, furniture, and home appliance parts.
• MIRAMER M262 Tricyclodecane dimethanol diacrylate (manufactured by MIWON Co., Ltd.)
• MIRAMER M240 Bisphenol A EO-modified diacrylate (manufactured by MIWON Co., Ltd.)
• Aronix M-315 Tris(2-acryloyloxyethyl) isocyanurate (manufactured by Toagosei Co., Ltd.)
• Aronix M-305 a reaction product of pentaerythritol and acrylic acid, with pentaerythritol triacrylate as the main component (manufactured by Toagosei Co., Ltd.)
• Aronix MT-3545 a reaction product of dipentaerythritol and acrylic acid, with dipentaerythritol tetraacrylate as the main component (manufactured by Toagosei Co., Ltd.)
• urethane oligomer (C-2) having the above formula (C2) as the main component was obtained.
• Mn number average molecular weight
• the number average molecular weight (Mn) of the urethane oligomer (C-4) was 800.
• urethane oligomer (C-5) having the above formula (C5) as the main component was obtained.
• the number average molecular weight (Mn) of the urethane oligomer (C-5) was 800.
• urethane oligomer (C-6) composed mainly of the above formula (C6) was obtained.
• Mn number average molecular weight
• the number average molecular weight (Mn) of the urethane oligomer (C-7) was 900.
• urethane oligomer (C-8) having the above formula (C8) as the main component was obtained.
• the number average molecular weight (Mn) of the urethane oligomer (C-8) was 1400.
• Example 1 Preparation of curable resin composition (1)
• MIRAMER M262 manufactured by MIWON
• EXOLIT AP 422 manufactured by Clariant Chemicals
• Omnirad 819 manufactured by IGM Resins
• Curable resin compositions (2) to (23) were obtained in the same manner as in Example 1, except that the photopolymerizable monomer (A), the phosphorus-based flame retardant (B), and the urethane oligomer (C) were changed to the compositions and blending amounts (unit: parts by weight) shown in Tables 1 to 3.
• Curable resin compositions (R1) to (R4) were obtained in the same manner as in Example 1, except that the urethane resin and the (meth)acrylic compound were changed to the compositions and blending amounts shown in Table 3.
• stereolithography was performed using a stereolithography 3D printer ("Vittro P100" manufactured by 3D'LIGHT). Stereolithography was performed at an illuminance of 2.5 mW/ cm2 per layer, an exposure time of 5 seconds, and a pitch of 100 ⁇ m along the z-axis (height direction), to create test pieces shaped according to each test method.
• the shaped objects were washed with isopropyl alcohol and dried at room temperature for 1 hour. The samples were evaluated for bending strength, heat resistance, and flame retardancy. The evaluation results are shown in Tables 1 to 3.
• a deflection temperature under load test (HDT) was performed according to ASTM D648.
• the deflection temperature under load (heat distortion temperature) was rated as ⁇ (very good) when it was 90°C or higher, ⁇ (good) when it was 60°C or higher but less than 90°C, ⁇ (slightly poor) when it was 45°C or higher but less than 60°C, and ⁇ (poor) when it was less than 45°C.
• Flammability tests were conducted based on the UL 94 standard. Samples (test pieces: length 125 mm, width 13.0 mm) with thicknesses (heights) of 3 mm and 2 mm, as well as 4 mm, were prepared in the same manner as above. The flame retardancy was evaluated as follows: “1" to "5" were considered to be acceptable. 5: Test piece thickness 2 mm, 3 mm, 4 mm all V-0 level 4: Test piece thickness 3 mm, 4 mm V-0 level 3: Test piece thickness 4 mm V-0 level 2: Test piece thickness 4 mm V-1 level 1: Test piece thickness 4 mm V-2 level Fail: Other than the above
• compositions of Examples 1 to 8 which contain a photopolymerizable monomer (A) and a phosphorus-based flame retardant (B), are able to maintain high flame retardancy while also maintaining flexural strength and heat resistance. It can also be seen that the compositions of Examples 9 to 23, which further contain a urethane oligomer (C), are able to maintain high flame retardancy while also maintaining flexural strength and heat resistance.

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