Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/62—Photochemical radical initiators
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
  • A61K6/65—Dyes
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
  • A61K6/884—Preparations for artificial teeth, for filling teeth or for capping teeth comprising natural or synthetic resins
  • A61K6/887—Compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
• • 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
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
  • C08F2/00—Processes of polymerisation
  • C08F2/46—Polymerisation initiated by wave energy or particle radiation

Definitions

• the present invention relates to an energy beam-curable composition for stereolithography, a dental structure, a mouthpiece, an orthodontic mouthpiece, and a method for producing a dental structure.
• optical three-dimensional modeling technology that creates a modeled object by curing a photocurable resin based on three-dimensional CAD data by scanning a laser beam or projecting beams using a projector method, and laminating the formed cured layers. has been drawing attention.
• optical stereolithography technology products and prototypes can be produced simply and quickly without preparing metal molds or molds. Therefore, it is possible to reduce the time and cost required from product development design to production, and it is easy to manufacture custom-made products.
• three-dimensional modeling technology has been adopted in a wide variety of industrial fields, such as automobile parts, electrical equipment, and medical equipment.
• optical stereolithography is also referred to as "stereolithography”.
• Examples of dental structures include trays used for positioning brackets, orthodontic mouthpieces such as aligners and retainers used for orthodontics, mouthpieces for treatment of sleep disorders and temporomandibular joint disorders, occlusal splints, sports and mouth guards for teeth, materials for dentures, and the like.
• orthodontic mouthpieces such as aligners and retainers used for orthodontics
• mouthpieces for treatment of sleep disorders and temporomandibular joint disorders occlusal splints
• sports and mouth guards for teeth
• materials for dentures, and the like are used for dentures, and the like.
• These applications require high aesthetics due to their strong impact on the patient's facial features, as well as colorlessness for visibility and therapeutic LED light transmission.
• it is essential to suppress the yellow tint that gives the impression of uncleanliness and deterioration of the material, and it is required that the teeth look natural when the above-mentioned various mouthpieces are worn in the oral cavity.
• these materials are in direct contact with the patient's soft
• Patent Document 1 discloses a curable resin composition containing a purple or blue colorant having a p-toluidine structure. Patent Literature 1 describes that this curable resin composition can produce a three-dimensional object with a low degree of yellowness and high transparency.
• Patent Document 2 discloses a resin composition for optical stereolithography containing 0.01 to 10 ppm of a purple dye and a blue dye. Patent Literature 2 describes that this resin composition for optical stereolithography has a low environmental impact despite the use of a cationic polymerization system, and that an optical stereolithography object with a low degree of yellowness can be obtained.
• Patent Document 1 does not describe anything about the flexibility and water resistance of the shaped article.
• Patent Literature 2 does not provide an explanation based on an example or the like that directly shows that the molded article has an effect of water resistance, and does not mention anything about flexibility.
• these documents do not consider the use of the energy beam-curable composition for three-dimensional modeling in dental structures, and in addition to having moderate flexibility and high water resistance, dental structures No mention is made of the technical problem of obtaining a dental structure with a high level of aesthetics, such as that required for the body.
• the problem to be solved by the present invention is to provide an energy ray-curable composition for three-dimensional modeling with which a three-dimensional model having excellent flexibility, water resistance and color tone can be obtained. Further, to provide a dental structure, a mouthpiece, and an orthodontic mouthpiece using the energy beam-curable composition for stereolithography, and to provide a method for producing the dental structure. Make it an issue.
• the present inventors have made intensive studies to solve the above problems, and as a result, an energy ray-curable composition for stereolithography containing a polymerizable monomer having an oxygen atom directly linked to an aromatic ring and an indigoid dye
• a product can solve the above-mentioned problems, further research based on this finding, and have completed the present invention. That is, the present invention includes the following inventions.
• An energy ray-curable composition for stereolithography comprising a polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring, an indigoid dye (B), and a photopolymerization initiator (C), , b* measured in accordance with JIS Z 8722:2009, condition c, 24 hours after modeling of a 1 mm-thick cured product obtained by curing the energy ray-curable composition for three-dimensional shaped article
• An energy ray-curable composition for stereolithography which has a yellowness of ⁇ 10 to 10.
• the polymerizable monomer (A) has a phenyl ether skeleton having a structure in which an oxygen atom directly attached to an aromatic ring is further bonded to a hydrocarbon group, and an oxygen atom directly attached to an aromatic ring is further a carbonyl
• the energy beam-curable composition for stereolithography according to any one of the above [1] to [4], which contains at least one of a phenyl ester skeleton that is a structure bonded to a group.
• R 2 is a group represented by the following general formula (i) or a group represented by general formula (ii), and X is a divalent hydrocarbon group having 1 to 6 carbon atoms or It is an oxygen atom.
• X is a divalent hydrocarbon group having 1 to 6 carbon atoms
• R 2 is a group represented by formula (i).
• the content of the indigoid dye (B) is 0.001 to 0.050 parts by mass with respect to 100 parts by mass of the urethane (meth)acrylate compound (D).
• a dental structure comprising a cured product of the energy ray-curable composition for stereolithography according to any one of [1] to [16] above.
• Cured product of an energy ray-curable composition for stereolithography containing a polymerizable monomer (A) having an oxygen atom directly bonded to an aromatic ring, an indigoid dye (B), and a photopolymerization initiator (C)
• a dental structure that is The dental structure having a thickness of 1 mm has a yellowness of -10 to 10, represented by b*, measured according to JIS Z 8722: 2009, condition c, 24 hours after molding. structure.
• a mouthpiece comprising the dental structure according to any one of [17] to [19] above.
• An orthodontic mouthpiece comprising the dental structure according to any one of [17] to [19] above.
• a method for producing a dental structure comprising a step of curing the energy beam-curable three-dimensional modeling composition according to any one of [1] to [16] above by irradiating it with an energy beam.
• the energy ray-curable composition for three-dimensional modeling of the present invention According to the energy ray-curable composition for three-dimensional modeling of the present invention, a three-dimensional article having excellent flexibility, water resistance and color tone can be obtained. Further, it is possible to provide a dental structure, a mouthpiece, an orthodontic mouthpiece, and a method for producing the dental structure using the energy beam-curable composition for stereolithography.
• the energy beam-curable composition for three-dimensional modeling comprises a polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring, an indigoid dye (B), and photopolymerization initiation containing an agent (C),
• the content of the indigoid dye (B) is 0.0015 to 0.100 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A).
• the energy beam-curable composition for three-dimensional modeling comprises a polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring, an indigoid dye (B), and photopolymerization initiation
• the expressed yellowness is -10 to 10.
• the yellowness is determined by applying an energy ray having a wavelength of 385 nm and an irradiation intensity of 2,000 ⁇ W/mm 2 or more so that the cumulative amount of light is 12 mJ/cm 2 or more.
• a xenon lamp having an irradiation intensity of 0.1 mW/mm 2 or more is used to perform a photocuring treatment so that the integrated light amount becomes 60 mJ/cm 2 or more. It is measured on a cured product with a thickness of 1 mm obtained by heat treatment at 15° C. or higher for 15 minutes. Specifically, it is measured according to the procedure described in Examples.
• the energy ray-curable three-dimensional modeling composition according to the first embodiment and the energy ray-curable three-dimensional modeling composition according to the second embodiment are collectively referred to as “this embodiment. It is sometimes referred to as "energy ray-curable composition for stereolithography in the form of a form”.
• a polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring used in the energy ray-curable three-dimensional modeling composition of the present embodiment (hereinafter simply referred to as "polymerizable monomer (A)") ) has an aromatic ring, so it is highly hydrophobic and improves the water resistance of the model.
• the oxygen atom is directly linked to the aromatic ring, the mobility of the molecule is high and it becomes supple, improving the flexibility of the modeled object.
• a radically polymerizable monomer is preferably used, and specific examples thereof include (meth)acrylate-based polymerizable monomers; (meth)acrylamide-based polymerizable monomers; Esters such as ⁇ -cyanoacrylic acid, ⁇ -halogenated acrylic acid, crotonic acid, cinnamic acid, sorbic acid, maleic acid and itaconic acid; vinyl esters; vinyl ethers and the like. From the viewpoint of curability, (meth)acrylate-based polymerizable monomers and (meth)acrylamide-based polymerizable monomers are preferred.
• the polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring used in the energy ray-curable composition for three-dimensional modeling of the present embodiment is a polymerizable monomer having one polymerizable group.
• Functional polymerizable monomers and polyfunctional polymerizable monomers that are polymerizable monomers having a plurality of polymerizable groups are exemplified.
• Monofunctional polymerizable monomers are preferred from the viewpoint of improving the flexibility of the shaped article.
• the oxygen atom is directly linked to a benzene ring, a naphthalene ring, an anthracene ring, or the like. Also includes cases.
• a structure in which an oxygen atom directly attached to an aromatic ring is further bonded to a hydrocarbon group is referred to as a "phenyl ether skeleton", and an oxygen atom directly attached to an aromatic ring is further bonded to a carbonyl group.
• a polymerizable monomer containing at least one of a phenyl ether skeleton and a phenyl ester skeleton is preferable.
• a polymerizable monomer (a-1) containing a phenyl ether skeleton and not containing a phenyl ester skeleton hereinafter referred to as "having only a phenyl ether skeleton Polymerizable monomer (a-1) containing"
• polymerizable monomer (a-2) containing a phenyl ester skeleton and not containing a phenyl ether skeleton hereinafter referred to as "containing only a phenyl ester skeleton Polymerizable monomer (a-2)"
• the polymerizable monomer (a-1) containing only a phenyl ether skeleton is preferable from the viewpoint of high stability against decomposition by heat, oxidation, energy rays, and the like.
• the polymerizable monomer (a-2) containing only a phenyl ester skeleton and the polymerizable monomer (a-3) containing a phenyl ether skeleton and a phenyl ester skeleton are preferable, and the phenyl ester A polymerizable monomer (a-2) containing only a skeleton is more preferred.
• the polymerizable monomer (A) contained in the energy ray-curable composition for three-dimensional modeling has a low odor and is excellent in safety for workers who perform three-dimensional modeling.
• R 1 is a group represented by the following general formula (i).
• R 2 is a group represented by the following general formula (i) or a group represented by general formula (ii)
• X is a divalent hydrocarbon group having 1 to 6 carbon atoms or It is an oxygen atom.
• R 2 is a group represented by formula (i).
• R 3 and R 5 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms
• R 4 and R 6 are each independently a hydrogen atom or a methyl group
• k and l are each independently an integer from 0 to 6.
• Monofunctional polymerizable monomers containing only a phenyl ether skeleton include phenoxymethyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxybutyl (meth)acrylate, phenoxypropyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate.
• acrylates phenoxydibutylene glycol (meth)acrylate, phenoxydipropylene glycol (meth)acrylate, o-phenylphenoxymethyl (meth)acrylate, m-phenylphenoxymethyl (meth)acrylate, p-phenylphenoxymethyl (meth)acrylate, 4.000-phenylphenoxyethyl (meth)acrylate, m-phenylphenoxyethyl (meth)acrylate, p-phenylphenoxyethyl (meth)acrylate, Occasionally-phenylphenoxypropyl (meth)acrylate, m-phenylphenoxypropyl (meth)acrylate, p-phenylphenoxypropyl (meth)acrylate, o-phenylphenoxybutyl (meth)acrylate, m-phenylphenoxybutyl (meth)acrylate, p-phenylphenoxybutyl (meth)acrylate, o-phen
• polyfunctional polymerizable monomers containing only a phenyl ether skeleton examples include 2,2-bis[4-(3-acryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis[4-(3 -methacryloyloxy)-2-hydroxypropoxyphenyl]propane (commonly known as “Bis-GMA”), 2,2-bis(4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth) acryloyloxypolyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydiethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxytetraethoxyphenyl)propane, 2,2- Bis(4-(meth)acryloyloxypentaethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxydipropoxy
• Monofunctional polymerizable monomers containing only a phenyl ester skeleton include phenyl (meth) acrylate, 2-methylphenyl (meth) acrylate, 3-methylphenyl (meth) acrylate, 4-methylphenyl (meth) acrylate, 2-ethylphenyl (meth) acrylate, 3-ethylphenyl (meth) acrylate, 4-ethylphenyl (meth) acrylate, 2-butylphenyl (meth) acrylate, 3-butylphenyl (meth) acrylate, 4-butylphenyl ( meth)acrylate, 2-propylphenyl (meth)acrylate, 3-propylphenyl (meth)acrylate, 4-propylphenyl (meth)acrylate, 2-isopropylphenyl (meth)acrylate, 3-isopropylphenyl (meth)acrylate, 4 - isopropylphenyl (meth
• polyfunctional polymerizable monomers containing only a phenyl ester skeleton examples include 2,2-bis((meth)acryloyloxyphenyl)propane.
• Examples of the monofunctional polymerizable monomer (a-3) containing a phenyl ether skeleton and a phenyl ester skeleton include m-phenylphenoxy(meth)acrylate and p-phenylphenoxy(meth)acrylate.
• R 1 is a group represented by the following general formula (i).
• R 2 is a group represented by the following general formula (i) or a group represented by general formula (ii)
• X is a divalent hydrocarbon group having 1 to 6 carbon atoms or It is an oxygen atom.
• R 2 is a group represented by formula (i).
• R 3 and R 5 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms
• R 4 and R 6 are each independently a hydrogen atom or a methyl group
• k and l are each independently an integer from 0 to 6.
• the glass transition temperature is preferably 40° C. or less, and phenyl (meth) acrylate, m-phenoxybenzyl (meth) acrylate, O-phenylphenoxyethyl (meth)acrylate and the like are preferred.
• the content of the polymerizable monomer (A) is preferably 5 to 55 mass parts with respect to 100 parts by mass of the total mass of the polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling of the present embodiment. parts, more preferably 5 to 53 parts by mass, still more preferably 5 to 50 parts by mass, still more preferably 5 to 45 parts by mass, even more preferably 10 to 40 parts by mass, particularly preferably 15 to 35 parts by mass .
• the content of the polymerizable monomer (A) containing an oxygen atom directly linked to an aromatic ring is 100 parts by mass in the total mass of the polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling of the present embodiment.
• the effects of water resistance and flexibility are likely to be exhibited.
• the content of the polymerizable monomer (A) containing an oxygen atom directly linked to an aromatic ring is 55 parts by mass or less in 100 parts by mass of the total amount of polymerizable monomers, the compound that causes discoloration The amount is small and the aesthetics are likely to be improved.
• the indigoid dye (B) used in the energy ray-curable composition for three-dimensional modeling of the present embodiment includes an indigo dye and a thioindigo dye in which an amino group contained in the ring structure of the indigo dye is substituted with a mercapto group. , and mixtures thereof.
• Indigo-type dyes are preferable as the indigoid-based dye (B) from the viewpoint of making it easy to secure a highly aesthetic color tone.
• indigo-type dyes examples include indigo, isoindigo, meisoindigo, disodium indigodisulfonate (indigo carmine), dipotassium indigodisulfonate, indigodinitro, tetrapotassium indigotetrasulfonate, dipotassium indigodisulfonate, and 6,6'-dibromo.
• Thioindigo type dyes include thioindigo, 4,7,4′,7′-tetramethyl-5,5′-dichlorothioindigo (thioindigo magenta), 3,6,3′,6′-tetrachlorothioindigo ( thioindigo Bordeaux) and the like. These may be used alone or in the form of an aluminum lake. An aluminum lake of each dye is preferable because it is difficult to dissolve in the oral cavity.
• Indigo-type dyes are preferable, and indigo carmine, dipotassium indigodisulfonate, and 6,6'-dibromoindigo are more preferable in terms of excellent suppression of discoloration of the polymerizable monomer (A) containing an oxygen atom directly linked to an aromatic ring.
• the indigoid dye (B) contains indigo carmine, 6,6'-dibromoindigo, and aluminum thereof. It is preferably at least one selected from the group consisting of lakes.
• the indigoid dye (B) is preferably an aluminum lake of indigo carmine.
• the mechanism by which the indigoid dye (B) is effective in suppressing the discoloration of the polymerizable monomer (A) having an oxygen atom directly linked to the aromatic ring is currently unclear.
• discoloration does not occur when irradiated with a UV irradiator, and discoloration occurs during three-dimensional modeling. They presume as follows. During modeling, the energy ray-curable composition for three-dimensional modeling is repeatedly irradiated with extremely strong energy rays.
• the indigoid dye reductant After completion of the energy beam irradiation, the indigoid dye reductant returns to the oxidized indigoid dye due to atmospheric oxygen.
• the oxidized form of the indigoid dye is blue, yellowing caused by a slightly generated quinone form or residual initiator can also be canceled by the complementary color.
• the present inventors have found that by adjusting the wavelength and amount of the indigoid dye (B) so that the color tone of the molded object is slightly bluer than colorless, it is possible to obtain excellent aesthetics, especially in mouthpieces. Found it. A phenomenon called the opal effect occurs on the tooth surface, and it appears bluish in bright light by reflecting blue to violet light. However, wearing a mouthpiece may attenuate the opal effect. Many patients who choose mouthpiece orthodontic treatment want the treatment to go unnoticed when they face each other and to have excellent aesthetics.
• a dental structure such as a mouthpiece shaped using the energy ray-curable three-dimensional shaping composition of the present embodiment can compensate for the reflection of blue light, and has natural teeth and a natural facial appearance that are closer to natural teeth. is given.
• the content of the indigoid dye (B) in the energy beam-curable composition for stereolithography according to the first embodiment of the present invention is 100 masses of the polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring. 0.0015 to 0.100 parts by mass per part.
• the content of the indigoid dye (B) is less than the lower limit of the above numerical range, yellowing may occur.
• the content of the indigoid dye (B) exceeds the upper limit of the above numerical range, the shaped article may become excessively blue and the aesthetics may be impaired.
• the content of the indigoid dye (B) is set to 0 with respect to 100 parts by mass of the polymerizable monomer (A). 0.0015 to 0.100 parts by mass is preferable.
• the content of the indigoid dye (B) in the energy ray-curable three-dimensional modeling composition according to the first and second embodiments is 0.00 per 100 parts by mass of the total amount of the polymerizable monomer (A). 004 to 0.08 parts by mass is more preferable, and 0.008 to 0.05 parts by mass is more preferable in that it can compensate for the reflection of blue light and give natural teeth and a natural facial appearance that are closer to natural teeth. preferable.
• the content of the indigoid dye (B) in the energy ray-curable composition for stereolithography of the present embodiment is It is preferably 0.0015 to 0.0090 parts by mass.
• the content of the indigoid dye (B) is at least the lower limit of the above numerical range, it becomes easier to suppress the occurrence of yellowing.
• the content of the indigoid dye (B) is equal to or less than the upper limit of the above numerical range, excessive bluishness of the shaped article is suppressed, and aesthetics can be easily maintained.
• the content of the indigoid dye (B) in the energy beam-curable three-dimensional modeling composition of the present embodiment is more preferably 0.0018 to 0.0085 parts by mass with respect to 100 parts by mass of the total amount of polymerizable monomers. , It is more preferably 0.0020 to 0.0085 in that it can compensate for the reflection of blue light, and can give natural teeth and a natural facial appearance that are closer to natural teeth, and 0.0020 to 0.0080 parts by mass Even more preferred.
• the content of the indigoid dye (B) in the energy ray-curable three-dimensional modeling composition according to the present embodiment is, from the viewpoint of making it easy to ensure good aesthetics, the energy ray-curable three-dimensional modeling composition as a whole. It is preferably 0.0013 to 0.0090% by mass, more preferably 0.0013 to 0.0089% by mass, still more preferably 0.0014 to 0.0089% by mass, based on the mass.
• the content of the indigoid dye (B) in the energy ray-curable three-dimensional modeling composition of the present embodiment is, from the viewpoint of facilitating securing of good aesthetics, relative to 100 parts by mass of the photopolymerization initiator (C). , preferably 0.01 to 1.00 parts by mass, more preferably 0.03 to 0.700 parts by mass, still more preferably 0.05 to 0.600 parts by mass, still more preferably 0.06 to 0.06 parts by mass. 500 parts by mass.
• the indigoid dye (B) in the energy ray-curable composition for three-dimensional modeling of the present embodiment has an absorbance of A 600 at a wavelength of 600 nm and an absorbance of A 650 at a wavelength of 650 nm, where A 600 /A 650 is 0. 80 or more is preferable.
• Absorption near a wavelength of 600 nm is absorption of yellow light, but when the wavelength exceeds 650 nm, it shifts to absorption of red light, and tends to be tinged with green, resulting in an unnatural color tone. If the indigoid dye (B) has the above properties, it becomes easier to prevent the resulting cured product from having an unnatural color tone.
• the A 600 /A 650 of the indigoid dye (B) is more preferably 0.90 or more, which can compensate for the reflection of blue light, and can give natural teeth and a natural facial appearance that are closer to natural teeth.
• a 600 /A 650 is more preferably 1.00 or more.
• the absorption spectrum of the indigoid dye (B) can be measured with any spectrophotometer.
• the indigoid dye (B) is dissolved or dispersed in ethanol to 0.01 wt%, the solution is placed in a quartz cell with an optical path length of 1 cm, and a spectrophotometer U-1900 (Hitachi High Tech Co., Ltd.) is used. can be measured by
• the photopolymerization initiator (C) can be selected from polymerization initiators used in general industry as long as the effects of the present invention are achieved, and among them, radical polymerization initiators are preferably used.
• Radical polymerization initiators include ketals, ⁇ -diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, ⁇ -aminoketone compounds, (bis)acylphosphine oxides, oxime ester compounds, acridine compounds, metallocenes. system compounds and the like.
• cationic polymerization initiators include sulfonium salts, iodonium salts, phenacylsulfonium salts, hydroxyphenylsulfonium salts, sulfoxonium salts, sulfonic acid derivatives, phosphoric acid esters, phenolsulfonic acid esters, carboxylic acid esters, and aryldiazonium. salts, iron arene complexes, pyridinium salts, quinolinium salts, o-nitrobenzyl group-containing compounds, diazonaphthoquinones, N-hydroxyimidosulfonates and the like. These may be used individually by 1 type, and may be used in mixture of 2 or more types.
• photopolymerization initiators (C) especially when the light source wavelength used for stereolithography is 385 nm, (bis) acylphosphine oxides and salts thereof, oxime ester compounds, and acridine compounds It is preferable to use at least one selected from the group consisting of: Among these, (bis)acylphosphine oxides and salts thereof are particularly preferred.
• acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine.
• bisacylphosphine oxides include bis(2,6-dichlorobenzoyl)phenylphosphine oxide, bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,6-dichlorobenzoyl) )-4-propylphenylphosphine oxide, bis(2,6-dichlorobenzoyl)-1-naphthylphosphine oxide, bis(2,6-dimethoxybenzoyl)phenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2, 4,4-trimethylpentylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,5-dimethylphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, bis(2,5,6 -trimethylbenzoyl)-2,4,4-trimethylpentyl
• 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt are preferably used, and from the viewpoint of particularly excellent curability, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,4,6- Preference is given to using trimethylbenzoyl)phenylphosphine oxide.
• oxime ester compounds examples include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyloxime)], ethanone, 1-[9-ethyl-6-(2 -methylbenzoyl)-9H-carbazol-3-yl]-1-(O-acetyloxime), 2-(acetyloxyiminomethyl)thioxanthen-9-one and the like.
• Commercially available products include "Irgacure OXE01", “Irgacure OXE02” (manufactured by BASF), and "N-1919" (manufactured by ADEKA Corporation).
• heterocyclic structures in the molecule as an oxime ester compound. By having a heterocyclic structure, it has excellent absorption of light with a wavelength of about 385 nm or light with a wavelength of about 405 nm, and can improve sensitivity.
• heterocyclic structures may have at least one selected from the group consisting of a carbazole skeleton, a xanthene skeleton, and a thioxanthone skeleton, and may be a compound having a carbazole skeleton.
• Examples of the acridine-based compound include the following general formula [III] (In the formula, R 7 represents a halogen atom, an amino group, a carboxy group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or an alkylamino group having 1 to 6 carbon atoms.
• R 8 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms.
• R 8 represents an alkylene group having 2 to 20 carbon atoms, an oxadialkylene group having 2 to 20 carbon atoms, or a thiodialkylene group having 2 to 20 carbon atoms.
• Examples of the acridine compound represented by the general formula [III] include 9-phenylacridine, 9-(p-methylphenyl)acridine, 9-(m-methylphenyl)acridine, 9-(p-chlorophenyl)acridine , 9-(m-chlorophenyl)acridine, 9-aminoacridine, 9-dimethylaminoacridine, 9-diethylaminoacridine, 9-pentylaminoacridine.
• Examples of the acridine compound represented by the general formula [IV] include 1,2-bis(9-acridinyl)ethane, 1,3-bis(9-acridinyl)propane, 1,4-bis(9 -acridinyl)butane, 1,5-bis(9-acridinyl)pentane, 1,6-bis(9-acridinyl)hexane, 1,7-bis(9-acridinyl)heptane, 1,8-bis(9-acridinyl) ) Octane, 1,9-bis(9-acridinyl)nonane, 1,10-bis(9-acridinyl)decane, 1,11-bis(9-acridinyl)undecane, 1,12-bis(9-acridinyl)dodecane , 1,14-bis (9-acridinyl) tetradecane, 1,16-bis (9-acridinyl) hexadecane, 1,
• bis(9-acridinyl)alkane 1,3-bis(9-acridinyl)-2-oxapropane, 1,3-bis(9-acridinyl)-2-thiapropane, 1,5-bis(9-acridinyl)- and 3-thiapentane. These may be used individually by 1 type, and may be used in mixture of 2 or more types.
• the content of the photopolymerization initiator (C) in the energy ray-curable composition for three-dimensional modeling of the present embodiment is not particularly limited as long as the effect of the present invention is exhibited. From the viewpoint of curability and the like, it is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling. If the content of the photopolymerization initiator (C) is 0.01 part by mass or more with respect to 100 parts by mass of the total polymerizable monomer contained in the energy ray-curable composition for three-dimensional modeling, curing can be sufficiently advanced, and the problem of not being able to obtain a molded product can be easily avoided.
• the content of the photopolymerization initiator (C) in the energy ray-curable composition for three-dimensional modeling of the present embodiment is 100 parts by mass of the total weight of the polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling. , more preferably 0.05 parts by mass or more, more preferably 0.1 parts by mass or more, even more preferably 0.3 parts by mass or more, even more preferably 0.5 parts by mass or more, 0.7 parts by mass The above is even more preferable.
• the content of the photopolymerization initiator (C) is 10 parts by mass or less with respect to 100 parts by mass of the total polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling, photopolymerization Even if the solubility of the initiator (C) itself is low, it is difficult to precipitate from the energy ray-curable composition for three-dimensional modeling, and it becomes easy to suppress yellowing of the cured product due to increased absorption in the visible light region.
• the content of the photopolymerization initiator (C) is more preferably 7.5 parts by mass or less with respect to 100 parts by mass of the total mass of the polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling, and 5 parts by mass. parts by mass or less is more preferable, 4 parts by mass or less is even more preferable, and 3.5 parts by mass or less is even more preferable.
• the energy ray-curable composition for three-dimensional modeling of the present embodiment may further contain a urethane (meth)acrylate polymerizable monomer (D).
• a urethane (meth)acrylate polymerizable monomer (D) By including the urethane (meth)acrylate polymerizable monomer (D), it becomes easier to improve the flexibility of the shaped article of the energy ray-curable composition for three-dimensional shaping.
• the urethane (meth)acrylate-based polymerizable monomer (D) may be any compound having a urethane bond introduced adjacent to the (meth)acrylate group. , a polyether, a polyconjugated diene, and a hydrogenated polyconjugated diene.
• Acrylate-based polymerizable monomers are preferred.
• those containing at least one member from the group consisting of an aromatic ring, an alicyclic structure, an unbranched alkyl group, and a branched alkyl group in the repeating units constituting the polymer skeleton are more preferable.
• the viscosity of the composition is reduced, the operability is excellent, and the molded product is excellent in flexibility, those containing branched alkyl groups in the repeating units constituting the polymer skeleton are more preferable.
• the urethane (meth)acrylate polymerizable monomer (D) used in the energy ray-curable three-dimensional modeling composition of the present embodiment does not contain a compound corresponding to the polymerizable monomer (A).
• a urethane-modified (meth)acrylate-based polyfunctional polymerizable monomer having a polymer skeleton includes, for example, a polyol containing the polymer skeleton, a compound having an isocyanate group (--NCO), and a hydroxyl group (--OH). It can be easily synthesized by addition reaction with a (meth)acrylate compound possessed.
• the urethane-modified (meth)acrylate-based polyfunctional polymerizable monomer is a (meth)acrylate compound having a hydroxyl group, after ring-opening addition reaction to a lactone or alkylene oxide, and a hydroxyl group at one end obtained. can be easily synthesized by subjecting a compound having an isocyanate group to an addition reaction.
• the polyol containing the above polymer skeleton is not particularly limited as long as it has the above structure.
• polycarbonates include polycarbonates derived from aliphatic diols having 2 to 12 carbon atoms, polycarbonates derived from bisphenol A, and polycarbonates derived from aliphatic diols having 2 to 12 carbon atoms and bisphenol A.
• polyurethane examples include polymers of aliphatic diols having 2 to 12 carbon atoms and diisocyanates having 1 to 12 carbon atoms.
• Polyethers include polyethylene glycol, polypropylene glycol, polybutylene glycol, poly(1-methylbutylene glycol) and the like.
• Polyconjugated dienes and hydrogenated polyconjugated dienes include 1,4-polybutadiene, 1,2-polybutadiene, polyisoprene, poly(butadiene-isoprene), poly(butadiene-styrene), poly(isoprene-styrene), polyfarnesene, and hydrogenated products thereof.
• Examples of compounds having an isocyanate group include hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), xylylene diisocyanate (XDI), diphenylmethane diisocyanate (MDI), isophorone diisocyanate (IPDI), and trimethylhexamethylene diisocyanate (TMHMDI). , tricyclodecane diisocyanate (TCDDI), and adamantane diisocyanate (ADI).
• HDI hexamethylene diisocyanate
• TDI tolylene diisocyanate
• XDI xylylene diisocyanate
• MDI diphenylmethane diisocyanate
• IPDI isophorone diisocyanate
• THMDI trimethylhexamethylene diisocyanate
• THCMDI tricyclodecane diisocyanate
• ADI adamantane diisocyan
• (Meth)acrylate compounds having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10 - hydroxydecyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, glycerin mono (meth)acrylate, N-hydroxyethyl (meth)acrylamide, N,N-bis(2-hydroxyethyl)(meth)acrylamide, 2-hydroxy-3-acryloyloxypropyl(meth)acrylate, 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxy Hydroxy (propoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy]ethane, pentaerythritol tri
• the addition reaction between the compound having an isocyanate group and the (meth)acrylate compound having a hydroxyl group can be carried out according to a known method and is not particularly limited.
• the urethanized (meth)acrylate polyfunctional polymerizable monomer obtained by the above method is selected from the group consisting of polyesters, polycarbonates, polyurethanes, polyethers, polyconjugated dienes, and hydrogenated polyconjugated dienes.
• a reactant of any combination of a polyol having at least one selected structure, a compound having an isocyanate group, and a (meth)acrylate compound having a hydroxyl group can be mentioned.
• the weight average molecular weight (Mw) of the urethane-modified (meth)acrylate-based polyfunctional polymerizable monomer having a polymer skeleton is preferably 500 to 50,000, more preferably 750 to 30,000, from the viewpoint of viscosity and strength. More preferably, 1,000 to 15,000 is even more preferable.
• the mass average molecular weight (Mw) means the mass average molecular weight of polystyrene conversion calculated
• the urethane-modified (meth)acrylate-based polyfunctional polymerizable monomer having no polymer skeleton is, for example, 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate (commonly known as “UDMA” ), N,N-(2,2,4-trimethylhexamethylene)bis[2-(aminocarboxy)propane-1,3-diol]tetra(meth)acrylate, phenyl glycidyl ether acrylate hexamethylene diisocyanate urethane prepolymer, Pentaerythritol triacrylate hexamethylene diisocyanate urethane prepolymer, pentaerythritol triacrylate toluene diisocyanate urethane prepolymer, pentaerythritol triacrylate isophorone diisocyanate urethane prepolymer, dip
• the content of the urethane (meth)acrylate polymerizable monomer (D) in the energy ray-curable composition for three-dimensional modeling of the present embodiment is the polymerizable monomer contained in the energy ray-curable composition for three-dimensional modeling. It is preferably 5 to 90 parts by mass with respect to 100 parts by mass of the total mass of the body.
• the content of the urethane (meth)acrylate polymerizable monomer (D) is 5 parts by mass with respect to the total mass of 100 parts by mass of the polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling. If it is above, it becomes easy to ensure flexibility.
• the content of the urethane (meth)acrylate polymerizable monomer (D) is 90 parts by mass with respect to the total mass of 100 parts by mass of the polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling. If it is not more than parts by mass, it becomes easy to suppress the increase in viscosity of the composition, and it becomes easy to avoid impairing the operability. In addition, it becomes easier to suppress yellowing of the modeled object due to discoloration caused by the remaining organotin catalyst, and it becomes easier to avoid impairing the aesthetics.
• the content of the urethane (meth)acrylate polymerizable monomer (D) is 10 to 85 parts by mass in 100 parts by mass of the total polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling. is more preferable, 12 to 83 parts by mass is more preferable, and 15 to 80 parts by mass is even more preferable.
• the urethane (meth)acrylate polymerizable monomer (D) tends to exacerbate discoloration due to the polymerizable monomer (A) containing an oxygen atom directly linked to the aromatic ring. Although the reason for this is not clear, the present inventors have found that the organotin catalyst used in the synthesis of the urethane (meth)acrylate polymerizable monomer (D) accelerates the excitation and oxidation of the phenoxy radicals and phenoxide ions described above.
• the energy beam-curable composition for stereolithography of the present embodiment contains the urethane (meth)acrylate polymerizable monomer (D)
• the content of the indigoid dye (B) is the urethane ( Meth) per 100 parts by mass of acrylate polymerizable monomer (D), preferably 0.001 to 0.050 parts by mass, more preferably 0.002 to 0.050 parts by mass, still more preferably 0.0025 ⁇ 0.050 parts by mass, more preferably 0.025 to 0.048 parts by mass, even more preferably 0.0025 to 0.025 parts by mass, still more preferably 0.0040 to 0.010 parts by mass .
• a polymerizable monomer other than the polymerizable monomer (A) and the urethane acrylate-based polymerizable monomer (D) is used within the range in which the effects of the present invention are exhibited.
• the radically polymerizable monomer examples include (meth)acrylate polymerizable monomers; (meth)acrylamide polymerizable monomers; ⁇ -cyanoacrylic acid, ⁇ -halogenated acrylic acid, crotonic acid , cinnamic acid, sorbic acid, maleic acid, and itaconic acid; vinyl esters; vinyl ethers; mono-N-vinyl derivatives; Polymerizable monomers other than the polymerizable monomer (A) and the urethane acrylate polymerizable monomer (D) include (meth)acrylate polymerizable monomers and (meth)acrylamide from the viewpoint of curability. system polymerizable monomers are preferred. Monofunctional polymerizable monomers having one polymerizable group and polyfunctional polymerizable monomers having a plurality of polymerizable groups are also exemplified.
• Monofunctional (meth)acrylate polymerizable monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 3-hydroxypropyl (meth)acrylate, 4-hydroxybutyl (meth) Acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, propylene glycol mono (meth)acrylate, glycerol mono (meth)acrylate, erythritol mono (meth)acrylate, methyl (meth)acrylate, ethyl ( meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, sec-butyl (meth) acrylate, t-butyl (meth) acrylate, isobutyl (meth) acrylate, n-hexyl ( meth)acrylate, cyclohexyl (
• Monofunctional (meth)acrylamide polymerizable monomers include (meth)acrylamide, N-(meth)acryloylmorpholine, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N , N-di-n-propyl (meth)acrylamide, N,N-di-n-butyl (meth)acrylamide, N,N-di-n-hexyl (meth)acrylamide, N,N-di-n-octyl (Meth)acrylamide, N,N-di-2-ethylhexyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N,N-bis(2-hydroxyethyl)acrylamide, N-(meth)acryloylcarbazole, N -methyl-N-phenyl(meth)acrylamide, N-(meth)acryloylmorpholine, N-piperidinylacrylamide,
• the structure of the polyfunctional polymerizable monomer is not particularly limited.
• bifunctional polymerizable monomers include glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, and diethylene glycol.
• the energy ray-curable composition for three-dimensional modeling of the present embodiment further includes a phenolic compound (E) having no polymerizable group (hereinafter simply referred to as "phenolic compound (E)"). may be included).
• phenolic compound (E) used in the energy ray-curable composition for stereolithography is clearly distinguished from the polymerizable monomer (A) in that it does not have a polymerizable group.
• the phenolic compound (E) can be selected from phenol derivatives used in general industry, such as hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, t-butylcatechol 2-t-butyl- 4,6-dimethylphenol, 2,6-di-t-butylphenol, and 3,5-di-t-butyl-4-hydroxytoluene. Among these, 3,5-di-t-butyl-4-hydroxytoluene is preferred.
• the content of the phenolic compound (E) in the energy ray-curable composition for three-dimensional modeling of the present embodiment is not particularly limited, but the total amount of polymerizable monomers contained in the energy ray-curable composition for three-dimensional modeling With respect to 100 parts by mass, preferably 0.001 to 2.0 parts by mass, more preferably 0.002 to 2.0 parts by mass, still more preferably 0.003 to 2.0 parts by mass, still more preferably 0.005 to 2.0 parts by mass, more preferably 0.01 to 2.0 parts by mass.
• the energy beam-curable composition for stereolithography of the present embodiment contains a polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring, an indigoid dye (B), and a photopolymerization initiator (C).
• A polymerizable monomer having an oxygen atom directly linked to an aromatic ring
• B indigoid dye
• C photopolymerization initiator
• other components may be included in addition to the urethane (meth)acrylate polymerizable monomer (D) and phenolic compound (E) described above.
• the content of other components in the energy ray-curable three-dimensional modeling composition may be less than 50% by mass, may be less than 20% by mass, or may be less than 10% by mass. It may be less than % by mass.
• the above-described energy ray-curable composition for three-dimensional modeling may further contain a sensitizer, a chain transfer agent, an oxygen quencher, or the like for use in combination with the initiator, within a range that does not impede the effects of the present invention. good.
• additives can be added to the energy ray-curable three-dimensional modeling composition of the present embodiment for the purpose of adjusting the mechanical properties and the viscosity of the composition.
• additives include inorganic particles, organic particles, organic solvents, and thickeners.
• the method for producing the energy ray-curable three-dimensional modeling composition of the present embodiment is not particularly limited, and can be produced according to a known method such as putting the above components into a container and mixing them with a stirring device.
• the energy ray-curable composition for three-dimensional modeling of the present embodiment is not particularly limited, and can be used for various known applications.
• the energy ray-curable composition for three-dimensional modeling is preferably a dental energy ray-curable composition for three-dimensional modeling.
• the dental energy ray-curable composition for three-dimensional modeling is a composition for producing various dental structures by three-dimensional modeling.
• the energy ray-curable composition for stereolithography of the present embodiment is excellent in flexibility, water resistance and color tone when molded by stereolithography. Therefore, the energy ray-curable composition for three-dimensional modeling of the present embodiment can be applied to applications where such advantages can be utilized, and by carrying out modeling by the three-dimensional modeling method, for example, the production of dental structures; Manufacture of various molded products such as film-like products or molded products by roll molding or cast molding; can be used for coating, vacuum forming molds, etc., especially the energy beam-curable three-dimensional modeling of this embodiment
• the cured product of the composition for oral use can be used as mouthpieces such as orthodontic mouthpieces, mouthpieces for treatment of sleeping disorders, mouthpieces for treatment of temporomandibular joint disorders, and protective mouthpieces for protecting teeth, temporomandibular joints, etc. It can be used preferably.
• the dental structure according to the present embodiment contains an energy ray-curable polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring, an indigoid dye (B), and a photopolymerization initiator (C).
• a dental structure that is a cured product of a composition for three-dimensional modeling, The yellowness index represented by b* measured according to JIS Z 8722:2009, condition c of the 1 mm-thick dental structure 24 hours after molding is -10 to 10.
• the dental structure has the above configuration and properties, it is possible to obtain a shaped article having excellent flexibility, water resistance, and color tone.
• the content of the indigoid dye (B) is 0.0015 to 0.100 parts by mass with respect to 100 parts by mass of the resin component of the dental structure, from the viewpoint of easily ensuring good aesthetics. is preferred.
• An embodiment of the method for producing the dental structure includes a method for producing a modeled article by a stereolithography method using any of the energy ray-curable compositions for three-dimensional modeling described above. Specifically, there is a method for producing a dental structure, which includes a step of curing the energy ray-curable composition for stereolithography by irradiating it with an energy ray.
• active energy rays are preferably used as the light energy for curing the resin.
• active energy ray means an energy ray capable of curing a photocurable resin composition, such as ultraviolet rays, electron beams, X-rays, radiation, and high frequencies.
• the active energy ray may be ultraviolet light having a wavelength of 300-400 nm.
• Light sources for active energy rays include lasers such as Ar lasers and He—Cd lasers; lighting such as halogen lamps, xenon lamps, metal halide lamps, LEDs, mercury lamps and fluorescent lamps, etc.
• Lasers are particularly preferred. When a laser is used as the light source, it is possible to shorten the modeling time by increasing the energy level, and by utilizing the good light-gathering properties of the laser beam, it is possible to obtain a model with high modeling accuracy. .
• any of conventionally known methods and conventionally known stereolithography system devices can be employed, but there is no particular limitation.
• preferably used three-dimensional modeling methods include a step of selectively irradiating an energy beam-curable three-dimensional modeling composition with an active energy ray so as to obtain a cured layer having a desired pattern to form a cured layer (first step), then an uncured liquid energy ray-curable composition for three-dimensional modeling is further supplied to the cured layer, and an active energy ray is similarly irradiated to newly form a cured layer continuous with the cured layer.
• a method of finally obtaining a desired shaped object by repeating the stacking step (second step) can be exemplified.
• the shaped article thus obtained may be used as it is, or in some cases, in a third step, at least one of post-curing by light irradiation and post-curing by heat may be performed to improve its mechanical properties and shape. You may make it use it after making stability etc. higher.
• the structure, shape, size, etc. of the modeled object obtained by the three-dimensional modeling method are not particularly limited, and can be determined according to each application.
• Typical application fields of the three-dimensional modeling method include various structures as final products and parts; models for verifying appearance designs during design; creation of models for checking the functionality of parts. etc. More specifically, by taking advantage of the characteristics of the color tone of the hardened material and good modeling accuracy, we are developing dental splints (mouthpieces) including orthodontic splints (aligners and retainers) and sleep apnea treatment splints. ) and other dental structures and prototypes thereof.
• the energy ray-curable three-dimensional object composition according to the first embodiment (X-1) of the present invention is a polymerizable monomer having an oxygen atom directly linked to an aromatic ring.
• a polymerizable monomer (A), an indigoid dye (B), and a photopolymerization initiator (C) are included, and the content of the indigoid dye (B) is 100 masses of the polymerizable monomer (A) 0.0015 to 0.100 parts by mass per part.
• the energy beam-curable composition for stereolithography (X-2) includes a polymerizable monomer having an oxygen atom directly linked to an aromatic ring ( A), a dye, and a photopolymerization initiator (C).
• a cured product with a thickness of 1 mm obtained by curing the product, 24 hours after modeling, JIS Z 8722: 2009, yellowness represented by b * measured in accordance with condition c -10 to 10 is.
• an energy ray-curable composition further comprising a urethane (meth)acrylate polymerizable monomer (D) Compositions for stereolithography may be mentioned.
• the polymerizable monomer (A) is a monofunctional polymerizable monomer and an energy ray-curable composition for three-dimensional modeling.
• the polymerizable monomer (A) has an oxygen atom directly attached to an aromatic ring.
• Energy beam curing comprising at least one of a phenyl ether skeleton, which is a structure further bonded to a hydrocarbon group, and a phenyl ester skeleton, which is a structure in which an oxygen atom directly bonded to an aromatic ring is further bonded to a carbonyl group. and a composition for physical stereolithography.
• the polymerizable monomer (A) is a polymerizable monomer containing the phenyl ether skeleton and not containing the phenyl ester skeleton.
• An energy ray-curable composition for stereolithography which is the body (a-1), can be mentioned.
• the polymerizable monomer (A) is represented by the following general formula (I) or An energy ray-curable composition for stereolithography, which is a monofunctional polymerizable monomer represented by the following general formula (II), may be mentioned.
• R 1 is a group represented by the following general formula (i).
• R 2 is a group represented by the following general formula (i) or a group represented by general formula (ii)
• X is a divalent hydrocarbon group having 1 to 6 carbon atoms or It is an oxygen atom.
• R 2 is a group represented by formula (i).
• R 3 and R 5 are each independently a divalent hydrocarbon group having 1 to 10 carbon atoms
• R 4 and R 6 are each independently a hydrogen atom or a methyl group
• k and l are each independently an integer from 0 to 6.
• the indigoid dye (B) is indigo carmine, 6,6′-dibromoindigo , and at least one selected from the group consisting of aluminum lakes thereof.
• the indigoid dye (B) is an aluminum lake of indigo carmine, and an energy beam-curable composition for a three-dimensional object is provided. mentioned.
• the content of the indigoid dye (B) is 0 with respect to 100 parts by mass of the polymerizable monomer (A). 0.0015 to 0.100 parts by mass of the energy ray-curable three-dimensional object composition.
• the content of the indigoid dye (B) is 0.0015 to 0.0090 parts by weight of the composition for energy ray-curable stereolithography, based on 100 parts by weight of the total weight of the polymerizable monomers contained in the composition.
• the content of the indigoid dye (B) is 0.0013 to 0.0090% by mass based on the total mass of the composition.
• the content of the indigoid dye (B) is equal to that of the photopolymerization initiator (C ) is 0.01 to 1.00 parts by mass with respect to 100 parts by mass, an energy ray-curable three-dimensional object.
• the content of the indigoid dye (B) is 0.001 to 0.050 parts by mass of an energy ray-curable composition for a three-dimensional shaped article.
• a composition for a three-dimensional modeled article is mentioned.
• Another embodiment (X-17) is a dental structure comprising a cured product of the energy ray-curable three-dimensional modeling composition according to any one of the above embodiments (X-1) to (X-16). is mentioned.
• Another embodiment (X-18) is an energy ray-curable composition for stereolithography, comprising a polymerizable monomer (A) having an oxygen atom directly linked to an aromatic ring, a dye, and a photopolymerization initiator (C).
• a dental structure having a yellowness index represented by b* measured according to condition c of ⁇ 10 to 10 is mentioned.
• the content of the indigoid dye (B) is 0.0015 to 0.100 parts by mass with respect to 100 parts by mass of the resin component of the dental structure.
• a dental structure is mentioned.
• Another embodiment (X-20) includes a mouthpiece comprising the dental structure according to any one of the above embodiments (X-17) to (X-19).
• Another embodiment (X-21a) includes an orthodontic mouthpiece comprising the dental structure according to any one of the above embodiments (X-17) to (X-19).
• Another embodiment (X-21b) includes a mouthpiece for treatment of sleep disorders comprising the dental structure according to any one of the above embodiments (X-17) to (X-19).
• Another embodiment (X-21c) includes a mouthpiece for treating temporomandibular joint disease comprising the dental structure according to any one of the above embodiments (X-17) to (X-19).
• Another embodiment (X-21d) is a protective mouse for protecting teeth and temporomandibular joints comprising the dental structure according to any one of the above embodiments (X-17) to (X-19). piece.
• the polymerizable monomer contained in the energy ray-curable composition for three-dimensional modeling Based on the total mass of 100 parts by mass, 5 to 45 parts by mass of the polymerizable monomer (A), 0.0015 to 0.0090 parts by mass of the indigoid dye (B), and a photopolymerization initiator ( C) may be an energy ray-curable three-dimensional object composition containing 0.01 to 10 parts by mass.
• the polymerizable monomer contained in the energy ray-curable composition for three-dimensional modeling Based on the total mass of 100 parts by mass, 10 to 40 parts by mass of the polymerizable monomer (A), 0.0020 to 0.0085 parts by mass of the indigoid dye (B), and a photopolymerization initiator ( C) can be exemplified by an energy ray-curable three-dimensional object composition containing 0.05 to 7.5 parts by mass.
• the monomer (A) is a monofunctional polymerizable monomer
• the content of the indigoid dye (B) is 0.0015 to 0.001 parts per 100 parts by mass of the polymerizable monomer (A). 100 parts by mass, and the content of the indigoid dye (B) is 0.001 to 0.050 parts by mass with respect to 100 parts by mass of the urethane (meth)acrylate compound (D).
• a three-dimensional object composition is mentioned.
• Another embodiment (X-25) includes a dental structure comprising a cured product of the energy ray-curable three-dimensional modeling composition described in the above embodiment (X-24).
• Another embodiment (X-26) includes a mouthpiece comprising the dental structure described in the above embodiment (X-25).
• the amount of each component can be changed as appropriate based on the above description, and any component can be added, deleted, etc. can be done. Further, in any of the above-described embodiments (X-1) to (X-26), the composition of each composition and the value of each property (formability, yellowness, flexibility, water resistance, etc.) may be changed as appropriate. can also be combined.
• the energy beam-curable stereolithography according to any one of the above embodiments (X-1) to (X-16) and (X-22) to (X-24) and a method for producing a dental structure, comprising a step of curing a dental composition by irradiating it with an energy ray.
• the energy beam-curable stereolithography according to any one of the above embodiments (X-1) to (X-16) and (X-22) to (X-24)
• the first cured layer is applied to the above embodiments (X-1) to (X-16) and (X- 22)
• a second cured layer continuous with the first cured layer by newly supplying the energy ray-curable three-dimensional modeling composition according to any one of (X-24) and irradiating with an active energy ray.
• a manufacturing method of a dental structure includes a second step of laminating to form a new layer, and obtaining a final modeled object by repeating the second step.
• the final model obtained by repeating the second step is subjected to post-curing by light irradiation and heat.
• a method for manufacturing a dental structure further comprising a third step of performing at least one of post-curing with.
• the present invention includes embodiments in which the above configurations are combined in various ways within the scope of the technical idea of the present invention as long as the effects of the present invention are exhibited.
• Indigoid dye (B) ⁇ Indigo carmine (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) ⁇ Blue No. 2 aluminum lake (indigo carmine aluminum lake, manufactured by Daiwa Kasei Co., Ltd.) ⁇ Tyrian Purple: Tyrian Purple, genuine (6-bromoindigo, 6,6′-dibromoindigo mixture, manufactured by Kremer Pigments Inc.) ⁇ Thioindigo (manufactured by Tokyo Kasei Co., Ltd.)
• polyester skeleton urethane acrylate (d-1) (1-1) 250 g of isophorone diisocyanate, 250 g of isophorone diisocyanate, and 0.15 g of di-n-butyltin dilaurate were added and heated to 70° C. with stirring.
• polyester polyol (“Kuraray Polyol (registered trademark) P-2050” manufactured by Kuraray Co., Ltd.; polymer composed of adipic acid and 3-methylpentanediol, mass average molecular weight Mw 2,000) 2,500 g
• the solution in the above (1-1) in the flask was added dropwise at a constant rate over 4 hours while the internal temperature of the flask was maintained at 65 to 75°C while stirring. Furthermore, after completion of dropping, the mixture was stirred at the same temperature for 2 hours to react.
• Examples 1 to 12 and Comparative Examples 1 to 6 Each component in the amount shown in Table 1 was mixed at room temperature (20 ° C. ⁇ 15 ° C., JIS (Japanese Industrial Standard) Z 8703: 1983), and energy beam curing according to Examples 1 to 12 and Comparative Examples 1 to 6 A composition for stereolithography was prepared.
• JIS Japanese Industrial Standard
• the produced sheet was subjected to the following treatment in order to be subjected to a performance test to be described later.
• the sheet prepared in the formability test was washed with air and ethanol to remove excess polymerizable monomers.
• a light irradiator (Otoflash (registered trademark) G171 manufactured by EnvisionTEC)
• only one side was irradiated with 5,000 flashes of light for photocuring treatment.
• a heat treatment at 60° C. was performed for 15 minutes before and after the light irradiation using a thermostat DKM600 (manufactured by Yamato Scientific Co., Ltd.).
• the energy ray-curable composition for a three-dimensional object is irradiated with an energy ray having a wavelength of 385 nm and an irradiation intensity of 2,000 mW/mm 2 or more so that the cumulative amount of light is 25 mJ/cm 2 or more to irradiate the composition. Cured into a sheet. After that, using a xenon lamp with an irradiation intensity of 0.1 mW/mm 2 or more, a light curing treatment with an integrated light amount of 60 mJ/cm 2 or more and a heat treatment at 60 ° C. or more for 15 minutes are performed to obtain a thickness of 1 mm. A sheet-like cured product was produced.
• This sheet-like cured product was punched out with a circular punch having a diameter of 15.0 mm to prepare a color tone measuring disk having a diameter of 15.0 mm and a thickness of 1.0 mm.
• polishing with silicon carbide paper No. 1,000 followed by polishing with a dental wrapping film (manufactured by 3M), a spectrophotometer (manufactured by Konica Minolta Co., Ltd., SPECTROPHOTOMETER CM-3610A, JIS Z 8722: 2009, conditions c, D65 illuminant), yellowness b* values were measured 24 hours after modeling.
• a test piece having the same dimensions as the dumbbell-shaped No. 8 test piece described in JIS K 6251: 2010 (vulcanized rubber and thermoplastic rubber-determination of tensile properties) is prepared with a punching blade. bottom. Using the prepared test piece, a tensile test was performed at a distance between chucks of 10 mm and a test speed of 500 mm/min (n 5). The tensile elongation in this test is preferably 25% or more, more preferably 50% or more, and even more preferably 100% or more.
• Tensile elongation (%) (distance between chucks at break (mm) - initial distance between chucks (mm)) / initial distance between chucks (mm) x 100
• the energy ray-curable three-dimensional modeling compositions of Examples 1 to 12 have sculptability, and the cured products thereof are excellent in color tone, flexibility and water resistance, and have no odor. It turns out that there is none or few.
• the energy ray-curable three-dimensional modeling compositions of Comparative Examples 1 to 3 and 6 caused significant discoloration in the cured products.
• the energy ray-curable compositions for three-dimensional modeling of Comparative Examples 4 and 6 were poor in flexibility, and produced a significant odor as compared with Examples.
• the energy ray-curable composition for three-dimensional modeling of Comparative Example 5 was poor in water resistance.
• the energy ray-curable composition for three-dimensional modeling of the present invention is suitable as a material for producing a three-dimensional model that requires aesthetics in addition to flexibility and water resistance.
• dental structures such as orthodontic splints (aligners and retainers), dental splints (mouthpieces) including sleep apnea treatment splints, etc., and prototypes thereof.

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• 2022
  • 2022-12-28 WO PCT/JP2022/048447 patent/WO2023127934A1/ja not_active Ceased
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