Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/10—Fastening of artificial teeth to denture palates or the like
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
  • A61C13/01—Palates or other bases or supports for the artificial teeth; Making same
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61C—DENTISTRY; APPARATUS OR METHODS FOR ORAL OR DENTAL HYGIENE
  • A61C13/00—Dental prostheses; Making same
• • 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
  • 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
  • B33Y10/00—Processes of 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
  • B33Y70/00—Materials specially adapted for additive manufacturing
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J4/00—Adhesives based on organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond ; adhesives, based on monomers of macromolecular compounds of groups C09J183/00 - C09J183/16
  • C09J4/06—Organic non-macromolecular compounds having at least one polymerisable carbon-to-carbon unsaturated bond in combination with a macromolecular compound other than an unsaturated polymer of groups C09J159/00 - C09J187/00
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K6/00—Preparations for dentistry
  • A61K6/30—Compositions for temporarily or permanently fixing teeth or palates, e.g. primers for dental adhesives
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
  • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
  • B29L2031/00—Other particular articles
  • B29L2031/753—Medical equipment; Accessories therefor
  • B29L2031/7532—Artificial members, protheses
  • B29L2031/7536—Artificial teeth
• • 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

Definitions

• the present invention relates to a method for manufacturing dentures, characterized by bonding a photofabricated denture base and artificial teeth using a specific adhesive composition.
• the lost wax method has been used to manufacture dentures.
• a mold of the patient's oral cavity is taken, and a base plate is formed on a plaster model made based on this, and a gingiva made of wax called a wax is built up on top to create an occlusal bed.
• artificial teeth made of acrylic resin are arranged, and the wax denture is completed through occlusal adjustment and gingival formation.
• the wax is melted and removed with hot water.
• acrylic resin is poured into the cavity wall, After hardening, the final denture is completed through finishing work.
• This method not only requires a large number of manufacturing steps, but also requires extremely high dimensional accuracy on the order of several micrometers for manufacturing dentures, requiring not only a great deal of time but also the skill of technicians.
• CAD/CAM is used to design dentures on the screen using a computer and to manufacture dentures by cutting from resin material or ceramic blocks.
• Systems are attracting attention, and denture design and manufacturing systems, such as the CEREC system, are becoming widespread.
• systems using stereolithographic 3D printers are rapidly expanding.
• stereolithography the floor and the artificial tooth part are manufactured separately, so it is necessary to bond them together after they are manufactured.
• a polymerizable compound having particularly high curability must be used because the composition is instantly cured by light, and a cross-linking monomer or a monomer exhibiting a high cohesive force is used.
• the denture base material produced by stereolithography has a high crosslink density and a strong cohesive force.
• an adhesive consisting of methyl methacrylate (MMA) containing a polymerization initiator and acrylic resin powder is used to bond artificial teeth and floors for restoration purposes. has the problem that it is difficult to penetrate and sufficient adhesion cannot be obtained.
• adhesive materials for dental use include those applied to dentin, those applied to dental composite resins, and other dental prostheses made of metals and ceramics. It is widely known that it is applied to Dental adhesive materials intended for these uses form chemical bonds with each adherend, such as acidic monomers, silane coupling agents, and sulfur-containing monomers. Adhesive materials for are quite different in technology and mechanism of development of adhesion from adhesive materials in these applications.
• Patent Document 1 discloses a denture made by bonding a denture base manufactured using a CAD/CAM system and an acrylic resin artificial tooth with a liquid-powder resin composed of MMA and PMMA. A fabrication example is provided.
• Patent Document 1 is an example in which a base is designed to have a specific shape, and does not describe the problem of adhesiveness between a denture base manufactured by stereolithography and an artificial tooth.
• an object of the present invention is to provide a method for manufacturing a denture, which is characterized by strongly bonding a denture base manufactured by stereolithography and an artificial tooth made of an acrylic resin.
• the denture base which is the stereolithographic object of (I), and the artificial tooth made of acrylic resin (II)
• Composition containing a (meth)acrylic polymerizable monomer component (C) containing the same (meth)acrylic polymerizable monomer (m) as contained in the curable composition (I) A method for manufacturing a denture, characterized in that the adhesive composition containing III) is used for bonding.
• the polyfunctional (meth)acrylic polymerizable monomer (a-1) is a urethanized (meth)acrylic acid ester compound and an aromatic compound-based (meth)acrylic compound containing no urethane bond.
• the content of the (meth)acrylic polymerizable monomer (m) is 100% by mass of the (meth)acrylic polymerizable monomer component (A).
• the content of the (meth)acrylic polymerizable monomer (m) is, in 100% by mass of the (meth)acrylic polymerizable monomer component (C), The method for manufacturing a denture according to any one of [1] to [7], wherein the content is 50% by mass or more.
• Step (2) Applying the adhesive composition to the denture base and the artificial tooth. [12] bonding the denture base and the artificial tooth by irradiating the adhesive composition with an active energy ray and curing the adhesive composition, wherein the [ 1] The method for manufacturing a denture according to any one of [11].
• a method for manufacturing a denture which is characterized by firmly bonding a denture base manufactured by stereolithography and an artificial tooth made of acrylic resin.
• the upper limit and lower limit of the numerical range can be combined as appropriate. That is, in this specification, the lower and upper limits described stepwise for numerical ranges for the same item can be independently combined. For example, from the statement “preferably 10 to 90, more preferably 30 to 60" for the same matter, combining “preferred lower limit (10)” and “more preferred upper limit (60)", “10 to 60 ” can also be used.
• the upper limit is not particularly defined, and only the lower limit side is “10 or more” or “30 or more” Similarly, it is also possible to specify “90 or less” or “60 or less” only on the upper limit side without specifying the lower limit. Unless otherwise specified, simply describing "10 to 90" as a numerical range indicates a range of 10 or more and 90 or less.
• composition (I) refers to the adhesiveness between the denture base and the artificial tooth.
• a method for producing a denture which is one aspect of the present invention, comprises a (meth)acrylic polymerizable monomer component (A) containing a (meth)acrylic polymerizable monomer (m) as a main monomer, and light
• the denture base which is a stereolithographic product of the curable composition (I) containing a polymerization initiator, and the artificial tooth made of the acrylic resin (II) are included in the curable composition (I). Bonding using an adhesive composition containing a composition (III) containing a (meth)acrylic polymerizable monomer component (C) containing the (meth)acrylic polymerizable monomer (m) It is characterized by
• the denture base which is a stereolithographic product of the curable composition (I), contains the same (meth)acrylic polymerizable monomer (m) as contained in the curable composition (I) (meth)
• the adhesive composition containing the composition (III) containing the acrylic polymerizable monomer component (C) as an adhesive
• the denture base surface shaped from the curable composition (I) The adhesive composition containing the composition (III) is easily permeated.
• the interaction of the (meth)acrylic polymerizable monomer (m), which is the same component contained in the curable composition (I) and the composition (III) such as hydrogen bonding, hydrophobic interaction, ⁇ Since electronic interaction is obtained, it is presumed that stronger adhesiveness can be obtained.
• composition (III) also has an affinity for the acrylic resin (II), a denture base that is stereolithography of the curable composition (I) and an artificial tooth made of the acrylic resin (II) It is presumed that the can be adhered more strongly.
• a denture base that is stereolithography of the curable composition (I) and an artificial tooth made of the acrylic resin (II) It is presumed that the can be adhered more strongly.
• composition (I) contains a (meth)acrylic polymerizable monomer (m) (hereinafter simply “monomer It contains a (meth)acrylic polymerizable monomer component (A) (hereinafter also simply referred to as “component (A)”) containing (also referred to as “body (m)”), and a photopolymerization initiator.
• Composition (I) has photocurability.
• the (meth)acrylic polymerizable monomer component (A) is a component composed of one type of (meth)acrylic polymerizable monomer alone or two or more types, and the main monomer is ( Contains a meth)acrylic polymerizable monomer (m).
• the "main monomer” means the (meth)acrylic polymerizable monomer having the highest content among the (meth)acrylic polymerizable monomers constituting the component (A). refers to the quanta.
• (meth)acrylic polymerizable monomer component refers to a component composed of one or more (meth)acrylic polymerizable monomers, The same applies to the component (A) and the “(meth)acrylic polymerizable monomer component (C)" described later.
• (meth)acrylic polymerizable monomer refers to one specific compound constituting the "(meth)acrylic polymerizable monomer component", i.e., a specific ( Meth) refers to an acrylic polymerizable monomer, the monomer (m), and the “polyfunctional (meth)acrylic polymerizable monomer (a-1)” and “monomer The same applies to the functional (meth)acrylic polymerizable monomer (a-2).
• the content of the monomer (m) contained as the main monomer is the largest in the component (A), and the (meth)acrylic polymerizable monomer other than the monomer (m)
• the content of the compound (o) (hereinafter also simply referred to as "monomer (o)") is not less than the content, but for example, in 100% by mass of component (A), preferably 20% by mass or more , More preferably 30% by mass or more, still more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass or more, still more preferably 60% by mass or more, still more preferably 65% by mass % or more, for example, 100% by mass or less, preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, even more preferably 85% by mass or less, still more preferably 80% by mass % or less.
• the content of the monomer (m) in component (A) is preferably 20 to 100% by mass, more preferably 30 to 100% by mass, in 100% by mass of component (A). %, more preferably 40 to 98 mass %, still more preferably 50 to 95 mass %, still more preferably 55 to 90 mass %, still more preferably 60 to 85 mass %, still more preferably 65 to 80 mass % is.
• the component (A) is a component composed of the monomer (m) alone or the monomer (m) and the monomer (o). Component (A) may contain a plurality of monomers (o). Therefore, the total content of monomer (m) and monomer (o) in component (A) is 100% by mass.
• Examples of the (meth)acrylic polymerizable monomer constituting the component (A) include (meth)acrylic acid ester polymerizable monomers and (meth)acrylamide polymerizable monomers.
• As the (meth)acrylic polymerizable monomer a polyfunctional (meth)acrylic polymerizable monomer (a-1) having a plurality of polymerizable groups (hereinafter simply referred to as “polyfunctional monomer (a-1)”.), and a monofunctional (meth)acrylic polymerizable monomer having one polymerizable group (a-2) (hereinafter simply referred to as “monofunctional monomer ( a-2)”.).
• the component (A) preferably contains a polyfunctional monomer (a-1), and contains (meth)acrylic polymerizable as a main monomer More preferably, the monomer (m) is the polyfunctional monomer (a-1).
• the component (A) preferably contains a monofunctional monomer (a-2), the composition (I) is excellent in curability, the penetration of the adhesive agent described later into the denture base is easily obtained, From the viewpoint of easier expression of excellent adhesiveness, it is more preferable to contain both the polyfunctional monomer (a-1) and the monofunctional monomer (a-2), and a large number of main monomers It further preferably contains a functional monomer (a-1) and further contains a monofunctional monomer (a-2).
• the component (C) which will be described later, contains the monomer (a-2), the composition (III) has excellent curability, and the penetration of the adhesive composition into the denture base and the artificial tooth is easily obtained.
• the component (A) may contain one type of polyfunctional monomer (a-1) alone or two or more types, and similarly, one type of monofunctional monomer (a-2) alone. or may contain two or more kinds.
• the polyfunctional monomer (a-1) is a urethanized (meth)acrylic acid ester compound, an aromatic compound containing no urethane bond, from the viewpoint of improving the curability and adhesiveness of the composition (I).
• At least one selected from group compound-based (meth)acrylic acid ester compounds is more preferable, and a urethanized (meth)acrylic acid ester compound is even more preferable.
• the component (A) includes, as the polyfunctional monomer (a-1) described above, a urethanized (meth)acrylic acid ester compound, an aromatic compound-based (meth)acrylic compound containing no urethane bond, It preferably contains at least one selected from the group consisting of an acid ester compound and an alicyclic (meth)acrylic acid ester compound, a urethanized (meth)acrylic acid ester compound, and an aromatic compound that does not contain a urethane bond It is more preferable to contain at least one selected from (meth)acrylic acid ester compounds of (meth)acrylic acid ester compounds, and it is still more preferable to contain a urethanized (meth)acrylic acid ester compound.
• the component (A) includes a polyfunctional monomer (a-1) as a (meth)acrylic polymerizable monomer (m) contained as a main monomer.
• a polyfunctional monomer (a-1) as a (meth)acrylic polymerizable monomer (m) contained as a main monomer.
• a polyfunctional monomer (a-1) preferably contains at least one selected from the group consisting of acrylic acid ester compounds, aromatic (meth)acrylic acid ester compounds containing no urethane bonds, and alicyclic (meth)acrylic acid ester compounds, It is more preferable to contain at least one selected from urethane-modified (meth)acrylate compounds and aromatic compound-based (meth)acrylate compounds that do not contain urethane bonds, and urethane-modified (meth)acrylate compounds.
• an aromatic compound-based (meth)acrylic acid ester compound that does not contain a urethane bond the compound contains at least one selected from the group consisting of a hydroxyl group, a primary amino group, and a secondary amino group. is more preferable.
• these compounds not only promote curing by the dielectric effects of urethane bonds, aromatic skeletons, hydroxyl groups, primary amino groups, and secondary amino groups, but also chemical bonds such as hydrogen bonding and ⁇ electron action. is presumed to generate Among them, urethane-modified (meth)acrylic acid ester compounds having urethane bonds are highly effective in imparting toughness to dentures. It is preferable because it can express
• the urethane-modified (meth)acrylic acid ester compound includes, for example, a compound containing one or more selected from an alkylene skeleton and a phenylene skeleton and having an isocyanate group, and a (meth)acrylate compound having a hydroxyl group (—OH).
• a compound containing one or more selected from an alkylene skeleton and a phenylene skeleton and having an isocyanate group and a (meth)acrylate compound having a hydroxyl group (—OH).
• the weight average molecular weight of the urethanized (meth)acrylic acid ester compound is preferably 1000 or less from the viewpoint that the composition (I) has a low viscosity and can be easily shaped, and the adhesive composition described later can easily penetrate. .
• the adhesive composition when the component (C), which will be described later, contains a urethane-modified (meth)acrylic acid ester compound, the adhesive composition has a low viscosity and is easy to apply, and the penetration of the adhesive composition into the denture base and the artificial tooth is obtained.
• the weight average molecular weight is more preferably 750 or less, and even more preferably 500 or less.
• the weight average molecular weight as used herein means the polystyrene-equivalent weight average molecular weight determined by gel permeation chromatography (GPC).
• the urethanized (meth)acrylic acid ester compound does not contain a polymer structure, there is no concept of weight average molecular weight, so the molecular weight is applied.
• the urethanized (meth)acrylic acid ester compound is preferably a compound that does not contain a polymer structure such as polyester, polycarbonate, polyurethane, polyether, and the like. By not containing these structures, an increase in the concentration of polar functional groups can be suppressed, and a decrease in adhesiveness in the presence of moisture such as in the oral cavity can be suppressed.
• the number of urethane bonds in one molecule is preferably 3 or less, more preferably 2 or less, from the viewpoint of adhesion in the presence of moisture.
• the number of urethane bonds in the urethanized (meth)acrylate compound is preferably 1 to 3 per molecule, more preferably 1 or 2 per molecule.
• Compounds containing at least one selected from an alkylene skeleton and a phenylene skeleton and having an isocyanate group include, for example, methylene diisocyanate (abbreviated as "MDI”), hexamethylene diisocyanate (abbreviated as “HDI”), and isophorone diisocyanate (abbreviated as “HDI”).
• MDI methylene diisocyanate
• HDI hexamethylene diisocyanate
• HDI isophorone diisocyanate
• IPDI trimethylhexamethylene diisocyanate
• TMHMDI tricyclodecane diisocyanate
• ADI adamantane diisocyanate
• TDI tolylene diisocyanate
• XDI xylylene diisocyanate
• DPMDI diphenylmethane diisocyanate
• (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, 2-hydroxy-3-acryloyloxypropyl (Meth)acrylate, 2,2-bis[4-[3-(meth)acryloyloxy-2-hydroxypropoxy]phenyl]propane, 1,2-bis[3-(meth)acryloyloxy-2-hydroxypropoxy] Hydroxy(meth)acrylate compounds such as ethane, pentaerythritol tri(meth)acrylate, tri- or tetra(meth)acrylate of dipentaeryth
• 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 2-hydroxy-3-acryloyloxypropyl (meth) acrylate are preferable from the viewpoint of easily exhibiting excellent adhesiveness.
• 2-Hydroxyethyl (meth)acrylate is more preferred.
• An addition reaction between a compound containing at least one selected from an alkylene skeleton and a phenylene skeleton and having an isocyanate group and a (meth)acrylate compound having a hydroxyl group can be carried out according to a known method, and is not particularly limited. do not have.
• UDMA 2,2,4-tri
• 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate N,N'-(2,2,4-trimethylhexamethylene)bis[2 -(Aminocarboxy)propane-1,3-diol]tetramethacrylate is preferred, and 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl)dimethacrylate is more preferred.
• component (A) contains a urethanized (meth)acrylic acid ester compound that is a polyfunctional monomer (a-1), in component (A), the urethaned (meth)acrylic acid ester compound
• the content is preferably 10 to 100% by mass in 100% by mass of component (A), more preferably 30 to 95% by mass, more preferably 50 to 90% by mass from the viewpoint of better adhesion. more preferably 60 to 80% by mass.
• the content of the urethanized (meth)acrylic acid ester compound is preferably 50 to 100% by mass in the total 100% by mass of the polyfunctional monomer (a-1), and more Preferably 60 to 100% by mass, more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.
• aromatic (meth)acrylic acid ester compounds containing no urethane bond include 2,2-bis((meth)acryloyloxyphenyl)propane, 2,2-bis[4-(3-acryloyloxy)- 2-hydroxypropoxyphenyl]propane, 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane (abbreviation “Bis-GMA”), 2,2-bis[4- ⁇ 2- (3-acryloyloxy-2-hydroxypropoxy)propyl ⁇ phenyl]propane, 2,2-bis[4- ⁇ 2-(3-methacryloyloxy-2-hydroxypropoxy)propyl ⁇ phenyl]propane, 2,2-bis (4-(meth)acryloyloxyethoxyphenyl)propane, 2,2-bis(4-(meth)acryloyloxypolyethoxypheny
• component (A) contains an aromatic compound-based (meth)acrylic acid ester compound that does not contain a urethane bond, which is the polyfunctional monomer (a-1), the urethane bond in component (A)
• the content of the aromatic compound-based (meth)acrylic acid ester compound that does not contain is preferably 5 to 95% by mass in 100% by mass of component (A), and from the viewpoint of better adhesion, 10 to It is more preferably 90% by mass, even more preferably 20 to 85% by mass, even more preferably 30 to 80% by mass, and even more preferably 50 to 70% by mass.
• the content of the aromatic compound-based (meth)acrylic acid ester compound containing no urethane bond is preferably in the total 100% by mass of the polyfunctional monomer (a-1). Is 50 to 100% by mass, more preferably 60 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, still more preferably 95 ⁇ 100% by mass.
• Alicyclic (meth)acrylic acid ester compounds include tricyclodecanedimethanol di(meth)acrylate, cyclohexanediol di(meth)acrylate, adamantanediol di(meth)acrylate, and the like. Among these, tricyclodecanedimethanol di(meth)acrylate is preferred.
• component (A) contains an alicyclic (meth)acrylic acid ester compound that is the polyfunctional monomer (a-1), the alicyclic (meth)acrylic acid ester in component (A)
• the content of the compound is preferably 30 to 100% by mass in 100% by mass of the component (A), more preferably 50 to 98% by mass from the viewpoint of better strength of the denture, and 70 to 95% by mass. % by mass is more preferred.
• the content of the alicyclic (meth)acrylic acid ester compound is preferably 50 to 100% by mass in the total 100% by mass of the polyfunctional monomer (a-1), More preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, still more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass.
• ⁇ Other polyfunctional (meth)acrylic acid ester-based polymerizable monomers Polyfunctional (meth)acrylic acid other than the urethane-modified (meth)acrylic acid ester compound, aromatic compound-based (meth)acrylic acid ester compound containing no urethane bond, and alicyclic (meth)acrylic acid ester compound
• Ester-based polymerizable monomers, i.e., other polyfunctional (meth)acrylic acid ester-based polymerizable monomers include: Glycerol di(meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate,
• glycerol di (meth) acrylate 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, triethylene glycol di (meth) acrylate are preferred from the viewpoint of better adhesion, and triethylene Glycol di(meth)acrylate is more preferred.
• glycerol di (meth) acrylate 1,2-bis (3-methacryloyloxy-2-hydroxypropoxy) ethane, triethylene glycol di (meth) acrylate are preferred from the viewpoint of better adhesion, and triethylene Glycol di(meth)acrylate is more preferred.
• These may be used individually by 1 type, and may use 2 or more types together.
• component (A) contains other polyfunctional (meth)acrylic acid ester polymerizable monomers, other polyfunctional (meth)acrylic acid ester polymerizable monomers in component (A)
• the content of the monomer is preferably 1 to 50% by mass, more preferably 5 to 40% by mass, more preferably 8 to 35% by mass, based on 100% by mass of component (A). preferable.
• the component (A) contains another polyfunctional (meth)acrylic acid ester-based polymerizable monomer, other polyfunctional (meth)acrylic acid ester
• the content of the system polymerizable monomer is preferably 1 to 50% by mass, more preferably 1 to 40% by mass, more preferably 1 in the total 100% by mass of the polyfunctional monomer (a-1) to 35% by mass, more preferably 1 to 30% by mass.
• the total content of the polyfunctional monomer (a-1) in the component (A) is 100 mass of the component (A) %, preferably 10 to 100% by mass, more preferably 50 to 100% by mass, more preferably 50 to 95% by mass, from the viewpoint of improving the adhesiveness, More preferably 55 to 85% by mass, and even more preferably 60 to 80% by mass.
• component (A) preferably contains a monofunctional monomer (a-2).
• the monofunctional monomer (a-2) lowers the viscosity of the resin composition (I), reduces the crosslink density of the resulting shaped article, and increases the permeability of the adhesive composition described below. Adhesion can be further improved.
• One polymerizable group possessed by the monofunctional monomer (a-2) refers to a (meth)acryloyl group.
• the monofunctional monomer (a-2) includes an aromatic ring-containing (meth)acrylic acid ester polymerizable monomer, an alicyclic (meth)acrylic acid ester polymerizable monomer, a nitrogen atom Contained cyclic (meth)acrylic acid ester polymerizable monomers, chain (meth)acrylic acid ester polymerizable monomers, cyclic (meth)acrylamide compounds, chain (meth)acrylamide compounds, and the like.
• the (meth) acrylic acid ester polymerizable monomer containing an aromatic ring, the alicyclic (meth) acrylic which tends to have a high boiling point and is less likely to feel an odor.
• Acid ester-based polymerizable monomers nitrogen atom-containing cyclic (meth)acrylic acid ester-based polymerizable monomers, and cyclic (meth)acrylamide compounds are preferred, and among these, the curability and adhesiveness of the resulting composition From the viewpoint of improvement, a (meth)acrylic acid ester-based polymerizable monomer containing an aromatic ring is more preferable.
• the component (A) includes, as the above-mentioned monofunctional monomer (a-2), a (meth)acrylic acid ester polymerizable monomer containing an aromatic ring, an alicyclic (meth) It preferably contains at least one selected from the group consisting of acrylic ester-based polymerizable monomers, nitrogen atom-containing cyclic (meth)acrylic ester-based polymerizable monomers, and cyclic (meth)acrylamide compounds, It is more preferable to contain a (meth)acrylic acid ester-based polymerizable monomer containing an aromatic ring.
• Aromatic ring-containing (meth)acrylic acid ester polymerizable monomer, alicyclic (meth)acrylic acid ester polymerizable monomer, nitrogen atom-containing cyclic (meth)acrylic acid ester polymerizable monomer cyclic (meth)acrylamide compounds tend to have a higher boiling point and a lower odor than linear (meth)acrylic acid ester-based polymerizable monomers at the same molecular weight. It is presumed that this is due to the effect of minute polarization due to interaction and fixed conformation.
• Examples of (meth)acrylic acid ester-based polymerizable monomers containing an aromatic ring include o-phenylphenol (meth)acrylate, m-phenylphenol (meth)acrylate, p-phenylphenol (meth)acrylate, methoxy Chemical-o-phenylphenol (meth)acrylate, Methoxylated-m-phenylphenol (meth)acrylate, Methoxylated-p-phenylphenol (meth)acrylate, Ethoxylated-o-phenylphenol (meth)acrylate, Ethoxylated- m-phenylphenol (meth)acrylate, ethoxylated-p-phenylphenol (meth)acrylate, propoxylated-o-phenylphenol (meth)acrylate, propoxylated-m-phenylphenol (meth)acrylate, propoxylated-p- Phenylphenol (meth)acrylate, butoxylated-o-phenylphenol (meth)acryl
• Examples of the alicyclic (meth) acrylic acid ester-based polymerizable monomers include 2-(1-adamantyl) propyl (meth) acrylate, 2-methyladamantyl-2-yl (meth) acrylate, (meth) ) 2-ethyladamantyl-2-yl acrylate, 2-n-propyladamantyl-2-yl (meth) acrylate, 2-isopropyladamantyl-2-yl (meth) acrylate, 1-(meth) acrylate Adamantan-1-yl)-1-methylethyl, 1-(adamantan-1-yl)-1-ethylethyl (meth)acrylate, 1-(adamantan-1-yl)-1-methylpropyl (meth)acrylate , 1-(adamantan-1-yl)-1-ethylpropyl (meth)acrylate, and the like.
• Nitrogen atom-containing cyclic (meth)acrylic acid ester polymerizable monomers include, for example, pentamethylpiperidinyl (meth)acrylate, tetramethylpiperidinyl (meth)acrylate, 4-(pyrimidin-2-yl ) piperazin-1-yl (meth)acrylate and the like.
• chain (meth)acrylic acid ester polymerizable monomers examples include 2-ethylhexyl (meth)acrylate, decyl (meth)acrylate, undecyl (meth)acrylate, lauryl (meth)acrylate, and tridecyl (meth)acrylate.
• tetradecyl (meth)acrylate pentadecyl (meth)acrylate, cetyl (meth)acrylate, palmitoleyl (meth)acrylate, heptadecyl (meth)acrylate, oleyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate , 4-hydroxybutyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, 10-hydroxydecyl (meth)acrylate, glycerol mono (meth)acrylate, erythritol mono (meth)acrylate, isobornylcyclohexyl (meth)acrylate etc.
• Cyclic (meth)acrylamide compounds include, for example, N-(meth)acryloylmorpholine, N-(meth)acryloylpyrrolidine, N-(meth)acryloylpiperidine, N-(meth)acryloyl-2-methylpiperidine, N-( meth)acryloyl-2,2,6,6-tetramethylpiperidine and the like.
• chain (meth)acrylamide compounds include N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-di-n-propyl(meth)acrylamide, N-isopropyl ( 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-(2-hydroxyethyl)(meth)acrylamide, N,N,N-bis(2-hydroxyethyl)(meth)acrylamide and the like.
• the monofunctional monomer (a-2) includes o-phenoxybenzyl (meth)acrylate and m-phenoxybenzyl (meth) from the viewpoint of improving the curability and adhesion of the resulting composition.
• the total content of the monofunctional monomer (a-2) in the component (A) is 100 mass of the component (A) %, preferably 1 to 60% by mass, more preferably 5 to 50% by mass, further preferably 10 to 50% by mass, from the viewpoint of improving the adhesiveness, and 15 It is even more preferably 45% by mass, and even more preferably 20 to 40% by mass.
• the content of the (meth)acrylic acid ester-based polymerizable monomer containing an aromatic ring is preferably in the total 100% by mass of the monofunctional monomer (a-2). Is 50 to 100% by mass, more preferably 60 to 100% by mass, more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, still more preferably 95 ⁇ 100% by mass.
• the (meth)acrylic polymerizable monomer contained in component (A) is substantially a polyfunctional monomer (a-1), or a polyfunctional monomer (a -1) and a monofunctional monomer (a-2).
• (Meth) acrylic polymerizable monomer is substantially a polyfunctional monomer (a-1), or a polyfunctional monomer (a-1) and a monofunctional monomer (a-2 ) consists only of the polyfunctional monomer (a-1), or the polyfunctional monomer (a-1) and the monofunctional monomer (a-2) other than
• the total content of meth)acrylic polymerizable monomers is less than 10.0% by mass, preferably less than 5.0% by mass, more preferably 1 in 100% by mass of the total amount of component (A) 0% by weight, more preferably less than 0.1% by weight, and even more preferably less than 0.01% by weight.
• the total content of the polyfunctional monomer (a-1) and the monofunctional monomer (a-2) in the component (A) is 100% by mass of the component (A) , preferably 80 to 100% by mass, more preferably 90 to 100% by mass, still more preferably 95 to 100% by mass, even more preferably 99 to 100% by mass, even more preferably 99.9 to 100% by mass, more More preferably, it is 99.99 to 100% by mass.
• the content of component (A) in composition (I) is preferably 40% by mass or more, more preferably 45% by mass, based on 100% by mass of composition (I). % or more, more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and preferably 99.99% by mass or less , more preferably 99.5% by mass or less, still more preferably 99% by mass or less, and even more preferably 98% by mass or less. As described above, these stepwise lower and upper limits can be independently combined.
• the content of component (A) in composition (I) is 100% by mass of composition (I), preferably 40 to 99.99% by mass, more preferably 45 to 99.99% by mass, more preferably 50 to 99.5% by mass, even more preferably 60 to 99.5% by mass, even more preferably 80 to 99% by mass, still more preferably 90 to 98% by mass .
• the photopolymerization initiator can be selected from polymerization initiators used in general industry, and among them, photopolymerization initiators used for dental applications are preferable.
• Photopolymerization initiators include (bis)acylphosphine oxides, thioxanthones or quaternary ammonium salts of thioxanthones, ketals, ⁇ -diketones, coumarins, anthraquinones, benzoin alkyl ether compounds, ⁇ -aminoketones. compounds and the like.
• a photoinitiator may be used individually by 1 type, and may use 2 or more types together.
• acylphosphine oxides include, for example, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,6-dimethoxybenzoyldiphenylphosphine oxide, and 2,6-dichlorobenzoyldiphenylphosphine oxide.
• 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide 2,4,6-trimethylbenzoylethoxyphenylphosphine oxide, 2,3,5,6-tetramethylbenzoyldiphenylphosphine oxide, benzoyldi(2,6-dimethylphenyl ) phosphonate, 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt, 2,4,6-trimethylbenzoylphenylphosphine oxide potassium salt, ammonium salt of 2,4,6-trimethylbenzoyldiphenylphosphine oxide.
• bisacylphosphine oxides include, for example, bis(2,6-dichlorobenzoyl)phenylphosphine oxide and bis(2,6-dichlorobenzoyl)-2,5-dimethylphenylphosphine.
• (bis)acylphosphine oxides 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethylbenzoylmethoxyphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine It is preferable to use at least one selected from the group consisting of oxide and 2,4,6-trimethylbenzoylphenylphosphine oxide sodium salt as a photopolymerization initiator.
• ⁇ -diketones examples include diacetyl, benzyl, camphorquinone, 2,3-pentadione, 2,3-octadione, 9,10-phenanthrenequinone, 4,4'-oxybenzyl, and acenaphthenequinone.
• camphorquinone is preferred when a light source in the visible light region is used.
• the content of the photopolymerization initiator in the composition (I) is not particularly limited, but from the viewpoint of the curability of the resulting composition, the amount of the photopolymerization initiator is 0.00 per 100 parts by weight of the component (A). 01 to 20 parts by mass is preferred. When the content of the photopolymerization initiator is 0.01 parts by mass or more, the polymerization can sufficiently proceed. From such a point of view, the content of the photopolymerization initiator in the composition (I) is more preferably 0.05 parts by mass or more with respect to 100 parts by mass of the component (A), and more preferably 0.1 parts by mass or more. It is preferably 0.5 parts by mass or more, and even more preferably 1.0 parts by mass or more.
• the content of the photopolymerization initiator is 20 parts by mass or less, precipitation from the composition is suppressed even when the solubility of the photopolymerization initiator itself is low.
• the content of the photopolymerization initiator in the composition (I) is more preferably 15 parts by mass or less, still more preferably 10 parts by mass or less, with respect to 100 parts by mass of the component (A). 0 parts by mass or less is even more preferable. As described above, these stepwise lower and upper limits can be independently combined.
• the content of the photopolymerization initiator in composition (I) is preferably 0.01 to 20 parts by mass, more preferably 0.01 to 20 parts by mass, per 100 parts by mass of component (A).
• Composition (I) may optionally contain components other than component (A) and the photopolymerization initiator as long as the gist of the present invention is not compromised.
• Composition (I) can be produced according to a known method.
• the composition (I) can contain a polymerization accelerator for the purpose of improving the photocurability within a range that does not impair the gist of the present invention.
• polymerization accelerators include 4-(N,N-dimethylamino)ethyl benzoate, 4-(N,N-dimethylamino)methyl benzoate, 4-(N,N-dimethylamino)benzoate n- butoxyethyl, 2-(methacryloyloxy)ethyl 4-(N,N-dimethylamino)benzoate, 4-(N,N-dimethylamino)benzophenone, butyl 4-(N,N-dimethylamino)benzoate be done.
• ethyl 4-(N,N-dimethylamino)benzoate, n-butoxyethyl 4-(N,N-dimethylamino)benzoate, from the viewpoint of imparting excellent curability to composition (I) , and 4-(N,N-dimethylamino)benzophenone is preferably used.
• One of the polymerization accelerators may be used alone, or two or more thereof may be used in combination.
• the composition (I) may contain a filler, if necessary, from the viewpoints of, for example, adjusting the viscosity of the composition, imparting strength to the denture base, imparting antibacterial properties, and the like.
• a filler examples include organic fillers, inorganic fillers, organic-inorganic composite fillers, and the like.
• a filler may be used individually by 1 type, and may use 2 or more types together.
• Materials for the organic filler include, for example, polymethyl methacrylate, polyethyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, crosslinked polymethyl methacrylate, crosslinked polyethyl methacrylate, polyester, polyamide, polycarbonate, Polyphenylene ether, polyoxymethylene, polyvinyl chloride, polystyrene, polyethylene, polypropylene, chloroprene rubber, nitrile rubber, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-styrene-butadiene A copolymer is mentioned. These may be used individually by 1 type, and may use 2 or more types together.
• the shape of the organic filler is not particularly limited, and the particle size of the filler can be appropriately selected and used.
• inorganic filler materials include quartz, silica, alumina, silica-titania, silica-titania-barium oxide, silica-zirconia, silica-alumina, lanthanum glass, borosilicate glass, soda glass, barium glass, strontium glass, glass-ceramic, aluminosilicate glass, barium boroaluminosilicate glass, strontium boroaluminosilicate glass, fluoroaluminosilicate glass, calcium fluoroaluminosilicate glass, strontium fluoroaluminosilicate glass, barium fluoroaluminosilicate glass, strontium calcium fluoroaluminosilicate glass be done. These may also be used individually by 1 type, and may use 2 or more types together.
• the shape of the inorganic filler is not particularly limited, and an amorphous filler, a spherical filler, or the like can be appropriately selected and used.
• organic-inorganic composite fillers examples include those in which inorganic fillers are dispersed in organic fillers, and organic-inorganic composite fillers in which inorganic fillers are coated with various polymerizable monomers.
• the content of the filler in the composition (I) is 100% by mass of the component (A). It is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, and still more preferably 1 part by mass or more.
• the content of the filler in the composition (I) is preferably 20 parts by mass or less with respect to 100 parts by mass of the component (A). , more preferably 10 parts by mass or less, and still more preferably 5 parts by mass or less.
• the content of the filler in the composition (I) is preferably 0.1 to 0.1 to 100 parts by mass of the component (A). 20 parts by mass, more preferably 0.5 to 10 parts by mass, still more preferably 1 to 5 parts by mass.
• a polymer may be added to the composition (I) for the purpose of improving flexibility, fluidity, etc., within the scope of the present invention.
• polystyrene-polyisoprene-polystyrene block copolymer polystyrene-polybutadiene-polystyrene block copolymer
• poly( ⁇ -methylstyrene)-polybutadiene-poly( ⁇ -methylstyrene ) block copolymers poly(p-methylstyrene)-polybutadiene-poly(p-methylstyrene) block copolymers, and hydrogenated products thereof.
• These polymers may be used individually by 1 type, and may use 2 or more types together.
• Softener Composition (I) may contain a softening agent, if desired.
• softening agents include petroleum softening agents such as paraffinic, naphthenic and aromatic process oils, and vegetable oil softening agents such as paraffin, peanut oil and rosin. These softeners may be used alone or in combination of two or more.
• the content of the softening agent in composition (I) is not particularly limited as long as it does not impair the gist of the present invention. to 30 parts by mass, more preferably 5 to 20 parts by mass.
• composition (I) may contain a known stabilizer for the purpose of suppressing deterioration or adjusting photocurability.
• the stabilizer include polymerization inhibitors, ultraviolet absorbers, and antioxidants.
• polymerization inhibitors examples include hydroquinone, hydroquinone monomethyl ether, dibutylhydroquinone, dibutylhydroquinone monomethyl ether, 4-t-butylcatechol, 2-t-butyl-4,6-dimethylphenol, 2,6-di-t- Butylphenol, 3,5-di-t-butyl-4-hydroxytoluene can be mentioned.
• the content of the polymerization inhibitor is preferably 0.001 to 5.0 parts by mass, more preferably 0.01 to 3.0 parts by mass, and 0.1 to 2.0 parts by mass with respect to 100 parts by mass of component (A). Parts by mass are more preferred.
• the composition (I) may contain a coloring agent within a range not impairing the gist of the present invention, for example, when it is desired to adjust the color tone of the denture base to a gingival color or the like.
• a coloring agent for example, pigments or dyes can be used.
• the pigments are roughly classified into inorganic pigments and organic pigments, and they may be used in combination.
• inorganic pigments include oxides, hydroxides, sulfides, chromates, silicates, sulfates, carbonates, ferrocyanic compounds, phosphates, carbon, etc. Among them, oxides are preferably used. . Specific examples of oxides include red iron oxide, yellow iron oxide, black iron oxide, titanium oxide (TiO 2 ), alumina, and zirconia. Red iron oxide is red iron oxide and hematite, which is iron oxide represented by the chemical formula Fe 2 O 3 . Yellow iron oxide is goethite, which is iron oxide represented by the chemical formula FeOOH, and black iron oxide. is magnetite, an iron oxide represented by the chemical formula Fe 3 O 4 .
• organic pigments examples include azo-based pigments, phthalocyanine pigments, condensed polycyclic pigments, nitro-based pigments, nitroso-based pigments, and fluorescent pigments. Among them, azo-based pigments and phthalocyanine pigments are preferably used. Specific examples of azo pigments include Novoperm Yellow 4G, Chromophtal Yellow 3G, Chromophtal Yellow 3RLP, Novoperm Red BN, Chromophtal Scarlet RN, Chromophtal Blue 4GNP, and Blue No. 2 Aluminum Lake. . Specific examples of phthalocyanine pigments include phthalocyanine blue and phthalocyanine green.
• the color tone of the composition (I) is desired to be a gingival color
• preferably red iron oxide is exemplified as a pigment that can be mainly used.
• the total content of the colorant in composition (I) is not particularly limited, but is preferably 0.0005, for example, per 100 parts by mass of component (A). ⁇ 5.0 parts by mass.
• the colorant is a pigment, the same applies to the preferred range of the total content.
• additives In addition to the above-described components, other known additives may be added to the composition (I) as necessary, such as for adjusting paste properties, within a range that does not impair the gist of the present invention.
• the other additives include thickeners, prepolymers (oligomers), aryl compounds (eg, aryliodonium salts), and the like. Such other additives may be used singly or in combination of two or more.
• the method for obtaining a denture base, which is a stereolithographic product of composition (I) is not particularly limited as long as it is stereolithography, and known methods and apparatuses can be used.
• known methods and apparatuses can be used.
• methods using a CAD/CAM system such as the method using a 3D printer for stereolithography described above can be used.
• the denture base that is a stereolithographic product of the composition (I) may be a denture base that is partially a stereolithographic product of the composition (I), and the entirety of the denture base is a stereolithographic product of the composition (I).
• the part that comes into contact with the adhesive composition described later is a stereolithographic object of composition (I), and the part that comes into contact with the adhesive composition described later is It is preferable that all of them are stereolithographic objects of the composition (I).
• the acrylic resin (II) is a component constituting the artificial tooth, and is a polymer of (meth)acrylic polymerizable monomers, preferably a polymer of (meth)acrylic acid ester polymerizable monomers. It is a coalescence.
• the (meth)acrylic polymerizable monomer that can be used in the acrylic resin (II) include various (meth)acrylic acid ester polymerizable compounds described in the section of the curable composition (I) above, And other examples include methyl methacrylate, ethyl methacrylate, and the like.
• the acrylic resin (II) may further contain a filler in order to impart strength and antibacterial properties to the artificial tooth.
• a filler examples include organic fillers, inorganic fillers, organic-inorganic composite fillers, and the like described in the section of the curable composition (I) above.
• a filler may be used individually by 1 type, and may use 2 or more types together.
• composition (II) may further contain a coloring agent, for example, from the viewpoint of matching the color tone of the artificial tooth to a crown color or the like.
• a coloring agent for example, from the viewpoint of matching the color tone of the artificial tooth to a crown color or the like.
• the coloring agent include various coloring agents described in the composition (I) section above. Colorants may be used singly or in combination of two or more.
• Composition (II) may also contain various additives used for other artificial teeth within the scope of the present invention.
• An artificial tooth is a cured product of acrylic resin (II), and the method for obtaining an artificial tooth made of acrylic resin (II) is not particularly limited, and any known method and apparatus can be used.
• the method for obtaining an artificial tooth made of acrylic resin (II) is not particularly limited, and any known method and apparatus can be used.
• the artificial tooth made of the cured acrylic resin (II) may be an artificial tooth partially made of the cured acrylic resin (II), or the whole is made of the cured acrylic resin (II).
• At least a part of the part that comes into contact with the adhesive composition described later is a cured product of acrylic resin (II), and the part that comes into contact with the adhesive composition described later. It is preferable that the cured product consists entirely of the acrylic resin (II).
• the adhesive composition includes a (meth)acrylic polymerizable monomer component (C ) containing composition (III) (hereinafter also simply referred to as “composition (III)”).
• composition (III) composition (hereinafter also simply referred to as “composition (III)”.
• the adhesive composition is used as an adhesive for bonding a denture base, which is a stereolithographic product of composition (I), and an artificial tooth made of acrylic resin (II).
• composition (III) as an adhesive, stronger adhesiveness can be obtained for the denture base, which is a stereolithographic product of composition (I).
• it has affinity with acrylic resin (II) it is presumed that the denture base and the artificial tooth can be adhered to each other more strongly.
• composition (III) is a (meth)acrylic polymerizable monomer component ( C) (hereinafter also simply referred to as “component (C)”).
• component (C) a (meth)acrylic polymerizable monomer component
• Composition (III) preferably has curability, more preferably photocurability.
• the (meth)acrylic polymerizable monomer component (C) is a component composed of one type of (meth)acrylic polymerizable monomer alone or two or more types, and the composition (I) contains the same monomer (m) as contained in As described above, the component (C) is a (meth)acrylic polymerizable monomer contained as a main monomer among the (meth)acrylic polymerizable monomers constituting the component (A). By containing the same (meth)acrylic polymerizable monomer as the monomer (m), excellent adhesiveness can be obtained.
• the same (meth)acrylic polymerizable monomer as the monomer (m) refers to being the same as the monomer (m) as a specific compound.
• the monomer (m) in component (A) is UDMA
• the monomer (m) that must be included in component (C) refers to UDMA. Therefore, for example, when the monomer (m) in component (A) is UDMA which is a polyfunctional monomer (a-1), component (C) is the same polyfunctional monomer ( Even if it contains Bis-GMA, which falls under the category of a-1), it does not mean that it contains "the same (meth)acrylic polymerizable monomer as the monomer (m)".
• component (m) when there are a plurality of monomers (m) serving as main monomers in component (A), for example, two kinds of (meth)acrylic polymerizable monomers are present in component (A), When each is contained in an amount of 50% by mass, component (C) may contain any one monomer (m) in component (A), and all monomers in component (A) The body (m) may not be included.
• the content of monomer (m) in component (C) is preferably 20% by mass or more, more preferably 30% by mass, based on 100% by mass of component (C). % or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 55% by mass or more, still more preferably 60% by mass or more, and even more preferably 65% by mass or more, for example , 100% by mass or less, preferably 98% by mass or less, more preferably 95% by mass or less, even more preferably 90% by mass or less, even more preferably 85% by mass or less, and even more preferably 80% by mass or less. As described above, these stepwise lower and upper limits can be independently combined.
• the content of the monomer (m) in the component (C) is preferably 20 to 100% by mass in 100% by mass of the component (C), more preferably 30 to 100% by mass, more preferably 40 to 98% by mass, even more preferably 50 to 95% by mass, even more preferably 55 to 90% by mass, even more preferably 60 to 85% by mass, still more preferably 65 to 80% by mass % by mass.
• the same (meth)acrylic polymerizable monomers as described above for the component (A) can be used.
• the type of (meth)acrylic polymerizable monomer is also the same as described above for component (A).
• the content of each (meth)acrylic polymerizable monomer that may be contained in the component (C) and its preferred range, as long as the content of the monomer (m) is satisfied the "component ( The content of component (A) is the same as described above except that the notation "A) in 100% by mass” is changed to "in component (C) in 100% by mass”.
• component (C) is a component composed of the monomer (m) alone or the monomer (m) and the monomer (o).
• Component (C) may contain a plurality of monomers (o). Therefore, the total content of monomer (m) and monomer (o) in component (C) is 100% by mass.
• the component (C) is not only the monomer (m) common to the component (A), but also the monomer (o ) preferably contains the same (meth)acrylic polymerizable monomer as in ).
• the same (meth)acrylic polymerizable monomer as the monomer (o) refers to the above-mentioned "the same (meth)acrylic polymerizable monomer as the monomer (m)”. is similar to Moreover, when component (A) contains a plurality of compounds as monomers (o), component (C) also preferably contains all of these compounds as monomers (o).
• the absolute value of the difference between the content of the monomer (m) in the component (C) and the content of the monomer (m) in the component (A) is 10 mass % or less, more preferably 5 mass % or less, even more preferably 3 mass % or less, and even more preferably 1 mass % or less.
• the absolute value of the difference between the content of monomer (m) in component (C) and the content of monomer (m) in component (A) is It is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, still more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass.
• the absolute value of the difference between the content of the monomer (o) in the component (C) and the content of the monomer (o) in the component (A) is 10% by mass or less. is preferably 5% by mass or less, more preferably 3% by mass or less, and even more preferably 1% by mass or less.
• the absolute value of the difference between the content of the monomer (o) in the component (C) and the content of the monomer (o) in the component (C) is preferably 0 to 10% by mass, more preferably 0 to 5% by mass, even more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass.
• component (A) contains a plurality of compounds as the monomer (o)
• component (C) also contains a plurality of the same compounds as the component (A) as the monomer (o)
• each corresponding The absolute value of the difference between the content of the compound in component (A) and the content in component (C) is also independently preferably 10% by mass or less, more preferably 5% by mass or less. Preferably, it is 3% by mass or less, and even more preferably 1% by mass or less.
• component (A) contains a plurality of compounds as monomers (o)
• component (C) also contains the same plurality of compounds as component (A) as monomers (o).
• the absolute value of the difference between the content of each corresponding compound in component (A) and the content in component (C) is also independently preferably 0 to 10% by mass, more preferably is 0 to 5% by mass, more preferably 0 to 3% by mass, and even more preferably 0 to 1% by mass.
• the total content of monomer (m) and monomer (o) in component (C) is 100% by mass.
• the component (C) is the (meth)acrylic polymerizable monomer component (A) obtained by (meth)acrylic polymerization.
• the content is preferably 70% by mass or more, more preferably 80% by mass or more, still more preferably 90% by mass or more, and 100% by mass. It is preferable to contain the following.
• the component (C) is obtained by adding the (meth)acrylic polymerizable monomer component (A) to 100 mass of the (meth)acrylic polymerizable monomer component (C) %, preferably 70 to 100 mass %, more preferably 80 to 100 mass %, still more preferably 90 to 100 mass %.
• the component (C) contains the (meth)acrylic polymerizable monomer component (A) in 100% by mass of the (meth)acrylic polymerizable monomer component (C). % by mass is even more preferable. That is, it is even more preferable to use component (A) as component (C).
• the composition of component (C) (combination of (meth)acrylic polymerizable monomers and content ratio (mass ratio) thereof) is the composition of component (A) ((meth)acrylic More preferably, the combination of polymerizable monomers and the content ratio (mass ratio) thereof are the same.
• the content of component (C) in composition (III) is preferably 40% by mass or more, more preferably 45% by mass, based on 100% by mass of composition (III). % or more, more preferably 50 mass % or more, still more preferably 60 mass % or more, still more preferably 80 mass % or more, still more preferably 90 mass % or more, still more preferably 95 mass % or more, and , 100% by mass or less, preferably 99.99% by mass or less, more preferably 99.5% by mass or less, even more preferably 99% by mass or less, and even more preferably 98% by mass or less. As described above, these stepwise lower and upper limits can be independently combined.
• the content of component (C) in composition (III) is preferably 40 to 100% by mass, more preferably 45 to 99% by mass, based on 100% by mass of composition (III). 99% by mass, more preferably 50 to 99.99% by mass, even more preferably 60 to 99.5% by mass, even more preferably 80 to 99% by mass, even more preferably 90 to 99% by mass, still more preferably is 95 to 98% by mass.
• composition (III) may contain components other than component (C), if necessary, within the scope of the present invention.
• Composition (III) can be produced according to a known method.
• Composition (III) preferably contains a photopolymerization initiator from the viewpoint of improving adhesiveness.
• the photopolymerization initiator that can be used in the composition (III) include the same photopolymerization initiators as those described above for the photopolymerization initiator contained in the composition (I).
• the type of is also the same as the content described above in the column of composition (I).
• composition (III) contains a photopolymerization initiator
• the preferred content range is also changed from “composition (I)” to “composition (III)”
• the content of the photopolymerization initiator contained in composition (I) is the same as described above, except that the notation of "component (A) 100 parts by mass” is changed to “component (C) 100 parts by mass”.
• composition (III) may contain a polymerization accelerator within the scope of the present invention.
• Polymerization accelerators that can be used in composition (III) include the same polymerization accelerators as those previously described as polymerization accelerators that composition (I) may contain.
• One of the polymerization accelerators may be used alone, or two or more thereof may be used in combination.
• the composition (III) may contain a filler to adjust the viscosity of the composition within the scope of the present invention.
• a filler to adjust the viscosity of the composition within the scope of the present invention.
• examples of fillers that can be used in the composition (III) include the organic fillers, inorganic fillers, organic-inorganic composite fillers, etc. described in the section of the curable composition (I) above.
• a filler may be used individually by 1 type, and may use 2 or more types together.
• the content of the filler in the composition (III) is preferably 0 with respect to 100 parts by mass of the component (C). 0.1 parts by mass or more, more preferably 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more.
• the content of the filler in the composition (III) is preferably 10 parts by mass or less with respect to 100 parts by mass of the component (C). More preferably 5 parts by mass or less, still more preferably 3 parts by mass or less.
• the content of the filler in the composition (III) is preferably 0.1 to 0.1 to 100 parts by mass of the component (C). 10 parts by mass, more preferably 0.3 to 5 parts by mass, still more preferably 0.5 to 3 parts by mass.
• composition (III) may contain a polymer within the scope of the present invention.
• examples of the polymer that can be used in the composition (III) include the same polymers as those described above as the polymer that the composition (I) may contain.
• a polymer may be used individually by 1 type, and may use 2 or more types together.
• a known stabilizer can be added to the composition (III) for the purpose of suppressing deterioration or adjusting curability.
• the stabilizer include polymerization inhibitors, ultraviolet absorbers, and antioxidants.
• Polymerization inhibitors that can be used in composition (III) include the same polymers as those previously described as polymerization inhibitors that composition (I) may contain.
• a polymerization inhibitor may be used individually by 1 type, and may use 2 or more types together.
• the content of the polymerization inhibitor is preferably 0.001 to 5.0 parts by weight, preferably 0.01 to 3.0 parts by weight, based on 100 parts by weight of the component (C). Parts by mass are more preferable, and 0.1 to 2.0 parts by mass are even more preferable.
• composition (III) brings the color tone of the adhesive composition closer to the color tone of the denture base or the artificial tooth, thereby further improving the appearance of the resulting denture, and thus does not impair the gist of the present invention.
• it may contain coloring agents.
• the coloring agent include various coloring agents described in the section of composition (I) above. Colorants may be used singly or in combination of two or more.
• red iron oxide is preferably exemplified as a pigment that can be mainly used.
• the adhesive composition is desired to be colored to the color tone of an artificial tooth, for example, a crown color, it preferably contains titanium oxide or alumina as a main component, and red iron oxide, yellow iron oxide, black iron oxide, or black It is preferable to adjust the blending amount of iron oxide.
• the phrase "mainly containing titanium oxide or alumina" means that the coloring agent contained in the composition in the largest amount is titanium oxide or alumina.
• the total content of the colorant in the composition (III) is not particularly limited, but is preferably 0.0005, for example, relative to 100 parts by mass of the component (C). ⁇ 5.0 parts by mass.
• the colorant is a pigment, the same applies to the preferred range of the total content.
• additives may be added to the composition (III) as necessary, for example, to adjust the paste properties, within a range that does not impair the gist of the present invention.
• the other additives include thickeners, softeners, prepolymers (oligomers), aryl compounds (eg, aryliodonium salts), and the like. Such other additives may be used singly or in combination of two or more.
• the composition (III) contains the composition (I) in an amount of 70% by mass or more based on 100% by mass of the composition (III).
• the content is preferably 80% by mass or more, more preferably 90% by mass or more, and preferably 100% by mass or less.
• the composition (III) contains the composition (I) in 100% by mass of the composition (III), preferably 70 to 100% by mass, more preferably 80 to 100% by mass %, more preferably in the range of 90 to 100% by mass.
• the adhesive composition may optionally contain components other than the composition (III) as long as the gist of the present invention is not impaired.
• polymerizable monomers, organic solvents, and other additives not included in composition (III) are blended.
• organic solvents include ethyl acetate, butyl acetate, methylene chloride, acetone, ethanol, isopropanol, methyl methacrylate and the like.
• An organic solvent may be used individually by 1 type, and may use 2 or more types together. Among these, ethyl acetate, ethanol, and isopropanol are preferable from the viewpoint of safety and moderate volatility.
• the content of the organic solvent is preferably 90% by mass or less, more preferably 80% by mass or less, and still more preferably 100% by mass of the adhesive composition. It is 60% by mass or less, more preferably 50% by mass or less, even more preferably 40% by mass or less, still more preferably 20% by mass or less, and even more preferably 10% by mass or less.
• the lower limit of the content of the organic solvent is not particularly limited. is. As described above, these stepwise lower and upper limits can be independently combined.
• the content of the organic solvent is preferably 1 to 90% by mass in 100% by mass of the adhesive composition, and more Preferably 1 to 80% by mass, more preferably 1 to 60% by mass, still more preferably 1 to 50% by mass, still more preferably 1 to 40% by mass, still more preferably 1 to 20% by mass, still more preferably is 1 to 10% by mass.
• the content of the composition (III) is preferably 10% by mass or more, more preferably 20% by mass or more, based on 100% by mass of the adhesive composition. preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, still more preferably 80% by mass or more, still more preferably 90% by mass or more, and 100% by mass It is preferable to contain the following.
• the content of composition (III) is preferably 10 to 100% by mass, more preferably 20 to 100% by mass, and still more preferably 100% by mass of the adhesive composition.
• the adhesive composition further preferably contains 100% by mass of composition (III) in 100% by mass of the adhesive composition. That is, it is even more preferable to use composition (III) as the adhesive composition.
• a step of bonding a denture base, which is a photofabricated article of composition (I), and an artificial tooth made of acrylic resin (II) using the adhesive composition (hereinafter simply referred to as " Also referred to as "adhesion step”.) is not particularly limited. That is, a denture, characterized in that a denture base, which is a stereolithographic product of the composition (I), and an artificial tooth made of the acrylic resin (II) are adhered using the adhesive composition.
• a method of adhering a floor and an artificial tooth is also included in one aspect of the present invention.
• the adhesive composition is applied to the adhesive surface of one or both of the denture base and the artificial tooth, and the denture base and the artificial tooth are attached via the adhesive composition.
• the denture base and the artificial tooth can be bonded together by laminating them together and curing the adhesive composition.
• Step (2) Applying the adhesive composition to the denture base and the artificial tooth. crimping each other through
• Step (3) A step of bonding the denture base and the artificial tooth by photocuring the adhesive composition.
• the method of applying the adhesive composition to the denture base and/or artificial teeth is not particularly limited, and known methods and instruments or devices can be used. For example, it can be applied manually using a brush or the like.
• the surface of the denture base that comes into contact with the adhesive composition may be previously polished before use.
• the surface of the artificial tooth that comes into contact with the adhesive composition may be previously polished before use.
• the method for manufacturing a denture which is one aspect of the present invention, it is possible to manufacture a denture in which the denture base and the artificial tooth are strongly bonded together and the denture base and the artificial tooth are integrated.
• secondary polymerization is usually carried out after the stereolithography to polymerize unreacted polymerizable monomers derived from the composition forming the stereolithography.
• the method for carrying out the secondary polymerization is not particularly limited, and conventionally known methods and devices can be used, and a method using a dental light irradiator, a secondary polymerization device for stereolithography, or the like may be used. .
• the adhesive composition is applied to the denture base and/or the artificial tooth, and a bonding operation is performed to obtain higher adhesiveness. Therefore, the denture base and the artificial tooth include cases before secondary polymerization. Before the secondary polymerization, the adhesive composition is applied, and then the secondary polymerization is carried out, whereby the unreacted polymerizable monomer of the denture base and/or the artificial tooth and the adhesive composition are Since it can be copolymerized with the constituent polymerizable monomers, it is thought that higher adhesiveness is likely to be obtained.
• the method for manufacturing a denture which is one aspect of the present invention, is characterized by excellent adhesiveness even in a state in which polymerization has progressed to a high degree after the above-described secondary polymerization and after a long time has passed since stereolithography. Therefore, it is possible to manufacture a denture with sufficiently excellent adhesiveness even after a long time has passed since the manufacture of the denture base and/or the artificial tooth.
• a conventionally known dental light irradiation device for example, Morita Co., Ltd. “ ⁇ -Light V”
• a post cure for stereolithography A device (for example, "Otoflash (registered trademark) G171" manufactured by EnvisionTEC) can be used.
• an active energy ray as the light energy for curing the adhesive composition. That is, it is preferable to bond the denture base and the artificial tooth by irradiating the adhesive composition with an active energy beam and curing the adhesive composition.
• Step (3) is more preferably the following step (3A).
• active energy ray means energy rays such as ultraviolet rays, electron beams, X-rays, radiation, high frequency rays, etc., capable of curing the resin composition for stereolithography.
• Light sources for active energy rays include halogen lamps, xenon lamps, metal halide lamps, LEDs, mercury lamps, fluorescent lamps, and the like. Among these, halogen lamps and LEDs are preferred.
• TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
• curable composition (I)-1 700 g of UDMA, 300 g of POBA, 30 g of TPO, and 5.0 g of BHT were placed in a 2 L brown wide-mouthed polyethylene bottle, and a mechanical stirrer was inserted to stir at 25° C. for 48 hours to confirm that they were completely dissolved. confirmed. The resulting composition was designated as curable composition (I)-1.
• the composition of curable composition (I)-1 is shown in Table 1 below.
• curable composition (I)-2 600 g of Bis-GMA, 400 g of POBA, 30 g of TPO, and 5.0 g of BHT were placed in a 2 L wide-mouthed brown polyethylene bottle, and a mechanical stirrer was inserted to stir at 25° C. for 48 hours to completely dissolve. It was confirmed. The resulting composition was designated as curable composition (I)-2.
• the composition of curable composition (I)-2 is shown in Table 1 below.
• curable composition (I)-3 900 g of TCDDMA, 100 g of EPPA, 30 g of TPO, and 5.0 g of BHT were added to a 2 L wide-mouthed brown polyethylene bottle, and a mechanical stirrer was inserted to stir at 25° C. for 48 hours to confirm that they were completely dissolved. confirmed. The resulting composition was designated as curable composition (I)-3.
• the composition of curable composition (I)-3 is shown in Table 1 below.
• curable composition (I)-4 Put 700 g of UDMA, 300 g of TEGDMA, 30 g of TPO, and 5.0 g of BHT into a 2 L brown wide-mouthed polyethylene bottle, insert a mechanical stirrer, and stir at 25° C. for 48 hours to confirm that they are completely dissolved. confirmed. The resulting composition was designated as curable composition (I)-4.
• the composition of curable composition (I)-4 is shown in Table 1 below.
• curable composition (I)-5 900 g of TCDDMA, 100 g of TEGDMA, 30 g of TPO, and 5.0 g of BHT were added to a 2 L wide-mouthed brown polyethylene bottle, and a mechanical stirrer was inserted to stir at 25° C. for 48 hours to confirm that they were completely dissolved. confirmed. The resulting composition was designated as curable composition (I)-5.
• the composition of curable composition (I)-5 is shown in Table 1 below.
• curable composition (I)-6 Put 400 g of UDMA, 300 g of TEGDMA, 300 g of POBA, 30 g of TPO, and 5.0 g of BHT into a 2 L brown wide-mouthed polyethylene bottle, insert a mechanical stirrer, and stir at 25° C. for 48 hours to completely dissolve. I confirmed that I did. The resulting composition was designated as curable composition (I)-6.
• the composition of curable composition (I)-6 is shown in Table 1 below.
• BV resin teeth "Bellacia (registered trademark)” (manufactured by Shofu Co., Ltd.)
• BS Resin teeth "Surpass (registered trademark)” (manufactured by GC Corporation)
• Examples 1 to 9 and Comparative Examples 1 to 6 As described below, the optically modeled article of the curable composition (I) obtained in each reference example and the artificial tooth made of the acrylic resin (II) were combined as shown in Tables 2 and 3 below. Using the adhesive described below, the adhesive was adhered according to the method described later, photo-cured to prepare a test piece, and the adhesion was evaluated. In Examples 1 to 6 and Comparative Examples 1 to 5, composition (III) having the same composition as curable composition (I) shown in Tables 2 and 3 was used as an adhesive.
• Example 9 the curable composition (I)-1 obtained in Reference Example 1 was diluted to 40% by mass with PMMA (polymethyl methacrylate “Hypar (registered trademark) D-250ML”, manufactured by Negami Kogyo Co., Ltd.).
• Composition (III) which has the same composition as curable composition (I)-1, was added to 15% by mass with ethyl acetate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.).
• a diluted adhesive composition was used as the adhesive.
• "Unifast (registered trademark) III” was used as the adhesive.
• the base surfaces of the resin teeth "BV” and “BS” were polished with #600 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) to form flat surfaces.
• JIS T6611: Method B of 2009 is applied mutatis mutandis, and the resin tooth is used as an embedding material for dental impression tray resin (trade name: "Tray Resin (registered trademark) II", manufactured by Shofu Co., Ltd.). , embedded in a stainless steel ring holder for fitting in a jig for shear testing.
• the polished surface of the resin tooth is parallel to the ground surface of the stainless ring holder. It was embedded so that it was fixed so that it would be so that it would be fine and exposed from the embedding material. Thereafter, the resin tooth and embedding material in the stainless steel ring holder were polished with #600 silicon carbide paper (manufactured by Nihon Kenshi Co., Ltd.) under running water. The polished surface of the resin tooth was polished so as not to be higher than the contact surface of the stainless ring holder and not higher than 1 mm from the surface of the embedding material. After polishing, water on the surface of the resin tooth was dried by air blowing to obtain an adherend corresponding to an artificial tooth.
• #600 silicon carbide paper manufactured by Nihon Kenshi Co., Ltd.
• the adhesive is applied to the polished surface of the adherend corresponding to the denture base obtained.
• About 0.01 is applied with a brush, the polished surface of the adherend corresponding to the artificial tooth is pressed, and the excess adhesive is wiped off. ) was flashed 1000 times.
• a total of 5 test samples were prepared, stored in water at 37 ° C.
• the adhesive strength is 5 MPa or more, it can be used clinically, if it is 10 MPa or more, it is as good as the conventional method, and if it is 15 MPa or more, it is extremely excellent adhesive strength exceeding the conventional method. .
• the state of the interface of the test piece after the measurement was observed, and if either the adherend corresponding to the denture base photofabricated from the curable composition (I) or the adhesive was destroyed, the adhesiveness was evaluated. "A” is considered to be excellent, and the adherend corresponding to the denture base stereolithographed from the curable composition (I), or the artificial tooth made of the acrylic resin (II). It was rated as "F” because it was inferior in terms of durability. The results are shown in Tables 2 and 3 below.

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