WO2023042915A1 - 光造形用有床義歯作製キット、及び有床義歯の製造方法 - Google Patents
光造形用有床義歯作製キット、及び有床義歯の製造方法 Download PDFInfo
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- WO2023042915A1 WO2023042915A1 PCT/JP2022/034835 JP2022034835W WO2023042915A1 WO 2023042915 A1 WO2023042915 A1 WO 2023042915A1 JP 2022034835 W JP2022034835 W JP 2022034835W WO 2023042915 A1 WO2023042915 A1 WO 2023042915A1
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- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 125000002889 tridecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 description 1
- 125000002948 undecyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 235000015112 vegetable and seed oil Nutrition 0.000 description 1
- 239000008158 vegetable oil Substances 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- 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
- A61C13/08—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
- A61C13/10—Fastening of artificial teeth to denture palates or the like
-
- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/78—Pigments
Definitions
- the present invention provides a specific denture base using a stereolithographic denture base preparation kit composed of a stereolithographic denture base curable composition and an artificial tooth composition, and a specific adhesive composition.
- the present invention relates to a method for manufacturing a denture, characterized by adhering an artificial tooth to a denture.
- 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 it is generally necessary to bond a photolithographic floor and an artificial tooth.
- the artificial teeth include, for example, PMMA artificial teeth produced by injection molding, hard resin teeth produced by cutting, and artificial teeth shaped from a photocurable resin composition different from the base.
- 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. Further, Patent Document 2 describes an example of a denture base material excellent in strength and toughness for stereolithography.
- Patent Literatures 1 and 2 do not describe the strength and toughness of the denture base and artificial teeth bonded together. Accordingly, an object of the present invention is to provide a denture excellent in strength and toughness in combination of a denture base and an artificial tooth produced by stereolithography.
- the present invention includes the following inventions.
- Curing for denture base containing a (meth)acrylic polymerizable monomer component (A) containing a (meth)acrylic polymerizable monomer (m) as a main monomer and a photopolymerization initiator sexual composition (I); containing a (meth)acrylic polymerizable monomer component (B) containing the same (meth)acrylic polymerizable monomer (m) as contained in the denture base curable composition (I); A composition for artificial teeth, wherein the content of the (meth)acrylic polymerizable monomer (m) is 20% by mass or more in 100% by mass of the (meth)acrylic polymerizable monomer component (B).
- the kit for manufacturing a fixed denture for stereolithography according to [2] above, wherein the (meth)acrylic polymerizable monomer (m) is a polyfunctional (meth)acrylic polymerizable monomer (a-1). Denture preparation kit for use. [3] 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 kit for manufacturing a fixed denture for stereolithography according to [2] above, which is at least one selected from acid ester compounds.
- the monofunctional (meth)acrylic polymerizable monomer (a-2) is an aromatic ring-containing (meth)acrylic acid ester polymerizable monomer, or [5] The kit for manufacturing a fixed denture for stereolithography.
- the content of the (meth)acrylic polymerizable monomer (m) is the same as the (meth)acrylic polymerizable monomer component (A).
- the kit for making a plated denture for stereolithography according to any one of [1] to [6], which is 50% by mass or more in 100% by mass.
- the content of the (meth)acrylic polymerizable monomer (m) is 100 mass of the (meth)acrylic polymerizable monomer component (B). %, the kit according to any one of the above [1] to [7], which is 50% by mass or more. [9] The above [1] to [8, wherein the (meth)acrylic polymerizable monomer component (A) is contained in an amount of 40% by mass or more based on 100% by mass of the curable composition for denture base (I). ] The kit for manufacturing a plate denture for stereolithography according to any one of .
- an artificial tooth made of a hardened material of material (II), containing a (meth)acrylic polymerizable monomer component (C) containing the same (meth)acrylic polymerizable monomer (m) as contained in the denture base curable composition (I); , a composition (III ).
- 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.
- the terms “strength” and “toughness” refer to the “strength” and “toughness” of the denture produced from the kit for producing a plated denture for stereolithography, which is one aspect of the present invention. "Toughness”.
- the term “denture” refers to a denture manufactured from a kit for manufacturing a plate denture for stereolithography, which is one aspect of the present invention.
- a kit for making a fixed denture for stereolithography which is one aspect of the present invention, includes a (meth)acrylic polymerizable monomer component (A ), and a denture base curable composition (I) containing a photopolymerization initiator, and the same (meth)acrylic polymerizable monomer contained in the denture base curable composition (I) (m) containing a (meth)acrylic polymerizable monomer component (B), wherein the content of the (meth)acrylic polymerizable monomer (m) is a (meth)acrylic polymerizable monomer and an artificial tooth composition (II) that is 20% by mass or more in 100% by mass of the polymer component (B).
- composition (I) contains a (meth)acrylic polymerizable monomer (m) (hereinafter simply A (meth)acrylic polymerizable monomer component (A) (hereinafter also simply referred to as “component (A)”) containing (also referred to as “monomer (m)”), and a photopolymerization initiator do.
- 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 (B)” and “(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 30% by mass 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, still more preferably 65% by mass or more, for example, 100% by mass %, 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.
- the content of the monomer (m) in component (A) is preferably 30 to 100% by mass, more preferably 40 to 98% by mass, in 100% by mass of component (A). %, 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 %.
- 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 (meth)acrylic polymerizable monomers constituting 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)acryl as a main monomer. More preferably, the system polymerizable monomer (m) is the polyfunctional monomer (a-1).
- the component (A) preferably contains a monofunctional monomer (a-2), and from the viewpoint of improving the strength and toughness of the denture, the polyfunctional monomer (a-1 ) and a monofunctional monomer (a-2), including a polyfunctional monomer (a-1) as a main monomer, and further a monofunctional monomer (a- 2) is even more preferred.
- 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-based (meth)acrylic acid ester compound containing no urethane bond, and At least one selected from the group consisting of alicyclic (meth)acrylic acid ester compounds is preferable, and urethanized (meth)acrylic acid ester compounds and aromatic compound-based (meth)acrylic acid ester compounds that do not contain urethane bonds At least one selected from is more preferable, and a urethane-modified (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.
- urethane-modified (meth)acrylic acid ester compounds with urethane bonds have a great effect of imparting toughness to dentures, so breakage and cracks from the adhesive interface and coating film are less likely to occur, and the resulting dentures have better bending properties. It is preferable because strength can be expressed.
- 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).
- the weight-average molecular weight of the urethanized (meth)acrylic acid ester compound is preferably 1,000 or less, from the viewpoints that the composition (I) has a low viscosity and can be easily shaped, and from the viewpoint that a decrease in the strength of the denture can be suppressed.
- the weight average molecular weight is more preferably 750 or less, even more preferably 500 or less.
- 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. It is the same from the viewpoint that it becomes easy to be broken and it becomes easy to improve the strength of the denture.
- 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 concentration of polar functional groups can be suppressed, and a decrease in the strength of the denture 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 the strength of the denture in the presence of water.
- 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 used from the viewpoint of making it easier for dentures to exhibit excellent high strength.
- 2-hydroxyethyl (meth)acrylate is preferred, and 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), the urethaned (meth)acrylic acid ester compound in component (A)
- 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 strength of the denture. is more preferable, and 60 to 80% by mass is even more preferable.
- the content of the urethanized (meth)acrylic acid ester compound is the polyfunctional monomer In total 100% by mass of the body (a-1), preferably 50 to 100% by mass, more preferably 60 to 100% by mass, still more preferably 70 to 100% by mass, even more preferably 80 to 100% by mass, more More preferably 90 to 100 mass %, still more preferably 95 to 100 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
- a compound containing a hydroxyl group is preferable.
- 2,2-bis[4-(3-methacryloyloxy-2-hydroxypropoxy)phenyl]propane is more preferred.
- 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 strength of the denture, 10 It is more preferably up to 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, and triethylene glycol di(meth)acrylate are preferred from the viewpoint of better strength of the denture.
- Ethylene 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 strength and toughness of the denture. It is more preferably 55 to 85% by mass, 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 composition (I) and reduces the crosslink density of the resulting molded product, thereby further improving the toughness of the denture.
- 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.
- (Meth)acrylic acid ester-based polymerizable monomer containing 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 of the obtained composition and improving the strength of the denture.
- 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, more preferably 10 to 50% by mass, from the viewpoint of improving the strength and toughness of the denture. It is more preferably 15 to 45% by mass, 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 the component (A) in the denture base curable composition (I) is preferably 40% by mass in 100% by mass of the composition (I). % or more, more preferably 45% 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, and even more preferably 90% by mass or more, and It is 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 (A) in curable composition (I) for denture base is preferably 40 to 99.99% by mass, based on 100% by mass of composition (I), More preferably 45 to 99.99% by mass, still more preferably 50 to 99.5% by mass, even more preferably 60 to 99.5% by mass, still 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 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)phenyl phosphine oxide, bis(2,5,6-trimethylbenzo
- (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).
- the curable composition for denture base (I) may optionally contain components other than the aforementioned component (A) and the photopolymerization initiator within the scope of the present invention.
- Composition (I) can be produced according to a known method.
- the denture base curable composition (I) may contain a coloring agent, for example, from the viewpoint of toning the color tone of the denture base to a gum color or the like.
- the method for toning the composition (I) is not particularly limited, and for example, it can be toned by blending a known coloring agent.
- the 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 composition (I) preferably satisfies the following condition (1).
- Condition (1) L * a * of a test piece having a diameter of 15.0 ⁇ 0.1 and a thickness of 1.00 ⁇ 0.01 mm, formed from the cured denture base curable composition (I).
- b * Chromaticity on a white background according to the color system is 70.0 ⁇ L * white ⁇ 90.0, 10.0 ⁇ a * white ⁇ 25.0 (preferably 10.0 ⁇ a * white ⁇ 25.0). 0), 10.0 ⁇ b * white ⁇ 35.0, and 10.0 ⁇ L ⁇ 40.0.
- red iron oxide is preferably exemplified as a pigment that can be mainly used.
- the lightness difference ⁇ L between the lightness L * black obtained by colorimetry with a black background and the lightness L * white obtained by colorimetry with a white background according to the L * a * b * color system is preferably 10.0 or more.
- the value of a * white measured against a white background according to the L * a * b * color system is 15.0 ⁇ 0.1 in diameter and 15.0 ⁇ 0.1 in thickness formed from the cured composition (II) for artificial teeth. It is preferably larger than the a * white value measured on a white background according to the L * a * b * color system of a test piece with a thickness of 1.00 ⁇ 0.01 mm.
- the total content of the coloring agent in the composition (I) is not particularly limited. For example, it is preferably 0.0005 to 5.0 parts by mass. When the total content of the colorants in composition (I) is 0.0005 parts by mass or more, it is preferable because it facilitates imparting a desired color tone. On the other hand, when the total content of the colorants is 5.0 parts by mass or less, the effect on the curability of the composition (I) can be suppressed, and the reduction in toughness of the denture can be suppressed, which is preferable.
- the total content of the colorants in composition (I) is more preferably 0.0008 parts by mass or more, still more preferably 0.001 parts by mass or more, relative to 100 parts by mass of component (A). and more preferably 1.0 parts by mass or less, and still more preferably 0.5 parts by mass or less.
- these stepwise lower and upper limits can be independently combined.
- the total content of the colorant in composition (I) is preferably 0 per 100 parts by mass of component (A). 0.0005 to 5.0 parts by mass, more preferably 0.0008 to 1.0 parts by mass, still more preferably 0.001 to 0.5 parts by mass.
- the colorant is a pigment
- the preferred range of the total content is the same as the total content of the colorant.
- the composition (I) may 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 0.3 parts by mass or more, and still more preferably 0.5 parts by mass or more.
- the content of the filler in composition (I) is It is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 5 parts by mass or less based on 100 parts by mass of component (A).
- these stepwise lower and upper limits can be independently combined.
- 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 0.3 to 10 parts by mass, still more preferably 0.5 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.
- stabilizer A known stabilizer can be added to the composition (I) for the purpose of suppressing deterioration or adjusting photocurability.
- examples of 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.
- Composition (I) may contain other known additives in addition to the components described above, as long as the gist of the present invention is not impaired, for example, adjustment of paste properties, etc.
- the other additives include thickeners, prepolymers (oligomers), aryl compounds (eg, aryliodonium salts), and the like. These other additives may be used singly or in combination of two or more.
- composition (II) contains the same (meth)acrylic polymer as contained in the denture base curable composition (I).
- (Meth)acrylic polymerizable monomer component (B) (hereinafter also simply referred to as "component (B)") containing a polymonomer (m).
- the composition (II) preferably has curability, more preferably photocurability.
- the (meth)acrylic polymerizable monomer component (B) is a component composed of one type of (meth)acrylic polymerizable monomer alone or two or more types, and the composition (I) 20% by mass or more of the same monomer (m) as contained in component (B) in 100% by mass. That is, the component (B) is a (meth)acrylic polymerizable monomer contained as a main monomer among the (meth)acrylic polymerizable monomers constituting the component (A).
- the same (meth)acrylic polymerizable monomer as component (m) must be contained in an amount of 20% by mass or more based on 100% by mass of component (B).
- 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
- component (B) in 100% by mass of component (B), 20% by mass or more of monomer (m) and refers to the UDMA.
- component (B) is the same polyfunctional monomer ( Bis-GMA, which falls under the category a-1), in 100% by mass of the component (B), even if it contains 20% by mass or more, it alone has the same (meth)acrylic polymerizability as the monomer (m). not contain "monomers".
- component (A) 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),
- component (B) When each is contained at 50% by mass, component (B) may contain at least 20% by mass of any one monomer (m) in component (A). It does not have to contain all monomers (m) in an amount of 20% by mass or more.
- the content of the monomer (m) in the component (B) is preferably 30% by mass or more, more preferably 30% by mass or more, based on 100% by mass of the component (B). is 40% by mass or more, more preferably 50% by mass or more, even more preferably 55% by mass or more, even more preferably 60% by mass or more, and even more preferably 65% by mass or more, for example, 100% by mass or less, It is 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 component (B) is 20 to 100% by mass, preferably 30 to 100% by mass, based on 100% by mass of component (B). , More preferably 40 to 98% by mass, still 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 .
- the same (meth)acrylic polymerizable monomers as those 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 component (B) and its preferred range are also such that the monomer (m) is 20% by mass in 100% by mass of component (B). % or more of component (A), except that the expression "in 100% by mass of component (A)" is changed to "in 100% by mass of component (B)".
- the component (B) is a component composed of the monomer (m) alone or the monomer (m) and the monomer (o). Moreover, the component (B) may contain a plurality of monomers (o). Therefore, the total content of monomer (m) and monomer (o) in component (B) is 100% by mass.
- the component (B) 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 Further, when component (A) contains a plurality of compounds as monomers (o), component (B) 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 (B) 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 the monomer (m) in the component (B) and the content of the monomer (m) in the 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 (B) 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 (B) and the content of the monomer (o) in the component (A) 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 monomers (o) and component (B) also contains a plurality of the same compounds as component (A) as monomers (o)
- each corresponding The absolute value of the difference between the content of the compound in component (A) and the content in component (B) 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 (B) 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 (B) 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 (B) is 100% by mass.
- the component (B) comprises the (meth)acrylic polymerizable monomer component (A), (meth) In 100% by mass of the acrylic polymerizable monomer component (B), the content is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and It is preferable to contain 100% by mass or less.
- the component (B) is obtained by adding the (meth)acrylic polymerizable monomer component (A) to 100 mass of the (meth)acrylic polymerizable monomer component (B) %, preferably 70 to 100 mass %, more preferably 80 to 100 mass %, still more preferably 90 to 100 mass %. Further, in this aspect, the component (B) contains the (meth)acrylic polymerizable monomer component (A) in 100% by mass of the (meth)acrylic polymerizable monomer component (B). % by mass is even more preferable. That is, it is even more preferable to use component (A) as component (B).
- the composition of the component (B) (the “composition” represents a "(meth)acrylic polymerizable monomer combination and its content ratio (mass ratio)".
- component ( “Composition of A)” and “Composition of Component (C)” have the same meaning.) is more preferably the same as the composition of Component (A).
- the content of the component (B) in the composition (II) for artificial teeth is preferably 40% by mass or more, based on 100% by mass of the composition (II). , More preferably 45% 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, still more preferably 95% by 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 (B) in composition (II) for artificial teeth is preferably 40 to 100% by mass, more preferably 45% by mass, based on 100% by mass of composition (II). ⁇ 99.99% 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, still more preferably 90 to 99% by mass, Even more preferably, it is 95 to 98% by mass.
- composition for artificial teeth (II) may optionally contain components other than the component (B) as long as the gist of the present invention is not impaired.
- Composition (II) can be produced according to a known method.
- Composition (II) preferably contains a photopolymerization initiator from the viewpoint of improving the strength and toughness of the denture.
- the photopolymerization initiator that can be used in the composition (II) 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 described above in the column of composition (I).
- composition (II) contains a photopolymerization initiator
- the preferred content range is also changed from “composition (I)” to “composition (II)”
- the content of the photopolymerization initiator contained in the composition (I) is the same as described above, except that the notation “component (A) 100 parts by mass” is changed to “component (B) 100 parts by mass”.
- the composition (II) may contain a coloring agent, for example, from the viewpoint of toning the color tone of the artificial tooth to a crown color or the like.
- the method for toning the composition (II) is not particularly limited, and for example, it can be toned by blending a known coloring agent.
- Colorants include, for example, the same colorants as those described above for the colorants that composition (I) may contain.
- the composition (II) preferably satisfies the following condition (2).
- Condition (2) L * a * b * of a test piece having a diameter of 15.0 ⁇ 0.1 and a thickness of 1.00 ⁇ 0.01 mm formed from the cured product of the artificial tooth composition (II) Chromaticity on a white background according to the color system is 70.0 ⁇ L * white ⁇ 90.0, -4.0 ⁇ a * white ⁇ 10.0, 10.0 ⁇ b * white ⁇ 35.0, 10 .0 ⁇ L ⁇ 40.0.
- titanium oxide or alumina as a main component, and red iron oxide, yellow oxide
- the blending amounts of iron and black iron oxide are adjusted.
- 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 lightness difference ⁇ L between the lightness L * black obtained by colorimetry with a black background and the lightness L * white obtained by colorimetry with a white background in the a * b * color system is preferably 10.0 to 40.0. 0 or less, more preferably 10.0 or more and 20.0 or less, still more preferably 10.0 or more and 18.0 or less.
- the total content of the coloring agent in the composition (II) is not particularly limited. For example, it is preferably 0.0005 to 5.0 parts by mass. When the total content of the colorants in the composition (II) is 0.0005 parts by mass or more, it is preferable because it facilitates imparting a desired color tone. On the other hand, when the total content of the colorants is 5.0 parts by mass or less, the effect on the curability of the composition (II) can be suppressed, and a decrease in the toughness of the denture can be suppressed, which is preferable.
- the total content of the colorant in composition (II) is more preferably 0.0008 parts by mass or more, still more preferably 0.001 parts by mass or more, relative to 100 parts by mass of component (B). , more preferably 0.005 parts by mass or more, more preferably 1.0 parts by mass or less, and even more preferably 0.5 parts by mass or less.
- these stepwise lower and upper limits can be independently combined.
- the total content of the colorant in the composition (II) is preferably 0 with respect to 100 parts by mass of the component (B).
- the colorant is a pigment
- the preferred range of the total content is the same as the total content of the colorant.
- composition (II) may contain a polymerization accelerator within the scope of the present invention.
- Polymerization accelerators that can be used in composition (II) 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.
- a filler may be added to the composition (II) in order to impart strength and antibacterial properties to the artificial tooth.
- the filler include organic fillers, inorganic fillers, organic-inorganic composite fillers, and the like, and fillers that the composition (I) may contain include the same fillers as those described 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 (II) is preferably 150 parts by mass or less, more preferably 125 parts by mass or less, still more preferably 110 parts by mass or less, and even more preferably 105 parts by mass or less, relative to 100 parts by mass of component (B).
- the lower limit of the content of the filler is not particularly limited.
- the filler in the composition (II) is preferably 1 to 150 parts by mass, more preferably 5 to 150 parts by mass, still more preferably 10 to 125 parts by mass, still more preferably 25 to 110 parts by mass, based on 100 parts by mass of component (B), Even more preferably, it is 40 to 105 parts by mass.
- the content of the filler in the composition (II) is preferably 20 parts by mass or less, more preferably 10 parts by mass or less, and still more preferably 100 parts by mass of the component (B). It is 5 parts by mass or less.
- the content of the filler in the composition (II) is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the component (B).
- the content of the filler in the composition (II) is preferably 0.1 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, relative to 100 parts by mass of the component (B). parts by mass, more preferably 0.5 to 5 parts by mass.
- composition (II) may contain a polymer within the scope of the present invention.
- examples of the polymer that can be used in the composition (II) 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 (II) 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 (II) 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 in the composition (II) is preferably 0.001 to 5.0 parts by mass with respect to 100 parts by mass of the component (B), 0.01 to 3.0 parts by mass is more preferable, and 0.1 to 2.0 parts by mass is even more preferable.
- Composition (II) may contain other known additives other than the above-mentioned components, as necessary, such as adjusting paste properties, within the scope 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 kit for manufacturing a denture with a stereolithography includes, in addition to the curable composition for denture base (I) and the composition for artificial teeth (II), the denture base contains a (meth)acrylic polymerizable monomer component (C) containing the same (meth)acrylic polymerizable monomer (m) as contained in the curable composition (I), ) Adhesion containing a composition (III) in which the content of the acrylic polymerizable monomer (m) is 20% by mass or more in 100% by mass of the (meth)acrylic polymerizable monomer component (C) and an agent composition.
- the adhesive composition is used as an adhesive for bonding a denture base prepared from the composition (I) and an artificial tooth prepared from the composition (II).
- composition (III) is a (meth)acrylic polymerizable monomer containing the same (meth)acrylic polymerizable monomer (m) as contained in the denture base curable composition (I).
- Contains body component (C) hereinafter also simply referred to as “component (C)”.
- 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) 20% by mass or more of the same monomer (m) as contained in component (C) in 100% by mass. That is, the component (C) is a (meth)acrylic polymerizable monomer contained as a main monomer among the (meth)acrylic polymerizable monomers constituting the component (A).
- the same (meth)acrylic polymerizable monomer as component (m) must be contained in an amount of 20% by mass or more based on 100% by mass of component (C).
- the same (meth)acrylic polymerizable monomer as the monomer (m) is included in 20% by mass or more in 100% by mass of the component (C), which is the same as the explanation for the component (B).
- the adhesive composition contains a component (C ), so when making a denture, the adhesiveness to both the denture base made from the composition (I) and the artificial tooth made from the composition (II) better than Therefore, when the stereolithographic denture manufacturing kit further comprises the adhesive composition, the strength and toughness of the denture obtained by adhering the denture base and the artificial tooth are more excellent. It is preferable from the viewpoint of being able to
- the content of the monomer (m) in the component (C) is , in 100% by mass of component (C), preferably 30% by mass or more, more preferably 40% by mass or more, still more preferably 50% by mass or more, even more preferably 55% by mass or more, still more preferably 60% by mass or more , 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, still more preferably 90% by mass or less, still more preferably 85% by mass or less , and more preferably 80% by mass or less.
- these stepwise lower and upper limits can be independently combined.
- the content of the monomer (m) in component (C) is 20 to 100% by mass, preferably 30 to 100% by mass, based on 100% by mass of component (C). , More preferably 40 to 98% by mass, still 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 .
- 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 are also such that the monomer (m) is 20% by mass in 100% by mass of the component (C). % or more of component (A), except that the notation "in 100% by mass of component (A)" is changed to "in 100% by mass of component (C)".
- the component (C) is a component composed of the monomer (m) alone or the monomer (m) and the monomer (o). Moreover, the 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 ). Moreover, when component (A) contains a plurality of compounds as monomers (o), component (C) also preferably contains all of these compounds as monomers (o). Furthermore, in one aspect of the present invention, 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 (A) 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) has the same monomer (m) as the component (B), and the monomer (o) is the monomer (o) contained in the component (B). They may contain the same (meth)acrylic polymerizable monomer.
- component (C) when component (B) 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 (B) 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 monomer (m) in component (C) and the content of monomer (m) in component (B) 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 (B) 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 (B) 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 (B) contains a plurality of compounds as the monomer (o)
- component (C) also contains a plurality of the same compounds as the component (B) as the monomer (o)
- each corresponding The absolute value of the difference between the content of the compound in component (B) 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 (B) contains a plurality of compounds as monomers (o)
- component (C) also contains the same plurality of compounds as component (B) as monomers (o).
- the absolute value of the difference between the content of each corresponding compound in component (B) 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 component (A) or the component (B) which is a (meth)acrylic polymerizable monomer.
- the component (C) is preferably contained in an amount of 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and 100% by mass or less. preferably.
- the component (C) is the component (A) or the component (B) in 100% by mass of the (meth)acrylic polymerizable monomer component (C), preferably It is contained in the range of 70 to 100% by mass, more preferably 80 to 100% by mass, still more preferably 90 to 100% by mass. Further, in this aspect, it is more preferable to contain the component (A) or the component (B) in an amount of 100% by mass based on 100% by mass of the (meth)acrylic polymerizable monomer component (C). That is, it is more preferable to use component (A) or component (B) as component (C).
- the component (A) is more preferable to use the component (C) from the viewpoint of improving the strength and toughness of the denture.
- the composition of the component (C) is more preferably the same as the composition of the component (A) or the composition of the component (B), from the viewpoint of improving the strength and toughness of the denture. Therefore, it is more preferable that the composition of component (C) is the same as that of component (A).
- the content of the component (C) in the composition (III) is preferably 40% by mass or more, based on 100% by mass of the composition (III).
- 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%, in 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 It is preferably 95 to 98% by mass.
- composition (III) may optionally contain components other than the component (C) as long as the gist of the present invention is not impaired.
- Composition (III) can be produced according to a known method.
- Composition (III) preferably contains a photopolymerization initiator from the viewpoint of improving the strength and toughness of the denture.
- 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 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 the composition (I) is the same as described above, except that the notation "100 parts by mass of component (A)” is changed to "100 parts by mass of component (C)”.
- 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.
- Composition (III) may contain a filler to adjust the viscosity of the composition within the scope of the present invention.
- 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 (C) is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, and even more preferably 3 parts by mass or less with respect to 100 parts by mass.
- 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.
- the 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.
- the composition (III) preferably satisfies, for example, the condition (1) or (2).
- 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. Therefore, when the composition (III) contains a colorant, the preferred content range is also changed from “composition (I)” to “composition (III)” and “component (A) 100 parts by mass” is changed to "Component (C) 100 parts by mass", the colorant contained in composition (I) is the same as described above. When the colorant is a pigment, the preferred range of the total content is the same as the total content of the colorant.
- 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) is composed of the composition (I) or the composition (II) and the composition (III) 100
- 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 preferably 100% by mass or less.
- composition (III) comprises composition (I) or composition (II) in 100% by mass of composition (III), preferably 70 to 100% by mass, more
- the content is preferably 80 to 100% by mass, more preferably 90 to 100% by mass.
- the composition (I) or the composition (II) is contained in an amount of 100% by mass based on 100% by mass of the composition (III). More preferably, the composition (I) is contained in an amount of 100% by mass based on 100% by mass of the composition (III). That is, it is more preferable to use the composition (I) or the composition (II) as the composition (III), and it is even more preferable to use the composition (I).
- 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, based on 100% by mass of the adhesive composition. above, more preferably 40% by mass or more, still more preferably 50% by mass or more, still more preferably 60% by mass or more, even more preferably 80% by mass or more, still more preferably 90% by mass or more, and It is preferable to contain 100% by mass or less.
- 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 method for manufacturing a plate 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 a denture base comprising a cured denture base curable composition (I) containing a photopolymerization initiator, and the same (meth) acrylic as contained in the denture base curable composition (I)
- a (meth)acrylic polymerizable monomer component (B) containing a polymerizable monomer (m) is contained, and the content of the (meth)acrylic polymerizable monomer (m) is (meth)
- An artificial tooth made of a cured product of the artificial tooth composition (II), which is 20% by mass or more in 100% by mass of the acrylic polymerizable monomer component (B), and the curable composition for denture base (I ) contains a (meth)acrylic polymerizable
- curable composition for denture base (I) the composition for artificial teeth (II), the composition (III) and the adhesive composition used in the manufacturing method, and each component contained in each composition, These are the same as those described above in the section of the above-mentioned kit for making a plate denture for stereolithography, and the preferred embodiments thereof are also the same, so detailed description thereof will be omitted.
- composition (I), composition (II), composition (III) and adhesive composition that is, the preferred amount of each component contained in each composition, Since it is the same as the content (% by mass or parts by mass) of each component in each composition described above in the section of the above-mentioned kit for manufacturing a plate denture for stereolithography, detailed description thereof will be omitted.
- the manufacturing method includes a step of bonding a denture base made of the cured product of composition (I) and an artificial tooth made of the cured product of composition (II) using the adhesive composition
- a denture base made of the cured product of the composition (I) and an artificial tooth made of the cured product of the composition (II) are bonded using the adhesive composition
- a method of adhering a denture base 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.
- the adhesion step it is preferable to adhere by photocuring the adhesive composition. That is, for example, as one aspect of the production method, it is preferable to have the following steps (1) and (2) in this order.
- Step (1) A step of applying the adhesive composition to at least one selected from the denture base and the artificial tooth.
- 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 obtaining a denture base made of the cured product of composition (I) is not particularly limited, and any known method and apparatus can be used, but the photocured product of composition (I) is preferred. , more preferably obtained by stereolithography.
- the stereolithography method is not particularly limited, and known methods and apparatuses can be used. For example, methods using a CAD/CAM system such as the method of using a 3D printer by stereolithography described above can be used. can.
- the denture base made of the cured product of composition (I) may be a denture base partly composed of the cured composition (I), or entirely composed of the cured composition (I).
- composition (I) is preferably a denture base.
- the method for obtaining an artificial tooth composed of the cured product of composition (II) is not particularly limited, and any known method and apparatus can be used. Preferably, it is obtained by stereolithography.
- the artificial tooth made of the cured composition (II) may be an artificial tooth partially composed of the cured composition (II), or entirely composed of the cured composition (II). Although it may be an artificial tooth, it is preferable that at least a part of the part in contact with the adhesive composition is a cured product of composition (II), and all the parts in contact with the adhesive composition are composed of the composition (II). It is more preferably a cured product of product (II).
- the method for manufacturing a plated 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 adhesion is performed before the secondary polymerization of the denture base and/or the artificial tooth.
- Higher adhesion can be obtained by applying the agent composition to the denture base and/or the artificial tooth and performing the adhesion operation. Therefore, when the denture base and/or the artificial tooth is a photofabricated article, the denture base and the artificial tooth may be 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 plate denture which is one aspect of the present invention, is characterized by excellent adhesiveness even after the above-described secondary polymerization and after a long period of time from modeling, even in a state in which polymerization has progressed to a high degree. Therefore, it is possible to manufacture dentures with sufficiently excellent adhesiveness even after a long time has passed since the denture base and/or artificial teeth were manufactured.
- 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).
- Step (3A) A step of bonding the denture base and the artificial tooth by irradiating the adhesive composition with active energy rays to cure the adhesive composition.
- active energy ray means an energy ray such as ultraviolet rays, electron beams, X-rays, radiation, high frequency rays, etc., which can cure the resin composition for stereolithography.
- Light sources for active energy rays include halogen lamps, xenon lamps, metal halide lamps, LEDs, mercury lamps, fluorescent lamps, etc. Among these, halogen lamps and LEDs are preferred.
- TPO 2,4,6-trimethylbenzoyldiphenylphosphine oxide
- Tianium dioxide Japanese Pharmacopoeia Titanium oxide
- Red pigment Sicovit Red 30 E172 (manufactured by VENATOR)
- Yellow 10 Sicovit Yellow 10
- Black pigment Sicovit Black 80 E172 (manufactured by VENATOR)
- Inorganic filler 1 ⁇ -methacryloyloxypropyltrimethoxysilane treated “ADMAFINE (registered trademark)” SC4500-SMJ (manufactured by Admatechs Co., Ltd., average particle size: 1.0 ⁇ m)
- ⁇ L * L * black ⁇ L * white
- L * white, a * white, and b * white mean the results of colorimetry with a white background
- L * black means the results of colorimetry with a black background.
- the composition and chromaticity of the denture base curable composition (I)-3 are shown in Table 1 below.
- the composition and chromaticity of the denture base curable composition (I)-4 are shown in Table 1 below.
- the composition and chromaticity of the denture base curable composition (I)-5 are shown in Table 1 below.
- the composition and chromaticity of the denture base curable composition (II)-1 are shown in Table 2 below.
- the composition and chromaticity of the denture base curable composition (II)-2 are shown in Table 2 below.
- the composition and chromaticity of the denture base curable composition (II)-3 are shown in Table 2 below.
- the composition and chromaticity of the denture base curable composition (II)-4 are shown in Table 2 below.
- the composition and chromaticity of the denture base curable composition (II)-5 are shown in Table 2 below.
- Examples 1 to 7 and Comparative Examples 1 to 6 As described below, shaped articles of the compositions described in each reference example were bonded together using the adhesive described below in the combinations shown in Tables 3 and 4 below, and cured to prepare test pieces. Then, bending strength and toughness tests were performed. In Examples 1 to 3 and Comparative Examples 1 to 5, composition (III) having the same composition as denture base curable composition (I) used was used as an adhesive. In Examples 4 and 5, the composition (III) having the same composition as the artificial tooth composition (II) used was used as an adhesive.
- Example 6 an adhesive composition obtained by diluting Composition (III), which has the same composition as the curable composition for denture base (I)-1 used in Example 6, with ethyl acetate to 30% by mass was used as an adhesive. .
- Example 7 an adhesive composition obtained by diluting Composition (III), which has the same composition as the curable composition for denture base (I)-1 used in Example 7, with ethyl acetate to 15% by weight, was used as an adhesive. .
- Comparative Example 6 a commercially available denture base adhesive "Unifast (registered trademark) III” (manufactured by GC Co., Ltd., methyl methacrylate (MMA) and polymethyl methacrylate (PMMA) powder-liquid adhesive) was adhered. used as an agent.
- JIS T 6501: 2012 was applied mutatis mutandis to test pieces imagining dentures according to each example and each comparative example, which were stored in water at 37°C for one day, removed from the water, wiped off moisture, and tested for bending strength. was performed and evaluated.
- the bending strength of the test piece is preferably 80 MPa or higher, more preferably 90 MPa or higher, and even more preferably 100 MPa or higher.
- the breaking point displacement it is preferable not to break.
- the breaking point displacement when the fracture occurs at a displacement of 10 mm or more, the toughness is good “A”, when the fracture occurs at a displacement of more than 5 mm and less than 10 mm, the toughness is moderate “B”, and when the fracture occurs at a displacement of 5 mm or less, the toughness is low.
- a bad "F” was given, and a "B” or better was given as a pass.
- the adhesive strength may affect the measurement of bending strength and toughness, so the peeling state after fracture was observed.
- test pieces of a combination of a denture base and an artificial tooth produced from the curable composition for denture base (I) and the composition for artificial teeth (II) in Examples 1 to 7 The flexural strength and toughness were measured by comparing the strength and toughness of the test piece consisting of a combination of a denture base and an artificial tooth made from the curable denture base composition (I) and the artificial tooth composition (II) of Comparative Examples 1 to 6. It was superior to toughness. In any test piece, no peeling of the adhesive interface was observed after breaking, and the flexural strength and toughness were correctly measured.
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Abstract
Description
一般的に光造形法では、光造形された床と、人工歯を接着する必要がある。人工歯としては、例えば、射出成型で作製されたPMMA製の人工歯、切削加工で作製された硬質レジン歯、床と異なる光硬化性樹脂組成物で造形された人工歯などが挙げられる。接着剤としては、重合開始剤を配合したメチルメタクリレート(MMA)とアクリル樹脂粉から構成される粉液型レジンがほとんどである。ロストワックス法では、床、人工歯及び接着剤が、概ね同種の材料で構成されるため、床と人工歯の物性差が小さく、親和性が良好で接着が強固であるため、強度と靭性に優れた義歯が得られやすい。しかしながら、光造形法では光で瞬時に硬化させるため、特に硬化性の高い重合性化合物を使用する必要があり、架橋性モノマーや高い凝集力を発現するモノマーが使用されるため、脆化しやすいという問題があった。加えて、接着剤が浸透しにくく、十分な接着力が得られないだけでなく、床と人工歯に物性差があり一体化しにくいため、十分な義歯の強度と靭性が得られないという問題があった。
このような背景の中、特許文献1には、CAD/CAMシステムを用いて作製された義歯床とアクリル樹脂製の人工歯を、MMAとPMMAからなる粉液型のレジンで接着させた義歯の作製例が記載されている。また、特許文献2には光造形用の強度、靭性に優れた義歯床材料の例が記載されている。
そこで、本発明は、光造形によって作製される義歯床と人工歯の組み合わせにおいて、強度と靭性に優れた義歯を提供することを目的とする。
[1] 主単量体として(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(A)、及び光重合開始剤を含有する義歯床用硬化性組成物(I)と、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(B)100質量%中、20質量%以上である人工歯用組成物(II)と、
を備える光造形用有床義歯作製キット。
[2] 前記(メタ)アクリル系重合性単量体(m)が、多官能性の(メタ)アクリル系重合性単量体(a-1)である、前記[1]に記載の光造形用有床義歯作製キット。
[3] 前記多官能性の(メタ)アクリル系重合性単量体(a-1)が、ウレタン化(メタ)アクリル酸エステル化合物、及びウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物から選ばれる少なくとも1種である、前記[2]に記載の光造形用有床義歯作製キット。
[4] 前記(メタ)アクリル系重合性単量体成分(A)が、単官能性の(メタ)アクリル系重合性単量体(a-2)を含有する、前記[1]~[3]のいずれか1つに記載の光造形用有床義歯作製キット。
[5] 前記(メタ)アクリル系重合性単量体成分(B)が、単官能性の(メタ)アクリル系重合性単量体(a-2)を含有する、前記[1]~[4]のいずれか1つに記載の光造形用有床義歯作製キット。
[6] 前記単官能性の(メタ)アクリル系重合性単量体(a-2)が、芳香環を含有する(メタ)アクリル酸エステル系重合性単量体である、前記[4]又は[5]に記載の光造形用有床義歯作製キット。
[7] 前記義歯床用硬化性組成物(I)中、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(A)100質量%中、50質量%以上である、前記[1]~[6]のいずれか1つに記載の光造形用有床義歯作製キット。
[8] 前記人工歯用組成物(II)中、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(B)100質量%中、50質量%以上である、前記[1]~[7]のいずれか1つに記載の光造形用有床義歯作製キット。
[9] 前記(メタ)アクリル系重合性単量体成分(A)を、前記義歯床用硬化性組成物(I)100質量%中、40質量%以上含有する、前記[1]~[8]のいずれか1つに記載の光造形用有床義歯作製キット。
[10] 前記(メタ)アクリル系重合性単量体成分(B)を、前記人工歯用組成物(II)100質量%中、40質量%以上含有する、前記[1]~[9]のいずれか1つに記載の光造形用有床義歯作製キット。
[11] 前記義歯床用硬化性組成物(I)と、
前記人工歯用組成物(II)と、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(C)100質量%中、20質量%以上である組成物(III)を含有する接着剤組成物と、
を備える、前記[1]~[10]のいずれか1つに記載の光造形用有床義歯作製キット。
[12] 主単量体として(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(A)、及び光重合開始剤を含有する義歯床用硬化性組成物(I)の硬化物からなる義歯床と、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(B)100質量%中、20質量%以上である人工歯用組成物(II)の硬化物からなる人工歯とを、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(C)100質量%中、20質量%以上である組成物(III)を含有する接着剤組成物を用いて接着することを特徴とする、有床義歯の製造方法。
本明細書において、数値範囲(各成分の含有量、各成分から算出される値及び各物性等)の上限値及び下限値は適宜組み合わせ可能である。
すなわち、本明細書において、同一事項に対する数値範囲について、段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、同一事項に対する「好ましくは10~90、より好ましくは30~60」という記載から、「好ましい下限値(10)」と「より好ましい上限値(60)」とを組み合わせて、「10~60」とすることもできる。
また、数値範囲について、例えば、「好ましくは10~90、より好ましくは30~60」との記載に基づいて、上限値は特に規定せずに下限値側だけ「10以上」又は「30以上」と規定することもでき、同様に、下限値は特に規定せずに上限値側だけ「90以下」又は「60以下」と規定することもできる。
なお、特に言及しない限り、数値範囲として単に「10~90」と記載する場合、10以上90以下の範囲を表す。
前記同様、例えば、同一事項に対する「好ましくは10以上、より好ましくは30以上」の記載と「好ましくは90以下、より好ましくは60以下」という記載から、「好ましい下限値(10)」と「より好ましい上限値(60)」とを組み合わせて、「10以上60以下」とすることもできる。また、前記同様、下限値側だけ「10以上」又は「30以上」と規定することもでき、同様に、上限値側だけ「90以下」又は「60以下」と規定することもできる。
また、本明細書において、「(メタ)アクリル」との表記は、「メタクリル」又は「アクリル」の両者を包含する意味で用いられる。「(メタ)アクリレート」、「(メタ)アクリルアミド」、「(メタ)アクリロイルオキシ」等のこれに類する表記も同様である。
また、本明細書において、特に言及しない限り、同一の符号を有する用語(例えば、「組成物(I)」、「組成物(II)」、「組成物(III)」、「単量体(m)」、「単量体(o)」、「単量体(a-1)」、「単量体(a-2)」、「成分(A)」、「成分(B)」、「成分(C)」等)は、同一のものを指す。
また、本明細書において、特に言及しない限り、「強度」及び「靭性」との表記は、本発明の一態様である光造形用有床義歯作製キットから作製される義歯の「強度」及び「靭性」を指す。
また、本明細書において、以下の説明中、特に言及しない限り、「義歯」とは、本発明の一態様である光造形用有床義歯作製キットから作製される義歯を指す。
本発明の一態様である光造形用有床義歯作製キットは、主単量体として(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(A)、及び光重合開始剤を含有する義歯床用硬化性組成物(I)と、前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、(メタ)アクリル系重合性単量体成分(B)100質量%中、20質量%以上である人工歯用組成物(II)とを備える。
前記義歯床用硬化性組成物(I)(以下、単に「組成物(I)」ともいう。)は、主単量体として(メタ)アクリル系重合性単量体(m)(以下、単に「単量体(m)」ともいう。)を含む(メタ)アクリル系重合性単量体成分(A)(以下、単に「成分(A)」ともいう。)、及び光重合開始剤を含有する。
前記(メタ)アクリル系重合性単量体成分(A)は、(メタ)アクリル系重合性単量体1種単独で又は2種以上から構成される成分であって、主単量体として(メタ)アクリル系重合性単量体(m)を含む。
ここで、本明細書において、「主単量体」とは、成分(A)を構成する(メタ)アクリル系重合性単量体のうち、最も含有量が多い(メタ)アクリル系重合性単量体を指す。
また、本明細書において、「(メタ)アクリル系重合性単量体成分」とは、(メタ)アクリル系重合性単量体1種単独又は2種以上から構成される成分のことを指し、前記成分(A)、並びに、後述する「(メタ)アクリル系重合性単量体成分(B)」及び「(メタ)アクリル系重合性単量体成分(C)」についても同様である。
また、本明細書において、「(メタ)アクリル系重合性単量体」とは、「(メタ)アクリル系重合性単量体成分」を構成する具体的な1つの化合物、すなわち、特定の(メタ)アクリル系重合性単量体のことを指し、前記単量体(m)、並びに、後述する「多官能性の(メタ)アクリル系重合性単量体(a-1)」及び「単官能性の(メタ)アクリル系重合性単量体(a-2)」についても同様である。
成分(A)中、主単量体として含まれる単量体(m)の含有量は、成分(A)中で最も多く、単量体(m)以外の(メタ)アクリル系重合性単量体(o)(以下、単に「単量体(o)」ともいう。)の含有量以上であれば特に制限はないが、例えば、成分(A)100質量%中、好ましくは30質量%以上、より好ましくは40質量%以上、更に好ましくは50質量%以上、より更に好ましくは55質量%以上、より更に好ましくは60質量%以上、より更に好ましくは65質量%以上であり、例えば、100質量%以下、好ましくは98質量%以下、より好ましくは95質量%以下、更に好ましくは90質量%以下、より更に好ましくは85質量%以下、より更に好ましくは80質量%以下である。前述のとおり、これら段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、本発明の一態様において、成分(A)中、単量体(m)の含有量は、成分(A)100質量%中、好ましくは30~100質量%、より好ましくは40~98質量%、更に好ましくは50~95質量%、より更に好ましくは55~90質量%、より更に好ましくは60~85質量%、より更に好ましくは65~80質量%である。
前述のとおり、成分(A)は、単量体(m)単独で、又は、単量体(m)と単量体(o)とから構成される成分である。成分(A)は、単量体(o)を複数含有してもよい。したがって、成分(A)中、単量体(m)及び単量体(o)の合計含有量は100質量%である。
成分(A)を構成する(メタ)アクリル系重合性単量体としては、例えば、(メタ)アクリル酸エステル系重合性単量体、(メタ)アクリルアミド系重合性単量体が挙げられる。
前記(メタ)アクリル系重合性単量体としては、重合性基を複数有する多官能性の(メタ)アクリル系重合性単量体(a-1)(以下、単に「多官能性単量体(a-1)」ともいう。)、及び重合性基を1個有する単官能性の(メタ)アクリル系重合性単量体(a-2)(以下、単に「単官能性単量体(a-2)」ともいう。)が挙げられる。
そして、義歯の強度と靭性をより優れたものとする観点から、成分(A)は、多官能性単量体(a-1)を含むことが好ましく、主単量体として含む(メタ)アクリル系重合性単量体(m)が、多官能性単量体(a-1)であることがより好ましい。
また、成分(A)は、単官能性単量体(a-2)を含むことが好ましく、義歯の強度と靭性をより優れたものとする観点から、多官能性単量体(a-1)及び単官能性単量体(a-2)を共に含むことがより好ましく、主単量体として多官能性単量体(a-1)を含み、更に単官能性単量体(a-2)を含むことが更に好ましい。
また、成分(A)は、多官能性単量体(a-1)を1種単独で又は2種以上含んでもよく、同様に、単官能性単量体(a-2)を1種単独で又は2種以上含んでもよい。
多官能性単量体(a-1)は、義歯の強度向上の観点から、ウレタン化(メタ)アクリル酸エステル化合物、ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物、及び脂環式(メタ)アクリル酸エステル化合物からなる群より選ばれる少なくとも1種が好ましく、ウレタン化(メタ)アクリル酸エステル化合物、及びウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物から選ばれる少なくとも1種がより好ましく、ウレタン化(メタ)アクリル酸エステル化合物が更に好ましい。換言すれば、前記成分(A)は、前述した多官能性単量体(a-1)として、ウレタン化(メタ)アクリル酸エステル化合物、ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物、及び脂環式(メタ)アクリル酸エステル化合物からなる群より選ばれる少なくとも1種を含むことが好ましく、ウレタン化(メタ)アクリル酸エステル化合物、及びウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物から選ばれる少なくとも1種を含むことがより好ましく、ウレタン化(メタ)アクリル酸エステル化合物を含むことが更に好ましい。
また、前述のとおり、成分(A)は、主単量体として含む(メタ)アクリル系重合性単量体(m)として、多官能性単量体(a-1)であるウレタン化(メタ)アクリル酸エステル化合物、ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物、及び脂環式(メタ)アクリル酸エステル化合物からなる群より選ばれる少なくとも1種を含むことが好ましく、ウレタン化(メタ)アクリル酸エステル化合物、及びウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物から選ばれる少なくとも1種を含むことがより好ましく、ウレタン化(メタ)アクリル酸エステル化合物を含むことが更に好ましい。
ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物の場合、当該化合物は、水酸基、1級アミノ基、及び2級アミノ基からなる群より選ばれる少なくとも1種を含有していることがより好ましい。
これらの化合物は、ウレタン結合、芳香族骨格、水酸基、1級アミノ基、2級アミノ基の誘電的効果によって、硬化を促進するだけでなく、水素結合やπ電子の作用などの化学的な結合を生成するものと推測される。中でもウレタン結合を有するウレタン化(メタ)アクリル酸エステル化合物は、義歯に靭性を付与する効果も大きいため、接着界面及び塗膜からの破壊、ヒビが発生しにくく、得られる義歯がより優れた曲げ強さを発現できるため好ましい。
ウレタン化(メタ)アクリル酸エステル化合物は、例えば、アルキレン骨格及びフェニレン骨格から選ばれる1種以上を含有し、かつ、イソシアネート基を有する化合物と、水酸基(-OH)を有する(メタ)アクリレート化合物とを付加反応させることにより、容易に合成することができる。
また、組成物(I)が低粘度で造形し易くなる観点及び義歯の強度低下を抑制できる観点から、ウレタン化(メタ)アクリル酸エステル化合物の重量平均分子量は1000以下であることが好ましい。得られる組成物の粘度及び義歯の強度の観点から、前記重量平均分子量は750以下であることがより好ましく、500以下であることが更に好ましい。また、後述する成分(C)がウレタン化(メタ)アクリル酸エステル化合物を含む場合も、接着剤組成物が低粘度で塗布し易く、接着剤組成物の義歯床と人工歯に対する浸透性が得られやすくなり、義歯の強度を向上し易くなる観点から、同様である。ここでいう重量平均分子量とは、ゲル浸透クロマトグラフィー(GPC)で求めたポリスチレン換算の重量平均分子量を意味する。なお、ウレタン化(メタ)アクリル酸エステル化合物がポリマー構造を含有しない場合、重量平均分子量の概念がないため、分子量を適用する。
更に、ウレタン化(メタ)アクリル酸エステル化合物は、ポリエステル、ポリカーボネート、ポリウレタン、ポリエーテル等のポリマー構造を含有していない化合物であることが好ましい。これらの構造を含有していないことで、極性を有する官能基濃度の上昇が抑えられ、口腔内のような水分存在下での義歯の強度低下を抑制することができる。とりわけウレタン結合は水分存在下での義歯の強度の観点から1分子内に3個以下であることが好ましく、2個以下であることがより好ましい。換言すれば、ウレタン化(メタ)アクリル酸エステル化合物中のウレタン結合は、好ましくは1分子内に1~3個であり、より好ましくは1分子内に1個又は2個である。
また、本発明の一態様において、成分(A)が複数の多官能性単量体(a-1)を含む場合、ウレタン化(メタ)アクリル酸エステル化合物の含有量は、多官能性単量体(a-1)の合計100質量%中、好ましくは50~100質量%、より好ましくは60~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、より更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。
ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物としては、2,2-ビス((メタ)アクリロイルオキシフェニル)プロパン、2,2-ビス〔4-(3-アクリロイルオキシ)-2-ヒドロキシプロポキシフェニル〕プロパン、2,2-ビス〔4-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)フェニル〕プロパン(略称「Bis-GMA」)、2,2-ビス〔4-{2-(3-アクリロイルオキシ-2-ヒドロキシプロポキシ)プロピル}フェニル〕プロパン、2,2-ビス〔4-{2-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)プロピル}フェニル〕プロパン、2,2-ビス(4-(メタ)アクリロイルオキシエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシポリエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシジエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシテトラエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシペンタエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシジプロポキシフェニル)プロパン、2-(4-(メタ)アクリロイルオキシジエトキシフェニル)-2-(4-(メタ)アクリロイルオキシエトキシフェニル)プロパン、2-(4-(メタ)アクリロイルオキシジエトキシフェニル)-2-(4-(メタ)アクリロイルオキシトリエトキシフェニル)プロパン、2-(4-(メタ)アクリロイルオキシジプロポキシフェニル)-2-(4-(メタ)アクリロイルオキシトリエトキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシプロポキシフェニル)プロパン、2,2-ビス(4-(メタ)アクリロイルオキシイソプロポキシフェニル)プロパン、1,4-ビス(2-(メタ)アクリロイルオキシエチル)ピロメリテート等が挙げられる。これらは、1種を単独で用いてもよく、2種以上を併用してもよい。これらの中でも、義歯の強度向上の観点から、水酸基を含有する化合物が好ましく、具体的には、2,2-ビス〔4-(3-アクリロイルオキシ)-2-ヒドロキシプロポキシフェニル〕プロパン、2,2-ビス〔4-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)フェニル〕プロパン、2,2-ビス〔4-{2-(3-アクリロイルオキシ-2-ヒドロキシプロポキシ)プロピル}フェニル〕プロパン、2,2-ビス〔4-{2-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)プロピル}フェニル〕プロパンが好ましい。これらの中でも、2,2-ビス〔4-(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)フェニル〕プロパンがより好ましい。
また、本発明の一態様において、ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物の含有量は、多官能性単量体(a-1)の合計100質量%中、好ましくは50~100質量%、より好ましくは60~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、より更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。
脂環式(メタ)アクリル酸エステル化合物としては、トリシクロデカンジメタノールジ(メタ)アクリレート、シクロヘキサンジオールジ(メタ)アクリレート、アダマンタンジオールジ(メタ)アクリレート等が挙げられる。これらの中でも、トリシクロデカンジメタノールジ(メタ)アクリレートが好ましい。
また、本発明の一態様において、脂環式(メタ)アクリル酸エステル化合物の含有量は、多官能性単量体(a-1)の合計100質量%中、好ましくは50~100質量%、より好ましくは60~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、より更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。
前記ウレタン化(メタ)アクリル酸エステル化合物、ウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物、脂環式(メタ)アクリル酸エステル化合物以外の多官能性の(メタ)アクリル酸エステル系重合性単量体、すなわち、他の多官能性の(メタ)アクリル酸エステル系重合性単量体(以下、「他の多官能性重合性単量体」ともいう。)としては、グリセロールジ(メタ)アクリレート、エチレングリコールジ(メタ)アクリレート、ジエチレングリコールジ(メタ)アクリレート、トリエチレングリコールジ(メタ)アクリレート、プロピレングリコールジ(メタ)アクリレート、ブチレングリコールジ(メタ)アクリレート、ネオペンチルグリコールジ(メタ)アクリレート、ポリエチレングリコールジ(メタ)アクリレート、1,3-ブタンジオールジ(メタ)アクリレート、1,4-ブタンジオールジ(メタ)アクリレート、1,6-ヘキサンジオールジ(メタ)アクリレート、2-エチル-1,6-ヘキサンジオールジ(メタ)アクリレート、1,9-ノナンジオールジ(メタ)アクリレート、1,10-デカンジオールジ(メタ)アクリレート、1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)エタン、トリメチロールプロパントリ(メタ)アクリレート、トリメチロールエタントリ(メタ)アクリレート、トリメチロールメタントリ(メタ)アクリレート、ペンタエリスリトールトリ(メタ)アクリレート、ペンタエリスリトールテトラ(メタ)アクリレート、ジペンタエリスリトールペンタ(メタ)アクリレート等が挙げられる。これらの中でも、義歯の強度がより優れる観点から、グリセロールジ(メタ)アクリレート、1,2-ビス(3-メタクリロイルオキシ-2-ヒドロキシプロポキシ)エタン、トリエチレングリコールジ(メタ)アクリレートが好ましく、トリエチレングリコールジ(メタ)アクリレートがより好ましい。これらは、1種を単独で用いてもよく、2種以上を併用してもよい。
また、本発明の一態様において、成分(A)が、他の多官能性の(メタ)アクリル酸エステル系重合性単量体を含有する場合、他の多官能性の(メタ)アクリル酸エステル系重合性単量体の含有量は、多官能性単量体(a-1)の合計100質量%中、好ましくは1~50質量%、より好ましくは1~40質量%、更に好ましくは1~35質量%、より更に好ましくは1~30質量%である。
前述のとおり、成分(A)は、単官能性単量体(a-2)を含むことが好ましい。単官能性単量体(a-2)は、組成物(I)を低粘度化し、かつ得られる造形物の架橋密度を低減することによって、義歯の靭性をより向上させることができる。
単官能性単量体(a-2)が有する1個の重合性基とは、(メタ)アクリロイル基を指す。
芳香環を含有する(メタ)アクリル酸エステル系重合性単量体、脂環式(メタ)アクリル酸エステル系重合性単量体、窒素原子含有の環状(メタ)アクリル酸エステル系重合性単量体、環状(メタ)アクリルアミド化合物は、鎖状(メタ)アクリル酸エステル系重合性単量体と比較して、同等の分子量において、高沸点で低臭気となる傾向があるが、それぞれ、π電子相互作用、立体配座が固定されることによる微小な極性付与の効果によるものと推測される。
また、本発明の一態様において、芳香環を含有する(メタ)アクリル酸エステル系重合性単量体の含有量は、単官能性単量体(a-2)の合計100質量%中、好ましくは50~100質量%、より好ましくは60~100質量%、更に好ましくは70~100質量%、より更に好ましくは80~100質量%、より更に好ましくは90~100質量%、より更に好ましくは95~100質量%である。
前記光重合開始剤は、一般工業界で使用されている重合開始剤から選択して使用でき、中でも歯科用途に使用されている光重合開始剤が好ましい。
これらの光重合開始剤の中でも、(ビス)アシルホスフィンオキシド類と、α-ジケトン類とからなる群より選択される少なくとも1種を用いることが好ましい。これにより、紫外領域及び可視光域での光硬化性に優れ、レーザー、ハロゲンランプ、発光ダイオード(LED)、及びキセノンランプのいずれの光源を用いても十分な光硬化性を示す組成物が得られる。
(ビス)アシルホスフィンオキシド類のうち、ビスアシルホスフィンオキシド類としては、例えば、ビス(2,6-ジクロロベンゾイル)フェニルホスフィンオキシド、ビス(2,6-ジクロロベンゾイル)-2,5-ジメチルフェニルホスフィンオキシド、ビス(2,6-ジクロロベンゾイル)-4-プロピルフェニルホスフィンオキシド、ビス(2,6-ジクロロベンゾイル)-1-ナフチルホスフィンオキシド、ビス(2,6-ジメトキシベンゾイル)フェニルホスフィンオキシド、ビス(2,6-ジメトキシベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキシド、ビス(2,6-ジメトキシベンゾイル)-2,5-ジメチルフェニルホスフィンオキシド、ビス(2,4,6-トリメチルベンゾイル)フェニルホスフィンオキシド、ビス(2,5,6-トリメチルベンゾイル)-2,4,4-トリメチルペンチルホスフィンオキシド等が挙げられる。さらに、特開2000-159621号公報に記載されている化合物を挙げることができる。
義歯床用硬化性組成物(I)は、本発明の趣旨を損なわない範囲内で、必要に応じて、前述の成分(A)、及び光重合開始剤以外の成分を含んでいてもよい。組成物(I)は、公知の方法に準じて製造できる。
義歯床用硬化性組成物(I)は、例えば、義歯床の色調を歯肉色等に調色する観点から、着色剤を含有してもよい。組成物(I)を調色する方法としては、特に限定はなく、例えば、公知の着色剤を配合して調色することができる。
着色剤としては、例えば、顔料又は染料等を用いることができる。前記顔料は、無機顔料と有機顔料に大別されるが、混合して使用しても構わない。
条件(1):前記義歯床用硬化性組成物(I)の硬化物から形成される、直径15.0±0.1、厚さ1.00±0.01mmの試験片のL*a*b*表色系による白背景での色度が、70.0≦L*white≦90.0、10.0≦a*white≦25.0(好ましくは10.0<a*white≦25.0)、10.0≦b*white≦35.0、10.0≦ΔL≦40.0である。
例えば、組成物(I)を条件(1)の範囲を満たすように調色したい場合には、好ましくは、赤酸化鉄が主に使用することができる顔料として例示される。
また、本発明の一態様において、前記義歯床用硬化性組成物(I)の硬化物から形成される、直径15.0±0.1、厚さ1.00±0.01mmの試験片のL*a*b*表色系による黒背景で測色して得られる明度L*blackと白背景で測色して得られる明度L*whiteとの明度差ΔLは、好ましくは10.0以上40.0以下、より好ましくは20.0超40.0以下、更に好ましくは24.0以上40.0以下である。
また、本発明の一態様において、前記義歯床用硬化性組成物(I)の硬化物から形成される、直径15.0±0.1、厚さ1.00±0.01mmの試験片のL*a*b*表色系による白背景で測定されるa*whiteの値が、前記人工歯用組成物(II)の硬化物から形成される、直径15.0±0.1、厚さ1.00±0.01mmの試験片のL*a*b*表色系による白背景で測定されるa*whiteの値よりも大きいことが好ましい。
前記着色剤が顔料である場合、その合計含有量の好適範囲は前記着色剤の合計含有量と同様である。
組成物(I)は、本発明の趣旨を損なわない範囲内で、光硬化性の向上を目的として、重合促進剤を含むことができる。重合促進剤としては、例えば、4-(N,N-ジメチルアミノ)安息香酸エチル、4-(N,N-ジメチルアミノ)安息香酸メチル、4-(N,N-ジメチルアミノ)安息香酸n-ブトキシエチル、4-(N,N-ジメチルアミノ)安息香酸2-(メタクリロイルオキシ)エチル、4-(N,N-ジメチルアミノ)ベンゾフェノン、4-(N,N-ジメチルアミノ)安息香酸ブチルが挙げられる。これらの中でも、組成物(I)に優れた硬化性を付与する観点から、4-(N,N-ジメチルアミノ)安息香酸エチル、4-(N,N-ジメチルアミノ)安息香酸n-ブトキシエチル、及び4-(N,N-ジメチルアミノ)ベンゾフェノンからなる群より選択される少なくとも1つが好ましく用いられる。重合促進剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
組成物(I)には、例えば、組成物の粘度調整、義歯床への強度付与、抗菌性付与の観点等から、必要に応じて、フィラーが配合されていてもよい。当該フィラーとして、例えば、有機フィラー、無機フィラー、有機-無機複合フィラー等が挙げられる。フィラーは、1種を単独で用いてもよく、2種以上を併用してもよい。
組成物(I)には、本発明の趣旨を損なわない範囲内で、柔軟性、流動性等の改質を目的として重合体を添加することができる。例えば、天然ゴム、合成ポリイソプレンゴム、液状ポリイソプレンゴム及びその水素添加物、ポリブタジエンゴム、液状ポリブタジエンゴム及びその水素添加物、スチレン-ブタジエンゴム、クロロプレンゴム、エチレン-プロピレンゴム、アクリルゴム、イソプレン-イソブチレンゴム、アクリロニトリル-ブタジエンゴム、又はスチレン系エラストマーを添加することができる。添加可能な他の重合体の具体例としては、ポリスチレン-ポリイソプレン-ポリスチレンブロック共重合体、ポリスチレン-ポリブタジエン-ポリスチレンブロック共重合体、ポリ(α-メチルスチレン)-ポリブタジエン-ポリ(α-メチルスチレン)ブロック共重合体、ポリ(p-メチルスチレン)-ポリブタジエン-ポリ(p-メチルスチレン)ブロック共重合体、又はこれらの水素添加物等が挙げられる。これらの重合体は1種を単独で用いてもよく、2種以上を併用してもよい。
組成物(I)には、必要に応じて、軟化剤を含有していてもよい。軟化剤としては、例えば、パラフィン系、ナフテン系、芳香族系のプロセスオイル等の石油系軟化剤、及び、パラフィン、落花生油、ロジン等の植物油系軟化剤が挙げられる。これらの軟化剤は1種を単独で用いてもよく、2種以上を併用してもよい。軟化剤を用いる場合、組成物(I)中、軟化剤の含有量は、本発明の趣旨を損なわない限り特に制限はないが、通常、成分(A)100質量部に対して、好ましくは1~30質量部、より好ましくは5~20質量部である。
組成物(I)には、劣化の抑制、又は光硬化性の調整を目的として、公知の安定剤を配合することができる。前記安定剤としては、例えば、重合禁止剤、紫外線吸収剤、酸化防止剤が挙げられる。
組成物(I)には、本発明の趣旨を損なわない範囲内で、例えば、ペースト性状の調整等、必要に応じて、前述した成分以外にその他公知の添加剤を配合することができる。前記その他添加剤としては、例えば、増粘剤、プレポリマー(オリゴマー)、アリール化合物(例えば、アリールヨードニウム塩)が等挙げられる。これらのその他添加剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
前記人工歯用組成物(II)(以下、単に「組成物(II)」ともいう。)は、前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)(以下、単に「成分(B)」ともいう。)を含有する。
組成物(II)は、硬化性を有することが好ましく、光硬化性を有することがより好ましい。
前記(メタ)アクリル系重合性単量体成分(B)は、(メタ)アクリル系重合性単量体1種単独で又は2種以上から構成される成分であって、前記組成物(I)に含まれるのと同じ前記単量体(m)を、成分(B)100質量%中、20質量%以上含む。
すなわち、成分(B)は、前記成分(A)を構成する(メタ)アクリル系重合性単量体のうち、主単量体として含まれる(メタ)アクリル系重合性単量体である単量体(m)と同じ(メタ)アクリル系重合性単量体を、成分(B)100質量%中、20質量%以上含む必要がある。
ここで、「単量体(m)と同じ(メタ)アクリル系重合性単量体」とは、具体的な化合物として、単量体(m)と同じであることを指す。例えば、成分(A)中の単量体(m)がUDMAである場合、成分(B)において、成分(B)100質量%中、20質量%以上含む必要がある単量体(m)とは、当該UDMAのことを指す。
したがって、例えば、成分(A)における単量体(m)が、多官能性単量体(a-1)であるUDMAである場合に、成分(B)が、同じ多官能性単量体(a-1)の範疇であるBis-GMAを、成分(B)100質量%中、20質量%以上含んでいたとしても、それだけでは「単量体(m)と同じ(メタ)アクリル系重合性単量体」を含んでいることにはならない。
また、成分(A)中、主単量体となる単量体(m)が複数存在する場合、例えば、成分(A)中に、2種の(メタ)アクリル系重合性単量体が、それぞれ、50質量%含まれている場合、成分(B)は、成分(A)中のいずれか一つの単量体(m)を20質量%以上含んでいればよく、成分(A)中の全ての単量体(m)を20質量%以上含まなくてもよい。
また、前述のとおり、成分(B)は、単量体(m)単独で、又は、単量体(m)と単量体(o)とから構成される成分である。また、成分(B)は、単量体(o)を複数含有してもよい。したがって、成分(B)中、単量体(m)及び単量体(o)の合計含有量は100質量%である。
更に、本発明の一態様において、成分(B)中の単量体(m)の含有量と成分(A)中の単量体(m)の含有量との差の絶対値が、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(B)中の単量体(m)の含有量と成分(A)中の単量体(m)の含有量との差の絶対値は、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。
同様に、成分(B)中の単量体(o)の含有量と、当該単量体(o)の成分(A)中の含有量との差の絶対値が、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(B)中の単量体(o)の含有量と、当該単量体(o)の成分(A)中の含有量との差の絶対値は、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。また、成分(A)が単量体(o)として複数の化合物を含み、かつ、成分(B)も単量体(o)として成分(A)と同じ複数の化合物を含む場合、対応する各化合物の成分(A)中の含有量と成分(B)中の含有量との差の絶対値も、それぞれ独立に、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(A)が単量体(o)として複数の化合物を含み、かつ、成分(B)も単量体(o)として成分(A)と同じ複数の化合物を含む場合、対応する各化合物の成分(A)中の含有量と成分(B)中の含有量との差の絶対値も、それぞれ独立に、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。
ただし、前述のとおり、成分(B)中、単量体(m)及び単量体(o)の合計含有量は、100質量%である。
本発明の一態様において、成分(B)の組成(当該「組成」は「(メタ)アクリル系重合性単量体の組み合わせ及びその含有量比(質量比)」を表す。以下、「成分(A)の組成」、「成分(C)の組成」という場合の「組成」も同様の意味。)は、成分(A)の組成と同一であることがより更に好ましい。
人工歯用組成物(II)は、本発明の趣旨を損なわない範囲内で、必要に応じて、前述の成分(B)以外の成分を含んでいてもよい。組成物(II)は、公知の方法に準じて製造できる。
組成物(II)に用いることができる光重合開始剤としては、組成物(I)が含む光重合開始剤について前述したものと同様の光重合開始剤が挙げられ、その好適な光重合開始剤の種類も、組成物(I)の欄で前述した内容と同様である。
また、組成物(II)が光重合開始剤を含む場合、その好適な含有量範囲も、「組成物(I)」との表記を「組成物(II)」と変更すること、及び、「成分(A)100質量部」との表記を「成分(B)100質量部」と変更すること以外は、組成物(I)が含む光重合開始剤について前述した内容と同様である。
条件(2):前記人工歯用組成物(II)の硬化物から形成される、直径15.0±0.1、厚さ1.00±0.01mmの試験片のL*a*b*表色系による白背景での色度が、70.0≦L*white≦90.0、-4.0≦a*white≦10.0、10.0≦b*white≦35.0、10.0≦ΔL≦40.0である。
例えば、人工歯用組成物(II)を条件(2)の範囲を満たすように調色したい場合には、好ましくは酸化チタンやアルミナを主成分として、調整したい色調によって、赤酸化鉄、黄酸化鉄、黒酸化鉄の配合量が調節される。ここで、「酸化チタンやアルミナを主成分として」とは、組成物に配合される前記着色剤中、配合量が最も多い着色剤が酸化チタン又はアルミナであることを指す。
また、本発明の一態様において、前記人工歯用組成物(II)の硬化物から形成される、直径15.0±0.1、厚さ1.00±0.01mmの試験片のL*a*b*表色系による黒背景で測色して得られる明度L*blackと白背景で測色して得られる明度L*whiteとの明度差ΔLは、好ましくは10.0以上40.0以下、より好ましくは10.0以上20.0以下、更に好ましくは10.0以上18.0以下である。
前記着色剤が顔料である場合、その合計含有量の好適範囲は前記着色剤の合計含有量と同様である。
また、本発明の一態様において、組成物(II)がフィラーを含有する場合、例えば、組成物(II)の粘度上昇による造形性に対する影響をより一層抑える観点、及び、義歯の強度と靭性をより優れたものとする観点から、組成物(II)中、フィラーの含有量は、成分(B)100質量部に対し、好ましくは20質量部以下、より好ましくは10質量部以下、更に好ましくは5質量部以下である。また、当該一態様において、組成物(II)中、フィラーの含有量は、成分(B)100質量部に対し、好ましくは0.1質量部以上、より好ましくは0.5質量部以上であってもよい。前述のとおり、これら段階的に記載された下限値及び上限値は、それぞれ独立して組み合わせることができる。例えば、本発明の一態様において、組成物(II)がフィラーを含有する場合、例えば、組成物(II)の粘度上昇による造形性に対する影響をより一層抑える観点、及び、義歯の強度と靭性をより優れたものとする観点から、組成物(II)中、フィラーの含有量は、成分(B)100質量部に対し、好ましくは0.1~20質量部、より好ましくは0.1~10質量部、更に好ましくは0.5~5質量部である。
組成物(II)に用いることができる重合禁止剤としては、組成物(I)が含んでもよい重合禁止剤として前述したものと同様の重合体が挙げられる。重合禁止剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
組成物(II)が重合禁止剤を含む場合、組成物(II)中、重合禁止剤の含有量は、成分(B)100質量部に対し、0.001~5.0質量部が好ましく、0.01~3.0質量部がより好ましく、0.1~2.0質量部が更に好ましい。
本発明の一態様において、前記光造形用有床義歯作製キットは、前記義歯床用硬化性組成物(I)と、前記人工歯用組成物(II)に加えて、更に、前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、(メタ)アクリル系重合性単量体成分(C)100質量%中、20質量%以上である組成物(III)を含有する接着剤組成物と、を備える態様であることが好ましい。
前記接着剤組成物は、組成物(I)から作製される義歯床と、組成物(II)から作製される人工歯とを接着する接着剤として用いられる。
前記組成物(III)は、前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)(以下、単に「成分(C)」ともいう。)を含有する。
組成物(III)は、硬化性を有することが好ましく、光硬化性を有することがより好ましい。
前記(メタ)アクリル系重合性単量体成分(C)は、(メタ)アクリル系重合性単量体1種単独で又は2種以上から構成される成分であって、前記組成物(I)に含まれるのと同じ前記単量体(m)を、成分(C)100質量%中、20質量%以上含む。
すなわち、成分(C)は、前記成分(A)を構成する(メタ)アクリル系重合性単量体のうち、主単量体として含まれる(メタ)アクリル系重合性単量体である単量体(m)と同じ(メタ)アクリル系重合性単量体を、成分(C)100質量%中、20質量%以上含む必要がある。
ここで、単量体(m)と同じ(メタ)アクリル系重合性単量体を、成分(C)100質量%中、20質量%以上含む点は、成分(B)における説明と同様である。
前記接着剤組成物は、前記義歯床用硬化性組成物(I)、及び、前記人工歯用組成物(II)のいずれにも含まれる単量体(m)を特定量以上含む成分(C)を含有する組成物(III)を含有するので、義歯を作製する際、組成物(I)から作製される義歯床と、組成物(II)から作製される人工歯との両方に対する接着性により優れる。
したがって、前記光造形用有床義歯作製キットが、前記接着剤組成物を更に備える態様であると、前記義歯床と人工歯とを接着して得られる義歯の強度と靭性をより優れたものとすることができる観点から好ましい。
すなわち、成分(B)を構成する(メタ)アクリル系重合性単量体について前述した内容とも同様である。また、好適な態様及び範囲の設定理由も、特に言及していない限り、前述した内容と同様である。
また、前述のとおり、成分(C)は、単量体(m)単独で、又は、単量体(m)と単量体(o)とから構成される成分である。また、成分(C)は、単量体(o)を複数含有してもよい。したがって、成分(C)中、単量体(m)及び単量体(o)の合計含有量は100質量%である。
更に、本発明の一態様において、成分(C)中の単量体(m)の含有量と成分(A)中の単量体(m)の含有量との差の絶対値が、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(C)中の単量体(m)の含有量と成分(A)中の単量体(m)の含有量との差の絶対値は、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。
同様に、成分(C)中の単量体(o)の含有量と、当該単量体(o)の成分(A)中の含有量との差の絶対値が、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(C)中の単量体(o)の含有量と、当該単量体(o)の成分(A)中の含有量との差の絶対値は、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。また、成分(A)が単量体(o)として複数の化合物を含み、かつ、成分(C)も単量体(o)として成分(A)と同じ複数の化合物を含む場合、対応する各化合物の成分(A)中の含有量と成分(C)中の含有量との差の絶対値も、それぞれ独立に、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(A)が単量体(o)として複数の化合物を含み、かつ、成分(C)も単量体(o)として成分(A)と同じ複数の化合物を含む場合、対応する各化合物の成分(A)中の含有量と成分(C)中の含有量との差の絶対値も、それぞれ独立に、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。
ただし、前述のとおり、成分(C)中、単量体(m)及び単量体(o)の合計含有量は、100質量%である。
当該一態様において、更に、成分(C)中の単量体(m)の含有量と成分(B)中の単量体(m)の含有量との差の絶対値が、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(C)中の単量体(m)の含有量と成分(B)中の単量体(m)の含有量との差の絶対値は、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。
同様に、成分(C)中の単量体(o)の含有量と、当該単量体(o)の成分(B)中の含有量との差の絶対値が、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(C)中の単量体(o)の含有量と、当該単量体(o)の成分(B)中の含有量との差の絶対値は、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。また、成分(B)が単量体(o)として複数の化合物を含み、かつ、成分(C)も単量体(o)として成分(B)と同じ複数の化合物を含む場合、対応する各化合物の成分(B)中の含有量と成分(C)中の含有量との差の絶対値も、それぞれ独立に、10質量%以下であることが好ましく、5質量%以下であることがより好ましく、3質量%以下であることが更に好ましく、1質量%以下であることがより更に好ましい。換言すれば、本発明の一態様において、成分(B)が単量体(o)として複数の化合物を含み、かつ、成分(C)も単量体(o)として成分(B)と同じ複数の化合物を含む場合、対応する各化合物の成分(B)中の含有量と成分(C)中の含有量との差の絶対値も、それぞれ独立に、好ましくは0~10質量%、より好ましくは0~5質量%、更に好ましくは0~3質量%、より更に好ましくは0~1質量%である。
ただし、前述のとおり、成分(C)中、単量体(m)及び単量体(o)の合計含有量は、100質量%である。
また、本発明の一態様において、義歯の強度と靭性をより優れたものとする観点から、成分(C)として、成分(A)を用いることがより更に好ましい。
本発明の一態様において、成分(C)の組成は成分(A)の組成又は成分(B)の組成と同一であることがより更に好ましく、義歯の強度と靭性をより優れたものとする観点から、成分(C)の組成は成分(A)の組成と同一であることがより更に好ましい。
前記組成物(III)は、本発明の趣旨を損なわない範囲内で、必要に応じて、前述の成分(C)以外の成分を含んでいてもよい。組成物(III)は、公知の方法に準じて製造できる。
組成物(III)に用いることができる光重合開始剤としては、組成物(I)が含む光重合開始剤について前述したものと同様の光重合開始剤が挙げられ、その好適な光重合開始剤の種類も、組成物(I)の欄で前述した内容と同様である。
また、組成物(III)が光重合開始剤を含む場合、その好適な含有量範囲も、「組成物(I)」との表記を「組成物(III)」と変更すること、及び、「成分(A)100質量部」との表記を「成分(C)100質量部」と変更すること以外は、組成物(I)が含む光重合開始剤について前述した内容と同様である。
組成物(III)に用いることができるフィラーとしては、前述の硬化性組成物(I)の欄に記載の有機フィラー、無機フィラー、有機-無機複合フィラー等が挙げられる。フィラーは1種を単独で用いてもよく、2種以上を併用してもよい。
組成物(III)に用いることができる重合禁止剤としては、組成物(I)が含んでもよい重合禁止剤として前述したものと同様の重合体が挙げられる。重合禁止剤は、1種を単独で用いてもよく、2種以上を併用してもよい。
組成物(III)が重合禁止剤を含む場合、重合禁止剤の含有量は、成分(C)100質量部に対し、0.001~5.0質量部が好ましく、0.01~3.0質量部がより好ましく、0.1~2.0質量部が更に好ましい。
また、本発明の一態様において、組成物(III)が、例えば、前記条件(1)又は(2)を満たすものであることが好ましい。
前記着色剤が顔料である場合、その合計含有量の好適範囲は前記着色剤の合計含有量と同様である。
前記接着剤組成物は、本発明の趣旨を損なわない範囲内で、必要に応じて、前述の組成物(III)以外の成分を含んでいてもよい。例えば、義歯床及び人工歯への接着剤組成物の塗布性や浸透性を調整するため、組成物(III)に含まれていない重合性単量体や有機溶媒、及びその他の添加物を配合されていてもよい。
有機溶媒としては、例えば、酢酸エチル、酢酸ブチル、塩化メチレン、アセトン、エタノール、イソプロパノール、メチルメタクリレート等が挙げられる。有機溶媒は1種を単独で用いてもよく、2種以上を併用してもよい。これらの中でも、安全性、適度な揮発性の観点から、酢酸エチル、エタノール、イソプロパノールが好ましい。
本発明の一態様である有床義歯の製造方法は、主単量体として(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(A)、及び光重合開始剤を含有する義歯床用硬化性組成物(I)の硬化物からなる義歯床と、前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、(メタ)アクリル系重合性単量体成分(B)100質量%中、20質量%以上である人工歯用組成物(II)の硬化物からなる人工歯とを、前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、(メタ)アクリル系重合性単量体成分(C)100質量%中、20質量%以上である組成物(III)を含有する接着剤組成物を用いて接着することを特徴とする。
また、組成物(I)、組成物(II)、組成物(III)及び接着剤組成物の好適な組成、すなわち、各組成物中に含まれる各成分の好適な配合量についても、それぞれ、前述の光造形用有床義歯作製キットの欄で前述した前記各組成物中の各成分の含有量(質量%又は質量部)と同様であるため、その詳細な説明は省略する。
すなわち、前記組成物(I)の硬化物からなる義歯床と、前記組成物(II)の硬化物からなる人工歯とを、前記接着剤組成物を用いて、接着することを特徴とする、義歯床と人工歯との接着方法も、本発明の一態様に含まれる。
前記接着工程において、前記接着剤組成物を、義歯床と人工歯のいずれか一方の接着面又は両方の接着面に対して塗布し、前記接着剤組成物を介して義歯床と人工歯とを互いに貼合して、接着剤組成物を硬化させることにより、義歯床と人工歯とを接着することができる。当該接着工程において、前記接着剤組成物を光硬化させることにより接着させることが好ましい。
すなわち、例えば、前記製造方法の一態様として、下記工程(1)及び(2)をこの順で有することが好ましい。
工程(1):前記接着剤組成物を、前記義歯床及び前記人工歯から選ばれる少なくとも一方に塗布する工程
工程(2):前記義歯床と、前記人工歯とを、前記接着剤組成物を介して互いに圧着する工程
工程(3):前記接着剤組成物を光硬化させることによって、前記義歯床と、前記人工歯とを接着する工程
また、義歯床の接着剤組成物と接触する面を、予め、研磨して用いてもよい。
同様に、人工歯の接着剤組成物と接触する面を、予め、研磨して用いてもよい。
また、組成物(I)の硬化物からなる義歯床は、その一部が組成物(I)の硬化物である義歯床であってもよく、全体が組成物(I)の硬化物である義歯床であってもよいが、前記接着剤組成物と接触する部分の少なくとも一部が組成物(I)の硬化物であり、前記接着剤組成物と接触する部分の全部が組成物(I)の硬化物であることが好ましい。
また、組成物(II)の硬化物からなる人工歯は、その一部が組成物(II)の硬化物である人工歯であってもよく、全体が組成物(II)の硬化物である人工歯であってもよいが、前記接着剤組成物と接触する部分の少なくとも一部が組成物(II)の硬化物であることが好ましく、前記接着剤組成物と接触する部分の全部が組成物(II)の硬化物であることがより好ましい。
ここで、光造形では、通常、光造形物の造形後に、光造形物を形成する組成物由来の未反応の重合性単量体を重合させるために、2次重合が実施される。当該2次重合を行う方法は、特に制限はなく、従来公知の方法及び装置を用いることができ、歯科用光照射器、光造形用の2次重合装置等を用いる方法によって実施してもよい。
本発明の一態様である有床義歯の製造方法では、前記義歯床及び/又は人工歯を光造形物として得る場合、前記義歯床及び/又は人工歯の2次重合を行う前に、前記接着剤組成物を前記義歯床及び/又は人工歯に塗布して、接着操作を実施することによって、より高い接着性を得ることができる。
したがって、前記義歯床及び/又は人工歯が光造形物である場合、前記義歯床及び人工歯とは、2次重合前である場合も含む。
前記2次重合の前に、前記接着剤組成物を塗布し、その後、前記2次重合を行うことで、義歯床及び/又は人工歯の未反応の重合性単量体と接着剤組成物を構成する重合性単量体とを共重合させることができるため、より高い接着性が得られやすいと考えられる。
さらに、本発明の一態様である有床義歯の製造方法は、前述の2次重合後及び造形から長時間経過後の重合が高度に進んだ状態においても、接着性に優れるという特長を有しており、義歯床及び/又は人工歯の製造から長時間経過後であっても、十分に接着性に優れた義歯の製造が可能である。
工程(3A):活性エネルギー光線を前記接着剤組成物に対して照射し、前記接着剤組成物を硬化させることによって、前記義歯床と、前記人工歯とを接着する工程。
ここで「活性エネルギー光線」とは、紫外線、電子線、X線、放射線、高周波などのような光造形用樹脂組成物を硬化させ得るエネルギー線を意味する。活性エネルギー光線の光源としては、ハロゲンランプ、キセノンランプ、メタルハライドランプ、LED、水銀灯、蛍光灯などの照明などが挙げられ、これらの中では、ハロゲンランプ、LEDが好ましい。
<多官能性の(メタ)アクリル系重合性単量体(a-1)>
「UDMA」:2,2,4-トリメチルヘキサメチレンビス(2-カルバモイルオキシエチル)ジメタクリレート(共栄社化学株式会社製、分子量471)
「Bis-GMA」:2,2-ビス〔4-(3-メタクリロイルオキシ)-2-ヒドロキシプロポキシフェニル〕プロパン(新中村化学工業株式会社製)
「TCDDMA」:トリシクロデカンジメタノールジメタクリレート(共栄社化学株式会社製)
「TEGDMA」:トリエチレングリコールジメタクリレート(新中村化学工業株式会社製)
「POBA」:m-フェノキシベンジルアクリレート(共栄社化学株式会社製)
「EPPA」:エトキシ化-o-フェニルフェノールアクリレート(新中村化学工業株式会社製)
「TPO」:2,4,6-トリメチルベンゾイルジフェニルホスフィンオキシド
「BHT」:3,5-ジ-t-ブチル-4-ヒドロキシトルエン
「二酸化チタン」:日本薬局方酸化チタン
「赤顔料」:Sicovit Red 30 E172(VENATOR社製)
「黄顔料」:Sicovit Yellow 10 E172(VENATOR社製)
「黒顔料」:Sicovit Black 80 E172(VENATOR社製)
「無機フィラー1」:γ-メタクリロイルオキシプロピルトリメトキシシラン処理「アドマファイン(登録商標)」SC4500-SMJ(株式会社アドマテックス製、平均粒子径:1.0μm)
以下の各参考例で得られた組成物の色度は、次の方法を用いて測定した。
以下の各参考例で得られた組成物について、光造形機(DWS社製、「DIGITALWAX(登録商標) 020D」)を用いて、直径15.0mm、厚さ1.0mmの円盤を造形した。
次に、光照射機(EnvisionTEC社製、「Otoflash(登録商標)G171」)で2000回フラッシュして、硬化を完了させ、水研磨紙(#1000、#2000、#3000)を用いて直径15.0±0.1、厚さ1.00±0.01mmに仕上げ、試験片とした(n=1)。研磨後の板状物である試験片を、分光測色計(「CM-3610A」:コニカミノルタ株式会社製、D65光源、幾何条件c(di:8°、de:8°)、拡散照明:8°受光、測定モードSCI、測定径/照明径=φ8mm/φ11mm)により、白背景でのL*a*b*値(JIS Z 8781-4:2013 測色-第4部:CIE 1976 L*a*b*色空間)を測定した。
また、黒背景でも同様の測色を行い、L*black値を測定し、以下のように白背景と黒背景の明度差ΔL値を算出した。「白背景」とは、標準白色板(L*=98.68、a*=-0.07、b*=-0.31)を下敷きとして試験片の背景を白色にして(試験片に対して測定装置と反対側を白色にして)測定することを意味し、「黒背景」とは、標準黒色板(L*=25.64、a*=-0.19、b*=-0.80)を下敷きとして試験片の背景を黒色にして(試験片に対して測定装置と反対側を黒色にして)測定することを意味する。
ΔL*=L*black-L*white
但し、L*white、a*white、及びb*whiteは白背景での測色結果を意味し、L*blackは黒背景での測色結果を意味する。
2Lの褐色広口ポリエチレン製の瓶に、POBA 300g、TPO 30g、BHT 5.0g、二酸化チタン 0.01g、赤顔料 0.001gを投入し、超音波にて顔料を分散させた後、UDMA 700gを投入し、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を義歯床用硬化性組成物(I)-1とした。義歯床用硬化性組成物(I)-1の光造形物(硬化物)の色度は、L*white=78.25、a*white=12.50、b*white=22.74、ΔL=28.45であった。
義歯床用硬化性組成物(I)-1の組成、及び、色度について、下記表1に示す。
2Lの褐色広口ポリエチレン製の瓶に、POBA 400g、TPO 30g、BHT 5.0g、二酸化チタン 0.01g、赤顔料 0.001gを投入し、超音波にて顔料を分散させた後、Bis-GMA 600gを投入し、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を義歯床用硬化性組成物(I)-2とした。義歯床用硬化性組成物(I)-2の光造形物の色度は、L*white=78.12、a*white=11.93、b*white=25.12、ΔL=27.88であった。
義歯床用硬化性組成物(I)-2の組成、及び、色度について、下記表1に示す。
2Lの褐色広口ポリエチレン製の瓶に、TCDDMA 900g、EPPA 100g、TPO 30g、BHT 5.0g、二酸化チタン 0.01g、赤顔料 0.001gを投入し、超音波にて顔料を分散させた後、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を義歯床用硬化性組成物(I)-3とした。義歯床用硬化性組成物(I)-3の光造形物の色度は、L*white=80.03、a*white=11.76、b*white=19.82、ΔL=30.02であった。
義歯床用硬化性組成物(I)-3の組成、及び、色度について、下記表1に示す。
2Lの褐色広口ポリエチレン製の瓶に、TEGDMA 300g、TPO 30g、BHT 5.0g、二酸化チタン 0.01g、赤顔料 0.001gを投入し、超音波にて顔料を分散させた後、UDMA 700gを投入し、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を義歯床用硬化性組成物(I)-4とした。義歯床用硬化性組成物(I)-4の光造形物の色度は、L*white=76.87、a*white=14.82、b*white=26.69、ΔL=25.87であった。
義歯床用硬化性組成物(I)-4の組成、及び、色度について、下記表1に示す。
2Lの褐色広口ポリエチレン製の瓶に、TCDDMA900g、TEGDMA 100g、TPO 30g、BHT 5.0g、二酸化チタン 0.01g、赤顔料 0.001gを投入し、超音波にて顔料を分散させた後、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を義歯床用硬化性組成物(I)-5とした。義歯床用硬化性組成物(I)-5の光造形物の色度は、L*white=77.13、a*white=12.32、b*white=21.66、ΔL=27.65であった。
義歯床用硬化性組成物(I)-5の組成、及び、色度について、下記表1に示す。
2Lの褐色広口ポリエチレン製の瓶に、POBA 300g、TPO 30g、BHT 5.0g、二酸化チタン 0.15g、赤顔料 0.002g、黄顔料 0.005、黒顔料0.0005gを投入し、超音波にて顔料を分散させた後、UDMA 700gを投入し、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を人工歯用組成物(II)-1とした。人工歯用組成物(II)-1の光造形物の色度は、L*white=75.75、a*white=-1.20、b*white=18.53、ΔL=15.07であった。
義歯床用硬化性組成物(II)-1の組成、及び、色度について、下記表2に示す。
2Lの褐色広口ポリエチレン製の瓶に、POBA 400g、TPO 30g、BHT 5.0g、二酸化チタン 0.15g、赤顔料 0.002g、黄顔料 0.005、黒顔料0.0005gを投入し、超音波にて顔料を分散させた後、Bis-GMA 600gを投入し、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を人工歯用組成物(II)-2とした。人工歯用組成物(II)-2の光造形物の色度は、L*white=74.83、a*white=-0.63、b*white=19.58、ΔL=14.48であった。
義歯床用硬化性組成物(II)-2の組成、及び、色度について、下記表2に示す。
2Lの褐色広口ポリエチレン製の瓶に、TCDDMA 900g、EPPA 100g、TPO 30g、BHT 5.0g、二酸化チタン 0.15g、赤顔料 0.002g、黄顔料 0.005、黒顔料0.0005gを投入し、超音波にて顔料を分散させた後、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を人工歯用組成物(II)-3とした。人工歯用組成物(II)-3の光造形物の色度は、L*white=76.12、a*white=-1.92、b*white=16.39、ΔL=16.21であった。
義歯床用硬化性組成物(II)-3の組成、及び、色度について、下記表2に示す。
2Lの褐色広口ポリエチレン製の瓶に、TEGDMA 300g、TPO 30g、BHT 5.0g、二酸化チタン 0.15g、赤顔料 0.002g、黄顔料 0.005、黒顔料0.0005gを投入し、超音波にて顔料を分散させた後、UDMA 700gを投入し、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を人工歯用組成物(II)-4とした。人工歯用組成物(II)-4の光造形物の色度は、L*white=76.11、a*white=-1.36、b*white=17.99、ΔL=15.36であった。
義歯床用硬化性組成物(II)-4の組成、及び、色度について、下記表2に示す。
2Lの褐色広口ポリエチレン製の瓶に、TCDDMA900g、TEGDMA 100g、TPO 30g、BHT 5.0g、二酸化チタン 0.15g、赤顔料 0.002g、黄顔料 0.005、黒顔料0.0005gを投入し、超音波にて顔料を分散させた後、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、完全に溶解したことを確認した。得られた組成物を人工歯用組成物(II)-5とした。人工歯用組成物(II)-5の光造形物の色度は、L*white=77.02、a*white=-1.41、b*white=17.12、ΔL=16.21であった。
義歯床用硬化性組成物(II)-5の組成、及び、色度について、下記表2に示す。
2Lの褐色広口ポリエチレン製の瓶に、人工歯用組成物(II)-1 400g、TEGDMA 100g、無機フィラー1 500gを投入し、超音波にて顔料を分散させた後、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、分散したことを確認した。得られた組成物を人工歯用組成物(II)-6とした。人工歯用組成物(II)-6の光造形物の色度は、L*white=73.43、a*white=2.31、b*white=12.43、ΔL=13.25であった。
義歯床用硬化性組成物(II)-6の組成、及び、色度について、下記表2に示す。
2Lの褐色広口ポリエチレン製の瓶に、人工歯用組成物(II)-1 200g、TEGDMA 300g、無機フィラー1 500gを投入し、超音波にて顔料を分散させた後、メカニカル撹拌機を挿入して、25℃で48時間撹拌して、分散したことを確認した。得られた組成物を人工歯用組成物(II)-7とした。人工歯用組成物(II)-7の光造形物の色度は、L*white=73.58、a*white=2.22、b*white=12.83、ΔL=15.25であった。
義歯床用硬化性組成物(II)-7の組成、及び、色度について、下記表2に示す。
以下で説明するように、各参考例に記載した組成物の造形物を、下記表3及び4に示す組み合わせで、以下で説明する接着剤を用いて接着し、硬化させて試験片を作製して、曲げ強さ及び靭性試験を行った。
実施例1~3及び比較例1~5では使用した義歯床用硬化性組成物(I)と同一の組成である組成物(III)を接着剤として用いた。
実施例4及び5では使用した人工歯用組成物(II)と同一の組成である組成物(III)を接着剤として用いた。
実施例6では使用した義歯床用硬化性組成物(I)-1と同一の組成である組成物(III)を、酢酸エチルで30質量%に希釈した接着剤組成物を接着剤として用いた。
実施例7では使用した義歯床用硬化性組成物(I)-1と同一の組成である組成物(III)を、酢酸エチルで15質量%に希釈した接着剤組成物を接着剤として用いた。
比較例6では、市販の義歯床用接着剤である「ユニファスト(登録商標)III」(株式会社ジーシー製、メチルメタクリレート(MMA)とポリメチルメタクリレート(PMMA)の粉液型接着剤)を接着剤として用いた。
参考例で得られた義歯床用硬化性組成物(I)及び人工歯用組成物(II)について、光造形機(DWS社製、「DIGITALWAX(登録商標) 020D」)を用いて、JIS T 6501:2012(義歯床用アクリル系レジン)に記載の寸法の半分の厚さである、長さ64.0mm、幅10.0mm、厚さ1.65mmの試験片を造形した。続いて、表3及び4に示す組み合わせにて、義歯床用硬化性組成物(I)及び人工歯用組成物(II)から造形した試験片を、前述した接着剤約1gを介して圧着し、余剰の接着剤をふき取った後、光照射機(EnvisionTEC社製、「Otoflash(登録商標)G171」)で2000回フラッシュして、硬化を完了させて、JIS T 6501:2012(義歯床用アクリル系レジン)に記載の寸法の厚さである、長さ64.0mm、幅10.0mm、厚さ3.3mmの試験片を得た。但し、比較例6では、圧着後、37℃の空気中で1時間放置後、同様に光照射機で照射して、硬化を完了させた。
Claims (12)
- 主単量体として(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(A)、及び光重合開始剤を含有する義歯床用硬化性組成物(I)と、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(B)100質量%中、20質量%以上である人工歯用組成物(II)と、
を備える光造形用有床義歯作製キット。 - 前記(メタ)アクリル系重合性単量体(m)が、多官能性の(メタ)アクリル系重合性単量体(a-1)である、請求項1に記載の光造形用有床義歯作製キット。
- 前記多官能性の(メタ)アクリル系重合性単量体(a-1)が、ウレタン化(メタ)アクリル酸エステル化合物、及びウレタン結合を含有しない芳香族化合物系の(メタ)アクリル酸エステル化合物から選ばれる少なくとも1種である、請求項2に記載の光造形用有床義歯作製キット。
- 前記(メタ)アクリル系重合性単量体成分(A)が、単官能性の(メタ)アクリル系重合性単量体(a-2)を含有する、請求項1~3のいずれか1項に記載の光造形用有床義歯作製キット。
- 前記(メタ)アクリル系重合性単量体成分(B)が、単官能性の(メタ)アクリル系重合性単量体(a-2)を含有する、請求項1~4のいずれか1項に記載の光造形用有床義歯作製キット。
- 前記単官能性の(メタ)アクリル系重合性単量体(a-2)が、芳香環を含有する(メタ)アクリル酸エステル系重合性単量体である、請求項4又は5に記載の光造形用有床義歯作製キット。
- 前記義歯床用硬化性組成物(I)中、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(A)100質量%中、50質量%以上である、請求項1~6のいずれか1項に記載の光造形用有床義歯作製キット。
- 前記人工歯用組成物(II)中、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(B)100質量%中、50質量%以上である、請求項1~7のいずれか1項に記載の光造形用有床義歯作製キット。
- 前記(メタ)アクリル系重合性単量体成分(A)を、前記義歯床用硬化性組成物(I)100質量%中、40質量%以上含有する、請求項1~8のいずれか1項に記載の光造形用有床義歯作製キット。
- 前記(メタ)アクリル系重合性単量体成分(B)を、前記人工歯用組成物(II)100質量%中、40質量%以上含有する、請求項1~9のいずれか1項に記載の光造形用有床義歯作製キット。
- 前記義歯床用硬化性組成物(I)と、
前記人工歯用組成物(II)と、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(C)100質量%中、20質量%以上である組成物(III)を含有する接着剤組成物と、
を備える、請求項1~10のいずれか1項に記載の光造形用有床義歯作製キット。 - 主単量体として(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(A)、及び光重合開始剤を含有する義歯床用硬化性組成物(I)の硬化物からなる義歯床と、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(B)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(B)100質量%中、20質量%以上である人工歯用組成物(II)の硬化物からなる人工歯とを、
前記義歯床用硬化性組成物(I)に含まれるのと同じ前記(メタ)アクリル系重合性単量体(m)を含む(メタ)アクリル系重合性単量体成分(C)を含有し、前記(メタ)アクリル系重合性単量体(m)の含有量が、前記(メタ)アクリル系重合性単量体成分(C)100質量%中、20質量%以上である組成物(III)を含有する接着剤組成物を用いて接着することを特徴とする、有床義歯の製造方法。
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