WO2022224807A1 - 歯科用接着性組成物 - Google Patents
歯科用接着性組成物 Download PDFInfo
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- WO2022224807A1 WO2022224807A1 PCT/JP2022/016842 JP2022016842W WO2022224807A1 WO 2022224807 A1 WO2022224807 A1 WO 2022224807A1 JP 2022016842 W JP2022016842 W JP 2022016842W WO 2022224807 A1 WO2022224807 A1 WO 2022224807A1
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- agent
- adhesive composition
- silane coupling
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- HCXVPNKIBYLBIT-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 3,5,5-trimethylhexaneperoxoate Chemical compound CC(C)(C)CC(C)CC(=O)OOOC(C)(C)C HCXVPNKIBYLBIT-UHFFFAOYSA-N 0.000 description 1
- VNQXSTWCDUXYEZ-UHFFFAOYSA-N 1,7,7-trimethylbicyclo[2.2.1]heptane-2,3-dione Chemical compound C1CC2(C)C(=O)C(=O)C1C2(C)C VNQXSTWCDUXYEZ-UHFFFAOYSA-N 0.000 description 1
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- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000012756 surface treatment agent Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 125000004213 tert-butoxy group Chemical group [H]C([H])([H])C(O*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000012719 thermal polymerization Methods 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- SGCFZHOZKKQIBU-UHFFFAOYSA-N tributoxy(ethenyl)silane Chemical compound CCCCO[Si](OCCCC)(OCCCC)C=C SGCFZHOZKKQIBU-UHFFFAOYSA-N 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000010457 zeolite Substances 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
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K6/00—Preparations for dentistry
- A61K6/70—Preparations for dentistry comprising inorganic additives
- A61K6/71—Fillers
- A61K6/76—Fillers comprising silicon-containing compounds
-
- 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
- A61K6/60—Preparations for dentistry comprising organic or organo-metallic additives
Definitions
- the present invention relates to a dental adhesive composition.
- an adhesive curable composition containing a polymerizable monomer component containing a polymerizable monomer having an acidic group (hereinafter also referred to as "acidic monomer”), a filler and a polymerization initiator is widely used.
- acidic monomer a polymerizable monomer component containing a polymerizable monomer having an acidic group
- a filler it is blended for various purposes such as adjusting the viscosity of the paste and improving the aesthetics of the cured product.
- System fillers are often used (see Patent Documents 1 to 3).
- dental cement particularly dental resin cement
- resin cement is generally used to bond the prosthesis and the tooth substance.
- Dental (resin) cements especially self-adhesive resin cements, contain acidic monomers, so they have adhesiveness to tooth substance, metals, and zirconia.
- methacryloxypropyltriethoxysilane, etc. may be added to improve adhesion to restorations made of silica-based ceramics such as porcelain.
- the silane coupling agent should be divided into two parts and stored so that they do not coexist with the acid component such as the polymerizable monomer having an acidic group, and the two are mixed at the time of use. However, even if it is used in such a manner, the problem of storage stability remains.
- each agent is mixed with a filler in order not to cause a difference in the paste properties of the two agents, but when a silica-based filler is used as the filler, A problem arises that the silane coupling agent is deactivated due to the influence of the surface acid sites of the silica-based filler during long-term storage.
- Patent Literature 4 describes "a polymerizable monomer having an acidic group (a), a polymerizable monomer having no acidic group (b), a polymerization initiator (c), and a filler (d).
- a photopolymerization initiator (h), a polymerization inhibitor, a coloring agent, a fluorescent agent, an antibacterial substance, an ultraviolet absorber, a dye, a pigment, and the content other than the above components is 1.0 % by weight
- the polymerization initiator (c) is one or more selected from the group consisting of organic peroxides, inorganic peroxides and transition metal complexes, and a polymerization having no acidic group.
- a two-paste type dental curable composition comprising a second agent containing a silane coupling agent (g) represented by the following.
- the second agent containing a silane coupling agent needs to use a basic filler (e) such as barium glass as a filler.
- a silica-based filler is used as the filler (d) of Agent 1, it is difficult to match the paste properties of both agents (even if a silica-based filler is added to Agent 2 within a certain range).
- the present invention provides a dental adhesive composition that can be suitably used as a dental cement, particularly a dental resin cement, and which contains a silane coupling agent and has high adhesiveness even to silica-based ceramic restorations. and can be stably stored for a long period of time even when a silica-based filler and a silane coupling agent are coexistent.
- the present invention is intended to solve the above problems, and in a first form of the present invention, 1 to 30 parts by mass of the acidic group-containing polymerizable monomer (a1) and the balance being an acidic group-free polymerizable monomer
- silane coupling agent (C) 0.1 to 20 parts by mass 97% by mass or more of the silane coupling agent (C) is a monovalent radically polymerizable organic residue having at least one radically polymerizable functional group on a silicon atom.
- an ⁇ -branched alkoxysilane-based silane coupling agent (c1) comprising an organosilicon compound to which a branched alkoxy group having 3 to 5 carbon atoms and having a branch at the ⁇ -position is bonded.
- the dental adhesive composition of the above form preferably further contains a polymerization initiator (D), and the silane coupling agent It is preferable that 1.5 to 300 parts by mass of water (E) is included with respect to 100 parts by mass of (C).
- a second form of the present invention comprises a paste-like first agent and a paste-like second agent, which are separately packaged, and is used to prepare the dental adhesive composition of the present invention by mixing the two agents.
- a two-paste type dental adhesive composition wherein the first agent comprises an acidic group-containing polymerizable monomer (a1), an acidic group-free polymerizable monomer (a2), and a silica-based filler (B) and does not contain the silane coupling agent (C), and the second agent contains an acidic group-free polymerizable monomer (a2), a silica-based filler (B), and the silane coupling agent (C) and does not contain an acidic group-containing polymerizable monomer (a1), and the dental adhesive composition contains an acidic group-containing polymerizable monomer (a1) and an acidic group-free polymerizable monomer (a2) , In the case of containing components other than the silica-based filler (B) and the silane coupling agent (C
- the first agent and/or the second agent comprise the silane
- the coupling agent (C) 100 parts by mass of the coupling agent (C)
- the polymerizable monomer component (A) 100 parts by mass of the above 3 to 12 parts by mass of the ⁇ -branched alkoxysilane-based silane coupling agent (c1)
- the amount of the first agent is 1 part per 100 parts by mass of the ⁇ -branched alkoxysilane-based silane coupling agent (c1) 8 to 12 parts by mass of water (D)
- the first agent does not contain water (D) or contains 10 parts by mass or less of water (D).
- a third aspect of the present invention is a dental cement comprising the dental adhesive composition of the present invention.
- a fourth form of the present invention is a two-paste dental cement comprising the two-paste dental adhesive composition of the present invention.
- the adhesive composition for dental use of the present invention contains an acid monomer and a silane coupling agent, it has high adhesiveness not only to materials such as tooth substance, metals and zirconia but also to silica-based ceramics. Separation, specifically, the two-paste type dental adhesive composition of the present invention has an excellent feature that it can be stably stored for a long period of time. Furthermore, when dividing into two agents, the silane coupling agent (C) is stable even if it coexists with a silica-based filler, so the same type of filler can be blended in both agents, and the paste properties of both agents can be easily aligned. .
- the dental adhesive composition of the present invention and the two-paste type dental adhesive composition of the present invention can be suitably used as a dental (resin) cement.
- the silane coupling agent (hereinafter also referred to as "SC material”) is a "monovalent radically polymerizable organic compound having at least one radically polymerizable functional group on the silicon atom.
- SC material silane coupling agent
- An " ⁇ -branched alkoxysilane system” (sometimes abbreviated as a “branched RO system”) composed of an organosilicon compound in which a residue and a branched alkoxy group having 3 to 5 carbon atoms having a branch at the ⁇ -position are bonded. ).
- a silane coupling material (SC material) (c1) is used, and other silane coupling materials are not substantially contained, specifically 97% by mass or more of the SC material used, preferably The point is that 99% by mass or more is ⁇ -branched alkoxysilane-based SC material.
- the ⁇ -branched alkoxysilane-based SC material (c1) Although the details of why the effect is obtained by using the ⁇ -branched alkoxysilane-based SC material (c1) are unknown, the promoting effect is observed when water is included. It is assumed that this is due to the following reasons. That is, the ⁇ -branched alkoxysilane-based SC material has a bulky structure because the alkoxy, which becomes a leaving group during hydrolysis, has a branch at the ⁇ -position. It is presumed that the effect of the dots is blocked and hydrolysis and condensation are suppressed, resulting in high storage stability.
- silane coupling agent (g) represented by the formula [I] examples include vinyltriethoxysilane, vinyltris( ⁇ -methoxyethoxy)silane, vinyltriethoxysilane, Propoxysilane, vinyltributoxysilane, ⁇ -methacryloxypropyltriethoxysilane, ⁇ -methacryloxypropyltris( ⁇ -methoxyethoxy)silane, 6-(meth)acryloxyhexyltriethoxysilane, ⁇ -methacryloxydecyltriethoxysilane They are silane and 11-(meth)acryloyloxyundecyltriethoxysilane, and Patent Document 4 has no description of an ⁇ -branched alkoxysilane-based SC material.
- the polymerizable monomer component (A) in the adhesive composition for dental use of the present invention comprises an acidic group-containing polymerizable monomer (acidic monomer) (a1) and an acidic group-free polymerizable monomer (hereinafter referred to as " Also referred to as "non-acidic monomer") (a2).
- the amount of the acidic monomer (a1) in 100 parts by mass of the total amount of the polymerizable monomers (A) is 1 to 30 parts by mass. It is preferably 3 to 20 parts by mass, particularly preferably 5 to 10 parts by mass.
- the remaining amount after removing the amount of the acidic monomer (a1) is the amount of the acidic group-free polymerizable monomer (a2).
- Acidic monomer (a1) in the adhesive composition for dental use of the present invention, the acidic monomer (a1) means a polymerizable monomer having an acidic group such as a carboxyl group or its acid anhydride group or a phosphonooxy group in the molecule. Not only does it itself function as an adhesive component, but it also has the function of reacting with and activating the ⁇ -branched alkoxysilane-based SC material (C).
- acidic monomer (a1) acidic monomers used in conventional dental adhesive compositions can be used without particular limitation, and among them, from the viewpoint of polymerizability, (meth)acrylates having an acidic group in the molecule are preferred. used.
- acidic monomers examples include bis(6-(meth)acryloyloxyhexyl)hydrogenphosphate, bis(10-(meth)acryloyloxydecyl)hydrogenphosphate, bis ⁇ 2-(meth)acryloyloxy ethyl ⁇ hydrogen phosphate, bis ⁇ 2-(meth)acryloyloxy-(1-hydroxymethyl)ethyl ⁇ hydrogen phosphate, pentaerythritol tri(meth)acrylate halodrogen phosphate, dipentaerythritol penta(meth)acrylate halodro Jen phosphate etc. can be mentioned.
- 2-(meth)acryloyloxyethyl dihydrogenphosphate 2-(meth)acryloyloxyethyl dihydrogenphosphate, bis ⁇ 2-(meth)acryloyloxyethyl ⁇ hydrogenphosphate, 10-(meth)acryloyloxydecyldi Hydrogen phosphates are preferred.
- these acidic monomers may be used alone or in combination of two or more.
- Non-acidic monomer (a2) The non-acidic monomer (a2) is not particularly limited as long as it has at least one radically polymerizable unsaturated group in the molecule and does not have an acidic group.
- (Meth)acrylates are preferably used from the viewpoint of polymerizability and safety to the living body.
- Polymerizable monomers not containing acidic groups that can be suitably used include methyl (meth) acrylate, ethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, 2,2 -bis[4-(3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane, 2,2-bis(methacryloyloxypolyethoxyphenyl)propane, 2-hydroxyethyl methacrylate, 2,2,4-trimethylhexamethylenebis (2-carbamoyloxyethyl) dimethacrylate, 1,10-decanediol di(meth)acrylate and the like can be mentioned.
- These non-acidic monomers may be used alone or in combination of two or more.
- the non-acidic monomer may be di-, tri- or tetra-functional di-, tri- or tetra-functional monomers having a plurality of radically polymerizable groups. It is preferred to use a radically polymerizable monomer.
- silica-based filler (B) In the dental adhesive composition of the present invention, the silica-based filler (B) has the function of improving the mechanical strength of the composition and activating the ⁇ -branched alkoxysilane-based SC material (C).
- silica-based filler (B) silica-based fillers used in conventional dental materials and the like can be used without particular limitation. Moreover, only one type of silica-based filler may be used, or two or more types may be used in combination.
- Silica-based fillers are inorganic particles whose main component is silica. Having silica as a main component means that the filler contains 60% by mass or more of silica, preferably 70% by mass or more.
- the shape of the silica-based filler is not particularly limited, and may be amorphous particles or spherical particles.
- the average particle size of the silica-based filler is not particularly limited, it is preferably about 0.01 ⁇ m to 100 ⁇ m, more preferably about 0.1 ⁇ m to 50 ⁇ m.
- silica-based fillers examples include composite oxides containing silicon as a constituent element such as silica-titania and silica-zirconia; talc, montmorillonite, zeolite, calcium silicate containing silicon as a constituent element. Clay minerals or silicates may be mentioned. These silica-based fillers are surface-treated with a surface treatment agent such as a silane coupling agent in order to improve compatibility with the polymerizable monomer and improve the mechanical strength and water resistance of the resulting cured product. sometimes used.
- the silica-based filler is preferable because it has excellent chemical stability and can be easily surface-treated with a silane coupling agent or the like.
- Composite oxides containing silicon as a constituent element, such as silica-titania and silica-zirconia are used. Especially preferred.
- the content of the silica-based filler (B) is 50 to 1000 parts by mass with respect to 100 parts by mass of the polymerizable monomer (A) contained in the dental material from the viewpoint of kneadability and mechanical strength of the cured product. and preferably 100 to 300 parts by mass.
- Silane coupling agent (C) In the adhesive composition for dental use of the present invention, a silane coupling agent (SC material) (C) is added to 100 parts by mass of the polymerizable monomer component (A) in order to increase the adhesiveness to a silica-based ceramic restoration. 0.1 to 21 parts by mass, preferably 1 to 18 parts by mass, more preferably 3 to 12.5 parts by mass. In order to allow stable storage even when coexisting with a silica-based filler, 97% by mass or more of the SC material (C) is the ⁇ -branched alkoxysilane-based SC material (c1).
- the content of the ⁇ -branched alkoxysilane-based SC material (c1) is less than 97% by mass, it becomes difficult to obtain high storage stability.
- the proportion of the ⁇ -branched alkoxysilane-based SC material (c1) in the SC material is preferably 99% by mass or more.
- the ⁇ -branched alkoxysilane-based SC material (c1) will be described in detail below.
- ⁇ -branched alkoxysilane-based SC material (c1) is a monovalent radically polymerizable organic residue having at least one radically polymerizable functional group on the silicon atom and a carbon number of 3 to 5 having a branch at the ⁇ position. It means a silane coupling agent consisting of an organosilicon compound to which a branched alkoxy group is bonded.
- Preferred examples of the radically polymerizable functional group possessed by the monovalent radically polymerizable organic residue include a (meth)acryloyl group, a (meth)acryloyloxy group, a vinyl group, and a (meth)acrylamide group.
- a vinyl group or an alkyl group having 1 to 20 carbon atoms, particularly a hydrogen atom bonded to a terminal carbon atom of a linear alkyl group having 3 to 10 carbon atoms is radically polymerized. It is preferably a group substituted with a functional group.
- Examples of groups suitable for the monovalent radically polymerizable organic residue include vinyl group, 3-(meth)acryloxypropyl group, 5-(meth)acryloxypentyl group, 7-methacryloxyheptyl group, 9 -(meth)acryloxynonyl group and the like.
- Examples of the branched alkoxy group having 3 to 5 carbon atoms and having a branch at the ⁇ -position include an isopropoxy group, a cyclopropoxy group, a sec-butoxy group, a tert-butoxy group, and a cyclopentoxy group.
- the ⁇ -branched alkoxysilane-based SC material (c1) has a monovalent radically polymerizable organic residue in which two of the four groups bonded to the silicon atom are the above-mentioned radically polymerizable organic residue and a branched branch having 3 to 5 carbon atoms at the ⁇ -position. It may be an alkoxy group, and may have groups other than these groups (also referred to as "other groups"). When other groups are present, the other groups are preferably hydrocarbon groups having 1 to 6 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, hexyl and phenyl groups. .
- Examples of ⁇ -branched alkoxysilane-based SC materials (organosilicon compounds) that can be suitably used include vinyltriisopropoxysilane, vinyldiisopropoxymethylsilane, vinylisopropoxydimethylsilane, 1-(meth)acryloxymethyltri Isoprotosisilane, 2-(meth)acryloxyethyltriisopropoxysilane, 3-(meth)acryloxypropyltriisopropoxysilane, 5-(meth)acryloxypentyltriisopropoxysilane, 7-(meth)acryloxy butyltriisopropoxysilane, 9-(meth)acryloxynonyltriisopropoxysilane, 11-(meth)acryloxyundenyltriisopropoxysilane, 3-(meth)acryloxypropyldiisopropoxymethylsilane, 3- (Meth)acryloxypropyltritert-butoxysilane and the like can be mentioned.
- 3-(meth)acryloxypropyltriisopropoxysilane and 3-(meth)acryloxypropyltritert-butoxysilane are preferably used from the viewpoint of adhesiveness and availability.
- These ⁇ -branched alkoxysilane-based SC materials may be used alone or in combination of two or more.
- the amount of the ⁇ -branched alkoxysilane-based SC material (c1) is 0.1 to 20 parts per 100 parts by mass of the polymerizable monomer (A) contained in the dental material from the viewpoint of adhesiveness and mechanical strength. Parts by mass, preferably 1 to 17 parts by mass, particularly preferably 3 to 12 parts by mass.
- SC material (c2) other than ⁇ -branched alkoxysilane-based SC material An SC material other than an ⁇ -branched alkoxysilane-based SC material that may be contained in the SC material blended in the dental adhesive composition of the present invention as long as it is 3% by mass or less, preferably 1% by mass or less If (c2) satisfies these conditions, ⁇ -methacryloxypropyltriethoxysilane and ⁇ -methacryloxypropyltrimethoxysilane, which are blended in conventional dental adhesive compositions, An SC material composed of an organic silicon compound can be used without particular limitation.
- the ⁇ -branched alkoxysilane-based SC material is hydrolyzed to promote adhesion, thereby increasing the adhesive strength between the ⁇ -branched alkoxysilane-based SC material and the silica-based ceramic restoration.
- it is most preferably contained in an amount of 1.8 to 12 parts by mass.
- Non-silica filler (E) The dental adhesive composition of the present invention may contain fillers other than silica-based fillers (non-silica-based fillers) such as fluoroaluminosilicate glass, lanthanum glass, barium glass, and strontium glass. From the viewpoint of activating the ⁇ -branched alkoxysilane-based SC material (c1), the amount of the non-silica-based filler to be blended is preferably 10 parts by mass or less with respect to 100 parts by mass of the silica-based filler (B).
- Polymerization initiator (F) The polymerization initiator (F) has the function of polymerizing and curing the composition.
- examples of the polymerization initiator (F) include photopolymerization initiators, chemical polymerization initiators, and thermal polymerization initiators. Photopolymerization initiators and chemical polymerization initiators are particularly used in dental adhesives and cements from the viewpoint of operability in the oral cavity. Known materials can be used without any particular limitation. These polymerization initiators may be used singly or in combination of two or more.
- Typical photopolymerization initiators include ⁇ -diketones, ketals, thioxanthones, (bis)acylphosphine oxides, and ⁇ -aminoacetophenones.
- ⁇ -diketones and thioxanthones act as polymerization initiators when used in combination with amines. These polymerization initiators may be used singly or in combination of two or more.
- Amines include, for example, aromatic amines and aliphatic amines. These may be used individually by 1 type, and may be mix
- chemical polymerization initiators include chemical polymerization initiators that combine oxidizing agents, reducing agents, and, if necessary, transition metal compounds.
- Oxidants include organic peroxides and inorganic peroxides. These oxidizing agents may be used singly or in combination of two or more.
- Typical organic peroxides include hydroperoxides, peroxyesters, ketone peroxides, peroxyketals, dialkyl peroxides, diacyl peroxides, and peroxydicarbonates.
- An organic peroxide may be used individually by 1 type, and may use 2 or more types together.
- Inorganic peroxides include peroxodisulfate and peroxodiphosphate. Among these inorganic peroxides, one may be used alone, or two or more may be used in combination.
- reducing agents include amines, aromatic sulfinates, thiourea compounds, and arylborate compounds.
- One reducing agent may be used alone, or two or more reducing agents may be used in combination.
- transition metal compounds examples include fourth period transition metal compounds.
- the 4th period transition metal is a metal element of Groups 3 to 12 of the 4th period of the periodic table, preferably vanadium (V) or copper (Cu).
- V vanadium
- Cu copper
- Each of these transition metal elements can have multiple valences, but those with valences that can exist stably, for example, compounds of V (III to V) and Cu (I, II) are organic peroxides and used as a chemical polymerization initiator in combination with a reducing agent.
- +IV-valent and/or +V-valent vanadium compounds or +I-valent and/or +II-valent copper compounds are more preferable, and the most preferable ones are +IV-valent vanadium compounds and +II-valent copper compounds. , these can be used alone or in combination of two or more.
- the term “chemically inaccessible state” means (1) when one composition and another composition are in a “physically inaccessible state”, or (2) Even if one composition and another composition are in a state of physical contact, unidirectional or bidirectional molecular diffusion does not occur between one composition and another composition. means if A specific example of the latter (2) is a state in which one composition and another composition are in contact with each other in a completely solidified state in the temperature environment during storage of the compositions.
- the term “physically inaccessible state” means a state in which one composition and another composition are separated by an inhibitor that inhibits molecular diffusion between the two. do.
- the blocking member solid members such as resins, glass, metals, and ceramics, which are suitably used as materials for containers and bags, are generally used.
- a typical example of the "physically inaccessible state” is, for example, a state in which one type of composition is stored in a hermetically sealed container shielded from outside air and outside light.
- each component constituting the dental adhesive composition of the present invention is a combination of two or more partial compositions that are kept in a state where they cannot be chemically contacted with each other, each From the standpoint of storage stability, it is preferred that the components, which react with each other when mixed, are distributed among the respective partial compositions.
- the dental adhesive composition of the present invention preferably comprises a combination of two partial compositions, that is, the two-paste type dental adhesive composition of the present invention. .
- the two-paste type dental adhesive composition of the present invention will be described below.
- Two-Paste Type Dental Adhesive Composition of the Present Invention comprises a paste-like first agent and a second agent, which are separately packaged, and the two agents are mixed.
- the first agent contains an acidic group-containing polymerizable monomer (a1), an acidic group-free polymerizable monomer (a2), and a silica-based filler (B), and the silane coupling agent (C) It consists of a first partial composition that does not contain
- the second agent contains an acidic group-free polymerizable monomer (a2), a silica-based filler (B), and the silane coupling agent (C), and contains an acidic group-containing polymerizable monomer (a1). It consists of a second partial composition that does not contain
- the adhesive composition for dental use of the present invention contains other optional components, that is, the acidic group-containing polymerizable monomer (a1), the acidic group-free polymerizable monomer (a2), and the silica-based filler (B). and components other than the silane coupling agent (C), in the case of containing these components, the first agent and / or the second agent (first partial composition and / or second partial composition).
- the first agent contains water (D) and an ⁇ -branched alkoxysilane-based SC material ( c1) It is preferable to blend 1.8 to 12 parts by mass with respect to 100 parts by mass. If a large amount of water is added to the second agent, the adhesive strength tends to decrease. Therefore, it is preferable not to add water.
- first agent or the second agent may be blended. , and may be mixed separately.
- a polymerization initiator (F) as an optional component, care must be taken not to polymerize the polymerizable monomer component during storage. Specifically, when the polymerization initiator (F) is a photopolymerization initiator, even if it coexists with the monomer component (A), there is no problem as long as it is not activated, for example, by shielding it from light. Care should be taken when using chemical initiators. Since the non-acidic monomer (a2) is contained in both the first component and the second component, the chemical polymerization initiator is composed of a plurality of components, and each component alone has polymerization activity with respect to the monomer component (A).
- the oxidizing agent is preferably blended only in the first agent, but it can also be blended in the second agent depending on the type.
- the two-paste type dental adhesive composition of the present invention is prepared by mixing the first partial composition and the second partial composition.
- the two-part composition composition and its mixing ratio determine the composition of the dental adhesive composition of the present invention (which is a mixture of both part compositions) to be prepared.
- the amount of the component (also referred to as non-common component) that is blended only in either the first partial composition or the second partial composition (Parts by mass) is the blending amount (parts by mass) of the non-common component contained in the first partial composition or the second partial composition used for mixing, and the first partial composition or the second partial composition
- the blending amount of a component (also referred to as a common component) blended in both of the partial compositions is the blending amount of the common component contained in the first partial composition and the second partial composition used for mixing. It is the sum of the amounts (mass parts).
- the common component when allocating the common component to the first partial composition and the second partial composition, it is necessary to allocate them by assuming the mixing ratio.
- the mixing ratio is more preferably in the range of 1/3 to 3/1, particularly preferably 1/1.
- A Polymerizable monomer (monomer)
- a component (1-1) Acidic monomer (a1) MDP; 10-methacryloxydecyl dihydrogen phosphate SPM; 1:2 mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis ⁇ 2-methacryloyloxyethyl ⁇ hydrogen phosphate.
- Non-acidic monomer (a2) BisGMA; 2,2-bis[4-(3-methacryloyloxy)-2-hydroxypropoxyphenyl]propane D-2.6E; 2,2-bis(methacryloyloxypolyethoxyphenyl)propane 3G; triethylene glycol dimethacrylate UDMA; 2,2,4-trimethylhexamethylenebis(2-carbamoyloxyethyl) dimethacrylate HEMA; 2-hydroxyethyl methacrylate.
- silica-zirconia filler (2-1) Silica-based filler (B) According to the method disclosed in Japanese Patent No. 3277502, tetraethyl silicate and tetrabutyl zirconate were used to synthesize the following silica-zirconia filler.
- F1 Silica-zirconia filler with an average particle size of 3 ⁇ m (silica content: 80% by mass)
- F2 Silica-zirconia filler with an average particle size of 0.2 ⁇ m (silica content: 80% by mass).
- G1 glass filler with an average particle size of 3 ⁇ m (GM27884, manufactured by SHOTT, silica content of 55% by mass)
- G2 glass filler with an average particle size of 0.4 ⁇ m (GM27884, manufactured by SHOTT, silica content of 55% by mass)
- G3 Glass filler with an average particle size of 3 ⁇ m (G018-117, manufactured by SHOTT, silica content 50% by mass)
- G4 glass filler with an average particle size of 0.4 ⁇ m (G018-117, manufactured by SHOTT, silica content 50% by mass)
- G5 Glass filler with an average particle size of 3 ⁇ m (pulverized V-124-1125, manufactured by ESSTECH, silica content 57%)
- G6 Glass filler with an average particle size of 0.4 ⁇ m (pulverized V-124-1125, manufactured by ESSTECH, silica content: 57%).
- Example 1 Preparation of two-paste type dental adhesive composition (first agent and second agent) Using monomer composition I-1 for first agent and monomer composition II-1 for second agent, shown below A first part composition and a second part composition of the composition (both pasty compositions containing a monomer component and a filler component) were prepared to be the first part and the second part, respectively.
- composition of second agent (second part composition)] ⁇ Monomer (A) component Non-acidic monomer (a2): a mixture of 30 parts by mass of BisGMA and 20 parts by mass of 3G ⁇ Filler component Silica-based filler (B): a mixture of 54 parts by mass of F1 and 36 parts by mass of F2 ⁇ Silane coupling agent Components ⁇ -branched RO-based SC material (c1): 3 parts by mass of MPTiPS, - Polymerization initiator (F) component 2 parts by mass of PhBNa and 1 part by mass of AcTU.
- A component
- Non-acidic monomer (a2): a mixture of 30 parts by mass of BisGMA and 20 parts by mass of 3G ⁇ Filler component
- Silica-based filler (B): a mixture of 54 parts by mass of F1 and 36 parts by mass of F2 ⁇ Silane coupling agent
- the above composition is expressed so that the total amount of component (A) contained in the first agent and the second agent is 100 parts by mass.
- the first agent is prepared by mixing (a1), (a2) and (F) and completely dissolving and then mixing the silica-based filler (B), and the second agent is (b2) , (C), and (F) were mixed and completely dissolved, and then (B) was mixed.
- the porcelain was poured with water and polished with #800 water-resistant abrasive paper to carve out a flat surface. After blowing compressed air onto this flat surface to dry it, a double-faced tape having a circular hole with a diameter of 3 mm was fixed to define the adhesion area.
- the dental adhesive composition prepared by the above method was applied to a cylindrical metal attachment with a diameter of 8 mm, and the dental adhesive composition was applied so that the circular hole of the double-sided tape and the surface of the metal attachment were concentric.
- the coated surface of the object was pressed against the porcelain surface. After immersing this test sample in water at 37° C.
- Adhesion strength (MPa) maximum load (N) / adhesion area (mm ⁇ 2 >).
- Examples 2-35 and Comparative Examples 1-10 In the same manner as in Example 1, the first and second agents having the compositions shown in Tables 3-5 were prepared. In these tables, the notation method is the same as in Tables 1 and 2. In addition, the parts by weight of each component of the monomer composition for the first agent and the monomer composition for the second agent used in each example and comparative example in Tables 3 to 5 are the parts by weight in Tables 1 and 2. It can be applied as it is, and the total amount of component (A) contained in the first agent and the second agent is 100 parts by mass.
- the adhesive strength immediately after preparation and after storage was 10 MPa or more, showing high adhesive strength.
- the amount of the branched RO SC material (c1) is 3 to 12 parts by mass with respect to 100 parts by mass of the monomer (A), water (D) is used as the first agent, and the branched RO SC material is When 1.8 to 12 parts by mass of (c1) was added to 100 parts by mass, the adhesive strength immediately after preparation was as high as 20 MPa or more, and even after storage, the adhesive strength was approximately the same as immediately after preparation.
- Comparative Examples 1 to 10 which were blended so as not to satisfy the constitution shown in the present invention, good results were not obtained as shown in Table 5. That is, Comparative Examples 1 to 4 are examples in which the content of the acidic group-containing polymerizable monomer or the SC material did not satisfy the constitution shown in the present invention, and exhibited low adhesive strength. Comparative Examples 5 and 6 are examples containing only MPTES and MPTMS, which are SC materials (c2) other than the branched RO-based SC material (c1), and exhibited low adhesive strength after storage. Comparative Example 7 is an example in which the content of the branched RO system SC material (c1) in the SC material is equal to or lower than the lower limit, and exhibited low adhesive strength after storage. Comparative Examples 8 to 10 are examples in which no silica-based filler was used, and exhibited low adhesive strength at the initial stage and after storage.
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Abstract
Description
で表されるシランカップリング剤(g)を含む第2剤とから構成される2ペースト型歯科用硬化性組成物」が開示されている。
1-1.重合性単量体成分(A)
本発明の歯科用接着性組成物における重合性単量体成分(A)は、酸性基含有重合性単量体(酸性モノマー)(a1)及び酸性基非含有重合性単量体(以下、「非酸性モノマー」ともいう。)(a2)からなる。α分枝アルコキシシラン系SC材活性化及び硬化体の機械強度の観点から重合性単量体(A)の総量100質量部中に占める酸性モノマー(a1)の量は1~30質量部である必要があり、3~20質量部であることが好ましく、5~10質量部であることが特に好ましい。なお、上記酸性モノマー(a1)量を除いた残余の量は、酸性基非含有重合性単量体(a2)の量となる。
本発明の歯科用接着性組成物において、酸性モノマー(a1)とは、分子内に、カルボキシル基又はその酸無水物基、ホスホノオキシ基等の酸性基を有する重合性単量体を意味し、それ自体が接着成分として機能するだけでなく、α分枝アルコキシシラン系SC材(C)と反応し活性化する機能を有する。酸性モノマー(a1)としては、従来の歯科用接着性組成物で使用される酸性モノマーが特に制限なく使用でき、中でも重合性の観点から、分子内に酸性基を有する(メタ)アクリレートが好適に使用される。
非酸性モノマー(a2)は分子内に少なくとも1つのラジカル重合性不飽和基を有し、酸性基を有しないものであれば、特に限定されない。重合性の観点及び生体への安全性の観点からは、(メタ)アクリレートが好適に使用される。好適に使用できる酸性基非含有重合性単量体としては、メチル(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、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、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(メタクリロイルオキシポリエトキシフェニル)プロパン、2-ヒドロキシエチルメタクリレート、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、1,10-デカンジオールジ(メタ)アクリレート等を挙げことができる。これら非酸性モノマーは、1種類のみを用いてもよく、2種類以上を組み合わせて用いてもよい。
本発明の歯科用接着性組成物において、シリカ系フィラー(B)は組成物の機械強度の向上及びα分枝アルコキシシラン系SC材(C)を活性化させる機能を有する。シリカ系フィラー(B)としては、従来の歯科材料等で使用されているシリカ系フィラーが特に制限なく利用できる。また、シリカ系フィラーは1種類のみを用いてもよく、2種類以上を組合せて用いてもよい。
本発明の歯科用接着性組成物は、シリカ系セラミックス修復物に対する接着性を高めるためにシランカップリング材(SC材)(C)を重合性単量体成分(A):100質量部に対して0.1~21質量部、好ましくは1~18質量部が好ましく、より好ましくは3~12.5質量部含む。そして、シリカ系フィラーと共存しても安定に保管できるようにするためにSC材(C)の97質量%以上をα分枝アルコキシシラン系SC材(c1)とする。α分枝アルコキシシラン系SC材(c1)の含有率が97質量%未満であるときには、高い保存安定性を得ることが困難となる。効果の観点から、SC材中に占めるα分枝アルコキシシラン系SC材(c1)の割合は99質量%以上であることが好ましい。以下に、α分枝アルコキシシラン系SC材(c1)について詳しく説明する。
α分枝アルコキシシラン系SC材(c1)とは、ケイ素原子にラジカル重合性官能基を少なくとも1個有する1価のラジカル重合性有機残基及びα位に分枝を有する炭素数3~5の分岐アルコキシ基が結合した有機ケイ素化合物からなるシランカップリング材を意味する。
本発明の歯科用接着性組成物に配合されるSC材に、3質量%以下、好ましくは1質量%以下であれば含まれていてもよい、α分枝アルコキシシラン系SC材以外のSC材(c2)は、このような条件を満足するものであれば、従来の歯科用接着性組成物に配合されている、γ-メタクリロキシプロピルトリエトキシシラン、γ-メタクリロキシプロピルトリメトキシシシランの有機ケイ素化合物からなるSC材が特に制限なく使用できる。
1-4-1.水(D)
本発明の歯科用接着性組成物において、α分枝アルコキシシラン系SC材を加水分解することで接着を促し、α分枝アルコキシシラン系SC材とシリカ系セラミックス修復物の接着強さをより強固なものにするために水(D)を、α分枝アルコキシシラン系SC材(c1)100質量部に対して、1.5~300質量部、特に1.5~100質量部含有することが好ましく、1.8~12質量部含有することが最も好ましい。
本発明の歯科用接着性組成物には、フルオロアルミノシリケートガラス、ランタンガラス、バリウムガラス、ストロンチウムガラス等の、シリカ系フィラー以外のフィラー(非シリカ系フィラー)を配合しても良い。非シリカ系フィラーの配合量は、α分枝アルコキシシラン系SC材(c1)の活性化の観点からシリカ系フィラー(B)100質量部に対して、10質量部以下とすることが好ましい。
重合開始剤(F)は、組成物を重合、硬化させる働きを持つ。重合開始剤(F)として、例えば、光重合開始剤、化学重合開始剤、熱重合開始剤が挙げられる。歯科用接着剤やセメントでは、口腔内での操作性の観点から、光重合開始剤と化学重合開始剤が特に用いられる。これらは特に制限されることなく公知のものが使用できる。これら重合開始剤は、1種を単独で用いてもよく、2種以上を組み合わせて配合してもよい。
前記したように、シランカップリング材として実質的にα分枝アルコキシシラン系SC材(c1)のみを使用した場合においても、酸性モノマーと共存させて保管した場合には、良好な保存安定性を得ることはできない。このため、本発明の歯科用接着性組成物を構成する各成分、特にα分枝アルコキシシラン系SC材(c1)と酸性モノマー(a1)とが、互いに化学的に接触不可能な状態に維持された2つ以上の部分組成物の組合せとし、使用時にこれらを混合して用いることが好ましい。
本発明の2ペースト型歯科用接着性組成物は、互いに分包された、夫々ペースト状の第1剤と第2剤とからなり、両剤を混合することにより本発明の歯科用接着性組成物を調製するための2ペースト型歯科用接着性組成物である。
まず、実施例及び比較例において歯科用接着性組成物を調製する際に使用した各構成成分となる原材料について説明する。
(1-1)酸性モノマー(a1)
MDP;10-メタクリルオキシデシルジハイドロジェンホスフェート
SPM;2-メタクリロイルオキシエチルジハイドロジェンホスフェートとビス{2-メタクリロイルオキシエチル}ハイドロジェンホスフェートの1:2の混合物。
BisGMA;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
D-2.6E;2,2-ビス(メタクリロイルオキシポリエトキシフェニル)プロパン
3G;トリエチレングリコールジメタクリレート
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
HEMA;2-ヒドロキシエチルメタクリレート。
(2-1)シリカ系フィラー(B)
特許3277502号公報に開示されている方法に準じて、テトラエチルシリケート及びテトラブチルジルコネートを用いて、下記シリカジルコニア充填剤を合成した。
F1;平均粒径3μmのシリカジルコニア充填材(シリカ含有量80質量%)
F2;平均粒径0.2μmのシリカジルコニア充填材(シリカ含有量80質量%)。
G1:平均粒径3μmのガラス充填剤(GM27884、SHOTT社製、シリカ含有量55質量%)
G2:平均粒径0.4μmのガラス充填剤(GM27884、SHOTT社製、シリカ含有量55質量%)
G3:平均粒径3μmのガラス充填剤(G018-117、SHOTT社製、シリカ含有量50質量%)
G4:平均粒径0.4μmのガラス充填剤(G018-117、SHOTT社製、シリカ含有量50質量%)
G5:平均粒径3μmのガラス充填剤(V-124-1125を粉砕処理したもの、ESSTECH社製、シリカ含有量57%)
G6:平均粒径0.4μmのガラス充填剤(V-124-1125を粉砕処理したもの、ESSTECH社製、シリカ含有量57%)。
(3-1)α分枝アルコキシシラン系(分枝RO系)SC材(c1)
MPTiPS;3-メタクリロキシプロピルトリイソプロポキシシラン
MPDiPMS;3-メタクリロキシプロピルジイソプロポキメチルシシラン
MPTtBS;3-メタクリロキシプロピルトリtert-ブトキシシラン
MHTiPS;7-メタクリロキシへプチルトリイソプロポトキシシラン。
MPTES;γ-メタクリロキシプロピルトリエトキシシラン
MPTMS;γ-メタクリロキシプロピルトリメトキシシシラン。
CuA;酢酸銅(II)一水和物
CuAA;アセチルアセトン銅(II)
BMOV;ビス(マルトラート)オキソバナジウム(IV)
VOAA;酸化バナジウムアセチルアセトナート(IV)
BPT;t-ブチルペルオキシ-3,5,5-トリメチルヘキサノエート
TMBPH;1,1,3,3-テトラメチルブチルヒドロペルオキシド
CHP;クメンヒドロペルオキシド
CQ;カンファーキノン
PhBNa;テトラフェニルホウ素のナトリウム塩
PhBTEOA;テトラフェニルホウ素のトリエタノールアミン塩
AcTU;アセチルチオ尿素
BzTU;ベンゾイルチオ尿素
DMBE;4-ジメチルアミノ安息香酸エチル。
各実施例及び比較例において第1剤及び第2剤を調製する際に使用する、モノマー成分(A)と重合開始剤成分(F)をモノマー組成物として表1及び表2に示す組成の第1剤用モノマー組成物I-1~I―15及び第2剤用モノマー組成物II-1~II―6を調製して使用した。なお、表中の括弧内の数字は質量部を表し、「↑」は同上を意味する。また、X(x)/Y(y)の表記は、X:x質量部とY:y質量部の混合物であることを意味する。
実施例1
(1)2ペースト型歯科用接着性組成物(第一剤および第二剤)の調製
第1剤用モノマー組成物I-1及び第2剤用モノマー組成物II-1を用い、以下に示す組成の第一部分組成物及び第二部分組成物(何れもモノマー成分及びフィラー成分を含むペースト状組成物)を調製し、夫々を第1剤及び第2剤とした。
・モノマー(A)成分
酸性モノマー(a1):MDP 10質量部、
非酸性モノマー(a2):HEMA 10質量部、D-2.6E 10質量部及び3G 20質量部の混合物
・フィラー成分
シリカ系フィラー(B):F1 54質量部及びF2 36質量部の混合物、
・重合開始剤(F)成分
BPT 2質量部及びCuA 0.02質量部
・モノマー(A)成分
非酸性モノマー(a2):BisGMA 30質量部及び3G 20質量の混合物
・フィラー成分
シリカ系フィラー(B):F1: 54質量部及びF2 36質量部の混合物
・シランカップリング材成分
α分枝RO系SC材(c1):MPTiPS 3質量部、
・重合開始剤(F)成分
PhBNa 2質量部及びAcTU 1質量部。
上記の様にして調製した第一剤および第二剤を質量比1:1で混合して、評価対象となる歯科用接着性組成物を調製した。
(2)で得られた歯科用接着性組成物の接着強度を評価した。評価に際しては、第一剤および第二剤の保存安定性を調べる為に、試料として(a)第一剤および第二剤を調製してから3時間以内のものを用いて調製した歯科用接着性組成物からなる試料(「調製直後」試料)と、(b)第一剤および第二剤を調製してから夫々別容器に填入した状態にて、50℃で2週間保管した後に、これらを用いて調製した歯科用接着性組成物からなる試料(「保管後」試料)の2種の試料について測定を行った。また、接着強度は、シリカ系セラミックスであるポーセレンに対する接着強さとして次のようにして測定した。
上記した評価方法に基づいて評価を行った結果、ポーセレンに対する接着強さは、調製直後で15.4(MPa)であり、保管後で13.2(MPa)であった。この結果から、実施例1の歯科用接着性組成物は、優れた接着性及び保存安定性を有すことが判った。
実施例1と同様の方法で、表3~5に示す組成の第1剤及び第2剤を調製した。なお、これら表においても、表記の仕方は表1及び2と同様である。また、表3~5における各実施例及び比較例で使用される第1剤用モノマー組成物及び第2剤用モノマー組成物の各成分の質量部については、表1及び表2の質量部がそのまま適用でき、第1剤と第2剤に含まれる(A)成分の総量100質量部となっている。
Claims (8)
- 1~30質量部が酸性基含有重合性単量体(a1)であり、残余が酸性基非含有重合性単量体(a2)である重合性単量体成分(A):100質量部、
シリカ系フィラー(B):50~1000質量部、及び
シランカップリング材(C):0.1~20質量部
を含む歯科用接着性組成物であって、
前記シランカップリング材(C)の97質量%以上が、ケイ素原子にラジカル重合性官能基を少なくとも1個有する1価のラジカル重合性有機残基及びα位に分枝を有する炭素数3~5の分岐アルコキシ基が結合した有機ケイ素化合物からなるα分枝アルコキシシラン系シランカップリング材(c1)である、
ことを特徴とする歯科用接着性組成物。 - 前記シランカップリング材(C)100質量部に対して、1.5~300質量部の水(D)を含む、請求項1に記載の歯科用接着性組成物。
- 重合開始剤(E)を更に含んでなる、請求項1又は2に記載の歯科用接着性組成物。
- 互いに分包された、夫々ペースト状の第1剤と第2剤とからなり、両剤を混合することにより請求項1~3の何れか一項に記載の歯科用接着性組成物を調製するための2ペースト型歯科用接着性組成物であって、
第1剤は、酸性基含有重合性単量体(a1)、酸性基非含有重合性単量体(a2)、及びシリカ系フィラー(B)を含み、前記シランカップリング材(C)を含まず、
第2剤は、酸性基非含有重合性単量体(a2)、シリカ系フィラー(B)、及び前記シランカップリング材(C)を含み、酸性基含有重合性単量体(a1)を含まず、
前記歯科用接着性組成物が、酸性基含有重合性単量体(a1)、酸性基非含有重合性単量体(a2)、シリカ系フィラー(B)及び前記シランカップリング材(C)以外の成分を含む場合におけるこれら成分は、第1剤及び/又は第2剤に含まれる、
ことを特徴とする前記2ペースト型歯科用接着性組成物。 - 前記第1剤及び/又は前記2剤が、前記シランカップリング材(C)100質量部に対して、1.5~300質量部の水(D)を含む、請求項4に記載の2ペースト型歯科用接着性組成物。
- 前記重合性単量体成分(A):100質量部に対して前記α分枝アルコキシシラン系シランカップリング材(c1)を3~12質量部含み、且つ前記第1剤が、前記α分枝アルコキシシラン系シランカップリング材(c1)100質量部に対して、1.8~12質量部の水(D)を含み、前記第2剤が水(D)を含まないか又は10質量部以下含む、請求項5に記載の2ペースト型歯科用接着性組成物。
- 請求項1~3の何れか一項に記載の歯科用接着性組成物からなる歯科用セメント。
- 請求項4~6の何れか一項に記載の2ペースト型歯科用接着性組成物からなる2ペースト型歯科用セメント。
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US18/549,020 US20240122814A1 (en) | 2021-04-19 | 2022-03-31 | Dental adhesive composition |
EP22791582.4A EP4327798A1 (en) | 2021-04-19 | 2022-03-31 | Dental adhesive composition |
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JP2021070438A JP7160286B1 (ja) | 2021-04-19 | 2021-04-19 | 2ペースト型歯科用接着性組成物 |
JP2021-070438 | 2021-04-19 |
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US (1) | US20240122814A1 (ja) |
EP (1) | EP4327798A1 (ja) |
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WO (1) | WO2022224807A1 (ja) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6351308A (ja) | 1986-08-19 | 1988-03-04 | Kuraray Co Ltd | 歯科用接着性組成物 |
JPH0554155B2 (ja) | 1984-10-25 | 1993-08-11 | Tdk Electronics Co Ltd | |
JP3277502B2 (ja) | 1992-11-19 | 2002-04-22 | 株式会社トクヤマ | 無機充填材の製造方法及び歯科用充填修復材料 |
WO2009084586A1 (ja) | 2007-12-28 | 2009-07-09 | Kuraray Medical Inc. | 歯科用セメント |
JP6346086B2 (ja) | 2014-12-26 | 2018-06-20 | クラレノリタケデンタル株式会社 | 2ペースト型歯科用硬化性組成物 |
WO2019082855A1 (ja) * | 2017-10-23 | 2019-05-02 | クラレノリタケデンタル株式会社 | 歯科用組成物 |
-
2021
- 2021-04-19 JP JP2021070438A patent/JP7160286B1/ja active Active
-
2022
- 2022-03-31 WO PCT/JP2022/016842 patent/WO2022224807A1/ja active Application Filing
- 2022-03-31 EP EP22791582.4A patent/EP4327798A1/en active Pending
- 2022-03-31 US US18/549,020 patent/US20240122814A1/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0554155B2 (ja) | 1984-10-25 | 1993-08-11 | Tdk Electronics Co Ltd | |
JPS6351308A (ja) | 1986-08-19 | 1988-03-04 | Kuraray Co Ltd | 歯科用接着性組成物 |
JP3277502B2 (ja) | 1992-11-19 | 2002-04-22 | 株式会社トクヤマ | 無機充填材の製造方法及び歯科用充填修復材料 |
WO2009084586A1 (ja) | 2007-12-28 | 2009-07-09 | Kuraray Medical Inc. | 歯科用セメント |
JP6346086B2 (ja) | 2014-12-26 | 2018-06-20 | クラレノリタケデンタル株式会社 | 2ペースト型歯科用硬化性組成物 |
WO2019082855A1 (ja) * | 2017-10-23 | 2019-05-02 | クラレノリタケデンタル株式会社 | 歯科用組成物 |
Non-Patent Citations (1)
Title |
---|
TAKITA, KYOKO; KISHI, HIROTO; AKIZUMI, HIRONOBU; HIRATA, KOUICHIRO: "Influence of silane coupling agent in adhesive agent on bond strength of silica-based ceramics", PROGRAMS AND LECTURE ABSTRACTS OF THE MEETING OF THE JAPANESE SOCIETY OF CONSERVATIVE DENTISTRY, vol. 146, 1 January 2017 (2017-01-01), pages 93, XP009540561 * |
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Publication number | Publication date |
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JP7160286B1 (ja) | 2022-10-25 |
EP4327798A1 (en) | 2024-02-28 |
US20240122814A1 (en) | 2024-04-18 |
JP2022166342A (ja) | 2022-11-02 |
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