Source: https://patents.google.com/patent/US20050250868?oq=2040248
Timestamp: 2018-02-25 04:25:01
Document Index: 492648670

Matched Legal Cases: ['Art 2', 'Art 3', 'Art 4', 'Art 5', 'Art 6', 'Art 7', 'Art 8', 'Art 9']

US20050250868A1 - Cationically curable composition for dental use - Google Patents
US20050250868A1
US20050250868A1 US11114086 US11408605A US2005250868A1 US 20050250868 A1 US20050250868 A1 US 20050250868A1 US 11114086 US11114086 US 11114086 US 11408605 A US11408605 A US 11408605A US 2005250868 A1 US2005250868 A1 US 2005250868A1
US11114086
US7365106B2 (en )
(a×A):(b×B)=91:9 to 45:55 wherein A is a mol number of the oxetane compound, “a” is an average number of the oxetane functional group contained in one molecule of the oxetane compound, B is a mol number of the epoxy compound or the alkenyl ether compound, and “b” is an average number of the epoxy functional group contained in one molecule of the epoxy compound or an average number of the alkenyl ether functional group contained in one molecule of the alkenyl ether compound. The composition is not hindered by oxygen from being polymerized, cures quickly even without using a special polymerizable monomer or a particular polymerization initiator, little forms an unpolymerized layer on the surface even when polymerized and cured in a highly humid environment such as in the oral cavity, and is suited as a filling/restorative material for dental use.
Prior Art 2: JP-T-10-508067
Prior Art 3: JP-A-11-130945
Prior Art 4: JP-T-2001-520758
Prior Art 5: JP-T-2001-520759
Prior Art 6: JP-A-8-245783
Prior Art 7: JP-A-2004-149587
Prior Art 8: JP-A-2004-91553
Prior Art 9: JP-A-2004-91698
The cationically curable composition for dental use of the present invention uses the oxetane compound and the epoxy compound or the alkenyl ether compound as the cationically polymerizable monomers (II) in amounts of such a ratio that the ratio of the oxetane functional group and the epoxy functional group or the alkenyl ether functional group lies within a predetermined range. As compared to the dental materials using the conventional (meth)acrylate type radically polymerizable monomers, therefore, the cationically curable composition for dental use of the present invention contracts very little when it is polymerized and is not hindered by oxygen from being polymerized. Further, since it cures within short periods of time, use of the cationically curable composition in the oral cavity does not cause a large burden Lo the patient. Besides, the cationically curable composition is little hindered by water from being polymerized, does not almost change the color tone before and after the curing, and provides a cured body featuring excellent aesthetic appearance.
[Cationic Polymerization Initiator (1)]
bis(p-chlorophenyl)iodonium,
ditolyliodonium,
bis(p-tert-butylphenyl)iodonium,
p-isopropylphenyl-p-methylphenyliodonium,
bis(m-nitrophenyl)iodonium,
p-tert-butylphenylphenyliodonium,
p-methoxyphenylphenyliodonium,
bis(p-methoxyphenyl)iodonium,
p-octyloxyphenylphenyliodonium,
p-phenoxyphenylphenyliodonium, and
bis(p-dodecylphenyl)iodonium.
p-toluenesulfonato,
trifluoromethanesulfonato,
tetrakispentafluorophenylborate,
tetrakispentafluorophenylgallate,
hexafluoroarsenato, and
Among the diaryliodonium salt compounds containing the above cations and anions according to the present invention, it is desired to use those having, as an anion, p-toluenesulfonato, trifluoromethanesulfonato, tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenyl-gallate, hexafluorophosphate, hexafluoroarsenato or hexafluoroantimonate from the standpoint of solubility in the polymerizable monomer. In a state where the nucleophilic property is low and no light is irradiated, there can be preferably used those having, as an anion, hexafluoroantimonate, tetrakispentafluorophenylborate or tetrakispentafluorophenyl-gallate since it can be stably preserved as a mixture with the polymerizable monomer (II) that will be described later.
dimethylphenacylsulfonium,
dimethylbenzylsulfonium,
dimethyl-4-hydroxyphenylsulfonium,
dimethyl-4-hydroxynaphthylsulfonium,
dimethyl-4,7-dihydroxynaphthylsulfonium,
dimethyl-4,8-dihydroxynaphthylsulfonium,
p-tolyldiphenylsulfonium,
p-tert-butylphenyldiphenylsulfonium, and
diphenyl-4-phenylthiophenylsulfonium.
hexafluoroalcenato, and
The above variety of photo acid generators can be used in a single kind or in a combination of two or more kinds. There is no particular limitation on the amount of the photo acid generator that is used provided the polymerization can be initiated by the irradiation with light. In order to accomplish both a suitable rate of polymerization and various properties (e.g., weather-proof property and hardness) of the cured body that is obtained, however, the photo acid generator is usually used in an amount of 0.001 to 10 parts by mass and, particularly, 0.05 to 5 parts by mass per 100 parts by mass of the cationically polymerizable monomers (II) that will be described later.
1-methylnaphthalene,
1-ethylnaphthalene,
1,4-dimethylnaphthalene,
acenaphthene,
1,2,3,4-tetrahydrophenanthrene,
1,2,3,4-tetrahydroanthracene,
benzo[f]phthalan,
benzo [g]chroman,
benzo[g]isochroman,
N-methylbenzo[f]indolin,
N-methylbenzo[f]isoindolin,
4,5-dimethylphenanthrene,
1,8-dimethylphenanthrene,
acephenanthrene,
1-methylanthracene,
9-ethylanthracene,
9-cyclohexylanthracene,
9,10-dimethylanthracene,
9,10-diethylanthracene,
9,10-dicyclohexylanthracene,
9-(1-methoxyethyl)anthracene,
9-hexyloxymethylanthracene,
9,10-dimethoxymethylanthracene,
9-dimethoxymethylanthracene,
9-phenylmethylanthracene,
9-(1-naphthyl)methylanthracene,
9-hydroxymethylanthracene,
9-(1-hydroxyethyl)anthracene,
9,10-dihydroxymethylanthracene,
9-acetoxymethylanthracene,
9-(1-acetoxyethyl)anthracene,
9,10-diacetoxymethylanthracene,
9-benzoyloxymethylanthracene,
9,10-dibenzoyloxymethylanthracene,
9-ethylthiomethylanthracene,
9-(1-ethylthioethyl)anthracene,
9,10-bis(ethylthiomethyl)anthracene,
9-mercaptomethylanthracene,
9-(1-mercaptoethyl)anthracene,
9,10-bis(mercaptomethyl)anthracene,
9-ethylthiomethyl-10-methylanthracene,
9-methyl-10-phenylanthracene,
9-methyl-10-vinylanthracene,
9-allylanthracene,
9,10-diallylanthracene,
9-chloromethylanthracene,
9-iodomethylanthracene,
9-(1-chloroethyl)anthracene,
9-(1-bromoethyl)anthracene,
9-(1-iodoethyl)anthracene,
9,10-dichloromethylanthracene,
9,10-dibromomethylanthracene,
9,10-diiodomethylanthracene,
9-chloro-10-methylanthracene,
9-chloro-10-ethylanthracene,
9-bromo-10-methylanthracene,
9-bromo-10-ethylanthracene,
9-iodo-10-methylanthracene,
9-iodo-10-ethylanthracene,
9-methyl-10-dimethylaminoanthracene,
aceanthrene,
7,12-dimethylbenz(a)anthracene,
7,12-dimethoxymethylbenz(a)anthracene,
5,12-dimethylnaphthacene,
cholanthrene,
3-methylcholanthrene,
7-methylbenzo(a)pyrene,
3,4,9,10-tetramethylperylene,
3,4,9,10-tetrakis(hydroxymethyl)perylene,
violanthrene,
isoviolanthrene,
6,13-dimethylpentacene,
8,13-dimethylpentaphene,
5,16-dimethylhexacene, and
9,14-dimethylhexaphene.
As the condensed polycyclic aromatic compounds other than those described above, there can be exemplified naphthalene, phenanthrene, anthracene, naphthacene, benz[a]anthracene, pyrene and perylene.
[Cationically Polymerizable Monomers (II)]
These oxetane compounds may be used alone or may be used in a combination of a plurality of kinds. Among these oxetane compounds, further, it is desired to use the one having two or more oxetane functional groups in molecules from the standpoint of properties of the cured body that is obtained.
dlpentaerythritolhexaglycidyl ether, and
wherein R3 is an alkyl group that may have a substituent, and R4 is a hydrogen atom or a monovalent group, and a plurality of R4 may be different from each other.
There is no particular limitation on the alkenyl ether compound provided it can be cationically polymerized, and any known compound can be used. Generally, however, it is desired to use a compound in which R4 in the above formula (3) is a hydrogen atom or an alkyl group. From the standpoint of easy availability, further, it is desired to use a compound (vinyl ether compound) in which a plurality of R4 are all hydrogen atoms.
wherein A is a mol number of the oxetane compound, a is an average number of the oxetane functional group contained in one molecule of the oxetane compound, B is a mol number of the epoxy compound or the alkenyl ether compound, and b is an average number of the epoxy functional group contained in one molecule of the epoxy compound or an average number of the alkenyl ether functional group contained in one molecule of the alkenyl ether compound.
As will be understood from the above formula, the oxetane compound and the epoxy compound or the alkyl ether compound are used in combination such that a total number of the oxetane functional groups and a total number of the epoxy functional groups or the alkenyl ether functional groups lie in the above-mentioned range, whereby the contraction due to the polymerization greatly decreases, the polymerization is avoided from being hindered by oxygen or water, and the composition can be used even under a highly humid condition such as in the oral cavity. Further, a quick curing can be accomplished, and a cured product is obtained suppressing a change in the color tone before and after the curing and exhibiting excellent aesthetic appearance.
Average numbesr b of the functional group per one molecule of the epoxy compound and of the alkenyl ether compound may be calculated in the same manner as described above.
2-hydroxyethylmono(meth)acrylate,
2,2-bis[4-(meth)acryloyloxyethoxyphenyl]propane,
2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane,
2,2-bis{4-[2-hydroxy-3-(meth)acryloyloxypropoxy]phenyl}propane,
urethane di(meth)acrylate, and trimethylolpropane di(meth)acrylate.
When the above-mentioned (meta)acrylate monomers are used, it is desired that the oxetane compound, the epoxy compound or the alkenyl ether compound has a radical polymerizable group which can copolymerize with the (meta)acrylate monomers.
In the present invention, it is desired that the above inorganic fillers are treated with a surface-treating agent as represented by a silane coupling agent to improve affinity to the polymerizable monomers and to improve mechanical strength and resistance to water. The surface treatment can be conducted by a known method. As the silane coupling agent, there can be used methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris(2-methoxyethoxy)silane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltris(2-methoxyethoxy)silane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysi lane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, and 3-ethyl-3-[3-(triethoxysilyl)propoxymethyl]oxetane. From the standpoint of accomplishing good affinity to the cationically polymerizable monomers, in particular, it is desired to use a silane coupling agent having a cationically polymerizable functional group, such as 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, and 3-ethyl-3-[3-(triethoxysilyl)propoxymethyl]oxetane. The above silane coupling agents may be used in one kind or in a combination of two or more kinds.
2-methacryloxyethyl acetoacetylacetonato, and A): (ally (meth)acrylate.
1,5-Dentanediol di(meth)acrylate,
From the standpoint of improving adhesion on the interface between the obtained organic/inorganic composite filler and the cationically polymerizable monomers (II), further, it is also allowable to use a (meth)acrylate monomer having a cationically polymerizable functional group (hereinafter called cationically polymerizable (meth)acrylate) or a (meth)acrylate monomer (hereinafter called hydroxy (meth)acrylate) having a hydroxy group that reacts with the cationically polymerizable functional group. As the cationically polymerizable (meth)acrylate and hydroxy(meth)acrylate, there can be exemplified the following compounds.
3-methyl-3,4-epoxycyclohexylmethyl (meth)acrylate,
2-glycidyloxymethyl-2-ethyl-1,3-propanediol di(meth)acrylate, and A): (2-bisglycidyloxymethyl-1,3-propanediol di(meth)acrylate.
2,2-bis[4-(2-hydroxy-3-(meth)acryloxy)propoxyphenyl]]propane.
n-octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl) propionate,
tetrakis[methylene-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate]methane, and
tris(3,5-di-t-butyl-4-hydroxybenzyl)isocyanurate.
These hindered phenols can be used alone or in a combination of two more kinds. The amount of addition thereof is, usually, such that the amount of the hindered phenol groups is 0.001 to 1 mol and, particularly, 0.005 to 0.8 mols per mol of the diaryliodonium salt though it may vary depending upon other components that are used in combination.
2,6-dimethylpiperidine,
N-methyl-2,6-dimethylpiperidine,
N-methyl-2,6-dimethylpiperidine-4-one,
N-methyl-4-hydroxy-2,6-dimethylpiperidine,
N-methyl-2,2,6,6-tetramethylpiperidine,
N-methyl-2,2,6,6-tetramethylpiperidine-4-one,
N-methyl-4-hydroxy-2,2,6,6-tetramethylpiperidine,
bis(2,2,6,6-tetramethyl-4-piperidinyl)sebacate,
bis(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl) sebacate,
tetrakis(2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate,
tetrakis(N-methyl-2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-butane tetracarboxylate,
poly[(6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazi/2,4-diyl)[(2,2,6,6-tetramethyl-4-piperidinyl)imino]hexamethylene(2,2,6,6-tetramethyl-4-piperidinyl)iminol, and
polycondensate of dimethyl-1-(2-hydroxyethyl)4-hydroxy-2,2,6,6-tetramethyl-4-piperidine succinate.
These hindered amines can be used alone or in a combination of two or more kinds. The amount of addition thereof may vary depending upon other components used in combination but is, usually, such that the amount of the hindered amino groups is 0.001 to 1 mol and, particularly, 0.005 to 0.8 mols per mol of the diaryliodonium salt from the standpoint of not adversely affecting the properties of the cured product.
[Cationically Curable Composition for Dental Use]
C Q: Camphorquinone
DMPT: p-dimethylaminotoluidine
DMBE: ethyl 4-dimethylaminoethylbenzoate
APS: 3-aminopropyltrimethoxysilane
TN765:
Described below are methods of evaluating the properties in Examples and in Comparative Examples. As for the atmospheric conditions for effecting the curing, the conditions (1) consisted of a temperature of 22° C. and a relative humidity of 20%, and the conditions (2) consisted of a temperature of 37° C. and a relative humidity of 100%. The conditions (2) were set to resemble the environment in an oral cavity.
◯: The surfaces are neither sticky nor whitened (no unpolymerized portion is existing on the surfaces).
◯: Colored to a small degree as compared with the composition of before cured.
A sample curable composition (liquid composition) before cured was introduced into a 10-ml messflask of which the weight has been known while bringing the liquid level thereof into agreement with an indicator, and was preserved overnight in an incubator maintained at 23° C. After preserved, it was confirmed that the liquid level was in agreement with the indicator, and the weight was measured. The weight of the messflask of before being filled with the composition was subtracted from the measured weight, followed by the division by the volume thereof to calculate the density of the composition. The above operation was conducted using three or more samples, and an average value thereof was regarded to be the density dl of the composition.
Ratio of functional groups Polymerization
Oxetane Epoxy initiator Surface state Curing Contraction by
compound compound Parts by mass of cured product time polymerization
OX-1 EP-1 IMDPI DMBAn CQ Condition 1 Condition 2 (sec) (%)
Comparative 100 □ 0.1 0.03 0 ◯ X 90 3.8
Comparative 95 5 0.1 0.03 0 ◯ X 60 3.8
Comparative 92 8 0.1 0.03 0 ◯ Δ 33 3.8
Example 1 90 10 0.1 0.03 0 ◯ ◯ 22 3.9
Example 2 80 20 0.1 0.03 0 ◯ ◯ 19 3.9
Example 3 55 45 0.1 0.03 0 ◯ ◯ 16 3.9
Example 4 45 55 0.1 0.03 0 ◯ ◯ 23 4
Comparative 43 57 0.1 0.03 0 ◯ Δ 41 4
Comparative 40 60 0.1 0.03 0 ◯ Δ 65 4
Comparative 20 80 0.1 0.03 0 ◯ Δ 74 4.1
Comparative □ 100 0.1 0.03 0 ◯ Δ 128 4.1
Comparative 100 □ 0.1 0.03 0.03 ◯ X 92 3.8
Comparative 95 5 0.1 0.03 0.03 ◯ X 61 3.8
Comparative 92 8 0.1 0.03 0.03 ◯ Δ 35 3.8
Example 5 90 10 0.1 0.03 0.03 ◯ ◯ 25 3.9
Example 6 80 20 0.1 0.03 0.03 ◯ ◯ 23 3.9
Example 7 55 45 0.1 0.03 0.03 ◯ ◯ 19 3.9
Example 8 45 55 0.1 0.03 0.03 ◯ ◯ 28 4
Comparative 43 57 0.1 0.03 0.03 ◯ Δ 50 4
Comparative 40 60 0.1 0.03 0.03 ◯ Δ 69 4
Comparative 20 80 0.1 0.03 0.03 ◯ Δ 80 4.1
Oxetane Epoxy Curing Contraction by
compound compound Microhardness time polymerization
OX-1 EP-1 Condition 1 Condition 2 (sec) (%)
Comparative 100 — 10 could not be 33 1.1
Example 14 measured
Comparative 95 5 10 could not be 28 1.1
Example 15 measured
Comparative 92 8 10 4 20 1.1
Example 9 90 10 11 9 14 1.1
Example 10 80 20 12 10 11 1.2
Example 11 70 30 13 10 9 1.2
Example 12 55 45 12 10 9 1.2
Example 13 45 55 12 9 11 1.2
Comparative 43 57 12 8 18 1.2
Comparative 20 80 12 8 30 1.2
Comparative — 100 11 7 32 1.3
Comparative 100 — 11 could not be 30 1.2
Example 20 measured
Comparative 95 5 12 could not be 27 1.2
Example 21 measured
Comparative 92 8 12 could not be 18 1.2
Example 22 measured
Example 14 90 10 12 10 13 1.3
Example 15 80 20 12 11 10 1.3
Example 16 60 40 12 11 9 1.3
Example 17 45 55 13 10 10 1.3
Comparative 43 57 12 10 17 1.3
Comparative 20 80 11 10 30 1.3
OX-1 EP-2 Condition 1 Condition 2 (sec) (%)
Example 25 measured
Comparative 92 8 10 could not be 20 1.1
Example 26 measured
Example 18 90 10 11 8 14 1
Example 19 80 20 11 10 11 1
Example 20 60 40 12 10 10 1
Example 21 45 55 11 9 13 0.9
Comparative 43 57 11 9 35 0.9
Comparative 20 80 11 9 40 0.8
Comparative — 100 10 8 43 0.7
Oxetane Bicycloortho Curing Contraction by
compound ester Microhardness time polymerization
OX-1 compound Condition 1 Condition 2 (sec) (%)
Comparative 80 — 20 7 could not be 10 1.1
Example 30 measured
Comparative 55 — 45 6 could not be 12 1
Example 31 measured
Comparative — 80 20 8 could not be 9 1.2
Example 32 measured
Comparative — 55 45 6 could not be 10 1
Example 33 measured
Flexural Flexural modulus
strength/MPa of elasticity/GPa
Composite resin deviation) deviation)
Composition of 119.3(3.1) 10.2(0.83)
Composition of 119.1(3.8) 11.8(0.89)
Composition of 118.8(4.0) 10.9(0.95)
Oxetane Alkenyl ether Surface state of Discoloration
compound compound the cured product Observed
OX-1 DVE-1 Condition 1 Condition 2
E* by eyes
Comparative 100 — ◯ X 1 ⊚
Comparative 95 5 ◯ X 1 ⊚
Comparative 92 8 ◯ Δ 1 ⊚
Example 22 90 10 ◯ ◯ 1.1 ⊚
Example 23 70 30 ◯ ◯ 1.2 ⊚
Example 24 50 50 ◯ ◯ 2.3 ◯
Comparative 40 60 ◯ ◯ 5 X
Comparative 38 62 ◯ Δ 5.3 X
Comparative 35 65 ◯ Δ 6 X
Comparative 20 80 ◯ Δ 9.8 X
Comparative — 100 ◯ Δ 12 X
Oxetane ether Surface state of Discoloration
Comparative 100 — ◯ X 0.9 ⊚
Comparative 95 5 ◯ X 0.9 ⊚
Example 25 90 10 ◯ ◯ 1.1 ⊚
Example 26 70 30 ◯ ◯ 1.2 ⊚
Example 27 50 50 ◯ ◯ 2.3 ◯
Comparative 38 62 ◯ Δ 5.4 X
Comparative 35 65 ◯ Δ 6.1 X
Comparative 20 55 ◯ Δ 9.7 X
Oxetane Alkenyl ether Discoloration
compound compound Microhardness Observed
Comparative 100 — 10 could not be 0.9 ⊚
Example. 49 measured
Comparative 95 5 10 could not be 1 ⊚
Example 50 measured
Comparative 92 8 10 4 1 ⊚
Example 28 90 10 11 8 1 ⊚
Example 29 80 20 11 9 1 ⊚
Example 30 70 30 12 9 1.2 ⊚
Example 31 50 50 12 9 2.1 ◯
Comparative 40 60 13 6 3.2 ◯
Comparative 38 62 13 3 3.5 X
Comparative 20 80 13 could not be 3.8 X
Example 54 measured
Comparative — 100 14 could not be 4.1 X
Example 55 measured
Comparative 100 — 11 could not be 1 ⊚
Example 56 measured
Comparative 95 5 12 could not be 1.1 ⊚
Example 57 measured
Comparative 92 8 12 could not be 1.1 ⊚
Example 58 measured
Example 32 90 10 12 8 1.1 ⊚
Example 33 70 30 12 9 1.2 ⊚
Example 34 50 50 12 6 2.2 ◯
Comparative 40 60 13 5 3.4 ◯
Comparative 38 62 13 4 3.8 X
Comparative 20 80 14 could not be 4.2 X
Example 61 measured
OX-1 DVE-2 Condition 1 Condition 2
Example 62 measured
Comparative 92 8 10 could not be 1 ⊚
Example 63 measured
Example 35 90 10 10 8 1.2 ⊚
Example 36 70 30 10 9 1.2 ⊚
Example 37 50 50 11 8 2.3 ◯
Comparative 40 60 12 5 3.1 ◯
Comparative 38 62 12 3 3.4 X
Comparative 20 80 13 could not be 3.9 X
Example 66 measured
Comparative — 100 13 could not be 4.2 X
Example 67 measured
Flexural Flexual modulus
Composition of 117.2(4.3) 11.5(0.95)
Composition of 120.1(4.1) 12.0(0.88)
Surface state of Number of days
cured product preserved Curing time
Condition 1 Condition 2 before gelled (seconds)
Ex. 38 ∘ ∘ 43 10
Ex. 39 ∘ ∘ 1 8
Ex. 40 ∘ ∘ 4 8
Ex341 ∘ ∘ 12 10
Microhardness preserved Curing time
Ex. 42 12 10 30 12
Ex. 43 11 10 49 13
Ex. 44 12 11 1 10
6. A cationically curable composition for dental use according to claim 1, wherein said cationically curable composition is a filling/restorative material for dental use.
US11114086 2004-04-27 2005-04-26 Cationically curable composition for dental use Active 2026-03-18 US7365106B2 (en)
JP2004-131431 2004-04-27
JP2004131431A JP4494854B2 (en) 2004-04-27 2004-04-27 Dental cationically curable composition
JP2004-191380 2004-06-29
JP2004191380A JP4540409B2 (en) 2004-06-29 2004-06-29 Dental polymerizable composition
US20050250868A1 true true US20050250868A1 (en) 2005-11-10
US7365106B2 US7365106B2 (en) 2008-04-29
ID=34941057
US11114086 Active 2026-03-18 US7365106B2 (en) 2004-04-27 2005-04-26 Cationically curable composition for dental use
US (1) US7365106B2 (en)
DE (1) DE602005008805D1 (en)
EP (1) EP1591098B1 (en)
US20070123600A1 (en) * 2005-11-28 2007-05-31 Konica Minolta Medical & Graphic, Inc. Actinic ray curable composition, actinic ray curable ink, and image formation process employing the same
US20070249752A1 (en) * 2004-09-16 2007-10-25 Kuraray Medical Inc. Dental Polymerizable Core Build-Up Material of Separately Packed Type
KR100698917B1 (en) * 2004-06-22 2007-03-22 미쓰이 가가쿠 가부시키가이샤 Ionic compound, and resin composition containing the same and use thereof
US7037460B2 (en) * 2001-06-27 2006-05-02 Fusion Uv Systems, Inc. Free radical polymerization method having reduced premature termination, apparatus for performing the method, and product formed thereby
US7820733B2 (en) * 2004-09-16 2010-10-26 Kuraray Medical Inc. Dental polymerizable core build-up material of separately packed type
DE602005008805D1 (en) 2008-09-25 grant
EP1591098A1 (en) 2005-11-02 application
EP1591098B1 (en) 2008-08-13 grant
US7365106B2 (en) 2008-04-29 grant
Weinmann et al. 2005 Siloranes in dental composites
Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:SUZUKI, TAKESHI;KAZAMA, HIDEKI;REEL/FRAME:016804/0967