WO2019187351A1 - 歯科用充填材及び歯科用重合性組成物 - Google Patents
歯科用充填材及び歯科用重合性組成物 Download PDFInfo
- Publication number
- WO2019187351A1 WO2019187351A1 PCT/JP2018/044571 JP2018044571W WO2019187351A1 WO 2019187351 A1 WO2019187351 A1 WO 2019187351A1 JP 2018044571 W JP2018044571 W JP 2018044571W WO 2019187351 A1 WO2019187351 A1 WO 2019187351A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- dental
- meth
- filler
- acrylate
- epoxide
- Prior art date
Links
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
- A61K6/80—Preparations for artificial teeth, for filling teeth or for capping teeth
- A61K6/831—Preparations for artificial teeth, for filling teeth or for capping teeth comprising non-metallic elements or compounds thereof, e.g. carbon
- A61K6/836—Glass
Definitions
- the present invention relates to a dental filler and a dental polymerizable composition.
- an inorganic filler such as silica or barium glass is blended in the dental restorative material in order to improve the mechanical strength of the cured body.
- the dental restoration material in which the inorganic filler is blended has insufficient smoothness of the cured body.
- Patent Document 1 discloses a dental filler produced by surface-treating an inorganic filler with a silane coupling agent having a methacryloyl group and then reacting with (meth) acrylate.
- An object of one embodiment of the present invention is to provide a dental filler capable of satisfying both the operability of a dental restorative material and the lubricity and bending strength of a cured body of the dental restorative material.
- One embodiment of the present invention is a dental filler, which is produced by subjecting an inorganic filler to a surface treatment with a silane coupling agent having an epoxy group, followed by a ring-opening reaction with a composition containing an epoxide having a (meth) acryloyl group. Has been.
- Another aspect of the present invention is produced by reacting a composition containing a silane coupling agent having an epoxy group and an epoxide having a (meth) acryloyl group with an inorganic filler in a dental filler. Yes.
- a dental filler capable of achieving both smoothness and bending strength of a cured body of a dental restoration material.
- the inorganic filler is surface-treated with a silane coupling agent having an epoxy group, and the epoxy group is introduced onto the surface of the inorganic filler.
- Examples of the material constituting the inorganic filler include silica, barium glass, fluoroaluminosilicate glass, and the like.
- the average particle size of the inorganic filler is preferably 0.005 to 5 ⁇ m, and more preferably 0.05 to 0.5 ⁇ m.
- the silane coupling agent having an epoxy group has a general formula
- R 1 is an alkoxy group having 1 to 6 carbon atoms, an isocyanate group or a chlorine atom
- R 2 is a hydrocarbon group having 1 to 6 carbon atoms
- m is an integer of 1 to 3
- N is an integer from 1 to 20. It is preferable that it is a compound represented by these.
- silane coupling agent having an epoxy group examples include 3-glycidyloxypropyltrimethoxysilane.
- silane coupling agent may have two or more epoxy groups.
- the inorganic filler is surface-treated with a silane coupling agent having an epoxy group
- a known surface treatment method can be used.
- the inorganic filler having an epoxy group introduced on the surface thereof is subjected to a ring-opening reaction with an epoxy composition containing an epoxide having a (meth) acryloyl group to obtain a dental filler.
- an epoxy composition containing an epoxide having a (meth) acryloyl group to obtain a dental filler.
- the (meth) acryloyl group derived from the epoxide having a (meth) acryloyl group remains on the surface of the obtained dental filler.
- the dental filler may be pulverized as necessary.
- a known pulverizer When pulverizing the dental filler, a known pulverizer can be used.
- the (meth) acryloyl group means a methacryloyl group and / or an acryloyl group.
- Examples of the epoxide having a (meth) acryloyl group include a methacrylic acid adduct of bisphenol A diglycidyl ether, a methacrylic acid adduct of bisphenol E diglycidyl ether, and 3,4-epoxycyclohexylmethyl methacrylate.
- An epoxide having a (meth) acryloyl group has a general formula
- R 3 is a hydrogen atom or a methyl group
- X is a divalent organic group. It is preferable that it is a compound represented by these.
- epoxides having a (meth) acryloyl group include BAEM-50, BEEM-50 (manufactured by KSM), cyclomer M100 (manufactured by Daicel), and the like.
- the epoxide having a (meth) acryloyl group may have two or more (meth) acryloyl groups and / or epoxy groups.
- the epoxy composition is not particularly limited as long as it can undergo a ring-opening reaction with an epoxy group introduced on the surface of the inorganic filler.
- the epoxy composition preferably contains a known ring-opening reaction initiator.
- the ring-opening reaction initiator is not particularly limited as long as it can open an epoxy group.
- amines primary, secondary, tertiary amine, aromatic amine, amine complex
- polyamide resins polyamide resins
- imidazoles polymercaptans
- acid anhydrides organic acid hydrazides and the like.
- N, N-diethyl-1,3-diaminopropane, 2,2'-diaminodiethylamine, bis (4-aminophenyl) sulfone, phthalic anhydride and the like are preferable.
- the epoxy composition may further contain an epoxide having no (meth) acryloyl group. Thereby, a dental filler can be produced more easily.
- the epoxide which does not have a (meth) acryloyl group may have two or more epoxy groups.
- Examples of the epoxide having no (meth) acryloyl group include neopentyl glycol diglycidyl ether and 2,2-bis (4-glycidyloxyphenylphenyl) propane.
- the surface of the dental filler when using an inorganic filler having a silanol group on the surface is, for example, a general formula
- X is general formula (1), (Same as (2).) It has the structure represented by these.
- the bonding order of the epoxide having a (meth) acryloyl group and the epoxide having no (meth) acryloyl group is particularly It is not limited.
- Examples of the copolymer of an epoxide having a (meth) acryloyl group and an epoxide having no (meth) acryloyl group include a random copolymer, an alternating copolymer, and a block copolymer.
- a dental filler when manufacturing a dental filler, you may react the composition containing the silane coupling agent which has an epoxy group, and the epoxide which has a (meth) acryloyl group, and an inorganic filler.
- the dental filler may be surface-treated with a silane coupling agent having a (meth) acryloyl group to further introduce the (meth) acryloyl group on the surface of the inorganic filler.
- a silane coupling agent having a (meth) acryloyl group to further introduce the (meth) acryloyl group on the surface of the inorganic filler.
- the dental filler of this embodiment is manufactured by the method for manufacturing a dental filler of this embodiment.
- the content of the inorganic filler in the dental filler is preferably 40 to 95% by mass, more preferably 60 to 80% by mass.
- the content of the inorganic filler in the dental filler is 20% by mass or more, the bending strength of the cured product of the dental polymerizable composition described later is improved, and when it is 95% by mass or less, the dental polymerization is performed. The operability of the composition is improved.
- the content of the silane coupling agent having a (meth) acryloyl group in the dental filler when the dental filler of the present embodiment is surface-treated with a silane coupling agent having a (meth) acryloyl group is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass.
- the content of the silane coupling agent having a (meth) acryloyl group in the dental filler is 0.1% by mass or more and 20% by mass or less, the bending strength of the cured body of the dental polymerizable composition is further improved. To do.
- the dental polymerizable composition of this embodiment contains the dental filler of this embodiment and (meth) acrylate, and if necessary, a filler other than the polymerization initiator and the dental filler of this embodiment. Further, it may further contain a polymerization inhibitor, an antioxidant, an ultraviolet absorber, a pigment and the like.
- (meth) acrylate means a compound (for example, monomer, macromonomer) having one or more (meth) acryloyloxy groups.
- the (meth) acrylate is not particularly limited, but methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, hydroxypropyl (meth) acrylate , Tetrahydrofurfuryl (meth) acrylate, glycidyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-methoxyethyl (meth) acrylate 2-ethoxyethyl (meth) acrylate, 2-methylhexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxy-1,3-di (Met
- the content of (meth) acrylate in the dental polymerizable composition is preferably 0.5 to 70% by mass, and more preferably 10 to 60% by mass.
- the content of (meth) acrylate in the dental polymerizable composition is 0.5% by mass or more, the mechanical strength of the cured product of the dental polymerizable composition is improved and is 70% by mass or less. Thereby, content of another component can be ensured and the performance as a dental polymerizable composition improves.
- a silane coupling agent having a (meth) acryloyl group can also be used.
- the silane coupling agent having a (meth) acryloyl group is not particularly limited, but 3- (meth) acryloyloxypropyltrimethoxysilane, 3- (meth) acryloyloxypropylmethyldimethoxysilane, 3- (meth) acryloyloxy Propyltriethoxysilane, 3- (meth) acryloyloxypropylethyldiethoxysilane, 3- (meth) acryloyloxypropylmethyldiethoxysilane, 2- (meth) acryloyloxyethoxypropyltrimethoxysilane, etc. You may use together.
- the content of the silane coupling agent having a (meth) acryloyl group in the dental polymerizable composition is preferably 0.5 to 10% by mass, more preferably 1.5 to 5% by mass. .
- the content of the silane coupling agent having a (meth) acryloyl group in the dental polymerizable composition is 0.5% by mass or more, the mechanical strength of the cured body of the dental polymerizable composition is improved. By being 10 mass% or less, content of another component can be ensured and the performance as a dental polymerizable composition improves.
- the dental polymerizable composition of the present embodiment may further contain a polymerization initiator.
- the polymerization initiator a chemical polymerization initiator and / or a photopolymerization initiator can be used, but it is preferable to use a photopolymerization initiator.
- the photopolymerization initiator is not particularly limited, and examples thereof include ketone compounds, ⁇ -diketone compounds, ketal compounds, anthraquinone compounds, thioxanthone compounds, benzoin alkyl ether compounds, and acylphosphine oxide compounds.
- ketone compound examples include benzophenone, bis (4-dimethylaminophenyl) ketone, 4,4'-bis (diethylamino) benzophenone, and the like.
- Examples of the ⁇ -diketone compound include camphorquinone, benzyl, diacetyl, acenaphthenequinone, 9,10-phenanthraquinone, and the like.
- ketal compounds include benzyl ketal, diacetyl ketal, benzyl dimethyl ketal, benzyl diethyl ketal, benzyl bis ( ⁇ -phenylethyl) ketal, benzyl bis (2-methoxyethyl) ketal, 4,4′-dimethyl (benzyl dimethyl ketal). ) And the like.
- anthraquinone compound examples include anthraquinone, 1-chloroanthraquinone, 2-chloroanthraquinone, 1,2-benzanthraquinone, 1-hydroxyanthraquinone, 1-methylanthraquinone, 2-ethylanthraquinone, 1-bromoanthraquinone, and the like.
- thioxanthone compounds include thioxanthone, 2-isopropylthioxanthone, 2-nitrothioxanthone, 2-methylthioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 2-chloro- 7-trifluoromethylthioxanthone, thioxanthone-10,10-dioxide, thioxanthone-10-oxide, 2-ethylthioxanthone, 2-chlorothioxanthone, 2-hydroxy-3- (3,4-dimethyl-9-oxo-9H- And thioxanthen-2-yloxy) -N, N, N-trimethyl-1-propaneaminium chloride.
- benzoin alkyl ether compounds examples include benzoin methyl ether, benzoin ethyl ether, benzoin propyl ether, and benzoin isobutyl ether.
- acylphosphine oxide compound examples include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, 2,4,6-trimethoxybenzoyldiphenylphosphine oxide, 2,6-dimethylbenzoyldiphenylphosphine oxide, and 2,6-dimethoxy.
- examples include benzoyldiphenylphosphine oxide.
- the content of the photopolymerization initiator in the dental polymerizable composition is preferably 0.1 to 10% by mass, and more preferably 0.2 to 5% by mass.
- the content of the photopolymerization initiator in the dental polymerizable composition is 0.1% by mass or more, the mechanical strength of the cured product of the dental polymerizable composition is improved and is 10% by mass or less. This improves the storage stability of the dental polymerizable composition.
- the photopolymerization accelerator is not particularly limited, but N, N-dimethyl-p-toluidine, triethanolamine, tolyldiethanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, 4-dimethylaminobenzoate Tertiary amines such as isoamyl acid, barbituric acid, 1,3-dimethylbarbituric acid, 1,3,5-trimethylbarbituric acid, 1,3,5-triethylbarbituric acid, 5-butylbarbituric acid, Examples thereof include barbituric acid derivatives such as 1-benzyl-5-phenylbarbituric acid and 1-cyclohexyl-5-ethylbarbituric acid, and two or more of them may be used in combination.
- the content of the photopolymerization accelerator in the dental polymerizable composition is preferably 0.1 to 5% by mass, and more preferably 0.2 to 1% by mass.
- the content of the photopolymerization accelerator in the dental polymerizable composition is 0.1% by mass or more and 5% by mass or less, the polymerization efficiency of the dental polymerizable composition is further improved.
- Filler other than the dental filler of the present embodiment an organic filler and / or an inorganic filler can be used, but an inorganic filler is preferably used.
- the inorganic filler is not particularly limited, and examples thereof include silica powder, alumina powder, glass powder (for example, barium glass powder, fluoroaluminosilicate glass powder), and two or more kinds may be used in combination.
- the inorganic filler may be surface-treated with a silane coupling agent as necessary.
- the content of the filler in the dental polymerizable composition is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass.
- the content of the filler in the dental polymerizable composition is 0.1% by mass or more and 20% by mass or less, the mechanical strength of the cured body of the dental polymerizable composition is further improved.
- ⁇ Use of dental polymerizable composition> Although it does not specifically limit as a use of the dental polymerizable composition of this embodiment, Dental restoration material, dental cement, etc. are mentioned. Among these, a dental restoration material is preferable.
- a part means a mass part.
- Example 1 Preparation of epoxy composition
- BAEM-50 manufactured by KSM
- neopentylglycol diglycidyl ether 1500NP manufactured by Kyoeisha Chemical
- DEDAP N, N-diethyl-1,3-diaminopropane
- the filler paste was heated in the atmosphere at 80 ° C. for 2 days to cause a ring-opening reaction, and then pulverized to obtain a filler 2 having an average particle diameter of 10 ⁇ m.
- filler 2 To 100 parts of filler 2, a mixed solution of 10 parts of 3-methacryloyloxypropyltrimethoxysilane (MPS), 2 parts of distilled water and 0.2 part of acetic acid as a silane coupling agent having a methacryloyl group was added, After kneading for 30 minutes, it was dried at 80 ° C. for 3 hours to obtain a filler 3.
- MPS 3-methacryloyloxypropyltrimethoxysilane
- acetic acid a silane coupling agent having a methacryloyl group
- Example 2 and 3 A dental restorative material was obtained in the same manner as in Example 1 except that when the filler 3 was produced, the amount of MPS added was changed to 1 part and 15 parts, respectively.
- Example 4 A dental restorative material was obtained in the same manner as in Example 1 except that 8-glycidyloxyoctyltrimethoxysilane (GOS) was used as the silane coupling agent having an epoxy group when the filler 1 was produced. It was.
- GOS 8-glycidyloxyoctyltrimethoxysilane
- Example 5 (Preparation of epoxy composition) 30 parts of BAEM-50 (manufactured by KSM) as an epoxide having a methacryloyl group, 20 parts of 2,2-bis (4-glycidyloxyphenylphenyl) propane (Bis-GPP) as an epoxide having no methacryloyl group, neo 50 parts of pentyl glycol diglycidyl ether 1500NP (manufactured by Kyoeisha Chemical Co., Ltd.) and 7 parts of N, N-diethyl-1,3-diaminopropane (DEDAP) as a ring-opening reaction initiator were mixed to obtain an epoxy composition.
- BAEM-50 manufactured by KSM
- Bis-GPP 2,2-bis (4-glycidyloxyphenylphenyl) propane
- neo 50 parts of pentyl glycol diglycidyl ether 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
- a dental restorative material was obtained in the same manner as in Example 1 except that the obtained epoxy composition was used.
- Example 6 (Preparation of epoxy composition) 10 parts of BAEM-50 (manufactured by KSM) as an epoxide having a methacryloyl group, 40 parts of 2,2-bis (4-glycidyloxyphenylphenyl) propane (Bis-GPP) as an epoxide having no methacryloyl group, neo 50 parts of pentyl glycol diglycidyl ether 1500NP (manufactured by Kyoeisha Chemical Co., Ltd.) and 7 parts of N, N-diethyl-1,3-diaminopropane (DEDAP) as a ring-opening reaction initiator were mixed to obtain an epoxy composition.
- BAEM-50 manufactured by KSM
- Bis-GPP 2,2-bis (4-glycidyloxyphenylphenyl) propane
- neo 50 parts of pentyl glycol diglycidyl ether 1500NP manufactured by Kyoeisha Chemical Co., Ltd.
- a dental restorative material was obtained in the same manner as in Example 1 except that the obtained epoxy composition was used.
- Example 7 Except for changing the addition amount of the inorganic filler to 80 parts when producing the filler 1 and changing the addition amount of the epoxy composition to 15 parts when producing the filler paste. In the same manner as in Example 1, a dental restoration material was obtained.
- Example 8 When preparing the filler 1, a dental restorative material was obtained in the same manner as in Example 1 except that a fluoroaluminosilicate glass filler having an average particle size of 1.0 ⁇ m was used as the inorganic filler.
- Example 9 A dental restorative material was obtained in the same manner as in Example 5 except that BEEM-50 (manufactured by KSM) was used as the epoxide having a methacryloyl group when preparing the epoxy composition.
- Example 10 (Production of filler 2 ') 71.4 parts of fluoroaluminosilicate glass filler having an average particle size of 0.4 ⁇ m, 3.6 parts of 3-glycidyloxypropyltrimethoxysilane (GPS), and 25 parts of an epoxy composition were kneaded to obtain a paste for filler. .
- the filler paste was heated in the atmosphere at 80 ° C. for 2 days to cause a ring-opening reaction, and then pulverized to obtain a filler 2 ′ having an average particle diameter of 10 ⁇ m.
- a dental restorative material was obtained in the same manner as in Example 1 except that the filler 2 'was used instead of the filler 2.
- a dental restorative material was obtained in the same manner as in Example 1 except that the obtained epoxy composition was used.
- the filler paste was polymerized by heating at 80 ° C. for 2 days in the air, and then pulverized to obtain a filler 2 ′′ having an average particle diameter of 10 ⁇ m.
- a dental restorative material was obtained in the same manner as in Example 3 except that the filler 2 ′′ was used instead of the filler 2.
- the operability was evaluated by filling a first-order cavity model with a dental restoration material in an environment of 37 ° C. and 100% RH. The operability was determined according to the following criteria.
- a dental restoration material is filled in a 25 mm ⁇ 2 mm ⁇ 2 mm rectangular metal mold, both surfaces are pressed with a glass plate, and then, with respect to the surface, a photopolymerization irradiator G-Light Prima (made by GC) is used. The dental restorative material was cured by irradiating light at nine locations every second. Next, similarly to the front surface, the back surface was irradiated with light and then removed from the mold to obtain a cured body.
- a bending test was performed. Specifically, a bending test was performed using a bending strength tester autograph (manufactured by Shimadzu Corporation) under the conditions of a distance between fulcrums of 20 mm and a crosshead speed of 1 mm / min. At this time, the bending strength of the five cured bodies was measured, and the average value was obtained.
- the surface was polished for 30 seconds using Diashine (manufactured by GC), and the glossiness of the surface was visually evaluated.
- the lubricity was determined according to the following criteria.
- the dental restorative materials of Examples 1 to 10 have high operability, high bending strength and smoothness of the cured product.
- the dental restorative material of Comparative Example 1 does not contain an epoxide having a (meth) acryloyl group, the operability and the bending strength and lubricity of the cured body are low.
- the dental restorative material of Comparative Example 2 does not use an epoxy composition containing an epoxide having a (meth) acryloyl group, the operability and the bending strength of the cured body are low.
Landscapes
- Health & Medical Sciences (AREA)
- Oral & Maxillofacial Surgery (AREA)
- Plastic & Reconstructive Surgery (AREA)
- Epidemiology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Dental Preparations (AREA)
Abstract
Description
以下、本実施形態の歯科用充填材の製造方法を説明する。
で表される化合物であることが好ましい。
で表される構造を有する。ここで、(メタ)アクリロイル基を有するエポキシド及び(メタ)アクリロイル基を有しないエポキシドの共重合体における(メタ)アクリロイル基を有するエポキシド及び(メタ)アクリロイル基を有しないエポキシドの結合順序は、特に限定されない。
本実施形態の歯科用充填材は、本実施形態の歯科用充填材の製造方法により製造されている。
本実施形態の歯科用重合性組成物は、本実施形態の歯科用充填材と、(メタ)アクリレートを含み、必要に応じて、重合開始剤、本実施形態の歯科用充填材以外の充填材、重合禁止剤、酸化防止剤、紫外線吸収剤、顔料等をさらに含んでいてもよい。
(メタ)アクリレートとしては、特に限定されないが、メチル(メタ)アクリレート、エチル(メタ)アクリレート、イソプロピル(メタ)アクリレート、n-ブチル(メタ)アクリレート、イソブチル(メタ)アクリレート、ヒドロキシプロピル(メタ)アクリレート、テトラヒドロフルフリル(メタ)アクリレート、グリシジル(メタ)アクリレート、2-ヒドロキシエチル(メタ)アクリレート、2-ヒドロキシプロピル(メタ)アクリレート、3-ヒドロキシプロピル(メタ)アクリレート、2-メトキシエチル(メタ)アクリレート、2-エトキシエチル(メタ)アクリレート、2-メチルヘキシル(メタ)アクリレート、2-エチルヘキシル(メタ)アクリレート、ベンジル(メタ)アクリレート、2-ヒドロキシ-1,3-ジ(メタ)アクリロイルオキシプロパン、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、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、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、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、ペンタエリスリトールトリ(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テトラ(メタ)アクリレート、ポリブチレングリコールジ(メタ)アクリレート、ビスフェノールAジグリシジル(メタ)アクリレート、ジ-2-(メタ)アクリロイルオキシエチル-2,2,4-トリメチルヘキサメチレンジカルバメート、1,3,5-トリス[1,3-ビス{(メタ)アクリロイルオキシ}-2-プロポキシカルボニルアミノヘキサン]-1,3,5-(1H,3H,5H)トリアジン-2,4,6-トリオン、2,2-ビス-4-(3-(メタ)アクリロイルオキシ-2-ヒドロキシプロピル)-フェニルプロパン、N,N’-(2,2,4-トリメチルヘキサメチレン)ビス〔2-(アミノカルボキシ)プロパン-1,3-ジオール〕テトラメタクリレート、2,2’-ビス(4-ヒドロキシシクロヘキシル)プロパンと2-オキシパノンとヘキサメチレンジイソシアネートと2-ヒドロキシエチル(メタ)アクリレートとからなるウレタンオリゴマーの(メタ)アクリレート、1,3-ブタンジオールとヘキサメチレンジイソシアネートと2-ヒドロキシエチル(メタ)アクリレートとからなるウレタンオリゴマーの(メタ)アクリレート等が挙げられる。
本実施形態の歯科用重合性組成物は、重合開始剤をさらに含んでいてもよい。
光重合開始剤としては、特に限定されないが、ケトン系化合物、α-ジケトン系化合物、ケタール系化合物、アントラキノン系化合物、チオキサントン系化合物、ベンゾインアルキルエーテル系化合物、アシルホスフィンオキシド系化合物等が挙げられる。
光重合促進剤としては、特に限定されないが、N,N-ジメチル-p-トルイジン、トリエタノールアミン、トリルジエタノールアミン、4-ジメチルアミノ安息香酸メチル、4-ジメチルアミノ安息香酸エチル、4-ジメチルアミノ安息香酸イソアミル等の3級アミン、バルビツール酸、1,3-ジメチルバルビツール酸、1,3,5-トリメチルバルビツール酸、1,3,5-トリエチルバルビツール酸、5-ブチルバルビツール酸、1-ベンジル-5-フェニルバルビツール酸、1-シクロヘキシル-5-エチルバルビツール酸等のバルビツール酸誘導体等が挙げられ、二種以上併用してもよい。
本実施形態の歯科用充填材以外の充填材としては、有機充填材及び/又は無機充填材を用いることができるが、無機充填材を用いることが好ましい。
本実施形態の歯科用重合性組成物の用途としては、特に限定されないが、歯科用修復材、歯科用セメント等が挙げられる。これらの中でも、歯科用修復材が好ましい。
(エポキシ組成物の作製)
メタクリロイル基を有するエポキシドとしての、BAEM-50(ケーエスエム製)50部、メタクリロイル基を有しないエポキシドとしての、ネオペンチルグリコールジグリシジルエーテル1500NP(共栄社化学製)50部、開環反応開始剤としての、N,N-ジエチル-1,3-ジアミノプロパン(DEDAP)7部を混合し、エポキシ組成物を得た。
無機充填材としての、平均粒径0.4μmのフルオロアルミノシリケートガラスフィラー100部に対し、エポキシ基を有するシランカップリング剤としての、3-グリシジルオキシプロピルトリメトキシシラン(GPS)5部、蒸留水1部、酢酸0.1部の混合液を加え、30分間混練した後、80℃で3時間乾燥させ、エポキシ基が表面に導入されている充填材1を得た。
平均粒径0.4μmのフルオロアルミノシリケートガラスフィラー100部に対し、3-メタクリロイルオキシプロピルトリメトキシシラン(MPS)5部、蒸留水1部、酢酸0.1部の混合液を加え、30分間混練した後、80℃で3時間乾燥させ、充填材4を得た。
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(Bis-GMA)50部、ネオペンチルグリコールジメタクリレート(NPG)50部、光重合開始剤としての、(±)-カンファーキノン(CQ)0.5部、光重合促進剤としての、4-(N,N-ジメチルアミノ)安息香酸エチル(DMABE)0.5部を混合し、モノマー組成物を得た。
40部の充填材3、モノマー組成物20部、平均粒径0.016μmのアエロジル(登録商標)R972(日本アエロジル製)1部、39部の充填材4を混練した後、真空下で脱泡し、ペースト状の歯科用修復材を得た。
充填材3を作製する際に、MPSの添加量を、それぞれ1部、15部に変更した以外は、実施例1と同様にして、歯科用修復材を得た。
充填材1を作製する際に、エポキシ基を有するシランカップリング剤として、8-グリシジルオキシオクチルトリメトキシシラン(GOS)を用いた以外は、実施例1と同様にして、歯科用修復材を得た。
(エポキシ組成物の作製)
メタクリロイル基を有するエポキシドとしての、BAEM-50(ケーエスエム製)30部、メタクリロイル基を有しないエポキシドとしての、2,2-ビス(4-グリシジルオキシフェニルフェニル)プロパン(Bis-GPP)20部、ネオペンチルグリコールジグリシジルエーテル1500NP(共栄社化学製)50部、開環反応開始剤としての、N,N-ジエチル-1,3-ジアミノプロパン(DEDAP)7部を混合し、エポキシ組成物を得た。
(エポキシ組成物の作製)
メタクリロイル基を有するエポキシドとしての、BAEM-50(ケーエスエム製)10部、メタクリロイル基を有しないエポキシドとしての、2,2-ビス(4-グリシジルオキシフェニルフェニル)プロパン(Bis-GPP)40部、ネオペンチルグリコールジグリシジルエーテル1500NP(共栄社化学製)50部、開環反応開始剤としての、N,N-ジエチル-1,3-ジアミノプロパン(DEDAP)7部を混合し、エポキシ組成物を得た。
充填材1を作製する際に、無機充填材の添加量を80部に変更すると共に、充填材用ペーストを作製する際に、エポキシ組成物の添加量を15部に変更した以外は、実施例1と同様にして、歯科用修復材を得た。
充填材1を作製する際に、無機充填材として、平均粒径1.0μmのフルオロアルミノシリケートガラスフィラーを用いた以外は、実施例1と同様にして、歯科用修復材を得た。
エポキシ組成物を作製する際に、メタクリロイル基を有するエポキシドとして、BEEM-50(ケーエスエム製)を用いた以外は、実施例5と同様にして、歯科用修復材を得た。
(充填材2’の作製)
平均粒径0.4μmのフルオロアルミノシリケートガラスフィラー71.4部、3-グリシジルオキシプロピルトリメトキシシラン(GPS)3.6部、25部のエポキシ組成物を混練し、充填材用ペーストを得た。
(エポキシ組成物の作製)
メタクリロイル基を有しないエポキシドとしての、2,2-ビス(4-グリシジルオキシフェニルフェニル)プロパン(Bis-GPP)50部、ネオペンチルグリコールジグリシジルエーテル1500NP(共栄社化学製)50部、開環反応開始剤としての、N,N-ジエチル-1,3-ジアミノプロパン(DEDAP)7部を混合し、エポキシ組成物を得た。
(モノマー組成物の作製)
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(Bis-GMA)50部、ネオペンチルグリコールジメタクリレート(NPG)50部、重合開始剤としての、2,2’-アゾビス(イソブチロニトリル)(AIBN)0.5部を混合し、モノマー組成物を得た。
75部の充填材1、25部のモノマー組成物を混練し、充填材用ペーストを得た。
37℃、100%RHの環境下、1級窩洞の模型に歯科用修復材を充填することで、操作性を評価した。なお、以下の基準で、操作性を判定した。
良:歯科用修復材のペタつきやパサつきが少なく、充填しやすい場合
不可:歯科用修復材のベタつきやパサつきが強く、充填しにくい場合
[硬化体の曲げ強度]
25mm×2mm×2mmの直方体の金型に歯科用修復材を充填し、両面をガラス板で圧接した後、光重合照射器G-ライトプリマ(ジーシー製)を用いて、表面に対して、10秒間ずつ9ヶ所に光を照射し、歯科用修復材を硬化させた。次に、表面と同様にして、裏面に対しても、光を照射した後、金型から取り出し、硬化体を得た。
リング状の型に歯科用修復材を充填した後、両面にカバーガラスを置き、ガラス板で圧接した後、光重合照射器G-ライトプリマ(ジーシー製)を用いて、表面に対して、10秒間ずつ9ヶ所に光を照射し、歯科用修復材を硬化させた。次に、表面と同様にして、裏面に対しても、光を照射した後、金型から取り出し、直径15mm、厚さ1.0mmの硬化体を得た。
良:硬化体の表面の光沢度が優れる場合
不可:硬化体の表面の光沢度が劣る場合
表1に、歯科用修復材の操作性と、歯科用修復材の硬化体の曲げ強度及び滑沢性の評価結果を示す。
Claims (6)
- エポキシ基を有するシランカップリング剤で無機充填材を表面処理した後、(メタ)アクリロイル基を有するエポキシドを含む組成物と開環反応させて製造されている歯科用充填材。
- エポキシ基を有するシランカップリング剤と、(メタ)アクリロイル基を有するエポキシドとを含む組成物と、無機充填材を反応させて製造されている歯科用充填材。
- 請求項1に記載の歯科用充填材と、
(メタ)アクリレートを含む歯科用重合性組成物。 - 歯科用修復材である請求項3に記載の歯科用重合性組成物。
- 請求項2に記載の歯科用充填材と、
(メタ)アクリレートを含む歯科用重合性組成物。 - 歯科用修復材である請求項5に記載の歯科用重合性組成物。
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP18911935.7A EP3771461A4 (en) | 2018-03-29 | 2018-12-04 | DENTAL FILLING MATERIAL AND POLYMERISABLE DENTAL COMPOSITION |
JP2020509621A JP7074842B2 (ja) | 2018-03-29 | 2018-12-04 | 歯科用充填材及び歯科用重合性組成物 |
US17/040,708 US11433005B2 (en) | 2018-03-29 | 2018-12-04 | Dental filling material and dental polymerizable composition |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018-065671 | 2018-03-29 | ||
JP2018065671 | 2018-03-29 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2019187351A1 true WO2019187351A1 (ja) | 2019-10-03 |
Family
ID=68061146
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2018/044571 WO2019187351A1 (ja) | 2018-03-29 | 2018-12-04 | 歯科用充填材及び歯科用重合性組成物 |
Country Status (4)
Country | Link |
---|---|
US (1) | US11433005B2 (ja) |
EP (1) | EP3771461A4 (ja) |
JP (1) | JP7074842B2 (ja) |
WO (1) | WO2019187351A1 (ja) |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003095837A (ja) * | 2001-09-27 | 2003-04-03 | Gc Corp | グラスアイオノマーセメント用ガラス粉末 |
US20060004121A1 (en) * | 2004-03-10 | 2006-01-05 | Xingzhe Ding | Polymer-brush modified fillers for composites |
JP2007161510A (ja) * | 2005-12-12 | 2007-06-28 | Tokuyama Corp | 疎水性無機粉体及びその製造方法 |
JP2007314484A (ja) | 2006-05-29 | 2007-12-06 | Tokuyama Corp | 歯科用有機無機複合フィラー、該フィラーを用いた歯科用修復材組成物及びそれらの製造方法 |
US20130059941A1 (en) * | 2010-05-25 | 2013-03-07 | 3M Innovative Properties Company | Method of surface treating inorganic oxide particles, hardenable dental compositions, surface treated particles, and surface treatment compounds |
JP2015500302A (ja) * | 2011-12-15 | 2015-01-05 | デンツプライ デトレイ ゲー.エム.ベー.ハー. | 複合充填材粒子およびそれを調製するためのプロセス |
JP2018065671A (ja) | 2016-10-21 | 2018-04-26 | 奥田 智一 | 移送器具及び移送方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7365106B2 (en) * | 2004-04-27 | 2008-04-29 | Tokuyama Corporation | Cationically curable composition for dental use |
FR2903888A1 (fr) * | 2006-07-21 | 2008-01-25 | Rhodia Recherches & Tech | Composition dentaire reticulable/polymerisable par voie cationique stable. |
-
2018
- 2018-12-04 EP EP18911935.7A patent/EP3771461A4/en active Pending
- 2018-12-04 JP JP2020509621A patent/JP7074842B2/ja active Active
- 2018-12-04 WO PCT/JP2018/044571 patent/WO2019187351A1/ja active Application Filing
- 2018-12-04 US US17/040,708 patent/US11433005B2/en active Active
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2003095837A (ja) * | 2001-09-27 | 2003-04-03 | Gc Corp | グラスアイオノマーセメント用ガラス粉末 |
US20060004121A1 (en) * | 2004-03-10 | 2006-01-05 | Xingzhe Ding | Polymer-brush modified fillers for composites |
JP2007161510A (ja) * | 2005-12-12 | 2007-06-28 | Tokuyama Corp | 疎水性無機粉体及びその製造方法 |
JP2007314484A (ja) | 2006-05-29 | 2007-12-06 | Tokuyama Corp | 歯科用有機無機複合フィラー、該フィラーを用いた歯科用修復材組成物及びそれらの製造方法 |
US20130059941A1 (en) * | 2010-05-25 | 2013-03-07 | 3M Innovative Properties Company | Method of surface treating inorganic oxide particles, hardenable dental compositions, surface treated particles, and surface treatment compounds |
JP2015500302A (ja) * | 2011-12-15 | 2015-01-05 | デンツプライ デトレイ ゲー.エム.ベー.ハー. | 複合充填材粒子およびそれを調製するためのプロセス |
JP2018065671A (ja) | 2016-10-21 | 2018-04-26 | 奥田 智一 | 移送器具及び移送方法 |
Non-Patent Citations (3)
Title |
---|
DING, XINGZHE ET AL.: "Polymer-brush Modified Fillers for Dental Composites", POLYMER PREPRINTS, vol. 45, no. 2, August 2004 (2004-08-01), pages 339 - 340, XP009523224, ISSN: 0032-3934 * |
See also references of EP3771461A4 |
STANSBURY, JEFFREY W. ET AL.: "Epoxy-brush Modified Fillers for Dental Composites", POLYMER PREPRINTS, vol. 45, no. 2, August 2004 (2004-08-01), pages 341 - 342, XP009523246, ISSN: 0032-3934 * |
Also Published As
Publication number | Publication date |
---|---|
EP3771461A1 (en) | 2021-02-03 |
EP3771461A4 (en) | 2021-12-01 |
JPWO2019187351A1 (ja) | 2021-03-11 |
US11433005B2 (en) | 2022-09-06 |
US20210007939A1 (en) | 2021-01-14 |
JP7074842B2 (ja) | 2022-05-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP4986437B2 (ja) | 歯科用硬化性組成物 | |
WO2018071920A1 (en) | Curable urethane dimethacrylates and dental restorative compositions thereof | |
US11452675B2 (en) | Dental curable composition | |
JP4425568B2 (ja) | 歯科用組成物 | |
US9526677B2 (en) | Dental curing composition | |
JP5634298B2 (ja) | 分包型の歯科用重合性支台築造材料 | |
JPWO2017217122A1 (ja) | 歯科用重合性組成物 | |
JP2021187833A (ja) | 重合性組成物の製造方法、重合性組成物、及び硬化物 | |
JP7417609B2 (ja) | 抗菌ポリマー粒子を含む組成物 | |
JP4798680B2 (ja) | 歯科用硬化性組成物 | |
JP7074842B2 (ja) | 歯科用充填材及び歯科用重合性組成物 | |
JP6869741B2 (ja) | 表面に反応基を多く有する有機無機複合フィラー及びそれらを配合した歯科用硬化性組成物 | |
JP7121809B2 (ja) | 歯科材料用モノマー組成物、歯科材料用組成物及び歯科材料 | |
JP6369932B2 (ja) | 歯科用補綴物の作製方法 | |
JPWO2020153269A1 (ja) | 光重合開始剤、光硬化性組成物、硬化物、及び、歯科材料 | |
US11697694B2 (en) | Method of manufacturing polymerizable composition, polymerizable composition, and cured product | |
JPS6136204A (ja) | 歯牙用硬化性樹脂組成物 | |
JP7189049B2 (ja) | 有機ケイ素化合物、歯科用フィラー及び歯科用重合性組成物 | |
JP7044885B2 (ja) | 重合開始剤、硬化性組成物、歯科材料および硬化性組成物の調製用キット | |
JP2010202560A (ja) | 歯科用複合硬化性組成物 | |
JP2003095836A (ja) | 歯科用修復材組成物 | |
WO2022270601A1 (ja) | 歯科用接着キット | |
WO2023190678A1 (ja) | 歯科用接着性組成物 | |
WO2023248838A1 (ja) | 3次元造形用組成物、及び歯科用造形物の製造方法 | |
WO2022168429A1 (ja) | 歯科用接着性組成物 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 18911935 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2020509621 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2018911935 Country of ref document: EP |
|
ENP | Entry into the national phase |
Ref document number: 2018911935 Country of ref document: EP Effective date: 20201029 |