JP7232460B2 - Polymerizable dental resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a dental resin composition having polymerizability to active energy rays such as heat and light, and to dental materials, instruments and the like obtained by polymerizing the resin composition.

Dental materials are mainly classified into polymer materials, ceramic materials, metal materials, and composite materials that combine these materials. are used. These materials are required to be strong enough to withstand occlusion, as well as long-term safety, antibacterial properties, antifouling properties, adhesive durability, discoloration resistance, and corrosion resistance of alloys used in implants. It is

However, there are many resident bacteria in the oral cavity, and plaque is formed on the surface of teeth and dentures. There was a problem that periodontal pathogenic bacteria are likely to adhere to the mucosal surface of the implant and around the implant, and bacterial infection is likely to occur due to activation.

In order to suppress oral microbes and bacteria, oral rinses, toothpastes, gels, etc. containing antibacterial compounds such as domiphen bromide, chlorhexidine, triclosan, and quaternary ammonium salts have been developed. It cannot maintain its action, and it is difficult to reach fillings, crowns, denture bases, and around implants.In addition, there are many halogen-based products, and they are highly irritating. there was a problem with

In addition, a method of blending zeolite particles carrying silver ions as an antibacterial metal ion source into a resin such as a filling material or surface coating material used in dental treatment (Patent Document 1), an effective amount of an antibacterial lipid component and A curable antibacterial dental composition containing a curable component (Patent Document 2), and a photocurable resin (Patent Reference 3) proposed a dental adhesive compounded with an antibacterial monomer (12-?methacryloyloxydodecylpyridinium bromide (MDPB)) in which a polymerizable group was introduced into a quaternary ammonium salt (Non-Patent Document 1). However, there is an essential problem that both silver ions and lipid components are eluted over time, and phosphate residues and bromo ions, which are anions of MDPB, are replaced by acids in food and beverages and acids produced by oral bacteria. It cannot be said that it is safe for the human body, nor that it has permanent antibacterial properties. Fixtures (metal parts) are corroded, and there is concern about the fracture of implants.

Furthermore, plaque adhering to the surface and surroundings of teeth and dentures is a breeding ground for oral bacteria, and it was necessary to prevent plaque accumulation due to adhesion or adhesion of food residues and bacteria. However, none of the above-mentioned prior art documents mention the antifouling property, which is important as a dental material.

JP-A-1-254608 JP-A-2008-533009 JP-A-7-215814

Journal of Dentistry (1998), 26(3), 267-271

An object of the present invention is to provide a dental resin composition having antibacterial properties, antifouling properties, discoloration resistance, high safety, and excellent polymerizability against active energy rays such as heat and light. and The present invention also provides a highly safe dental material having semi-permanent antibacterial and antifouling properties, which contains a polymer obtained by homopolymerizing the above composition with heat or light or copolymerizing it with another polymerizable compound. The task is to provide Furthermore, the present invention provides a dental composite resin, a dental crown material, an adhesive, a filling material, a denture material, a denture base material obtained by blending the composition and/or the polymer, and the composition and An object of the present invention is to provide an antibacterial material for a three-dimensional object containing the polymer, a medical device surface-coated with an antifouling material, and a three-dimensional object having antibacterial and antifouling properties.

The present inventors have made intensive studies to solve the above problems, and as a result, a quaternary ammonium salt having an unsaturated group (A) and / or its homopolymerization or copolymerization with other polymerizable compounds Dental resin compositions, dental resins, fillers, adhesives, etc. that have long-term safety, antibacterial properties, antifouling properties, and discoloration resistance by containing polymers (also called oligomers and polymers) as essential components dental materials, antibacterial tree / antifouling ink for three-dimensional objects, medical devices coated with antibacterial and antifouling resins, three-dimensional objects having antibacterial and antifouling properties, etc. It has arrived.

（式中、Ｒ_１、Ｒ_２とＲ_３は互いに同一であっても異なっていてもよく、各々独立に炭素数１～３６の直鎖状又は分岐鎖状のアルキル基や水酸基或いはアミン基に置換されたアルキル基、炭素数１～３６の直鎖状又は分岐鎖状のアルケニル基や水酸基或いはアミン基に置換されたアルケニル基、或いはベンジル基を表し、Ｌは不飽和結合を表し、Ｙは炭素数１～３６のアルキレン基を表し、Ｑ^-は非ハロゲン系アニオンを表す。）
（２）不飽和基を有する第四級アンモニウム塩（Ａ）は、不飽和基として（メタ）アクリレート基、（メタ）アクリルアミド基、ビニル基、ビニルエーテル基、メチルビニルエーテル基、アリル基、（メタ）アリルエーテル基とマレイミド基からなる群より選択される１種以上の不飽和結合を有する官能基であることを特徴とする前記（１）に記載の重合性歯科用樹脂組成物、
（３）不飽和基を有する第四級アンモニウム塩（Ａ）は、カチオンとして(メタ)アクリロイルアミノプロピルトリメチルアンモニウム、(メタ)アクリロイルアミノプロピルジメチルベンジルアンモニウム、(メタ)アクリロイルオキシエチルトリメチルアンモニウム、(メタ)アクリロイルオキシエチルジメチルベンジルアンモニウム、ジアリルジメチルアンモニウムからなる群より選択される１種以上のカチオンであることを特徴とする前記（１）又は（２）に記載の重合性歯科用樹脂組成物、
（４）不飽和基を有する第四級アンモニウム塩（Ａ）は、アニオンとしてｐ－トルエンスルホン酸イオン、テトラフルオロホウ酸イオン、ヘキサフルオロリン酸イオン、トリフルオロメタンスルホン酸イオン、テトラフェニルホウ酸イオン、チオシアン酸イオン、ビス（フルオロスルホニル）イミドアニオン、ビス（トリフルオロメタンスルホニル）イミドアニオンとサッカリン酸イオンからなる群より選択される１種以上のアニオンであることを特徴とする前記（１）～（３）のいずれか一項に記載の重合性歯科用樹脂組成物、
（５）不飽和基を有する第四級アンモニウム塩（Ａ）を構成単位として０．１質量％以上含有することを特徴とする前記（１）～（４）のいずれか一項に記載の重合性歯科用樹脂組成物、
（６）前記（１）～（５）のいずれか一項に記載の重合性樹脂組成物を重合してなる重合物を含有することを特徴とする歯科用樹脂組成物、
（７）エチレン性不飽和基を有する化合物（Ｂ）（（Ａ）を除く）を５～９９質量％含有することを特徴とする前記（１）～（６）のいずれか一項に記載の歯科用樹脂組成物、
（８）エチレン性不飽和基を有する化合物（Ｂ）は、不飽和基として（メタ）アクリレート基、（メタ）アクリルアミド基、ビニル基、ビニルエーテル基、メチルビニルエーテル基、アリル基、（メタ）アリルエーテル基とマレイミド基からなる群より選択される１種以上の化合物であることを特徴とする前記（７）に記載の歯科用樹脂組成物、
（９）更に光重合開始剤（Ｃ）を０．１～１０質量％含有することを特徴とする前記（１）～（５）と前記（７）、（８）のいずれか一項に記載の光硬化型歯科用樹脂組成物、
（１０）前記（１）～（５）と前記（７）～（９）のいずれか一項に記載の重合性樹脂組成物を重合してなる重合物を含有することを特徴とする歯科用樹脂組成物、
（１１）前記（１）～（５）と前記（７）～（９）のいずれか一項に記載の重合性歯科用樹脂組成物を含有する歯科用コンポジットレジン、
（１２）前記（１）～（５）と前記（７）～（９）のいずれか一項に記載の重合性樹脂組成物を含有するする立体造形物用抗菌性インク、
（１３）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる歯科用材料、
（１４）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる歯冠材、
（１５）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる歯科用接着剤、
（１６）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる歯科用表面被覆材、
（１７）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる歯科用充填材料、
（１８）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる歯科用義歯材料、
（１９）前記（１）～（１０）のいずれか一項に記載の樹脂組成物を用いてなる義歯床用材料、
（２０）前記（１）～（１０）のいずれか一項に記載の樹脂組成物による表面被覆された医療器具、
（２１）前記（１２）に記載のインクを用いて形成される抗菌性立体造形物
を提供するものである。 That is, the present invention provides (1) a polymerizable dental resin composition containing a quaternary ammonium salt (A) having an unsaturated group represented by general formula (1),

(In the formula, R ₁ , R ₂ and R ₃ may be the same or different, and each independently represents a linear or branched alkyl group having 1 to 36 carbon atoms, a hydroxyl group or an amine group. represents a substituted alkyl group, a linear or branched alkenyl group having 1 to 36 carbon atoms, an alkenyl group substituted with a hydroxyl group or an amine group, or a benzyl group, L represents an unsaturated bond, Y represents represents an alkylene group having 1 to 36 carbon atoms, and Q ⁻ represents a non-halogen anion.)
(2) The quaternary ammonium salt (A) having an unsaturated group includes, as the unsaturated group, a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methylvinyl ether group, an allyl group, a (meth) The polymerizable dental resin composition according to (1) above, which is a functional group having one or more unsaturated bonds selected from the group consisting of an allyl ether group and a maleimide group;
(3) Quaternary ammonium salt (A) having an unsaturated group includes, as cations, (meth)acryloylaminopropyltrimethylammonium, (meth)acryloylaminopropyldimethylbenzylammonium, (meth)acryloyloxyethyltrimethylammonium, (meth) ) The polymerizable dental resin composition according to (1) or (2) above, which is one or more cations selected from the group consisting of acryloyloxyethyldimethylbenzylammonium and diallyldimethylammonium;
(4) The quaternary ammonium salt (A) having an unsaturated group includes p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, and tetraphenylborate as anions. , thiocyanate ion, bis(fluorosulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion and one or more anions selected from the group consisting of saccharinate ion (1) to ( The polymerizable dental resin composition according to any one of 3),
(5) The polymerization according to any one of (1) to (4) above, characterized by containing 0.1% by mass or more of a quaternary ammonium salt (A) having an unsaturated group as a structural unit. a dental resin composition,
(6) A dental resin composition comprising a polymer obtained by polymerizing the polymerizable resin composition according to any one of (1) to (5) above,
(7) The compound (B) having an ethylenically unsaturated group (excluding (A)) according to any one of (1) to (6), characterized by containing 5 to 99% by mass. dental resin composition,
(8) The compound (B) having an ethylenically unsaturated group includes, as the unsaturated group, a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, and a (meth)allyl ether. The dental resin composition according to (7) above, which is one or more compounds selected from the group consisting of groups and maleimide groups;
(9) Any one of (1) to (5) and (7) and (8) above, which further contains 0.1 to 10% by mass of a photopolymerization initiator (C). a photocurable dental resin composition of
(10) A dental product comprising a polymer obtained by polymerizing the polymerizable resin composition according to any one of (1) to (5) and (7) to (9). resin composition,
(11) A dental composite resin containing the polymerizable dental resin composition according to any one of (1) to (5) and (7) to (9) above,
(12) An antibacterial ink for a three-dimensional model containing the polymerizable resin composition according to any one of (1) to (5) and (7) to (9),
(13) A dental material using the resin composition according to any one of (1) to (10) above,
(14) A dental crown material using the resin composition according to any one of (1) to (10) above,
(15) A dental adhesive using the resin composition according to any one of (1) to (10) above,
(16) A dental surface coating material comprising the resin composition according to any one of (1) to (10) above,
(17) A dental filling material using the resin composition according to any one of (1) to (10) above,
(18) A dental denture material comprising the resin composition according to any one of (1) to (10) above,
(19) A denture base material comprising the resin composition according to any one of (1) to (10) above,
(20) A medical device surface-coated with the resin composition according to any one of (1) to (10) above,
(21) An antibacterial three-dimensional object formed using the ink described in (12) above is provided.

According to the present invention, by containing a quaternary ammonium salt (A) having an unsaturated group and / or a polymer (oligomer, polymer) obtained by copolymerizing it alone or with another polymerizable compound, antibacterial Acquired a polymerizable resin composition that has excellent heat resistance, antifouling properties, and discoloration resistance, has good thermal polymerizability, photocurability, and copolymerizability with other polymerizable compounds, and has high safety and storage stability. In addition, these polymerizable resin compositions can be thermally polymerized by irradiation of active energy rays such as heat and / or light, photocuring, or hybrid type or dual type curing using both heat and light to achieve antibacterial effects and antibacterial effects. Various dental materials that can maintain staining effect semipermanently and have good discoloration resistance, strength, hardness, surface smoothness, scratch resistance, and durability (hydrolysis resistance and abrasion resistance) , three-dimensional objects and medical instruments coated therewith can be obtained.

The present invention will be described in detail below.
The quaternary ammonium salt (A) having an unsaturated group used in the present invention is a compound represented by the general formula (1) (wherein R ₁ , R ₂ and R ₃ are the same may be different, each independently linear or branched alkyl group having 1 to 36 carbon atoms, alkyl group substituted with hydroxyl group or amine group, linear or branched chain having 1 to 36 carbon atoms represents an alkenyl group, a hydroxyl group, or an alkenyl group substituted with an amine group, or a benzyl group, L represents an unsaturated bond, Y represents an alkylene group having 1 to 36 carbon atoms, and Q ^- represents a non-halogen anion. show.). Specifically, it is a quaternary ammonium salt composed of an ammonium cation having an unsaturated group and a non-halogen anion as its counterion.

The quaternary ammonium salt (A) having an unsaturated group and/or oligomers and polymers thereof used in the present invention exhibit a wide antibacterial spectrum and , Hepatitis bacillus, black mold, candida, etc., and have excellent antibacterial activity against various bacteria and bacteria. Although the reason for this is not clear, it is due to interactions such as the balance between the hydrophilicity of the ammonium salt and the hydrophobicity of the N-substituted alkyl group, the high electron density of the ammonium salt, and the size of the functional group having an unsaturated bond. The inventors of the present invention presume that In addition, whether the quaternary ammonium salt (A) having an unsaturated group is blended as a monomer or blended after oligomerization or polymerization, it exhibits the same antibacterial and antifungal properties, and is a resin type and filler. It is suitably used as an antibacterial material such as type, photo-curing type, thermal polymerization/curing type, and the like. In addition, quaternary ammonium salts have excellent cytocompatibility and biocompatibility, so they not only do not irritate the user's natural teeth, dentures, or skin, but also have a protective effect on teeth and skin. It can also be suitably blended as a cosmetic material.

Specific examples of the cation of the quaternary ammonium salt (A) having an unsaturated group represented by the general formula (1) include aminoalkyl (Y) trialkyl (R ₁ ) ammonium having an unsaturated bond, unsaturated Aminoalkyl(Y)trialkyl(R ₂ )ammonium having a saturated bond, aminoalkyl(Y)trialkyl(R ₃ )ammonium having an unsaturated bond, aminoalkyl(Y)alkyl(R ₁ ) having an unsaturated bond Dialkyl(R ₂ )ammonium, unsaturated bond-containing aminoalkyl(Y)alkyl(R ₁ )dialkyl(R ₃ )ammonium, unsaturated bond-containing aminoalkyl(Y)alkyl(R ₂ )dialkyl(R ₁ )ammonium , aminoalkyl(Y ₎ alkyl(R ₂ )dialkyl(R 3 )ammonium having unsaturated bond, aminoalkyl(Y)alkyl(R ₃ )dialkyl(R ₁ )ammonium having unsaturated bond, having unsaturated bond aminoalkyl(Y)alkyl(R ₃ )dialkyl(R ₂ )ammonium, aminoalkyl(Y)alkyl(R ₁ )alkyl(R ₂ )alkyl(R ₃ )ammonium having unsaturated bond, amino having unsaturated bond Alkyl(Y)dialkyl(R ₁ )benzylammonium, aminoalkyl(Y)dialkyl(R ₂ )benzylammonium having unsaturated bond, aminoalkyl(Y)dialkyl(R ₃ )benzylammonium having unsaturated bond, unsaturated Aminoalkyl(Y)alkyl(R ₁ )alkyl(R ₂ )benzylammonium having a bond, aminoalkyl(Y)alkyl(R ₂ )alkyl(R ₃ )benzylammonium having an unsaturated bond, amino having an unsaturated bond Alkyl(Y)alkyl(R ₁ )alkyl(R ₃ )benzylammonium, unsaturated bond-containing aminoalkyl(Y)alkyl(R ₁ )dibenzylammonium, unsaturated bond-containing aminoalkyl(Y)alkyl(R ₂ ) dibenzylammonium, unsaturated bond-containing aminoalkyl(Y)alkyl(R ₃ )dibenzylammonium, unsaturated bond-containing aminoalkyl(Y)tribenzylammonium, unsaturated bond-containing oxyalkyl(Y)trialkyl (R ₁ ) ammonium, oxyalkyl (Y) trialkyl (R ₂ ) ammonium having an unsaturated bond oxyalkyl (Y) trialkyl (R ₃ ) ammonium having an unsaturated bond, oxyalkyl (Y) alkyl (R ₁ ) dialkyl (R ₂ ) ammonium having an unsaturated bond, oxyalkyl having an unsaturated bond ( Y)alkyl(R ₁ )dialkyl(R ₃ )ammonium, oxyalkyl(Y)alkyl(R ₂ )dialkyl(R ₁ )ammonium having unsaturated bond, oxyalkyl(Y)alkyl(R ₂ ) having unsaturated bond ) dialkyl(R ₃ )ammonium, oxyalkyl(Y)alkyl(R ₃ )dialkyl(R ₁ )ammonium having unsaturated bond, oxyalkyl(Y)alkyl(R ₃ )dialkyl(R ₂ ) having unsaturated bond ammonium, oxyalkyl(Y)alkyl(R ₁ )alkyl(R ₂ )alkyl(R ₃ )ammonium having unsaturated bond, oxyalkyl(Y)dialkyl(R ₁ )benzylammonium having unsaturated bond, unsaturated bond oxyalkyl (Y) dialkyl (R ₂ )benzylammonium having an unsaturated bond, oxyalkyl (Y) dialkyl (R ₃ )benzylammonium having an unsaturated bond, oxyalkyl (Y) alkyl (R ₁ )alkyl having an unsaturated bond ( R ₂ )benzylammonium, oxyalkyl(Y)alkyl(R ₂ )alkyl(R ₃ )benzylammonium having an unsaturated bond, oxyalkyl(Y)alkyl(R ₁ )alkyl(R ₃ )benzyl having an unsaturated bond ammonium, oxyalkyl(Y)alkyl(R ₁ )dibenzylammonium having an unsaturated bond, oxyalkyl(Y)alkyl(R ₂ )dibenzylammonium having an unsaturated bond, oxyalkyl(Y) having an unsaturated bond Alkyl (R ₃ ) dibenzylammonium, oxyalkyl (Y) tribenzylammonium having an unsaturated bond, and the like can be mentioned. Moreover, these quaternary ammonium salts (A) having an unsaturated group may be used singly or in combination of two or more.

The unsaturated group of the quaternary ammonium salt (A) having an unsaturated group includes a methacrylate group, an acrylate group, a methacrylamide group, an acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a methallyl ether group, A functional group having one or more unsaturated bonds selected from the group consisting of an allyl ether group and a maleimide group, which may have one type or two or more types of these unsaturated groups. .

The number of unsaturated groups in the quaternary ammonium salt having an unsaturated group (A) is preferably such that the total number of the various unsaturated groups (number of functional groups) is 1 to 10 per molecule, and , 2 to 6. If the number of functional groups is less than 1, the presence of the non-polymerizable compound causes the problem of insufficient photocurability and insufficient hardness and strength of the cured product when used as a photocurable dental material. On the other hand, when the number of functional groups exceeds 10, when used in a photocurable composite resin, the photocuring speed is remarkably increased, and a large amount of polymerization heat is generated, which may cause burns.

The anion (Q ⁻ ) of the quaternary ammonium salt (A) having an unsaturated group is not particularly limited as long as it is a non-halogen ion. For example, methanesulfonate, benzenesulfonate, p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, tetraphenylborate, thiocyanate, bis(fluoro sulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion, bis(pentafluoroethanesulfonyl)imide anion, nonafluorobutanesulfonate ion, linear sulfonimide anion, cyclic imide anion, formate ion, acetate ion, Hydroxycarboxylates such as carboxylate, glycolate, lactate, hydroxyacrylate, oxybutyrate, glycerate, malate, tartrate, and citrate ions, such as propionate, oxalate, and succinate ions It is at least one or more ions selected from aromatic carboxylate ions such as acid ions, salicylate ions, and benzoate ions, unsaturated acid ions such as saccharate ions, acrylate ions, and methacrylate ions.

For the quaternary ammonium salt (A) having an unsaturated group used in the present invention, one or two or more ions are arbitrarily selected from the above cations, and one or more of the above anions are selected. It is an onium salt composed by arbitrarily selecting two or more kinds of ions and combining a cation and an anion. These unsaturated group-containing quaternary ammonium salts (A) may be used alone or in combination of two or more.

In addition, from the viewpoint of excellent antibacterial properties and easy availability of industrial raw materials, the cations constituting the quaternary ammonium salt (A) having an unsaturated group include acryloylaminopropyltrimethylammonium, methacryloylaminopropyltrimethylammonium, acryloylamino Propyldimethylbenzylammonium, methacryloylaminopropyldimethylbenzylammonium, acryloyloxyethyltrimethylammonium, methacryloyloxyethyltrimethylammonium, acryloyloxyethyldimethylbenzylammonium, methacryloyloxyethyldimethylbenzylammonium, diallyldimethylammonium are preferred. Furthermore, from the viewpoint of long-term use in the oral cavity, acrylamide-based and methacrylamide-based acryloylaminopropyltrimethylammonium, methacryloylaminopropyltrimethylammonium, acryloylaminopropyldimethylbenzylammonium, and methacryloyl which are excellent in hydrolysis resistance and durability. Aminopropyldimethylbenzylammonium is more preferred.

Similarly, from the viewpoint of excellent antibacterial properties and easy availability of industrial raw materials, the anions constituting the quaternary ammonium salt (A) having an unsaturated group include p-toluenesulfonate ion, tetrafluoroborate ion, Preferred are hexafluorophosphate ion, trifluoromethanesulfonate ion, tetraphenylborate ion, thiocyanate ion, bis(fluorosulfonyl)imide anion, bis(trifluoromethanesulfonyl)imide anion and saccharinate ion. Furthermore, from the viewpoint of imparting an antifouling effect, organic fluorine anions such as tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, bis(fluorosulfonyl)imide anion, and bis(trifluoromethanesulfonyl)imide anion is more preferred.

Since the quaternary ammonium salt (A) having an unsaturated group has a high antibacterial effect, it can be blended as an antibacterial agent into the resin composition as a monomer. In addition, it is polymerized or oligomerized by thermal polymerization or photopolymerization (photocuring), and is incorporated into a resin composition as a semi-permanent polymer or oligomer type antibacterial agent having an antibacterial quaternary ammonium salt structure as a side chain. can do. Furthermore, when blended as a polymer type antibacterial agent or an oligomer type antibacterial agent, the possibility of bleeding out of the quaternary ammonium salt (A) having an unsaturated group is eliminated, and the antibacterial property is stable over a long period of time. can be given.

Oligomerization and polymerization by thermal polymerization of the quaternary ammonium salt (A) having an unsaturated group includes a method of homopolymerization or copolymerization with a general-purpose vinyl compound. The polymerization method is not particularly limited, and a known radical polymerization method can be used. Examples thereof include a bulk polymerization method, a solution polymerization method in an organic solvent or water, a suspension polymerization method, and an emulsion polymerization method. When a solution polymerization method in an organic solvent is employed, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol, etc. can be used alone or in combination as the polymerization solvent. Examples of polymerization initiators include generally known radical polymerization initiators such as azo-based, organic peroxide-based, inorganic peroxide-based, and redox-based initiators. The amount of radical polymerization initiator to be used is usually about 0.001 to 10% by mass based on the total amount of polymerizable components. Furthermore, usual radical polymerization techniques such as adjustment of molecular weight with a chain transfer agent are applied.

The oligomer of the quaternary ammonium salt (A) having an unsaturated group used in the present invention means that the structure of the quaternary ammonium salt (A) contains one or more units and has 200 to 10,000 is a compound having a weight average molecular weight of less than

The polymer of the quaternary ammonium salt (A) having an unsaturated group used in the present invention means that the structure of the quaternary ammonium salt (A) contains one or more units and has a weight of 10,000 or more. It is a compound with an average molecular weight.

The quaternary ammonium salt (A), its oligomer and its polymer depend on their molecular structure, molecular weight, etc., their state (liquid or solid) at room temperature, viscosity, solubility in water, general-purpose organic solvents, general-purpose acrylic monomers and acrylic resins, etc. , compatibility and photocurability are different, and there are no particular restrictions on the method of use, compounding amount, etc., and it can be used as a non-photocurable (thermal polymerization) dental material or as a photocurable dental material. , can be preferably used, and one or more selected from quaternary ammonium salts (A), oligomers and polymers can be used in combination according to the required physical properties of the antibacterial dental material.

When using an oligomer or polymer of a quaternary ammonium salt (A), the content of the quaternary ammonium salt (A) unit in the oligomer or polymer is 0.1 to 100% by mass, preferably 1 to 95. % by mass. If the content is less than 0.1% by mass, depending on the amount of the oligomer or polymer blended in the dental material, there is a possibility that sufficient antibacterial properties cannot be obtained. When the content is 1 to 95% by mass, a sufficient antibacterial effect can be obtained, and compatibility with additives such as primers and fillers can be easily adjusted. A dental material having good adhesiveness to teeth can be obtained, which is more preferable.

If the quaternary ammonium salt (A) oligomers or polymers used in the present invention are solid at room temperature, they can be incorporated into the dental resin composition as fillers. In addition, after dissolving in an organic solvent or a liquid polymerizable compound, applying the obtained solution on a dental crown, denture, medical device or substrate, and then evaporating the organic solvent, an antibacterial coating, an antibacterial A crown, an antibacterial denture, an antibacterial ink, an antibacterial medical device, and an antibacterial three-dimensional object are formed. In the case of non-solvent type, it is applied to crowns, dentures, medical instruments or substrates, or poured into the part of natural teeth to be filled or repaired, and then cured by heat or light, or a combination of heat and light. Antibacterial coatings, antibacterial crowns, antibacterial dentures, antibacterial inks, antibacterial medical instruments, antibacterial three-dimensional objects, etc. can be manufactured. In addition, when used as a thin dental surface coating material, it preferably contains 0.5% by mass or more of an oligomer or polymer of the quaternary ammonium salt (A) in order to maintain a sufficient antibacterial effect over a long period of time. , more preferably 1% by mass or more. On the other hand, when the oligomer or polymer of the quaternary ammonium salt (A) is incorporated into a photocurable dental resin or ink for three-dimensional modeling, part or all of the organic solvent is replaced with a photocurable component such as an acrylic monomer or oligomer. It is possible to be In that case, after applying the resulting slightly high-viscosity coating liquid to the surface of teeth, dentures, and appliances, the organic solvent is evaporated (if an organic solvent is blended), and a slightly thicker cured coating is formed by light irradiation. Objects (surface covering materials, crown materials, dentures formed by stereolithography, etc.) are formed. In this case, in order to impart a sufficient antibacterial effect, the content of the quaternary ammonium salt (A) oligomer or polymer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more.

The quaternary ammonium salt (A) having an unsaturated group used in the present invention can be incorporated into both non-photocurable dental materials and photocurable dental resin compositions. In addition, it is preferably incorporated into a photocurable dental material in order to prevent deterioration of antibacterial properties over time due to bleed out. When the content of the quaternary ammonium salt (A) having an unsaturated group in the photocurable dental material is 0.1% by mass or more, antibacterial and antifouling properties are exhibited, and a sustained antibacterial From the viewpoint of ensuring the properties and antifouling properties, it is preferably contained in an amount of 0.5% by mass or more.

The quaternary ammonium salt (A) having an unsaturated group, its oligomer, and its polymer used in the present invention can be used singly or in combination of two or more arbitrarily selected from the group consisting of them. If the total unit content of the quaternary ammonium salt (A) in the dental material is 0.1% by mass or more, antibacterial effects can be imparted. Moreover, if it is 0.5 or more, a stable and sufficient antibacterial effect can be maintained over a long period of time, which is more preferable.

The photocurable antibacterial dental resin composition of the present invention can contain a compound (B) having an ethylenically unsaturated group. The compound (B) having an ethylenically unsaturated group is a compound having an ethylenically unsaturated group excluding the quaternary ammonium salt (A) having an unsaturated group, and its content is particularly limited. However, it is preferably contained in an amount of 5 to 99% by mass with respect to the entire photocurable resin composition. Within this range, it has sufficient antibacterial properties, photocurability, adhesion to the base material of teeth and medical devices, adhesiveness, hardness, strength, discoloration resistance, and durability of the resulting dental crowns and dentures. It is possible to adjust characteristics such as sex in a well-balanced manner.

The unsaturated group of the compound (B) having an ethylenically unsaturated group includes a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group and maleimide. It is a functional group having one or more unsaturated bonds selected from the group consisting of groups. Further, the compound (B) having an ethylenically unsaturated group includes a compound having a monofunctional ethylenically unsaturated group (monofunctional unsaturated compound) (b1) and a compound having a bifunctional or higher ethylenically unsaturated group ( polyfunctional unsaturated compound) (b2). Only (b1) or (b2) is used as the compound (B) having an ethylenically unsaturated group depending on the type, structure, molecular weight, etc. of the quaternary ammonium salt (A) having an unsaturated group and its oligomer and polymer. However, by using (b1) and (b2) together, the hardness and durability of the resulting cured product (dental filling material, denture model, etc.) can be further improved.

The monofunctional unsaturated compound (b1) is not particularly limited as long as it is a monomer having one ethylenically unsaturated group in the molecule. In addition, the ethylenically unsaturated group is not particularly limited as long as it has radical polymerizability, and specifically includes a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, ( meth)allyl ether group, maleimide group and the like. The content of (b1) is preferably 5 to 99% by mass with respect to the entire photocurable resin composition. Moreover, when it is 10 to 90% by mass, the strength and hardness of the photocured product are good, and both the surface smoothness and durability of the dental crown and denture to be formed can be improved, which is more preferable.

Among the monofunctional unsaturated compounds (b1), the compound containing a (meth)acrylate group includes, for example, (meth)acrylic acid, and a linear, branched, or cyclic alkyl group having 1 to 22 carbon atoms. Alkyl (meth)acrylates, hydroxyalkyl (meth)acrylates into which linear, branched, or cyclic hydroxyalkyl groups having 1 to 18 carbon atoms are introduced, (meth)acrylic acid and hydroxyalkylcarboxylic acids (meth) (Meth)acrylate alkyl carboxylic acids such as ethyl acrylate carboxylic acid, ethyl (meth)acrylate succinate, ethyl (meth)acrylate phthalate, ethyl (meth)acrylate hexahydrophthalate, and having 1 to 18 carbon atoms Alkyl (meth)acrylates with linear, branched or cyclic alkylsulfonic acid groups introduced, C 1-18 alkyl (meth)acrylates with linear, branched or cyclic alkyl phosphate groups introduced Phosphoric acids, alkoxyalkylene glycol (meth)acrylates, alkoxydialkyleneglycol (meth)acrylates, alkoxytri Alkylene glycol (meth)acrylates, alkoxypolyalkylene glycol (meth)acrylates, and phenoxyalkylene glycol (meth)acrylates and phenoxydialkylenes into which a functional group consisting of a phenoxy group and an alkylene glycol group having 1 to 4 carbon atoms is introduced. Glycol (meth)acrylates, phenoxytrialkyleneglycol (meth)acrylates, phenoxypolyalkyleneglycol (meth)acrylates, N-alkylamino (meth)acrylates introduced with an aminoalkyl group having 1 to 6 carbon atoms, , N-alkylaminoalkyl (meth)acrylates introduced with an N-alkylaminoalkyl group consisting of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms, and N,N-dialkylaminoalkyl (meth)acrylates introduced with an N,N-dialkylaminoalkyl group consisting of an aminoalkyl group and an alkyl group having 1 to 6 carbon atoms, benzyl (meth)acrylate, phenoxyethyl (meth) Acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyl (meth)acrylates into which a cyclic structure is introduced such as nyloxyethyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, etc. , glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, and other epoxy group-introduced (meth)acrylates.

Among the monofunctional unsaturated compounds (b1), compounds containing a (meth)acrylamide group include (meth)acrylamide, mono- or disubstituted (meth)acrylamide, (meth)acryloylmorpholine, and (meth)diacetone acrylamide. and the like, and the mono- or di-substituted (meth)acrylamides include, for example, N-alkyl (meth)acrylamides having a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms, N,N- Dialkyl(meth)acrylamide, N-hydroxyalkyl(meth)acrylamide with hydroxyalkyl group having 1 to 6 carbon atoms introduced, N,N-di(hydroxyalkyl)(meth)acrylamide, N-hydroxyalkyl -N-(4-hydroxyphenyl)(meth)acrylamide, N-alkyl-N-hydroxyalkyl(meth)acrylamide introduced with a hydroxyalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms , N-alkyl-N-(4-hydroxyphenyl) (meth)acrylamide, 4-hydroxyphenyl (meth)acrylamide, N,N-di(4-hydroxyphenyl) (meth)acrylamide, having 1 to 6 carbon atoms N-alkoxyalkyl (meth)acrylamide, N,N-di(alkoxyalkyl)(meth)acrylamide, having 1 to 6 carbon atoms An alkoxyalkyl group consisting of an alkoxy group and an alkylene group having 1 to 6 carbon atoms, an N-alkyl-N-alkoxyalkyl (meth)acrylamide introduced with an alkyl group having 1 to 6 carbon atoms, and an alkyl group having 1 to 6 carbon atoms. N-sulfoalkylacrylamide having a sulfonic acid group introduced, N-alkylamino(meth)acrylamide having an aminoalkyl group having 1 to 6 carbon atoms introduced, an aminoalkyl group having 1 to 6 carbon atoms and an aminoalkyl group having 1 to 6 carbon atoms N-alkylaminoalkyl (meth)acrylamide into which an N-alkylaminoalkyl group consisting of an alkyl group of is introduced, N,N-dialkyl consisting of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms Examples thereof include N,N-dialkylaminoalkyl(meth)acrylamides into which an aminoalkyl group has been introduced.

Among the monofunctional unsaturated compounds (b1), examples of compounds containing a vinyl group include carboxylic acid vinyl esters obtained by introducing a carboxylic acid having 1 to 22 carbon atoms, linear, branched, and cyclic compounds having 1 to 22 carbon atoms. alkyl vinyl ether, vinyl chloride, N-vinylpyrrolidone, N-vinylcaprolactam, N-vinyloxazoline, maleic acid, maleic anhydride, fumaric acid, itaconic acid, itaconic anhydride, having 1 to Maleic acid monoalkyl ester, maleic acid dialkyl ester, maleic acid monoalkylamide, maleic acid dialkylamide, maleic acid alkylimide, fumaric acid monoalkyl ester, dialkyl fumaric acid into which a linear, branched, or cyclic alkyl group of 22 is introduced ester, fumaric acid monoalkylamide, fumaric acid dialkylamide, itaconic acid monoalkyl ester, itaconic acid dialkyl ester, itaconic acid monoalkylamide, itaconic acid dialkylamide, itaconic acid alkylimide, vinyl carboxylic acid, vinyl sulfonic acid, vinyl phosphoric acid etc.

Among the monofunctional unsaturated compounds (b1), the compound containing an allyl group includes a carboxylic acid allyl ester obtained by introducing a carboxylic acid having 1 to 22 carbon atoms, a linear, branched, or cyclic compound having 1 to 22 carbon atoms. alkyl allyl ethers, phenyl allyl ethers, alkylphenyl allyl ethers, allyl amines, branched or cyclic alkyl group-introduced mono- or di-alkyl allyl amines.

Among the monofunctional unsaturated compounds (b1), the compound containing a maleimide group includes N-alkylmaleimide, N-alkyl-α- methylmaleimide, N-alkyl-α-ethylmaleimide, N-alkyl-α,β-dimethylmaleimide, N-alkyl-α-phenylmaleimide, linear, branched or cyclic hydroxyalkyl groups having 1 to 12 carbon atoms; introduced N-hydroxyalkyl-maleimide, N-hydroxyalkyl-α-methylmaleimide, N-hydroxyalkyl-α-ethylmaleimide, N-hydroxyalkyl-α,β-dimethylmaleimide, N-hydroxyalkyl-α-phenylmaleimide, An alkoxysilane compound having a maleimide group, a carboxylic acid compound having a maleimide group, and the like can be mentioned.

These monofunctional unsaturated compounds (b1) may be used singly or in combination of two or more.

The polyfunctional unsaturated compound (b2) is not particularly limited as long as it is a monomer or oligomer having two or more ethylenically unsaturated groups in the molecule. In addition, the ethylenically unsaturated group is not particularly limited as long as it has radical polymerizability, and specifically includes a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, ( meth)allyl ether group, maleimide group and the like. Moreover, these ethylenically unsaturated groups may have two or more of the same functional groups in the molecule, or may be a combination of two or more different functional groups that can be arbitrarily selected. The content of (b2) is preferably 5 to 99% by mass with respect to the entire photocurable resin composition. In addition, when the content of (b2) is 5 to 80% by mass, the viscosity of the prepared photocurable resin composition is easily adjusted, and the coating properties, filling properties, adhesion to the tooth surface, and adhesiveness are improved. Both are satisfactory, and the resulting photocured product has excellent strength and sufficient durability, which is more preferable.

Among the polyfunctional unsaturated compounds (b2), for example, (di)ethylene glycol di(meth)acrylate, (tri)propylene glycol di(meth)acrylate, ditetraethylene glycol di(meth)acrylate, polyalkylene (carbon Numbers 1-4) Glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, 1,3 (or 1,4)-butanediol di(meth)acrylate, 1,6-hexanediol di(meth) Acrylates, cyclohexanedimethanol di(meth)acrylates, acrylate esters (dioxane glycol diacrylate), alkoxylated (cyclo)hexanediol di(meth)acrylates, epoxy di(meth)acrylates, dicyclopentanyl di(meth)acrylates, caprolactone modified dicyclopentenyl di(meth)acrylate, tricyclodecanedimethanol di(meth)acrylate, polyester di(meth)acrylate, ethylene oxide-modified bisphenol A di(meth)acrylate, propylene oxide-modified bisphenol A di(meth)acrylate, Polyurethane di(meth)acrylate, allyl(meth)acrylate, methylenebis(meth)acrylamide, ethylenebis(meth)acrylamide, polyurethane di(meth)acrylamide, allyl(meth)acrylamide, pentaerythritol tri(meth)acrylate, pentaerythritol tetra (meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tri(meth)acryloyloxyethoxytrimethylolpropane, glycerin polyglycidyl ether poly(meth)acrylate, isocyanurate ethylene oxide-modified tri(meth)acrylate, Ethylene oxide-modified dipentaerythritol penta(meth)acrylate, ethylene oxide-modified dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified pentaerythritol tri(meth)acrylate, ethylene oxide-modified pen Taerythritol tetra(meth)acrylate, succinic acid-modified pentaerythritol tri(meth)acrylate, and the like. These polyfunctional unsaturated compounds (b2) may be used singly or in combination of two or more.

In the compound (B) having an ethylenically unsaturated group used in the present invention, from the viewpoint of safety such as skin irritation and odor and compatibility with the quaternary ammonium salt (A) having an unsaturated group, a single The functional unsaturated compound (b1) is preferably a methacrylate-based monomer, a methacrylamide-based monomer, or an acrylamide-based monomer, and more preferably an acrylamide-based monomer from the viewpoint of curability. Furthermore, it is most preferable to use acrylamide-based monomers and methacrylate-based monomers together in order to control the amount of heat generated during curing.

The antibacterial dental resin composition of the present invention can be sufficiently cured by visible light or ultraviolet irradiation. The unsaturated group of the quaternary ammonium salt (A) having an unsaturated group and/or the compound (B) having an ethylenically unsaturated group is a maleimide group, an α-substituted maleimide group and an α,β-substituted maleimide group, a vinyl ether group, In the case of one or more functional groups selected from the group consisting of a methyl vinyl ether group, an allyl group, and a (meth)allyl ether group, these unsaturated groups generate active radicals upon irradiation with light, so that the photocurable resin composition The product may not contain a photopolymerization initiator.

The antibacterial dental resin composition of the present invention can contain a photopolymerization initiator (C). Examples of photopolymerization initiators include α-diketones such as camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone, Thioxanthones such as 2,4-diethylthioxanthone, 2-benzyl-dimethylamino-1-(4-morpholinophenyl)-butanone-1,2-benzyl-diethylamino-1-(4-morpholinophenyl)-butanone- 1,2-benzyl-dimethylamino-1-(4-morpholinophenyl)-propanone-1,2-benzyl-diethylamino-1-(4-morpholinophenyl)-propanone-1,2-benzyl-dimethylamino- α-Aminoacetophenones such as 1-(4-morpholinophenyl)-pentanone-1,2-benzyl-diethylamino-1-(4-morpholinophenyl)-pentanone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide and acylphosphine oxide derivatives such as bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide. These photoinitiator polymerization agents may be used singly or in combination of two or more.

The content of the photopolymerization initiator (C) is preferably 0.1 to 10% by mass with respect to the entire photocurable dental resin composition. When it is 0.1% by mass or more, it has sufficient curability even when applied thinly, and the obtained cured film has good strength and durability. When it is 10% by mass or less, the pot life of the photocurable resin composition is sufficiently long, and troubles such as gelation during storage do not occur. Furthermore, 0.5 to 5% by mass is more preferable.

Moreover, a polymerization accelerator can be blended as an auxiliary agent for the photopolymerization initiator. For example, N,N-dimethylaniline, N,N-diethylaniline, N,N-di-n-butylaniline, N,N-dibenzylaniline, N,N-dimethyl-p-toluidine, N,N-diethyl -p-toluidine, N,N-dimethyl-m-toluidine, p-bromo-N,N-dimethylaniline, m-chloro-N,N-dimethylaniline, p-dimethylaminobenzaldehyde, p-dimethylaminoacetophenone, p -dimethylaminobenzoic acid, methyl p-dimethylaminobenzoate, ethyl p-dimethylaminobenzoate, amyl p-dimethylaminobenzoate, N,N-dimethylanthranic acid methyl ester, N,N-dihydroxyethylaniline, N , N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N,N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N,N-dimethyl-α-naphthylamine , N,N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylhexylamine, N,N-dimethyldodecylamine, N,N- Tertiary amines such as dimethylstearylamine, N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethyl methacrylate, 2,2′-(n-butylimino)diethanol, 5-butyl barbituric acid, 1- Mercapto compounds such as barbituric acids such as benzyl-5-phenylbarbituric acid, dodecyl mercaptan, pentaerythritol tetrakis(thioglycolate) and the like. These polymerization accelerators may be used singly or in combination of two or more.

The content of the polymerization accelerator is preferably 0.01 to 2% by mass with respect to the entire photocurable dental resin composition. Within this range, a sufficient effect of the polymerization accelerator is obtained, and troubles such as coloring and deterioration of discoloration resistance caused by the polymerization accelerator are unlikely to occur. Furthermore, 0.05 to 1% by weight is more preferred.

The photocurable dental resin composition of the present invention can be used without containing a solvent. Moreover, in order to obtain a special product that requires more precise shape, gloss, hardness, surface smoothness, etc., water or an organic solvent may be contained as necessary. The organic solvent preferably has a boiling point of 50 to 120°C, more preferably 55 to 100°C, at normal pressure. Further, from the viewpoint of safety, water, acetone, ethyl acetate, butyl acetate, ethanol, isopropanol and the like are particularly preferable as solvents used for general nail polish, enamel and the like. These solvents may be used singly or in combination of two or more. When the solvent is contained, the content thereof is preferably 1.0 to 50% by mass, more preferably 5 to 30% by mass, based on the total photocurable resin composition. Within this range, the photocurable resin composition can be easily produced, and the mechanical properties of the cured product are not likely to be adversely affected.

Various additives can be added to the antibacterial dental resin composition (including non-photocurable and photocurable) of the present invention, if necessary. Specifically, additives include thermal polymerization inhibitors, antioxidants, ultraviolet sensitizers, preservatives, phosphate esters and other flame retardants, surfactants, antistatic agents, pigments, dyes, and the like. Colorants, fragrances, antifoaming agents, fillers, silane coupling agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softening agents, organic fillers, inorganic fillers, and the like can be added. The amount of these other components to be added is not particularly limited as long as it does not adversely affect the properties exhibited by the antibacterial dental resin composition according to the present invention. preferable. However, the filler has the effect of improving the strength and wear resistance of the cured product of the resin, and has the effect of adjusting the fluidity when the resin composition is applied or filled on the teeth. The range of 50% by mass or less is preferable with respect to

The antibacterial dental resin composition of the present invention can be used for application, filling, shaping, etc., of the user's own teeth, dentures, materials for denture bases, and medical instruments. Specifically, the antibacterial resin composition is applied to the surface of these objects and solidified by drying or cured by light irradiation to obtain a surface coating material or a surface-coated instrument as a solidified film or cured film. . In addition, the antibacterial resin composition is filled in the repaired portion of these objects and solidified by drying or cured by light irradiation to obtain adhesives or filling materials as solidified or cured products. Furthermore, in the case of forming by three-dimensional modeling, dentures, denture base materials, medical instruments, etc. are obtained by drying and curing while shaping. Since the antibacterial resin composition of the present invention has excellent adhesion and adhesiveness to natural teeth as well as to denture materials such as acrylic resins, ceramics, and metals, it can be used as a caries treatment resin and a dental crown material. It can also be used as a surface covering material for aesthetic treatment. In this case, if pretreatment such as polishing the surface of the natural tooth or wiping with alcohol is performed, the durability can be further improved. Further, since the solidified or cured film of the antibacterial resin composition has both strength, hardness and surface smoothness, polishing or the like is not particularly required after treatment. The antibacterial resin composition of the present invention has no odor or irritation, and is composed of components that do not bleed out. Therefore, it is highly safe and can be used as a tooth protective agent.

The antibacterial dental resin composition of the present invention contains a quaternary ammonium salt and has excellent antibacterial and antifouling properties. In addition, it is easily mixed uniformly with organic or inorganic fillers such as general-purpose pigments, brightening agents, and dyes. Furthermore, oligomers and polymers of quaternary ammonium salts can be designed with a wide variety of structures and molecular weights according to the required physical properties. It can be directly applied, filled, and repaired on surfaces such as A single layer coating of a thick film may be used, or a lamination coating of thin films may be used. Furthermore, a solid model can also be formed by a suitable solid model device.

Examples of inorganic fillers include silica, kaolin, clay, mica, mica, crystalline quartz, hydroxyapatite, alumina, titanium oxide, yttrium oxide, zirconia, calcium phosphate, barium sulfate, aluminum hydroxide, sodium fluoride, and potassium fluoride. , sodium monofluorophosphate, lithium fluoride, calcium fluoride, ytterbium fluoride, yttrium fluoride and the like. From the viewpoint of maintaining safety over a long period of time, silica, kaolin, clay, mica, mica, crystalline quartz, hydroxyapatite, alumina, and titanium oxide are preferred. These inorganic fillers may be used singly or in combination of two or more.

Examples of the organic filler include polymethyl methacrylate, polyethyl methacrylate, copolymers of polymethyl methacrylate and polyethyl methacrylate, polyfunctional methacrylate polymers, ethylene-vinyl acetate copolymers, acrylonitrile-butadiene-styrene copolymers. Coalescing, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, styrene-butadiene rubber. Oligomers and polymers of quaternary ammonium salts having unsaturated groups for use in the present invention can also be suitably used as organic fillers. These organic fillers may be used singly or in combination of two or more.

The light source used for photocuring the photocurable dental resin composition of the present invention is not particularly limited, and a general-purpose dental light irradiator can be used. For example, known light sources include sunlight, fluorescent lamps, high-pressure mercury lamps, metal halide lamps, ultraviolet (UV) lamps, light emitting diode (LED) lamps, ultraviolet light emitting diode (UV-LED) lamps, ultraviolet laser diodes (UV-LD). ) lamps and the like. In addition, from the viewpoint of small size, long life, high efficiency, low cost, and safety, the ultraviolet irradiation type using a 365 nm fluorescent tube and the visible light irradiation type using a 405 nm LED light source are becoming mainstream. more preferable

The irradiation energy required for photocuring the photocurable dental resin composition of the present invention varies somewhat depending on the application and the light source, but the irradiation energy (integrated light quantity) is preferably in the range of 1 to 1000 mJ/cm ² , more preferably 10 to 500 mJ. /cm ² is more preferred. This is because within this range, the resin composition can be sufficiently cured, and the hardness and strength of the cured product can be sufficiently satisfied. Further, the specific irradiation conditions may be appropriately adjusted according to repair by surface coating or filling of teeth, or formation of dentures by a stereolithography apparatus. For example, when curing a resin composition for a denture base material by UV irradiation, a commercially available dental UV lamp (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd.) is used as the light source, and irradiation is performed for 1 to 100 seconds. Also, when repairing natural teeth with visible light, it is particularly preferable to use a commercially available dental irradiator (Laborite LV-II) as a light source and irradiate for 0.1 to 2 minutes.

EXAMPLES The present invention will be described in more detail below with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. In addition, all "parts" and "%" below are based on mass unless otherwise specified.

Table 1 shows quaternary ammonium salts having unsaturated groups and their oligomers and polymers (A-1) to (A-10).

Monofunctional unsaturated compounds (b1) used in Examples and Comparative Examples are shown below.
b1-1: isobornyl acrylate (IBOA)
b1-2: 2-hydroxyethyl methacrylate (HEMA)
b1-3: N-(2-hydroxyethyl)maleimide (HEMI)
b1-4: methyl methacrylate (MMA)
b1-5: 4-hydroxybutyl acrylate (4HBA)
b1-6: ethoxydiethylene glycol acrylate (ECA)
b1-7: 2-hydroxyethyl vinyl ether (HEVE)
b1-8: Acryloylmorpholine (registered trademark "ACMO" of KJ Chemicals Co., Ltd.)
b1-9: Dimethylacrylamide (registered trademark of KJ Chemicals Co., Ltd. "DMAA")
b1-10: Diethylacrylamide (registered trademark "DEAA" of KJ Chemicals Co., Ltd.)
b1-11: N-(2-hydroxyethyl)acrylamide (registered trademark of KJ Chemicals Co., Ltd. "HEAA")
b1-12: Isopropyl acrylamide (registered trademark "NIPAM" of KJ Chemicals Co., Ltd.)
b1-13: Dimethylaminopropyl acrylamide (registered trademark "DMAPAA" of KJ Chemicals Co., Ltd.)
b1-14: diacetone acrylamide (registered trademark "Kohsylmer" DAAM of KJ Chemicals Co., Ltd.)
b1-15: 4-t-butylcyclohexyl acrylate ((KJ Chemicals Co., Ltd. registered trademark "Kohsylmer" TBCHA)
b1-16: N-vinylpyrrolidone (NVP)
b1-17: N-vinylcaprolactam (NVC)

Polyfunctional unsaturated compounds (b2) used in Examples and Comparative Examples are shown below.
b2-1: triethylene glycol diacrylate (TEGDA)
b2-2: dipentaerythritol hexaacrylate (DPHA)
b2-3: trimethylolprohane triacrylate (TMPTA)
b2-4: Tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Co., Ltd.)
b2-5: urethane diacrylate (UA, bifunctional, polyester skeleton, molecular weight 5000)
b2-6: urethane diacrylamide (UAm, bifunctional, polycarbonate skeleton, molecular weight 8000)

Photopolymerization initiators (C) used in Examples and Comparative Examples are shown below.
C-1: Camphorquinone (manufactured by Aldilich)
C-2: 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (IRGACURE-TPO, manufactured by BASF Japan Ltd.)
C-3: 1-hydroxycyclohexylphenyl ketone / benzophenone = 1/1 mixture (IRGACURE-500, manufactured by BASF Japan Ltd.)

Example 1 Preparation of photocurable antibacterial resin composition (D-1) 0.1 parts by mass of acryloylaminopropyltrimethylammonium p-toluenesulfonate (A-1) as (A), and "ACMO" as (B) (b1-8) 50.0 parts by mass, "HEAA" (b1-11) 1.9 parts by mass, TEGDA (b2-1) 20.0 parts by mass, UAm (b2-6) 25.0 parts by mass, ( As C), 3.0 parts by mass of camphorquinone (C-1) was added to each container and stirred at 40 ° C. for 1 hour to obtain a uniformly transparent photocurable antibacterial resin composition (D-1) of Example 1. ).

Examples 2 to 10 Preparation of photocurable antibacterial resin compositions (D-2) to (D-10) Photocurable antibacterial resin compositions (D-2) to (D-10) corresponding to were obtained.

Comparative Examples 1 to 3 Preparation of photocurable resin compositions (E-1) to (E-3) Corresponding to Comparative Examples 1 to 3 by performing the same operation as in Example 1 with the compositions shown in Table 2 Photocurable resin compositions (E-1) to (E-3) were obtained.

Using the photocurable antibacterial resin compositions obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3, evaluation was performed by the following method, and the results are shown in Table 3. shown in

Using the photocurable antibacterial resin compositions obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3, the solubility or dispersibility (insoluble inorganic filler or When a pigment or the like is blended) was observed, and the storage stability of the composition was evaluated. Table 3 shows the results. Furthermore, a photocurable dental material was prepared by the following method, and the photocurability of the resin composition and the surface smoothness, hardness and adhesive strength of the resulting dental material were evaluated. Table 3 shows the results. Antibacterial and antifouling properties were tested using typical oral bacteria Streptococcus mutans and Candida albicans, and the results are shown in Table 4.
1. Solubility (dispersibility)
A: The obtained resin composition was uniform and transparent.
Good: The obtained resin composition was uniform and translucent.
Δ: The obtained resin composition was cloudy and it was difficult to judge the uniformity.
x: The obtained resin composition was not completely mixed.
2. Storage Stability The photocurable dental resin compositions obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3 were placed in a light-shielding screw tube, the lid was closed, and the temperature was maintained at 40°C. and stored at 80° C. for 1 month and 80° C. for 2 weeks. The dissolved or dispersed state of the composition after storage was confirmed to evaluate the storage stability.
◯: There was no change in state after storage under both conditions of storage at 40° C. for 1 month and storage at 80° C. for 2 weeks.
Δ: State change after storage was confirmed under either one of 40° C. for 1 month or 80° C. for 2 weeks.
x: Change in state after storage was confirmed under both conditions of 1 month at 40°C and 2 weeks at 80°C.
3. Curability Using the photocurable dental resin compositions obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3, polytetrafluoroethylene having a hole with a diameter of 6 mm in the center A mold (20 mm × 20 mm × 10 mm) was filled with a resin composition, pressed with a polypropylene film, and a dental light irradiation device (Tokuso Power Light, manufactured by Tokuyama Dental, light output density 700 mW / cm ² , irradiation surface Light intensity of 640 to 650 mW/cm ² , light source is a halogen lamp, irradiation aperture 8 mm) is adhered to the polypropylene film and irradiated for 30 seconds. It was confirmed.
A: No stickiness at all (completely cured).
◯: Slightly sticky, but finger marks are not left on the surface (almost completely cured, wiping off uncured components is unnecessary).
Δ: Sticky, finger marks remain on the surface (incomplete curing, uncured components must be wiped off).
x: Extremely sticky, finger sticks to the surface (a large amount of uncured components remains and cannot be used as a cured film).
4. Surface Smoothness The surface of the cured product obtained in the curability evaluation was visually observed to confirm smoothness and glossiness.
A: The surface is smooth and glossy.
◯: The surface is almost smooth and slightly cloudy or slightly uneven.
Δ: The surface is cloudy as a whole, and some unevenness and graininess are observed.
x: The surface is entirely cloudy and covered with granular substances.
5. Hardness The surface of the cured product obtained in the above curability evaluation was buffed, and the Knoop hardness was measured with a microhardness tester manufactured by Matsuzawa Seiki under a load of 10 g and a load of 20 seconds. The measurement temperature was 23°C.
A: Knoop hardness is 200 KHN or more (equivalent to permanent tooth enamel).
○: Knoop hardness is 70 KHN or more and less than 200 KHN (equivalent to dentin).
Δ: Knoop hardness is less than 70 KHN.
x: Measurement could not be performed because it was not cured.
6. Adhesion strength (Dentin adhesion strength)
The cow's lower forehead anterior tooth was polished with #1000 water-resistant abrasive paper under water injection, the flat adhesive dentin surface was scraped out, dried by blowing compressed air for 10 seconds, and a tape with a hole of 3 mm in diameter was attached. , set the adherend surface. After that, an adhesion test piece was prepared by a known method (see the method described in JP-A-2010-208964). After the adhesive test piece was immersed in water at 37°C for 24 hours, the tensile adhesive strength was measured with an Instron universal tester (crosshead speed of 2 mm/min). Adhesive strength of the curable resin composition to enamel and dentin. The value of tensile bond strength is the average value of five test pieces.
⊚: The adhesive strength of both enamel and dentin is 20 Mpa or more.
○: The adhesive strength of only one of enamel and dentin is 20 Mpa or more.
Δ: The adhesive strength of both enamel and dentin is 7 Mpa or more.
x: Both adhesive strengths of enamel and dentin are less than 7 Mpa.
7. Antibacterial properties The photocurable resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 3 are fixed on a release film and are poured into a spacer having a thickness of 200 μm and an interior of 40 mm × 60 mm. After the solvent was completely removed (80° C., 1 minute) and cured by irradiation with ultraviolet light (accumulated light intensity 1000 mJ/cm 2 ), the release film was peeled off to obtain a cured film for antibacterial test. Pour the agar medium into a glass petri dish with an inner diameter of 90 mm, inoculate it with Streptococcus mutans or Candida, put a hardened film on it, close the lid, temperature 30 ± 5 ° C., humidity 85 ± 5% RH. It was cultured for 7 days in a constant temperature and humidity machine. The growth of the fungi was evaluated on a 4-point scale.
(double-circle): Growth of a microbe is not seen at all.
◯: Slight growth of bacteria is observed.
Δ: Slight growth of bacteria is observed.
x: Severe bacterial growth is observed.
8. Antifouling (prevents plaque adhesion)
By a known method (see the method described in JP-A-2015-214514), using the photocurable resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 3, plaques against the above two bacteria An adhesion suppression test was performed.
⊚: No plaque adhesion was observed.
◯: Slight adhesion of plaque was observed.
Δ: Slight adhesion of plaque was observed.
x: Severe adhesion of larks is observed.

As shown in the results of Examples and Comparative Examples, only when the quaternary ammonium salt (A) having an unsaturated group of the present invention and/or its oligomer or polymer is contained, the antibacterial property is excellent and the antibacterial property is excellent. It was possible to obtain a dental resin composition which satisfies all of the stain resistance, photocuring property and storage stability.

As described above, the antibacterial dental polymerizable resin composition of the present invention has excellent antibacterial properties and can be suitably used as a dental treatment material. In addition, it has good antifouling properties, safety, curability and storage stability of light-curing type, and has sufficient strength, hardness and adhesive strength for coating, thin coating, filling and thick coating, and is a material for aesthetic treatment. It can be suitably used as a denture material or a denture material, and it is also possible to obtain a three-dimensional model and a medical instrument coated with these.

Claims (19)

A polymerizable dental resin composition containing a quaternary ammonium salt (A) having an unsaturated group represented by formula (1).

(In the formula, R ₁ , R ₂ and R ₃ may be the same or different, and each independently represents a linear or branched alkyl group having 1 to 36 carbon atoms, a hydroxyl group or an amine group. represents a substituted alkyl group, a linear or branched alkenyl group having 2 to 36 carbon atoms, an alkenyl group substituted with a hydroxyl group or an amine group, or a benzyl group;
L represents an unsaturated group selected from a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group and a maleimide group;
Y represents an alkylene group having 1 to 36 carbon atoms,
Q ⁻ is p-toluenesulfonate, tetrafluoroborate, hexafluorophosphate, trifluoromethanesulfonate, tetraphenylborate, thiocyanate, bis(fluorosulfonyl)imide anion, bis(trifluoromethane sulfonyl) imide anion and saccharinate anion . ) The quaternary ammonium salt (A) having an unsaturated group includes, as cations, (meth)acryloylaminopropyltrimethylammonium, (meth)acryloylaminopropyldimethylbenzylammonium, (meth)acryloyloxyethyltrimethylammonium, (meth)acryloyloxy 2. The polymerizable dental resin composition according to claim 1, comprising one or more cations selected from the group consisting of ethyldimethylbenzylammonium and diallyldimethylammonium. 3. The polymerizable dental resin composition according to claim 1, which contains 0.1% by mass or more of the quaternary ammonium salt (A) having an unsaturated group. 4. The polymerizable dental resin composition according to any one of claims 1 to 3, characterized by containing 0.1% by mass or more of an oligomer of a quaternary ammonium salt (A) having an unsaturated group. 5. The polymerizable dental resin composition according to any one of claims 1 to 4, characterized by containing 0.1% by mass or more of the polymer of the quaternary ammonium salt (A) having an unsaturated group. 6. The dental resin composition according to any one of claims 1 to 5, characterized by containing 5 to 99% by mass of the compound (B) (excluding (A)) having an ethylenically unsaturated group. The compound (B) having an ethylenically unsaturated group includes, as unsaturated groups, a (meth)acrylate group, a (meth)acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, a (meth)allyl ether group and maleimide. 7. The dental resin composition according to claim 6, which is a compound having one or more ethylenically unsaturated groups selected from the group consisting of groups. 8. The polymerizable dental resin composition according to any one of claims 1 to 7, further comprising 0.1 to 10% by mass of a photopolymerization initiator (C). A polymerizable dental resin composition comprising a polymer obtained by polymerizing the polymerizable dental resin composition according to any one of claims 1 to 8. A dental composite resin containing the polymerizable dental resin composition according to any one of claims 1 to 9. An antibacterial ink for a three-dimensional dental object containing the polymerizable dental resin composition according to any one of claims 1 to 9. A dental material comprising the polymerizable dental resin composition according to any one of claims 1 to 9. A dental crown material comprising the polymerizable dental resin composition according to any one of claims 1 to 9. A dental adhesive comprising the polymerizable dental resin composition according to any one of claims 1 to 9. A dental surface coating material comprising the polymerizable dental resin composition according to any one of claims 1 to 9. A dental filling material comprising the polymerizable dental resin composition according to any one of claims 1 to 9. A dental denture material comprising the polymerizable dental resin composition according to any one of claims 1 to 9. A denture base material comprising the polymerizable dental resin composition according to any one of claims 1 to 9. An antibacterial three-dimensional dental article formed using the antibacterial ink for three-dimensional dental article according to claim 11 .