JP2020132590A - Polymerizable resin composition for dental use - Google Patents

Abstract

To provide a resin composition for dental use which has excellent antibacterial property and stain-resistant property, excellent safety and storage stability, high photosetting property, and is preferably used both in coating and filling, and various kinds of material for dental use which have excellent hardness, strength and durability obtained from the composition, and can maintain semi-permanent antibacterial action.SOLUTION: An antibacterial resin composition for dental use contains quaternary ammonium salt (A) having unsaturated group having non halogen-based anion and/or oligomer or polymer thereof.

Description

The present invention relates to a dental resin composition having polymerizability with respect to active energy rays such as heat and light, and 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, and are suitable for different purposes such as dental caries treatment, aesthetic treatment to make your teeth look white and beautiful, dentures, and implant treatment. Is used. These materials are required to be strong enough to withstand occlusion, and at the same time, they are also required to have long-term safety, antibacterial properties, antifouling properties, adhesive durability, discoloration resistance, and corrosion resistance of alloys used for implants. Has been done.

However, there are many indigenous bacteria in the oral cavity, plaque is formed on the surface of teeth and dentures, and the part treated with stuffing or crown tends to become cavities again, and the inner surface of dentures and denture base that have been used for many years There was a problem that periodontal pathogenic bacteria adhered to the mucosal surface and around the implant, and bacterial infection was likely to occur due to activation.

Oral rinse solutions, toothpastes, gels, etc. containing compounds with antibacterial activity such as domiphen bromide, chlorhexidine, triclosan, and quaternary ammonium salts have been developed to suppress oral microorganisms and bacteria. It cannot maintain its action, it is difficult to reach the filling, crown, denture base and implant area, and there are many halogen-based products, it is highly irritating, and there is concern about safety to the human body due to long-term use. There was a problem to do.

Further, a method of blending zeolite particles in which silver ions are carried as an antibacterial metal ion source in a resin such as a filler or a surface coating material used for dental treatment (Patent Document 1), and an effective amount of antibacterial lipid component A curable antibacterial dental composition containing a curable component (Patent Document 2) and a photocurable resin in which the antibacterial component is immobilized after curing by blending a polymerizable compound having a phosphate residue (Patent). Document 3) and a dental adhesive (Non-Patent Document 1) containing an antibacterial monomer (12-? Methadryloyloxydodecylpyridinium bromide (MDPB)) in which a polymerizable group is introduced into a quaternary ammonium salt have been proposed. 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 drinks and acids produced by oral bacteria. In some cases, it may be eluted, and it cannot be said that the safety to the human body is ensured, it cannot be said that it has permanent antibacterial properties, and further, the implants made of these phosphoric acid and bromo ions Fixtures (metal parts) are corroded, and there is concern about the problem of implant breakage.

Furthermore, the plaque adhering to the surface and surroundings of teeth and dentures is a hotbed of oral bacteria, and it is necessary to prevent plaque accumulation due to food residue, adhesion or adhesion of bacteria. However, none of the prior art documents mentioned above mentions the antifouling property, which is important as a dental material.

Japanese Unexamined Patent Publication No. 1-2454608 Japanese Unexamined Patent Publication No. 2008-533009 Japanese Unexamined Patent Publication No. 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 property, antifouling property, discoloration resistance, high safety, and excellent polymerization property with respect to active energy rays such as heat and light. And. Further, the present invention is a highly safe dental material having semi-permanent antibacterial and antifouling properties, which contains a polymer obtained by copolymerizing the composition alone or with another polymerizable compound by heat or light. The challenge is to provide. Further, the present invention relates to a dental composite resin, a crown material, an adhesive, a filling material, a denture material, a denture base material and the composition obtained by blending the composition and / or the polymer. / Or, it is an object of the present invention to provide an antibacterial material for a three-dimensional model containing the polymer, a medical device whose surface is coated with an antifouling material, and a three-dimensional model having antibacterial and antifouling properties.

As a result of diligent research to solve the above problems, the present inventors have obtained a quaternary ammonium salt (A) having an unsaturated group and / or copolymerization thereof alone or 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 a polymer (also called oligomer or polymer) as an essential component. Dental materials, antibacterial trees and antifouling inks for three-dimensional shaped objects, medical devices coated with antibacterial and antifouling resin, three-dimensional shaped objects with antibacterial and antifouling properties, etc. It has arrived.

That is, the present invention comprises (1) a polymerizable dental resin composition containing a quaternary ammonium salt (A) having an unsaturated group represented by the general formula (1).
(In the formula, R ₁ , R ₂ and R ₃ may be the same or different from each other, and each independently has a linear or branched alkyl group having 1 to 36 carbon atoms, a hydroxyl group or an amine group. It represents a substituted alkyl group, a linear or branched alkenyl group having 1-36 carbon atoms, an alkenyl group substituted with a hydroxyl group or an amine group, or a benzyl group, where L represents an unsaturated bond and Y represents an unsaturated bond. It represents an alkylene group having 1 to 36 carbon atoms, Q ^- represents a halogen-anion).
(2) The quaternary ammonium salt (A) having an unsaturated group has a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, and (meth) as unsaturated groups. 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) The quaternary ammonium salt (A) having an unsaturated group has (meth) acryloylaminopropyltrimethylammonium, (meth) acryloylaminopropyldimethylbenzylammonium, (meth) acryloyloxyethyltrimethylammonium, and (meth) as cations. ) The polymerizable dental resin composition according to (1) or (2) above, which is one or more cations selected from the group consisting of acryloyloxyethyl dimethylbenzylammonium and diallyldimethylammonium.
(4) The quaternary ammonium salt (A) having an unsaturated group has p-toluene sulfonate ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonate ion, and tetraphenylborate ion as anions. , Thiosic acid ion, bis (fluorosulfonyl) imide anion, bis (trifluoromethanesulfonyl) imide anion and one or more anions selected from the group consisting of saccharic acid ion. The polymerizable dental resin composition according to any one of 3).
(5) The polymerization according to any one of (1) to (4) above, wherein the quaternary ammonium salt (A) having an unsaturated group is contained in an amount of 0.1% by mass or more as a constituent unit. Sex dental resin composition,
(6) A dental resin composition, which comprises a polymer obtained by polymerizing the polymerizable resin composition according to any one of (1) to (5) above.
(7) The item according to any one of (1) to (6) above, wherein the compound (B) having an ethylenically unsaturated group (excluding (A)) is contained in an amount of 5 to 99% by mass. Dental resin composition,
(8) The compound (B) having an ethylenically unsaturated group has 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 as unsaturated groups. The dental resin composition according to (7) above, which is one or more compounds selected from the group consisting of a group and a maleimide group.
(9) The above-mentioned (1) to (5) and any one of the above (7) and (8), which further contain 0.1 to 10% by mass of the photopolymerization initiator (C). Photocurable dental resin composition,
(10) For dentistry, which contains 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).
(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 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 using 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 using the resin composition according to any one of (1) to (10) above.
(19) A material for a denture base using the resin composition according to any one of (1) to (10) above.
(20) A medical device whose surface is coated with the resin composition according to any one of (1) to (10) above.
(21) Provided is an antibacterial three-dimensional model formed by using the ink according to (12) above.

According to the present invention, it is antibacterial by containing a quaternary ammonium salt (A) having an unsaturated group and / or a polymer (oligomer, polymer) obtained by copolymerizing with the quaternary ammonium salt (A) alone or with another polymerizable compound. Obtained a polymerizable resin composition having excellent properties, stain resistance, discoloration resistance, thermal polymerizable property, photocurability, good copolymerizability with other polymerizable compounds, high safety and storage stability. In addition, these polymerizable resin compositions can be subjected to antibacterial effect and prevention by thermal polymerization by irradiation with active energy rays such as heat and / or light, photocuring, or hybrid type or dual type curing using both heat and light. Various dental materials that can sustain the stain effect semi-permanently and have good discoloration resistance, strength, hardness and surface smoothness, scratch resistance, and durability (hydrolysis resistance and abrasion resistance). , Three-dimensional shaped objects and medical instruments covered with them 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) (in the formula, even if R ₁ , R ₂ and R ₃ are the same as each other). They may be different, each independently having a linear or branched alkyl group having 1 to 36 carbon atoms, an alkyl group substituted with a hydroxyl group or an amine group, or a linear or branched alkyl group having 1 to 36 carbon atoms. alkenyl group or a hydroxyl group or an alkenyl group substituted amine group, or a benzyl group, L represents a unsaturated bond, Y represents an alkylene group having 1 to 36 carbon atoms, Q ^- is a non-halogen anion Represent.). Specifically, it is a quaternary ammonium salt composed of an ammonium cation having an unsaturated group and a non-halogen anion which is a counter ion thereof.

The quaternary ammonium salt (A) having an unsaturated group and / or its oligomer and polymer used in the present invention show a wide range of antibacterial spectra, and Escherichia coli, Pseudomonas aeruginosa, staphylococcus, MRSA, Bacillus cereus, and Bacillus cereus , Hepatitis bacillus, black mold, candida, etc. It has excellent antibacterial activity against various bacteria and bacteria. The reason is not clear, but it is due to the interaction 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 present inventors speculate. In addition, even if the quaternary ammonium salt (A) having an unsaturated group is blended as a monomer, or if it is blended after being oligomerized or polymerized, it exhibits the same antibacterial and antifungal properties, and is a resin type or filler. It is suitably used as an antibacterial material such as a type, a photocurable type, and a thermopolymerization / curing type. Furthermore, since the quaternary ammonium salt has excellent cell compatibility and biocompatibility, it not only does not irritate the user's own teeth, artificial teeth and skin, but also has a protective effect on the teeth and skin, and is a dental material. It can also be suitably blended as a material for cosmetics.

As cations of the quaternary ammonium salt having an unsaturated group represented by the general formula (1) (A), specifically, aminoalkyl (Y) trialkyl (R ₁₎ ammonium having an unsaturated bond, unsaturated Aminoalkyl (Y) trialkyl (R ₂ ) ammonium with an unsaturated bond, aminoalkyl (Y) trialkyl (R ₃ ) ammonium with an unsaturated bond, aminoalkyl (Y) alkyl (R ₁ ) with an unsaturated bond Dialkyl (R ₂ ) ammonium, aminoalkyl (Y) alkyl (R ₁ ) dialkyl (R ₃ ) ammonium with unsaturated bonds, aminoalkyl (Y) alkyl (R ₂ ) dialkyl (R ₁ ) ammonium with unsaturated bonds , Aminoalkyl (Y) alkyl (R ₂ ) dialkyl (R ₃ ) ammonium having an unsaturated bond, aminoalkyl (Y) alkyl (R ₃ ) dialkyl (R ₁ ) ammonium having an unsaturated bond, having an unsaturated bond Aminoalkyl (Y) alkyl (R ₃ ) dialkyl (R ₂ ) ammonium, aminoalkyl (Y) alkyl (R ₁ ) alkyl (R ₂ ) alkyl (R ₃ ) ammonium with unsaturated bonds, amino with unsaturated bonds Alkyl (Y) dialkyl (R ₁ ) benzylammonium, aminoalkyl (Y) dialkyl (R ₂ ) benzylammonium with unsaturated bond, aminoalkyl (Y) dialkyl (R ₃ ) benzylammonium with unsaturated bond, unsaturated Aminoalkyl (Y) alkyl (R ₁ ) alkyl (R ₂ ) benzylammonium with a bond, aminoalkyl (Y) alkyl (R ₂ ) alkyl (R ₃ ) benzylammonium with an unsaturated bond, amino with an unsaturated bond Alkyl (Y) alkyl (R ₁ ) alkyl (R ₃ ) benzylammonium, aminoalkyl (Y) alkyl (R ₁ ) dibenzylammonium with unsaturated bonds, aminoalkyl (Y) alkyl (R ₂ ) with unsaturated bonds ) dibenzyl ammonium, aminoalkyl (Y) alkyl (R ₃₎ dibenzyl ammonium having an unsaturated bond, aminoalkyl (Y) tribenzyl ammonium having an unsaturated bond, oxyalkyl (Y) trialkyl having an unsaturated bond (R ₁ ) ammonium, oxyalkyl (Y) trialkyl (R ₂ ) ammoni with unsaturated bonds Um, oxyalkyl (Y) trialkyl (R ₃ ) ammonium with unsaturated bonds, oxyalkyl (Y) alkyl (R ₁ ) dialkyl (R ₂ ) ammonium with unsaturated bonds, oxyalkyl with unsaturated bonds (R ₂ ) Y) alkyl (R ₁ ) dialkyl (R ₃ ) ammonium, oxyalkyl (Y) alkyl (R ₂ ) dialkyl (R ₁ ) ammonium with unsaturated bonds, oxyalkyl (Y) alkyl (R ₂ ) with unsaturated bonds ) Dialkyl (R ₃ ) ammonium, oxyalkyl (Y) alkyl (R ₃ ) dialkyl (R ₁ ) ammonium with unsaturated bonds, oxyalkyl (Y) alkyl (R ₃ ) dialkyl (R ₂ ) with unsaturated bonds Ammonium, oxyalkyl (Y) alkyl (R ₁ ) alkyl (R ₂ ) alkyl (R ₃ ) ammonium with unsaturated bonds, oxyalkyl (Y) dialkyl (R ₁ ) benzyl ammonium with unsaturated bonds, unsaturated bonds 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 ₁ ) R ₂ ) benzylammonium, oxyalkyl (Y) alkyl with unsaturated bond (R ₂ ) alkyl (R ₃ ) benzylammonium, oxyalkyl (Y) alkyl (R ₁ ) alkyl (R ₃ ) benzyl with unsaturated bond Ammonium, oxyalkyl (Y) alkyl (R ₁ ) dibenzylammonium with unsaturated bond, oxyalkyl (Y) alkyl (R ₂ ) dibenzylammonium with unsaturated bond, oxyalkyl (Y) with unsaturated bond Examples thereof include alkyl (R ₃ ) dibenzylammonium and oxyalkyl (Y) tribenzylammonium having an unsaturated bond. Further, the quaternary ammonium salt (A) having these unsaturated groups may be used alone or in combination of two or more.

Examples of the unsaturated group of the quaternary ammonium salt (A) having an unsaturated group include a methacrylate group, an acrylate group, a methacrylicamide group, an acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group and a metallicyl 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 or more of these unsaturated groups. ..

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

Anion of the quaternary ammonium salt having an unsaturated group (A) (Q ^-) as, if non-halogen ion, not be particularly limited. For example, methanesulfonic acid ion, benzenesulfonic acid ion, p-toluenesulfonic acid ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonic acid ion, tetraphenylborate ion, thiocyanate ion, bis (fluoro). Sulfonyl) imide anion, bis (trifluoromethanesulfonyl) imide anion, bis (pentafluoroethanesulfonyl) imide anion, nonafluorobutane sulfonic acid ion, linear sulfonimide anion, cyclic imide anion, formate ion, acetate ion, Hydrocarboxylic acids such as propionate ion, oxalate ion, succinate ion, glycolic acid ion, lactate ion, hydroxyacrylic acid ion, oxybutyrate ion, glycerate ion, malate ion, tartrate ion, citrate ion, etc. It is at least one or more ions selected from aromatic carboxylic acid ions such as acid ion, salicylate ion, and benzoate ion, and unsaturated acid ions such as saccharic acid ion, acrylic acid ion, and methacrylate ion.

For the quaternary ammonium salt (A) having an unsaturated group used in the present invention, one or more ions are arbitrarily selected from the above cations, and one or more of the above anions are further selected. It is an onium salt composed by arbitrarily selecting two or more types of ions and combining cations and anions. The quaternary ammonium salt (A) having these unsaturated groups may be used alone or in combination of two or more.

In addition, as cations constituting the quaternary ammonium salt (A) having an unsaturated group, acryloylaminopropyltrimethylammonium, methacryloylaminopropyltrimethylammonium, and acryloylamino are used because of their excellent antibacterial properties and easy availability of industrial raw materials. Preferables are propyldimethylbenzylammonium, methacryloylaminopropyldimethylbenzylammonium, acryloyloxyethyltrimethylammonium, methacryloyloxyethyltrimethylammonium, acryloyloxyethyldimethylbenzylammonium, methacryloyloxyethyldimethylbenzylammonium, and diallyldimethylammonium. 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, p-toluenesulfonate ion, tetrafluoroborate ion, as anions constituting the quaternary ammonium salt (A) having an unsaturated group, from the viewpoint of excellent antibacterial properties and easy availability of industrial raw materials, Hexafluorophosphate ion, trifluoromethanesulfonic acid ion, tetraphenylborate ion, thiocyanate ion, bis (fluorosulfonyl) imide anion, bis (trifluoromethanesulfonyl) imide anion, and saccharate ion are preferable. Furthermore, from the viewpoint of imparting an antifouling effect, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonic acid ion, bis (fluorosulfonyl) imide anion, and bis (trifluoromethanesulfonyl) imide anion, which are organic fluorine-based anions, are used. Is more preferable.

Since the quaternary ammonium salt (A) having an unsaturated group has a high antibacterial effect, it can be blended in the resin composition as a monomer as an antibacterial agent. In addition, it is polymerized or oligomerized by thermal polymerization or photopolymerization (photocuring) and blended into the resin composition as a semi-permanent polymer type 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, there is no possibility of bleed-out of the quaternary ammonium salt (A) having an unsaturated group, and the antibacterial property is stable over a long period of time. Can be given.

Examples of the oligomerization and polymerization of the quaternary ammonium salt (A) having an unsaturated group by thermal polymerization include homopolymerization or a method of copolymerizing with a general-purpose vinyl compound. The polymerization method is not particularly limited, and can be carried out by a known radical polymerization method. For example, a massive polymerization method, a solution polymerization method in an organic solvent or water, a suspension polymerization method, an emulsion polymerization method and the like can be mentioned. When the solution polymerization method in an organic solvent is adopted, toluene, xylene, ethyl acetate, butyl acetate, methyl ethyl ketone, methyl alcohol, ethyl alcohol and the like can be used alone or in combination as the polymerization solvent. In addition, examples of the polymerization initiator include generally known radical polymerization initiators such as azo-based, organic peroxide-based, inorganic peroxide-based, and redox-based. The amount of the radical polymerization initiator used is usually about 0.001 to 10% by mass with respect to the total amount of the polymerizable component. Further, ordinary radical polymerization techniques such as adjustment of molecular weight by a chain transfer agent are applied.

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

The quaternary ammonium salt (A), its oligomer and its polymer are soluble in the state at room temperature (liquid or solid), viscosity, water or general-purpose organic solvent, general-purpose acrylic monomer and acrylic resin, depending on the molecular structure and molecular weight. , Compatibility and photocurability are different, and their usage, blending amount, etc. are not particularly limited, and can be used as a non-photocurable (thermally polymerized) dental material or a photocurable dental material. , And can be preferably used, and one or a combination of two or more selected from a quaternary ammonium salt (A), an oligomer and a polymer can be used according to the required physical properties of the antibacterial dental material.

When an oligomer or polymer of the quaternary ammonium salt (A) is used, 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%. It is mass%. If the content is less than 0.1% by mass, sufficient antibacterial properties may not be obtained, depending on the amount of oligomers and polymers blended in the dental material. 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, resulting in hardness, surface smoothness, and self. A dental material having good adhesion to teeth can be obtained, which is more preferable.

When the oligomer or polymer of the quaternary ammonium salt (A) used in the present invention is solid at room temperature, they can be incorporated into the dental resin composition as a filler. Further, antibacterial coating and antibacterial properties are obtained by dissolving the obtained solution in an organic solvent or in a liquid polymerizable compound, applying the obtained solution on a crown, a denture, a medical device or a base material, and then evaporating the organic solvent. Crowns, antibacterial dentures, antibacterial inks, antibacterial medical instruments, and antibacterial three-dimensional shaped objects are formed. In the case of solvent-free system, it is applied on crowns, dentures, medical instruments and base materials, poured into the part of the tooth to be filled or repaired, and then cured by heat or light, or a combination of heat and light, and similarly. It is possible to manufacture antibacterial coatings, antibacterial crowns, antibacterial dentures, antibacterial inks, antibacterial medical instruments, antibacterial three-dimensional shaped objects, and the like. When used as a thin dental surface coating material, it preferably contains 0.5% by mass or more of an oligomer or polymer of a quaternary ammonium salt (A) in order to maintain a sufficient antibacterial effect for a long period of time. It is more preferable to contain 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 by a photocurable component such as an acrylic monomer or an oligomer. It is possible to be done. In that case, after applying the obtained slightly high-viscosity coating liquid to the surface of teeth, dentures and instruments, the organic solvent is evaporated (when an organic solvent is mixed), and a slightly thicker cured coating film and modeling are performed by light irradiation. Objects (surface covering materials, crown materials, dentures formed by three-dimensional modeling, etc.) are formed. In this case, in order to impart a sufficient antibacterial effect, the oligomer or polymer of the quaternary ammonium salt (A) is preferably contained in an amount of 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. Further, in order to prevent the antibacterial property from being reduced over time due to bleed-out, it is preferable to incorporate it into a photocurable dental material. 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 shown, and continuous antibacterial activity is exhibited. From the viewpoint of ensuring 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 may be used alone or in combination of two or more, which are arbitrarily selected from the group consisting of them. When the total unit content of the quaternary ammonium salt (A) in the dental material is 0.1% by mass or more, the antibacterial effect can be imparted. Further, when it is 0.5 or more, a stable and sufficient antibacterial effect can be maintained for 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. Although not, it is preferably contained in an amount of 5 to 99% by mass based on the entire photocurable resin composition. Within this range, it has sufficient antibacterial properties, photocurability, adhesion to the base material of teeth and medical instruments, adhesiveness, hardness, strength, discoloration resistance, durability of the obtained crown and denture. Characteristics such as sex can be adjusted in a well-balanced manner.

The unsaturated group of the compound (B) having an ethylenically unsaturated group is 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. A functional group having one or more unsaturated bonds selected from the group consisting of groups. 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 functional ethylenically unsaturated group (b1). Polyfunctional unsaturated compound) (b2). Depending on the type, structure, molecular weight, etc. of the quaternary ammonium salt (A) having an unsaturated group and its oligomer and its polymer, only (b1) or (b2) is used as the compound (B) having an ethylenically unsaturated group. However, by using (b1) and (b2) in combination, the hardness and durability of the obtained cured product (dental filling material, artificial tooth shaped product, 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. The ethylenically unsaturated group is not particularly limited as long as it has radical polymerizable properties, and specifically, a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, ( Meta) Examples thereof include an allyl ether group and a maleimide group. The content of (b1) is preferably 5 to 99% by mass with respect to the entire photocurable resin composition. Further, when it is 10 to 90% by mass, the strength and hardness of the photocured product are good, and the surface smoothness and durability of the formed crown and denture can be improved, which is more preferable.

Among the monofunctional unsaturated compounds (b1), as the compound containing a (meth) acrylate group, for example, (meth) acrylic acid, a linear, branched, or cyclic alkyl group having 1 to 22 carbon atoms was introduced. Alkyl (meth) acrylates, hydroxyalkyl (meth) acrylates with linear, branched, or cyclic hydroxyalkyl groups of 1 to 18 carbon atoms, (meth) acrylic acid and hydroxyalkylcarboxylic acids (meth). (Meta) alkylcarboxylic acids acrylates such as ethylcarboxylic acid acrylate, ethylsuccinic acid acrylate, ethylphthalic acid (meth) acrylate, ethylhexahydrophthalic acid acrylate, etc., having 1 to 18 carbon atoms. Alkyl sulfonic acids (meth) acrylates with linear, branched and cyclic alkylsulfonic acid groups, alkyl (meth) acrylates with linear, branched and cyclic alkylphosphate groups with 1-18 carbon atoms Phosphoric acids, alkoxyalkylene glycol (meth) acrylates introduced with a functional group consisting of an alkyl group having 1 to 18 carbon atoms and an alkylene glycol group having 1 to 4 carbon atoms, alkoxydialkylene glycol (meth) acrylates, alkoxytri Alkylene glycol (meth) acrylates, alkoxypolyalkylene glycol (meth) acrylates, phenoxyalkylene glycol (meth) acrylates introduced with a functional group consisting of a phenoxy group and an alkylene glycol group having 1 to 4 carbon atoms, phenoxydialkylene Glycol (meth) acrylates, phenoxytrialkylene glycol (meth) acrylates, phenoxypolyalkylene glycol (meth) acrylates, and N-alkylamino (meth) acrylates having an aminoalkyl group having 1 to 6 carbon atoms introduced therein. N-alkylaminoalkyl (meth) acrylates having an N-alkylaminoalkyl group composed of an aminoalkyl group having 1 to 6 carbon atoms and an alkyl group having 1 to 6 carbon atoms, and N-alkylaminoalkyl (meth) acrylates having 1 to 6 carbon atoms. N, N-dialkylaminoalkyl (meth) acrylates having an N, N-dialkylaminoalkyl group composed of an aminoalkyl group and an alkyl group having 1 to 6 carbon atoms, benzyl (meth) acrylate, and phenoxyethyl (meth) Aacrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopente (Meta) acrylate introduced with a cyclic structure such as nyloxyethyl (meth) acrylate, Bornyl (meth) acrylate, isobornyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2-methyl-2-adamantyl (meth) acrylate Examples include (meth) acrylates having an epoxy group introduced such as glycidyl (meth) acrylate and 4-hydroxybutyl (meth) acrylate glycidyl ether.

Among the monofunctional unsaturated compounds (b1), the compounds containing a (meth) acrylamide group include (meth) acrylamide, mono- or di-substituted (meth) acrylamide, (meth) acroylmorpholin, and (meth) diacetoneacrylamide. Examples of the mono- or di-substituted (meth) acrylamide include N-alkyl (meth) acrylamide having a linear, branched, or cyclic alkyl group having 1 to 18 carbon atoms introduced therein, N, N-. Dialkyl (meth) acrylamide, N-hirodoxyalkyl (meth) acrylamide introduced with hydroxyalkyl groups having 1 to 6 carbon atoms, N, N-di (hyrodoxyalkyl) (meth) acrylamide, N-hydroxyalkyl -N- (4-Hydroxyphenyl) (meth) acrylamide, N-alkyl-N-hirodoxyalkyl (meth) acrylamide introduced with hydroxyalkyl groups with 1 to 6 carbon atoms and alkyl groups with 1 to 6 carbon atoms. , N-alkyl-N- (4-hydroxyphenyl) (meth) acrylamide, 4-hydroxyphenyl (meth) acrylamide, N, N-di (4-hydroxyphenyl) (meth) acrylamide, carbon number 1-6 N-alkoxyalkyl (meth) acrylamide, N, N-di (alkoxyalkyl) (meth) acrylamide, which has an alkoxyalkyl group consisting of an alkoxy group and an alkylene group having 1 to 6 carbon atoms. An alkoxyalkyl group consisting of an alkoxy group and an alkylene group having 1 to 6 carbon atoms, N-alkyl-N-alkoxyalkyl (meth) acrylamide having an alkyl group having 1 to 6 carbon atoms introduced therein, and an alkyl having 1 to 6 carbon atoms. N-sulfoalkylacrylamide with sulfonic acid groups introduced, N-alkylamino (meth) acrylamide with aminoalkyl groups with 1 to 6 carbon atoms, aminoalkyl groups with 1 to 6 carbon atoms and 1 to 6 carbon atoms. N-alkylaminoalkyl (meth) acrylamide, which is an N-alkylaminoalkyl group composed of the above alkyl groups, N, N-dialkyl composed 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) acrylamide introduced with an aminoalkyl group.

Among the monofunctional unsaturated compounds (b1), the compound containing a vinyl group includes a carboxylic acid vinyl ester introduced with a carboxylic acid having 1 to 22 carbon atoms, and a linear, branched, cyclic compound 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 acid anhydride, having 1 to 1 carbon atoms. Maleic acid monoalkyl ester introduced with 22 linear, branched and cyclic alkyl groups, maleic acid dialkyl ester, maleic acid monoalkylamide, maleic acid dialkylamide, maleic acid alkylimide, fumaric acid monoalkyl ester, fumaric acid dialkyl Esters, fumaric acid monoalkylamides, fumaric acid dialkylamides, itaconic acid monoalkyl esters, itaconic acid dialkyl esters, itaconic acid monoalkylamides, itaconic acid dialkylamides, itaconic acid alkylimides, vinylcarboxylic acids, vinylsulfonic acids, vinylphosphates. And so on.

Among the monofunctional unsaturated compounds (b1), examples of the compound containing an allyl group include a carboxylic acid allyl ester introduced with a carboxylic acid having 1 to 22 carbon atoms, and a linear, branched, cyclic compound having 1 to 22 carbon atoms. Examples thereof include alkylallyl ethers introduced with the above alkyl group, phenylallyl ether, alkylphenylallyl ether, allylamine, branched mono- or dialkylallylamine introduced with a cyclic alkyl group.

Among the monofunctional unsaturated compounds (b1), the maleimide group-containing compounds include N-alkylmaleimide and N-alkyl-α- having linear, branched, and cyclic alkyl groups having 1 to 22 carbon atoms introduced. Methylmaleimide, N-alkyl-α-ethylmaleimide, N-alkyl-α, β-dimethylmaleimide, N-alkyl-α-phenylmaleimide, linear, branched, cyclic hydroxyalkyl groups with 1-12 carbon atoms Introduced N-hydroxyalkylmaleimide, N-hydroxyalkyl-α-methylmaleimide, N-hydroxyalkyl-α-ethylmaleimide, N-hydroxyalkyl-α, β-dimethylmaleimide, N-hydroxyalkyl-α-phenylmaleimide, Examples thereof include an alkoxysilane compound having a maleimide group and a carboxylic acid compound having a maleimide group.

These monofunctional unsaturated compounds (b1) may be used alone 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. The ethylenically unsaturated group is not particularly limited as long as it has radical polymerizable properties, and specifically, a (meth) acrylate group, a (meth) acrylamide group, a vinyl group, a vinyl ether group, a methyl vinyl ether group, an allyl group, ( Meta) Examples thereof include an allyl ether group and a maleimide group. Further, these ethylenically unsaturated groups in the molecule may have two or more of the same functional groups, or may be a combination of two or more types in which different functional groups can be arbitrarily selected. The content of (b2) is preferably 5 to 99% by mass with respect to the entire photocurable resin composition. When the content of (b2) is 5 to 80% by mass, the viscosity of the prepared photocurable resin composition can be easily adjusted, and the coatability, filling property, adhesion to the tooth surface, and adhesiveness are improved. Both are satisfactory, the strength of the obtained photocured product is excellent, and the durability is sufficient, 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 to 4) Glycoldi (meth) acrylate, polytetramethylene glycol di (meth) acrylate, 1,3 (or 1,4) -butanediol di (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, cyclohexanedimethanol di (meth) acrylate, acrylate ester (dioxane glycol diacrylate), alkoxylated (cyclo) hexanediol di (meth) acrylate, epoxy di (meth) acrylate, dicyclopentanyldi (meth) acrylate, caprolactone Modified dicyclopentenyldi (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 (Meta) Acrylate, Trimethylol Ethantri (Meta) Acrylate, Trimethylol Propantri (Meta) Acrylate, Dipentaerythritol Tri (Meta) Acrylate, Ditrimethylol Propanetetra (Meta) Acrylate, Dipentaerythritol Tetra (Meta) Acrylate, Dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, tri (meth) acryloyloxyethoxytrimethylol propane, 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 Examples thereof include taerythritol tetra (meth) acrylate and succinic acid-modified pentaerythritol tri (meth) acrylate. These polyfunctional unsaturated compounds (b2) may be used alone or in combination of two or more.

The compound (B) having an ethylenically unsaturated group used in the present invention is simply from the viewpoint of safety such as skin irritation and odor and compatibility with the quaternary ammonium salt (A) having an unsaturated group. The functionally 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. Further, in order to control the amount of heat generated during curing, it is most preferable to use an acrylamide-based monomer and a methacrylate-based monomer in combination.

The antibacterial dental resin composition of the present invention can be sufficiently cured by irradiation with visible light or ultraviolet rays. 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, When 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 by light irradiation, so that the photocurable resin composition The product does not have to contain a photopolymerization initiator.

The antibacterial dental resin composition of the present invention can contain a photopolymerization initiator (C). Examples of the photopolymerization initiator include α-diketones such as camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, 1,4-phenanthrenquinone, 3,4-phenanthrenquinone, and 9,10-phenanthrenquinone. Thioxanthons 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 , Bis (2,6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide and other acylphosphine oxide derivatives. One of these photoinitiator polymerization agents may be used alone, or two or more of them may be used in combination.

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 with a thin coating, and the strength and durability of the obtained cured film are good. 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. Further, 0.5 to 5% by mass is more preferable.

In addition, 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-dimethylaminostylben, 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-butylbarbituric acid, 1- Examples thereof include barbituric acids such as benzyl-5-phenylbarbituric acid, and mercapto compounds such as dodecyl mercaptan and pentaerythritol tetrakis (thioglycolate). These polymerization accelerators may be used alone 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, it has a sufficient effect of a polymerization accelerator, and troubles such as coloring and deterioration of discoloration resistance due to the polymerization accelerator are unlikely to occur. Further, 0.05 to 1% by weight is more preferable.

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

Various additives can be added to the antibacterial dental resin composition (including non-photocurable type and photocurable type) of the present invention, if necessary. Specifically, the additives include thermal polymerization inhibitors, antioxidants, ultraviolet sensitizers, preservatives, phosphate ester-based and other flame retardants, surfactants, antistatic agents, pigments, dyes and the like. Colorants, fragrances, defoamers, fillers, silane cup long agents, surface tension modifiers, plasticizers, surface lubricants, leveling agents, softeners, organic fillers, inorganic fillers and the like can be added. The amount of these other components added is not particularly limited as long as it does not adversely affect the characteristics developed by the antibacterial dental resin composition according to the present invention, and is in the range of 5% by mass or less with respect to the entire resin composition. preferable. However, since the filler has the effect of improving the strength and abrasion resistance of the cured resin product and also has the effect of adjusting the fluidity when the resin composition is applied or filled on the teeth, the entire resin composition The range is preferably 50% by mass or less.

The antibacterial dental resin composition of the present invention can be used for application, filling, modeling, etc. of a user's own teeth, dentures, denture floor materials, medical instruments, and the like. 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 a cured film. .. Further, the antibacterial resin composition is filled in the repaired portion of these objects and solidified by drying or cured by light irradiation to obtain an adhesive or a filling material as a solidified or cured product. Further, in the case of forming by three-dimensional modeling, dentures, denture floor materials, medical instruments and the like can be obtained by drying and hardening while modeling. Since the antibacterial resin composition of the present invention has excellent adhesion and adhesiveness to both natural teeth and acrylic resins, ceramics, metals and the like which are materials for dentures, it is a resin for treating dental caries and a crown material. However, it can also be used as a surface covering material for aesthetic treatment. In this case, if pretreatment such as surface polishing of the own tooth and wiping with alcohol is performed, the durability is further improved, but even if the pretreatment is not performed, sufficiently satisfactory adhesion and durability can be obtained. Further, since the solidified film or the cured film of the antibacterial resin composition has strength, hardness, and surface smoothness, polishing after treatment is not particularly necessary. Since the antibacterial resin composition of the present invention is composed of components that have neither odor nor irritation and do not bleed out, 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 properties and antifouling properties. In addition, it is easily mixed uniformly with organic or inorganic fillers such as general-purpose pigments, brighteners, and dyes. Furthermore, quaternary ammonium salt oligomers and polymers can be designed with a wide variety of structures and molecular weights according to the required physical properties, and can be used as dental adhesives, surface coating materials, and fillers for dentures and dentures. It can be applied, filled, and repaired directly on the surface. It may be a single layer coating of a thick film or a laminated coating of a thin film. Furthermore, a three-dimensional model can be formed by an appropriate three-dimensional model.

Examples of the inorganic filler 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, itterbium fluoride, yttrium fluoride and the like. Further, 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 preferable. One type of these inorganic fillers may be used alone, or two or more types may be used in combination.

Examples of the organic filler include polymethylmethacrylate, polyethylmethacrylate, a polymer of polymethylmethacrylate and polyethylmethacrylate, a polymer of polyfunctional methacrylate, an ethylene-vinyl acetate copolymer, and an acrylonitrile-butadiene-styrene copolymer. Examples thereof include coalescence, polyamide, polystyrene, polyvinyl chloride, chloroprene rubber, nitrile rubber, and styrene-butadiene rubber. Further, the oligomer and polymer of the quaternary ammonium salt having an unsaturated group used in the present invention can also be preferably used as the organic filler. One type of these organic fillers may be used alone, or two or more types may be used in combination.

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 die auto (LED) lamps, ultraviolet light emitting die auto (UV-LED) lamps, and ultraviolet laser die auto (UV-LD). ) Lamps and the like. Further, from the viewpoint of small size, long life, high efficiency, low cost and safety, an ultraviolet irradiation type using a 365 nm fluorescent tube and a visible light irradiation type having a 405 nm LED light source are becoming mainstream, and these can be used. More preferred

The irradiation energy required for photocuring of the photocurable dental resin composition of the present invention varies slightly depending on the application and the light source, but the irradiation energy (integrated light amount) is preferably in the range of 1 to 1000 mJ / cm ² , preferably 10 to 500 mJ. / Cm ² is more preferred. This is because the resin composition can be sufficiently cured within this range, and the hardness and strength of the cured product can be sufficiently satisfied. Further, the specific irradiation conditions may be appropriately adjusted by repairing by covering or filling the tooth surface, or by forming a denture by a three-dimensional modeling device. For example, when curing a resin composition for a denture floor material by UV irradiation, a commercially available dental UV lamp (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd.) is used as a light source and irradiated for 1 to 100 seconds. Further, when repairing a denture with visible light, it is particularly preferable to irradiate the tooth for 0.1 to 2 minutes using a commercially available dental irradiator (Laborite LV-II) as a light source.

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

Table 1 shows a quaternary ammonium salt having an unsaturated group and its oligomers and polymers (A-1) to (A-10).

The monofunctional unsaturated compound (b1) used in Examples and Comparative Examples is 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: Acryloylmorpholin (registered trademark "ACMO" of KJ Chemicals Co., Ltd.)
b1-9: Dimethylacrylamide (registered trademark "DMAA" of KJ Chemicals Co., Ltd.)
b1-10: Diethylacrylamide (registered trademark "DEAA" of KJ Chemicals Co., Ltd.)
b1-11: N- (2-Hydroxyethyl) acrylamide (registered trademark "HEAA" of KJ Chemicals Co., Ltd.)
b1-12: Isopropylacrylamide (registered trademark "NIPAM" of KJ Chemicals Co., Ltd.)
b1-13: Dimethylaminopropylacrylamide (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 ((registered trademark "Kohsylmer" TBCHA of KJ Chemicals Co., Ltd.))
b1-16: N-vinylpyrrolidone (NVP)
b1-17: N-vinylcaprolactam (NVC)

The polyfunctional unsaturated compound (b2) used in Examples and Comparative Examples is shown below.
b2-1: Triethylene glycol diacrylate (TEGDA)
b2-2: Dipentaerythritol hexaacrylate (DPHA)
b2-3: Trimethylolpropane triacrylate (TMPTA)
b2-4: Tricyclodecanedimethanol diacrylate (A-DCP, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.)
b2-5: Urethane diacrylate (UA, bifunctional, polyester skeleton, molecular weight 5000)
b2-6: Urethane diacrylamide (UAm, bifunctional, polycarbonate skeleton, molecular weight 8000)

The photopolymerization initiator (C) used in Examples and Comparative Examples is 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-Hydroxycyclohexylphenylketone / benzophenone = 1/1 mixture (IRGACURE-500, manufactured by BASF Japan Ltd.)

Example 1 Preparation of photocurable antibacterial resin composition (D-1) as (A) 0.1 part by mass of acryloylaminopropyltrimethylammonium p? Toluenesulfonate (A-1), as (B) "ACMO" (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, ( 3.0 parts by mass of camphorquinone (C-1) as C) was added to each container, and the mixture was stirred at 40 ° C. for 1 hour to obtain a uniform and transparent photocurable antibacterial resin composition (D-1) of Example 1. ) Was obtained.

Examples 2 to 10 Preparation of photocurable antibacterial resin compositions (D-2) to (D-10) Examples 2 to 10 by performing the same operations as in Example 1 with the compositions shown in Table 2. Photocurable antibacterial resin compositions (D-2) to (D-10) corresponding to the above 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. The photocurable resin compositions (E-1) to (E-3) to be used 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 carried out by the following methods, 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, they are visually soluble or dispersible (insoluble inorganic fillers and the like. (When a pigment or the like is blended) is observed, and the storage stability of the composition is evaluated, and the results are shown in Table 3. Further, a photocurable dental material was prepared by the following method, the photocurability of the resin composition, the surface smoothness, hardness, and adhesive strength of the obtained dental material were evaluated, and the results are shown in Table 3. The antibacterial and antifouling properties were tested using Streptococcus mutans and Candida albicans, which are typical oral bacteria, and the results are shown in Table 4.
1. 1. Soluble (dispersible)
⊚: The obtained resin composition was uniform and transparent.
〇: The obtained resin composition was uniform and translucent.
Δ: The obtained resin composition became cloudy and it was difficult to judge the uniformity.
X: The obtained resin composition was not completely mixed.
2. 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 40 ° C. It was stored under two conditions of 1 month and 2 weeks at 80 ° C. The dissolved or dispersed state of the composition after storage was confirmed, and the storage stability was evaluated.
◯: There was no change in state after storage under the two conditions of 40 ° C. for 1 month and 80 ° C. for 2 weeks.
Δ: A change of state after storage was confirmed under any one condition of 40 ° C. for 1 month or 80 ° C. for 2 weeks.
X: Under the two conditions of 40 ° C. for 1 month and 80 ° C. for 2 weeks, the state change after storage was confirmed.
3. 3. Curability Polytetrafluoroethylene having a pore with a diameter of 6 mm in the center using the photocurable dental resin compositions obtained in Examples 1 to 10 and the photocurable resin compositions obtained in Comparative Examples 1 to 3. A mold (20 mm x 20 mm x 10 mm) made of plastic is filled with a resin composition, pressure-welded with a polypropylene film, and a dental light irradiator (Tokuso Power Light, manufactured by Tokuyama Dental Co., Ltd., light output density 700 mW / cm ² , irradiation surface. Light intensity 640 to 650 mW / cm ² , light source is halogen lamp, irradiation diameter 8 mm) is closely attached to the polypropylene film and irradiated for 30 seconds, the polypropylene film is peeled off and the cured product is touched by hand, and there are no sticky or uncured components. It was confirmed.
⊚: No stickiness (complete curing).
◯: There is some stickiness, but no finger marks are left on the surface (almost completely cured, it is not necessary to wipe off uncured components).
Δ: Sticky, leaving finger marks on the surface (incompletely cured, uncured components need to be wiped off).
X: The stickiness is severe and the finger sticks to the surface (a large amount of uncured components remain 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 the smoothness and glossiness.
⊚: The surface is smooth and glossy.
◯: The surface is almost smooth, and a slight cloudiness or slight unevenness is observed.
Δ: The surface is cloudy as a whole, and some irregularities and graininess are confirmed.
X: The surface is entirely cloudy and covered with granular material.
5. Hardness Using a buffed surface of the cured product obtained in the above curability evaluation, the Knoop hardness was measured with a micro-hardness meter manufactured by Matsuzawa Seiki under a load of 10 g for 20 seconds. The measured temperature was 23 ° C.
⊚: 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: Noup hardness is less than 70 KHN.
X: Measurement was not possible because it did not cure.
6. Adhesive strength (dentin adhesive strength)
The anterior teeth of the cow's forehead are polished with # 1000 water-resistant abrasive paper under water injection, the flat adhesive dentin surface is carved out, compressed air is blown for 10 seconds to dry, and a tape with a hole with a diameter of 3 mm is attached. , The adherend surface was set. Then, an adhesion test piece was prepared by a known method (refer to the method described in JP-A-2010-208964). The adhesion test piece was immersed in water at 37 ° C. for 24 hours, and then the tensile adhesive strength was measured with an Instron universal tester (crosshead speed 2 mm / min), and the light prepared in Examples 1 to 10 and Comparative Examples 1 to 3 was used. The adhesive strength of the curable resin composition to enamel and dentin was used. The value of the tensile adhesive strength is an average value of five test pieces.
⊚: Adhesive strength of both enamel and dentin is 20 Mpa or more.
◯: Only one of the adhesive strengths of enamel and dentin is 20 Mpa or more.
Δ: Adhesive strength of both enamel and dentin is 7 Mpa or more.
X: The adhesive strength between enamel and dentin is less than 7 Mpa.
7. Antibacterial properties The photocurable resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 3 were poured into a spacer having a thickness of 200 μm and an inside of 40 mm × 60 mm fixed on a release film, and when there was a solvent, The solvent was completely removed (80 ° C., 1 minute), and the film was cured by irradiation with ultraviolet rays (cumulative light amount 1000 mJ / cm2), and then the release film was peeled off to obtain a cured film for antibacterial test. After pouring an agar medium into a glass petri dish with an inner diameter of 90 mm and inoculating it with mutans bacteria or Candida bacteria, place a cured film on it, close the lid, temperature 30 ± 5 ° C, humidity 85 ± 5% RH. The cells were cultured in a constant temperature and humidity chamber for 7 days. The growth status of fungi was evaluated in four stages.
⊚: No bacterial growth is observed.
◯: Slight bacterial growth is observed.
Δ: Slight bacterial growth is observed.
×: Violent bacterial growth is observed.
8. Antifouling property (suppression of plaque adhesion)
Plaque against the above two types of bacteria using the photocurable resin compositions prepared in Examples 1 to 10 and Comparative Examples 1 to 3 by a known method (refer to the method described in JP-A-2015-214514). An adhesion suppression test was conducted.
⊚: No plaque adhesion was observed.
◯: Slight plaque adhesion was observed.
Δ: A little plaque adhesion was observed.
X: Severe larks adhered.

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 prevention is prevented. We were able to obtain a dental resin composition that was satisfactory in terms of stain resistance, photocurable curability, 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 material for dental treatment. In addition, it has good antifouling properties, safety, photocurable curability and storage stability, 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 material for dentures and dentures, and it is also possible to obtain a three-dimensional model and a medical device coated on the three-dimensional object.

Claims (21)

A polymerizable dental resin composition containing a quaternary ammonium salt (A) having an unsaturated group represented by the general formula (1).
(In the formula, R ₁ , R ₂ and R ₃ may be the same or different from each other, and each independently has a linear or branched alkyl group having 1 to 36 carbon atoms, a hydroxyl group or an amine group. It represents a substituted alkyl group, a linear or branched alkenyl group having 1-36 carbon atoms, an alkenyl group substituted with a hydroxyl group or an amine group, or a benzyl group, where L represents an unsaturated bond and Y represents an unsaturated bond. It represents an alkylene group having 1 to 36 carbon atoms, Q ^- represents a halogen-anion). The quaternary ammonium salt (A) having an unsaturated group has 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 group as unsaturated groups. The polymerizable dental resin composition according to claim 1, wherein the functional group has one or more unsaturated bonds selected from the group consisting of a maleimide group and a maleimide group. The quaternary ammonium salt (A) having an unsaturated group has (meth) acryloylaminopropyltrimethylammonium, (meth) acryloylaminopropyldimethylbenzylammonium, (meth) acryloyloxyethyltrimethylammonium, and (meth) acryloyloxy as cations. The polymerizable dental resin composition according to claim 1 or 2, wherein the cation is one or more selected from the group consisting of ethyldimethylbenzylammonium and diallyldimethylammonium. The quaternary ammonium salt (A) having an unsaturated group has p-toluene sulfonic acid ion, tetrafluoroborate ion, hexafluorophosphate ion, trifluoromethanesulfonic acid ion, tetraphenylborate ion, and thiocyanic acid as anions. Any one of claims 1 to 3, wherein the anion is one or more selected from the group consisting of an ion, a bis (fluorosulfonyl) imide anion, a bis (trifluoromethanesulfonyl) imide anion and a saccharic acid ion. The polymerizable dental resin composition according to the section. The polymerizable dental resin composition according to any one of claims 1 to 4, wherein the quaternary ammonium salt (A) having an unsaturated group is contained in an amount of 0.1% by mass or more as a constituent unit. .. A dental resin composition comprising a polymer obtained by polymerizing the polymerizable resin composition according to any one of claims 1 to 5. The dental resin composition according to any one of claims 1 to 6, wherein the compound (B) having an ethylenically unsaturated group (excluding (A)) is contained in an amount of 5 to 99% by mass. The compound (B) having an ethylenically unsaturated group has a (meth) acrylate group, a (meth) acrylamide group, and a vinyl group as unsaturated groups, and a vinyl ether group, a methyl vinyl ether group, an allyl group, and a (meth) allyl ether group. The dental resin composition according to claim 7, wherein the compound is one or more compounds selected from the group consisting of maleimide groups. The photocurable dental resin composition according to any one of claims 1 to 5 and 7 and 8, further containing 0.1 to 10% by mass of the photopolymerization initiator (C). .. A dental resin composition comprising a polymer obtained by polymerizing the polymerizable resin composition according to any one of claims 1 to 5 and 7 to 9. A dental composite resin containing the polymerizable dental resin composition according to any one of claims 1 to 5 and 7 to 9. An antibacterial ink for a three-dimensional model containing the polymerizable resin composition according to any one of claims 1 to 5 and 7 to 9. A dental material using the resin composition according to any one of claims 1 to 10. A crown material using the resin composition according to any one of claims 1 to 10. A dental adhesive using the resin composition according to any one of claims 1 to 10. A dental surface coating material using the resin composition according to any one of claims 1 to 10. A dental filling material using the resin composition according to any one of claims 1 to 10. A dental denture material using the resin composition according to any one of claims 1 to 10. A material for a denture base using the resin composition according to any one of claims 1 to 10. A medical device whose surface is coated with the resin composition according to any one of claims 1 to 10. An antibacterial three-dimensional model formed by using the ink according to claim 12.