JP5036244B2 - Dental filling restoration material - Google Patents

Description

  The present invention relates to a dental filling and restorative material. More specifically, the present invention relates to a dental filling / restoration material that exhibits good operability even when the filler content is high.

  A dental filling restorative material called a composite resin has come to be used more and more widely in dental restorative treatment with the recent spread of the concept of MI (minimal intervention). Such dental filling and restorative materials are generally configured as a paste made of a polymerizable composition mainly composed of a polymerizable monomer (monomer), a filler, and a polymerization catalyst.

  As the filler used for the dental filling and restorative material, an inorganic filler having an average particle diameter of about several tens of μm obtained by grinding glass was originally used. However, using such an inorganic filler with a large particle size is not aesthetically pleasing because it is difficult to gloss even when the surface of the filling restorative material is polished, and appears to be less glossy than the surrounding natural teeth. It was. In addition, the surface was roughened over time, and the touch was sometimes uncomfortable.

  In order to solve this problem, it has been proposed to use fine inorganic fillers such as silica zirconia and silica titania having an average particle diameter of 1 μm or less as dental filling restorative materials (for example, Patent Documents 1 to 5). By this method, it was possible to make the filling and restorative material have a fairly good aesthetic, but on the other hand, such fine particles have a poor filling property in the paste, and it is difficult to uniformly contain a large amount thereof. The mechanical strength of the filling / restoring material was lowered.

  Further, in recent years, the use range of dental filling and restorative materials has been expanded in tooth restoration, and further higher performance has been demanded accordingly. Specifically, such filling restoration materials have been used instead of conventional amalgams and ceramics for repairing large cavities. Therefore, when used for this purpose, the filling restorative material is required to have a smaller polymerization shrinkage ratio when polymerized and cured than a conventional dental filling restorative material. And in order to achieve this, it is calculated | required that the filling rate of the said inorganic filler is made higher.

  However, as described above, it is difficult to uniformly contain a large amount of an inorganic filler with good aesthetics and a small average particle diameter, and from such a requirement, when the inorganic filler is filled in a large amount, The operability of the filling / restoring material as described below was greatly affected.

  Here, the operability of the dental filling / restoration material (hereinafter also referred to as a composite resin) will be described. Composite resins can be broadly classified into paste type and flowable type because of their operability. Take out the required amount of paste-type composite resin on kneaded paper, etc., use a metal filler to fill the cavity with the composite resin, adjust the shape, and then irradiate with light to polymerize and cure. used. On the other hand, the flowable type is used by attaching a thin tip called a filling tip to a composite resin syringe and filling the cavity directly from the tip of the filling tip. In either case, operability is very important. In the case of the paste type, if the paste is too hard, the paste will crack during filling and shaping operations, and a smooth surface cannot be obtained, or food in the fissures. Residues can remain and cause secondary caries. In addition, if the paste has a large stickiness, when the paste is placed in the cavity using the filling device, it adheres to the filling device and cannot be arranged as intended. In the case of the flowable type, if it is difficult to push out from the syringe, the hand shakes and the paste cannot be discharged to the target location, and if the paste is too stringed, the paste will adhere to the periphery of the cavity and cause poor adhesion It is necessary to use the nerve very much when performing the filling operation.

  Furthermore, in both cases of paste type and flowable type, if the filling rate is too high, the viscosity of the paste increases, the adhesiveness with the fossa wall decreases, and it is easy to cause marginal leakage, coloring and the appearance of brown lines It can be a cause of deterioration and secondary caries.

  From the above, the dental filling and restorative material is required to be blended with an inorganic filler having an average particle size as small as possible for improving aesthetics. In that case, it is difficult to contain a large amount, and sufficient mechanical properties can be obtained. Even if the strength could not be obtained and it could be filled, the operability was lowered and further improvement was necessary.

  In order to improve the fluidity and operability of the paste-like substance, it is generally known to use a surfactant. For example, Patent Document 6 discloses a composition containing a nonionic surfactant with respect to a curable composition containing an acidic group-containing vinyl monomer, an ion-eluting filler, and a polymerization initiator. However, as the ion-eluting filler, large particles having a particle size of 50 μm or less are shown, and fillers having an average particle size of 1.0 to 1.1 μm are also used as specific examples in the examples. Therefore, even if a compound having such a large particle size is blended, it is difficult to satisfy the esthetics in the obtained dental filling and restorative material, and from the technique using such a large filler, Problems with filling properties and operability that occur for the first time when inorganic fillers are used and their solutions cannot be predicted.

  Also, Patent Document 7 discloses a curable composition containing a surfactant, a radical polymerizable monomer, and a curing accelerator, and it is disclosed that this composition may contain a filler. Has been. However, there is no description at all about the particle diameter of the filler to be used when the filler is contained in this way. Further, in this curable composition, the purpose of blending the surfactant is to improve the wettability of the surface of the biological hard tissue, and is not intended to improve the esthetics when used as a dental filling restorative material. Absent. Therefore, also in this curable composition, the problem of filling property and operability generated when the above-described fine inorganic filler is used and the solution thereof cannot be predicted.

JP 58-110414 A JP 58-151321 A JP 58-156526 A JP 58-156524 A JP 58-152804 A JP-A-5-255035 JP 7-316391 A

  Therefore, the problem to be solved by the present invention is to provide a dental filling material having a paste property that can be easily filled in the oral cavity while maintaining the extremely high aesthetics and low shrinkage ratio required for a dental filling restoration material. It is to provide restorative materials.

  The present inventors have intensively studied to solve the above problems. Even in a dental filling and restorative material containing a large amount of an inorganic filler having a small average particle diameter, when a specific amount of a surfactant is contained, the inorganic filler is uniformly filled, and mechanical strength and operability of the paste are achieved. As a result, the present invention has been completed.

That is, the present invention comprises (A) 100 parts by mass of a polymerizable monomer, (B) 80 to 1000 parts by mass of an inorganic filler having an average particle size of 0.03 to 0.6 μm, and (C) a surfactant of 0.5 to It is a dental filling restorative material comprising 5 parts by mass and (D) 0.01 to 10 parts by mass of a polymerization initiator.

  The dental filling and restorative material of the present invention is easy to obtain gloss on the surface of the cured body and is excellent in its persistence, has a small shrinkage rate at the time of polymerization and curing, and is easy to perform paste filling operation in the oral cavity. It has both. This provides a dental filling and restorative material that can accommodate a very wide range of repair cases.

  The first component to be blended in the dental restorative material of the present invention is (A) a polymerizable monomer. As the polymerizable monomer, known polymerizable monomers are used without limitation, but radically polymerizable monomers and cationically polymerizable monomers are preferably used.

  As the radically polymerizable monomer, a (meth) acrylate polymerizable monomer having no acidic group (sulfonic acid group, carboxyl group, phosphoric acid residue, etc.) is used for curing speed and mechanical properties of the cured product. A polyfunctional (meth) acrylate polymerizable monomer having a plurality of polymerizable functional groups is particularly preferably used from the viewpoints of physical properties, water resistance, coloring resistance and the like. As the polyfunctional (meth) acrylate polymerizable monomer, known ones can be used without particular limitation. Examples of those generally used preferably include those shown in the following (I) to (III).

(I) Bifunctional polymerizable monomer (i) Aromatic compound type 2,2-bis (methacryloyloxyphenyl) propane, 2,2-bis [4- (3-methacryloyloxy) -2-hydroxypropoxy Phenyl] propane (hereinafter abbreviated as bis-GMA), 2,2-bis (4-methacryloyloxyphenyl) propane, 2,2-bis (4-methacryloyloxypolyethoxyphenyl) propane (hereinafter referred to as D-2. 6E), 2,2-bis (4-methacryloyloxydiethoxyphenyl) propane, 2,2-bis (4-methacryloyloxytetraethoxyphenyl) propane, 2,2-bis (4-methacryloyloxypentaethoxy) Phenyl) propane, 2,2-bis (4-methacryloyloxydipropoxyphenyl) propyl Pan, 2 (4-methacryloyloxydiethoxyphenyl) -2 (4-methacryloyloxytriethoxyphenyl) propane, 2 (4-methacryloyloxydipropoxyphenyl) -2- (4-methacryloyloxytriethoxyphenyl) propane, 2 , 2-bis (4-methacryloyloxypropoxyphenyl) propane, 2,2-bis (4-methacryloyloxyisopropoxyphenyl) propane and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, Methacrylates such as 3-chloro-2-hydroxypropyl methacrylate or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and diisocyanates Diaducts obtained from addition with a diisocyanate compound having an aromatic group such as methylbenzene and 4,4′-diphenylmethane diisocyanate.

(Ii) Aliphatic compound-based ethylene glycol dimethacrylate, diethylene glycol dimethacrylate, triethylene glycol dimethacrylate (hereinafter abbreviated as 3G), tetraethylene glycol dimethacrylate, neopentyl glycol dimethacrylate, 1,3-butanediol Dimethacrylate, 1,4-butanediol dimethacrylate, 1,6-hexanediol dimethacrylate and acrylates corresponding to these methacrylates; 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, 3-chloro-2-hydroxypropyl methacrylate Such as methacrylates or vinyl monomers having —OH groups such as acrylates corresponding to these methacrylates, and hexamethylene Diadducts obtained from adducts with diisocyanate compounds such as isocyanate, trimethylhexamethylene diisocyanate, diisocyanate methylcyclohexane, isophorone diisocyanate, methylenebis (4-cyclohexylisocyanate); 1,2-bis (3-methacryloyloxy-2-hydroxy Propoxy) ethyl and the like.

(II) Trifunctional polymerizable monomer Methacrylates such as trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, pentaerythritol trimethacrylate, trimethylolmethane trimethacrylate, and acrylates corresponding to these methacrylates.
(III) Tetrafunctional polymerizable monomer Pentaerythritol tetramethacrylate, pentaerythritol tetraacrylate and diisocyanate methylbenzene, diisocyanate methylcyclohexane, isophorone diisocyanate, hexamethylene diisocyanate, trimethylhexamethylene diisocyanate, methylenebis (4-cyclohexylisocyanate), 4 Diadduct obtained from an adduct of a diisocyanate compound such as 1,4-diphenylmethane diisocyanate and tolylene-2,4-diisocyanate and glycidol dimethacrylate.

  These polyfunctional (meth) acrylate polymerizable monomers may be used in combination of a plurality of types as required.

  Further, if necessary, monofunctional (meth) acrylate-based monomethacrylates such as methacrylates such as methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, hydroxyethyl methacrylate, tetrahydrofurfuryl methacrylate, glycidyl methacrylate, and acrylates corresponding to these methacrylates. A polymerizable monomer other than the above-mentioned (meth) acrylate monomer may be used. In order to obtain good cured product properties (mechanical strength, non-eluting properties, etc.) as a dental restoration material, the blending amount of monomers other than these polyfunctional (meth) acrylate monomers is The content of the radical polymerizable monomer is 30% by mass or less, preferably 10% by mass or less, more preferably 5% by mass or less.

  On the other hand, when the polymerizable monomer is a cationic polymerizable monomer, any known monomer that can be polymerized by Bronsted acid or Lewis acid is used without any limitation.

  Examples of typical cationic polymerizable monomers include vinyl ether compounds, cyclic ether compounds such as epoxy, oxetane, tetrahydrofuran and oxepane, bicyclic orthoester compounds such as bicycloorthoester and spiroorthoester, spiroorthocarbonate, cyclic Cyclic acetal compounds such as carbonate, 1,3,5-trioxane, 1,3-dioxolane, oxepane, 1,3-dioxepane, 4-methyl-1,3-dioxepane, 1,3,6-trioxacyclooctane, 2,6-dioxabicyclo [2.2.1] heptane, 2,7-dioxabicyclo [2.2.1] heptane, 6,8-dioxabicyclo [3.2.1] octane, etc. Cyclic acetal compounds are mentioned, but they are readily available and volume shrinkage, especially when considering dental applications Small, in terms polymerization reaction faster, oxetane compounds and the epoxy compound is preferably used among others.

  Specific examples of the oxetane compound include trimethylene oxide, 3-methyl-3-oxetanylmethanol, 3-ethyl-3-oxetanylmethanol, 3-ethyl-3-phenoxymethyloxetane, 3,3-diethyloxetane, Those having one oxetane ring such as 3-ethyl-3- (2-ethylhexyloxy) oxetane, 1,4-bis (3-ethyl-3-oxetanylmethyloxy) benzene, 4,4′-bis (3 -Ethyl-3-oxetanylmethyloxy) biphenyl, 4,4'-bis (3-ethyl-3-oxetanylmethyloxymethyl) biphenyl, ethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, diethylene glycol bis (3 -Ethyl-3-oxetanylmethyl) ether, bi (3-ethyl-3-oxetanylmethyl) Jifenoeto, trimethylolpropane tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, or a compound shown below

And compounds having two or more oxetane rings.

  In particular, those having two or more oxetane rings in one monomer molecule are preferably used from the viewpoint of physical properties of the obtained cured product.

  The epoxy compound is not particularly limited as long as it is a compound capable of cationic polymerization, and known compounds can be used. Specific examples of the epoxy compound include 1,2-epoxypropane, 1,2-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 1,2-epoxyhexane, 1,2-epoxy. Octane, 1,2-epoxydecane, 1,2-epoxydodecane, 1,2-epoxytetradecane, 1,2-epoxyhexadecane, 1,2-epoxyoctadecane, butadiene monooxide, 2-methyl-2-vinyloxirane, 1,2-epoxy-5-hexene, 1,2-epoxy-7-octene, 1,2-epoxy-9-decene, epichlorohydrin, epibromohydrin, glycidol, 2-methylglycidol, methylglydidi Ether, ethyl glycidyl ether, glycidyl propyl ether, butyl glycidyl ether , 2-ethylhexyl glycidyl ether, cyclooctene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecane epoxide, exo-2,3-epoxynorbornene, 4-vinyl-1-cyclohexene-1,2-epoxide, limonene oxide, styrene Oxide, (2,3-epoxypropyl) benzene, phenyl glycidyl ether, benzyl glycidyl ether, glycidyl 2-methylphenyl ether, 4-tert-butylphenyl glycidyl ether, 4-chlorophenyl glycidyl ether, glycidyl 4-methoxyphenyl ether, etc. One having an epoxy functional group, 1,3-butadiene dioxide, 1,2,7,8-diepoxyoctane, ethylene glycol jig Sidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, tetraethylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,3-propanediol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1 , 5-pentanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, 1,4-cyclohexanemethanol diglycidyl ether, diglycidyl glutarate, diglycidyl adipate, diglycidyl pimelate, diglycidyl suberate, di Glycidyl azelate, diglycidyl sebacate, 2,2-bis [4-glycidyloxyphenyl] propane, 2,2-bis [4-glycidyloxyphe Nyl] hexafluoropropane, 4-vinyl-1-cyclohexene diepoxide, limonene diepoxide, 1,2,5,6-diepoxycyclooctane, 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, Bis (3,4-epoxycyclohexylmethyl) glutarate, bis (3,4-epoxycyclohexylmethyl) adipate, bis (3,4-epoxycyclohexylmethyl) pimelate, bis (3,4-epoxycyclohexylmethyl) suberate, bis ( 3,4-epoxycyclohexylmethyl) zelate, bis (3,4-epoxycyclohexylmethyl) sebacate, 1,4-bis (3,4-epoxycyclohexylmethyloxymethyl) benzene, 1,4-bis (3,4) Epoxy (Rohexylmethyloxymethyl) biphenyl, bis (3,4-epoxycyclohexyl) methane, 2,2-bis (3,4-epoxycyclohexyl) propane, bis (3,4-epoxycyclohexyl) sulfone, methylbis [2- ( 7-oxabicyclo [4.1.0] hept-3-yl) ethyl] phenylsilane, dimethylbis [(7-oxabicyclo [4.1.0] hept-3-yl) methyl] silane, methyl [( 7-oxabicyclo [4.1.0] hept-3-yl) methyl] [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl] silane, 1,4-phenylenebis [Dimethyl [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl]] silane, 1,2-ethylenebis [dimethyl [2- (7-oxa Cyclo [4.1.0] hept-3-yl) ethyl]] silane, dimethyl [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl] silane, 1,3-bis [2- (7-Oxabicyclo [4.1.0] hept-3-yl) ethyl] -1,1,3,3-tetramethyldisiloxane, 2,5-bicyclo [2.2.1] heptylene bis [Dimethyl [2- (7-oxabicyclo [4.1.0] hept-3-yl) ethyl]] silane, 1,6-hexylenebis [dimethyl [2- (7-oxabicyclo [4.1. 0] hept-3-yl) ethyl]] silane and other compounds having two epoxy functional groups, or glycerol triglycidyl ether, trimethylolpropane triglycidyl ether, pentaerythritol triglycidyl ether, Pentaerythritol tetraglycidyl ether, dipentaerythritol hexaglycidyl ether, and

And those having three or more epoxy functional groups. These epoxy compounds may be used in combination.

  In particular, those having two or more epoxy functional groups in one molecule are suitably used from the viewpoint of physical properties of the obtained cured product.

  These cationic polymerizable monomers can be used alone or in combination of two or more. In particular, when A mole of an oxetane compound having an oxetane functional group having an average of 1 molecule per molecule and B mole of an epoxy compound having an epoxy functional group having an average of b molecules per molecule are used (a × A) : (B × B) prepared so as to be in the range of 90:10 to 45:55 is preferable in that the curing rate is high and the polymerization is not easily inhibited by moisture.

  The 2nd component mix | blended with the dental restoration material of this invention is (B) inorganic filler, and the average particle diameter of this inorganic filler is 0.03-0.6 micrometer. When the average particle diameter of the inorganic filler is small in this range, it is possible to satisfy the high esthetics required for dental filling and restorative materials. On the other hand, since the inorganic filler component is fine as described above, the filling property is lowered, and the phenomenon of deterioration in the operability of the paste when it is added in a large amount is likely to occur. (C) These problems are satisfactorily improved by blending the surfactant.

  Known inorganic fillers can be used without particular limitation. Examples of those generally used preferably include amorphous silica, silica-titania, silica-zirconia, silica-titania-zirconia, silica-calcia, silica-magnesia, silica-titania-barium oxide, quartz and the like. be able to. Furthermore, for the purpose of facilitating obtaining a dense inorganic filler when firing these inorganic fillers at a high temperature, a particle in which a small amount of Group I metal oxide is present in the inorganic filler is used. You can also. For dental use, an inorganic filler mainly composed of silica and zirconia is particularly preferably used because it has an easy refractive index adjustment with a polymerizable monomer and has X-ray contrast properties. .

  The average particle diameter of the inorganic filler is 0.03 to 0.6 μm. As the whole inorganic filler to be used, the average particle diameter may be within the above range, and the particle size distribution of the inorganic particles may be wider than the above range, but at least 60% of the particles, more preferably 80% It is preferable that it exists in the range of the said particle diameter of 0.03-0.6 micrometer. Here, the smaller the average particle diameter, the easier it is to obtain gloss when polishing the cured body, but the filling rate is difficult to increase, and the operability of the paste also decreases. On the other hand, when the average particle size is increased, the filling rate is easily increased, but gloss during polishing is difficult to obtain. For this reason, the average particle diameter of the inorganic filler is preferably in the range of 0.03 μm to 0.6 μm, particularly preferably in the range of 0.04 μm to 0.5 μm.

  In order to fill the inorganic filler with a high density, for example, as described in JP-A-8-12305, it is preferable to use a combination of an inorganic filler having a large particle size and an inorganic filler having a small particle size. Also in the invention, it is preferable to use a combination of two types having different particle diameters so that the total average particle diameter of the inorganic filler to be blended is in the range of 0.03 to 0.6 μm. Particularly preferably, with respect to the large particle size inorganic filler having an average particle size of 0.2 to 0.8 μm, more preferably 0.3 to 0.6 μm, and the average particle size of the large particle size inorganic filler to be used A small particle size inorganic filler having an average particle size of 1/3 to 1/7 is used as a whole inorganic filler in combination at a blending ratio such that the average particle size is in the range of 0.03 μm to 0.6 μm. Is preferred.

  In addition, the average particle diameter of the filler in the present invention is a median diameter measured by a laser diffraction-scattering method.

  In the present invention, the shape of the inorganic filler is not particularly limited, and may be an indefinite shape obtained by pulverization, but is spherical from the viewpoint of further improving the aesthetics and filling properties of the filling restoration material. Is preferred. Here, the spherical shape does not necessarily need to be a true sphere, and may be a substantially spherical shape. In general, a photograph of an inorganic filler is taken with a scanning electron microscope, 100 particles randomly observed in the unit field of view are selected at random, and the particle diameter in the direction perpendicular to the maximum particle diameter is set to the maximum diameter. If the average homogeneity gradually lowered is 0.6 or more, more preferably 0.8 or more, it can be used sufficiently.

  The inorganic filler is preferably treated with a surface treatment agent typified by a silane coupling agent in order to improve compatibility with the polymerizable monomer (A) and improve mechanical strength and water resistance. . The surface treatment may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (2-methoxyethoxy) silane, 3-methacryloyloxypropyltrimethoxysilane, 3-methacryloyloxypropyltris (2-methoxyethoxy) silane, 3-chloropropyltrimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 2- (3,4-epoxy Chlohexyl) ethyltrimethoxysilane, 5,6-epoxyhexyltriethoxysilane, 3-ethyl-3- [3- (triethoxysilyl) propoxymethyl] oxetane, N-phenyl-γ-aminopropyltrimethoxysilane, hexamethyl Disilazane and the like are preferably used. The said silane coupling agent should just be selected suitably according to a polymerizable monomer, and can use it combining 1 type or 2 types or more.

  The compounding quantity of the said inorganic filler is 80-1000 mass parts with respect to 100 mass parts of polymerizable monomers. When the filler is less than 80 parts by mass, the mechanical strength of the cured body is not sufficient, and the polymerization shrinkage rate is increased. Moreover, when it exceeds 1000 mass parts, it will become difficult to fill uniformly, and the fall of operativity is inevitable. From the viewpoint of making these properties more excellent, the blending amount of the inorganic filler is preferably 100 to 900 parts by mass.

  The amount of filler used may be determined appropriately depending on the operability of the composite resin described above, that is, whether it is a paste type or a flowable type. In any type, the amount of filler used is from the viewpoint of reducing the polymerization shrinkage rate. It should be as high as possible. The flowable type is preferably 100 to 400 parts by mass, and the paste type is preferably 150 to 900 parts by mass.

  The third component added to the dental restorative material of the present invention is (C) a surfactant. In general, a surfactant improves the wettability between two phases. In the case of the present invention, (A) a polymerizable monomer and (B) improve the familiarity of the filler and improve paste properties. is there. Conventionally, surfactants in dental materials have been used to improve adhesion to teeth, strength of hardened bodies, and colorability. In the present invention, however, the filling properties of dental restorative materials are improved. Used to improve operability.

  Any known surfactant can be used without any limitation. Specifically, any of nonionic surfactants, anionic surfactants, cationic surfactants, and amphoteric surfactants can be used, but from the viewpoint of satisfactorily exerting the effects of the present invention, preferably Nonionic surfactants and anionic surfactants.

  As the nonionic surfactant suitably used in the present invention, known ones can be used without particular limitation, but those having an HLB (hydrophilic lipophilic balance) of 3 or more, preferably 6-18 are used. preferable. Examples of such nonionic surfactants include those having a polyoxyethylene group as a hydrophilic group. Specific examples include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene lauryl phenyl ether, and the like. Examples thereof include fatty acid polyoxyethylene esters such as polyoxyethylene alkylphenyl ether and fatty acid polyoxyethylene lauryl ester, and polyoxyethylene sorbitan esters such as polyoxyethylene sorbitan lauryl ester.

  As the anionic surfactant suitably used in the present invention, known anionic surfactants can be used without particular limitation, but those having an HLB of 20 or more, preferably 30 to 50 are preferably used. Specific examples of such anionic surfactants include alkyl sulfates such as sodium decyl sulfate and sodium lauryl sulfate, sulfonates such as sodium hexanesulfonate and sodium decylsulfonate, sodium decylbenzenesulfonate, Alkyl benzene sulfonates such as sodium lauryl benzene sulfonate, aliphatic carboxylic acid salts such as sodium decanoate, sodium laurate, sodium stearate, sodium oleate, lauryl ether sulfate sulfated with adducts of lauryl alcohol and ethylene oxide Examples include alkyl ether sulfates such as sodium ester, sulfosuccinic diesters such as sodium sulfosuccinate, and phosphate esters of higher alcohol ethylene oxide adducts. Can.

  Further, known cationic surfactants used in the present invention can be used without particular limitation, and examples thereof include quaternary ammonium salts such as lauryltrimethylammonium chloride and cetylpyridinium bromide.

The compounding quantity of the said surfactant is 0.5-5 mass parts with respect to 100 mass parts of polymerizable monomers. The amount is small and not sufficient effect of the paste properties improved, also to affect the physical properties of the cured body and often amount.

  The fourth component to be blended in the dental filling / restoring material of the present invention is (D) a polymerization initiator. The polymerization initiator can be used without any limitation as long as the polymerizable monomer to be used can be polymerized and cured, and a known polymerization initiator can be used. As a polymerization initiator used in the dental field, as a radical polymerization initiator for polymerizing and curing a radical polymerizable monomer, a chemical polymerization initiator (room temperature redox initiator), a photopolymerization initiator, a thermal polymerization initiator, etc. However, in consideration of curing in the oral cavity, a chemical polymerization initiator and / or a photopolymerization initiator is preferable. Moreover, as a cationic polymerization initiator for polymerizing and curing the cationic polymerizable monomer, it is preferable to employ a so-called photoacid generator that generates a Lewis acid or a Bronsted acid by light irradiation.

  Photopolymerization initiators include benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin isopropyl ether, benzyl ketals such as benzyldimethyl ketal and benzyl diethyl ketal, diaryl ketones such as benzophenone, anthraquinone and thioxanthone, diacetyl , Benzyl, camphorquinone, α-diketones such as 9,10-phenanthraquinone, bis- (2,6-dichlorobenzoyl) phenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -2,5- Dimethylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -4-propylphenylphosphine oxide, bis- (2,6-dichlorobenzoyl) -1-naphthylphosphine oxa , Bis (2,4,6-trimethylbenzoyl) - bisacylphosphine oxides such as triphenylphosphine oxide, and the like can be used.

  In addition, a reducing compound is often added to the photo radical polymerization initiator. Examples thereof include 2- (dimethylamino) ethyl methacrylate, ethyl 4-dimethylaminobenzoate, N-methyldiethanolamine, dimethylamino. Examples thereof include tertiary amines such as benzaldehyde and terephthalaldehyde, sulfur-containing compounds such as 2-mercaptobenzoxazole, 1-decanethiol, thiosalicylic acid and thiobenzoic acid, and N-phenylalanine.

  As the thermal polymerization initiator, peroxides such as benzoyl peroxide, p-chlorobenzoyl peroxide, tert-butylperoxy-2-ethylhexanoate, tert-butylperoxydicarbonate, diisopropylperoxydicarbonate, An azo compound such as azobisisobutyronitrile can be used.

  Examples of the chemical polymerization initiator include combinations of the above-described peroxides and tertiary amines exemplified as the reducing agent.

  Examples of the photoacid generator include diazonium salt compounds, iron-arene complex salt compounds, diaryliodonium salt compounds, sulfonium salt compounds, pyridinium salt compounds, sulfonic acid ester compounds, and halomethyl-substituted S-. Examples include triazine conductors.

  Among these, diaryliodonium salt compounds and sulfonium salt compounds are excellent in that the polymerization activity is particularly high. Specific examples of diaryl iodonium salt compounds include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl). ) Iodonium, p-isopropylphenyl-p-methylphenyliodonium, bis (m-nitrophenyl) iodonium, p-tert-butylphenylphenyliodonium, p-methoxyphenylphenyliodonium, bis (p-methoxyphenyl) iodonium, p- Cations such as octyloxyphenylphenyliodonium, p-phenoxyphenylphenyliodonium, chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate, Examples thereof include diaryl iodonium salt compounds composed of anions such as trafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate.

  Examples of sulfonium salt compounds include dimethylphenacylsulfonium, dimethylbenzylsulfonium, dimethyl-4-hydroxyphenylsulfonium, dimethyl-4-hydroxynaphthylsulfonium, dimethyl-4,7-dihydroxynaphthylsulfonium, dimethyl-4,8- Cations such as dihydroxynaphthylsulfonium, triphenylsulfonium, p-tolyldiphenylsulfonium, p-tert-butylphenyldiphenylsulfonium, diphenyl-4-phenylthiophenylsulfonium, chloride, bromide, p-toluenesulfonate, trifluoromethanesulfonate , Tetrafluoroborate, tetrakispentafluorophenylborate, tetrakispentafluorophenylgallate, hexaful Examples thereof include sulfonium salt compounds composed of anions such as orophosphate, hexafluoroarsenate and hexafluoroantimonate.

  The photoacid generator as described above usually has many compounds that do not absorb in the near ultraviolet to visible range, and a special light source is often required to excite the polymerization reaction. Therefore, it is preferable that a compound having absorption in the near ultraviolet to visible region is further added as a sensitizer in addition to the photoacid generator.

  Examples of the compound used as such a sensitizer include acridine dyes, benzoflavine dyes, condensed polycyclic aromatic compounds such as anthracene and perylene, and phenothiazine.

  Among these sensitizers, a condensed polycyclic aromatic compound is preferable in terms of good polymerization activity, and a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to the condensed polycyclic aromatic ring. Condensed polycyclic aromatic compounds having are preferred.

  Specific examples of such condensed polycyclic aromatic compounds having a structure in which a saturated carbon atom having at least one hydrogen atom is bonded to a condensed polycyclic aromatic ring include 1-methylnaphthalene and 1-ethylnaphthalene. 1,4-dimethylnaphthalene, acenaphthene, 1,2,3,4-tetrahydrophenanthrene, 1,2,3,4-tetrahydroanthracene, benzo [f] phthalane, benzo [g] chroman, benzo [g] isochroman, N-methylbenzo [f] indoline, N-methylbenzo [f] isoindoline, phenalene, 4,5-dimethylphenanthrene, 1,8-dimethylphenanthrene, acephenanthrene, 1-methylanthracene, 9-methylanthracene, 9-ethylanthracene , 9-cyclohexylanthracene, 9,10-dimethyl Luanthracene, 9,10-diethylanthracene, 9,10-dicyclohexylanthracene, 9-methoxymethylanthracene, 9- (1-methoxyethyl) anthracene, 9-hexyloxymethylanthracene, 9,10-dimethoxymethylanthracene, 9- Dimethoxymethylanthracene, 9-phenylmethylanthracene, 9- (1-naphthyl) methylanthracene, 9-hydroxymethylanthracene, 9- (1-hydroxyethyl) anthracene, 9,10-dihydroxymethylanthracene, 9-acetoxymethylanthracene 9- (1-acetoxyethyl) anthracene, 9,10-diacetoxymethylanthracene, 9-benzoyloxymethylanthracene, 9,10-dibenzoyloxymethylanthracene, 9 -Ethylthiomethylanthracene, 9- (1-ethylthioethyl) anthracene, 9,10-bis (ethylthiomethyl) anthracene, 9-mercaptomethylanthracene, 9- (1-mercaptoethyl) anthracene, 9,10-bis (Mercaptomethyl) anthracene, 9-ethylthiomethyl-10-methylanthracene, 9-methyl-10-phenylanthracene, 9-methyl-10-vinylanthracene, 9-allylanthracene, 9,10-diallylanthracene, 9-chloro Methyl anthracene, 9-bromomethylanthracene, 9-iodomethylanthracene, 9- (1-chloroethyl) anthracene, 9- (1-bromoethyl) anthracene, 9- (1-iodoethyl) anthracene, 9,10-dichloromethylanthracene 9,10-dibromomethylanthracene, 9,10-diiodomethylanthracene, 9-chloro-10-methylanthracene, 9-chloro-10-ethylanthracene, 9-bromo-10-methylanthracene, 9-bromo-10 -Ethylanthracene, 9-iodo-10-methylanthracene, 9-iodo-10-ethylanthracene, 9-methyl-10-dimethylaminoanthracene, acanthrene, 7,12-dimethylbenz (A) anthracene, 7,12- Dimethoxymethylbenz (a) anthracene, 5,12-dimethylnaphthacene, collanthrene, 3-methylcholanthrene, 7-methylbenzo (A) pyrene, 3,4,9,10-tetramethylperylene, 3,4,9, 10-tetrakis (hydroxymethyl) perylene, bio Nsuren, Isoviolanthrone Ren, 5,12-dimethyl-naphthacene, 6,13-dimethyl pentacene, 8,13- dimethyl penta Fen, 5,16- dimethyl hexamethylene Sen, 9,14- dimethyl hexa Fen and the like.

  Examples of the condensed polycyclic aromatic compound other than the above include naphthalene, phenanthrene, anthracene, naphthacene, benz [a] anthracene, pyrene, perylene and the like.

  Further, in order to further increase the activity of the photopolymerization initiator, it is possible to use the photoacid generator in combination as a photoradical polymerizable initiator. In this case, as the photopolymerization initiator, α-diketones such as camphorquinone are preferable, and a reducing agent such as 4-dimethylaminobenzoic acid is preferably used in combination.

  These polymerization initiators may be used alone or in combination of two or more. Moreover, what is necessary is just to select the compounding quantity according to the objective, but it is a ratio of 0.01-10 mass parts normally with respect to 100 mass parts of polymerizable monomers, More preferably, 0.1-5 mass parts Used at a rate of

  In the dental filling / restoration material of the present invention, in addition to the inorganic filler having the average particle diameter of 0.03 to 0.6 μm (B), other fillers may be blended within a range not impairing the effects of the present invention. it can. Examples of such other fillers include organic fillers and organic-inorganic composite fillers. The average particle size of the organic filler or organic-inorganic composite filler is about 1 μm to 100 μm. These are composed of an organic resin even if the particle size is large, or the inorganic filler contained in the organic-inorganic composite filler has a small particle size and is contained in the matrix of the organic resin. It does not affect the surface gloss of the composite resin. However, when the particle size is too large, the paste may become rough and affect operability. For this reason, Preferably it is 3-70 micrometers, More preferably, it is 5-50 micrometers.

  In particular, for the following reasons, the organic-inorganic composite filler is also preferably used in combination with the (B) inorganic filler. Since the organic-inorganic composite filler has a larger particle diameter than the inorganic filler which is the component (B) of the present invention, the filler filling rate can be further increased by blending it. In addition, since the inorganic filler contained in the organic-inorganic composite filler has a small particle size, it does not impair the beauty of the beauty such as high gloss obtained by polishing.

  The polymerizable organic matrix used for the organic-inorganic composite filler is not particularly limited, and a known polymerizable organic matrix is used. For example, a polymerizable organic matrix suitably used is exemplified by the polymerizable monomer described above as the component (A) in the dental filling / restoring material of the present invention, and the polymerization start described above as the component (C). Examples thereof include a cured product cured with an agent.

  The amount of the organic-inorganic composite filler is generally 70% by mass or less, preferably 10-60% by mass, based on the whole dental filling / restoration material of the present invention. An organic-inorganic composite filler is suitably blended in the dental filling / restoring material of the present invention.

  In addition to the above-mentioned components, the dental restorative material of the present invention may contain a polymerization inhibitor, an ultraviolet absorber, a pigment, a fluorescent pigment, a dye, and other known additives as components of dental composite resins. You may mix | blend an agent in the range which does not affect the effect of this invention.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. In addition, the abbreviations of the compounds used in the following Examples and Comparative Examples are shown below.
(1) Abbreviations / abbreviations (A) Polymerizable monomer / GMA: 2,2-bis [(3-methacryloyloxy-2-hydroxypropyloxy) phenyl] propane / D2.6E: 2,2-bis (4 -(Methacryloyloxypolyethoxyphenyl) propane, 3G: triethylene glycol dimethacrylate, UDMA: 1,6-bis (methacrylethyloxycarbonylamino) trimethyloxane, OX:

・ EP:

(B) Inorganic filler F-1: Spherical silica-zirconia having an average particle size of 0.4 μm and an average uniformity of 0.90 F-2: Average particle size of 0.07 μm and an average uniformity 0.80 spherical silica-zirconia F-3: average particle size 0.08 μm, and average silica homogeneity 0.85 spherical silica-titania F-4: average particle size 0.2 μm, Spherical silica-zirconia having an average degree of homogeneity of 0.93 *: The average particle size was measured by using a scanning electron microscope (XL-30S FEG, manufactured by PHILIPS), and photographs of inorganic particles were taken at 5000 to 100,000 times. Then, 100 particles are randomly selected from the primary particles observed in the unit field of view of the photograph, the particle diameters of each are obtained, and the average particle diameter in volume average (the cube root of the cube average of the measured particle diameter). Was calculated.

*: The average uniformity is measured by selecting 100 particles in the same manner as in the measurement of the average particle size, and gradually decreasing the particle size in the direction perpendicular to the maximum particle size by the maximum size. I asked for a degree.
(C) Surfactant SA-1: Polyoxyethylene (4) Lauryl ether HLB10
The numbers in parentheses are the number of repeating oxyethylene units. SA-2: Sodium hexadecyl sulfate HLB38
SA-3: Sodium decanoate HLB22
(D) Polymerization initiator CQ: camphorquinone DMBE: ethyl 4-dimethylaminobenzoate TEA: triethanolamine MDA: N-methyldiethanolamine TCT: 2,4,6-tris (trichloromethyl) -s -Triazine / IMDPI:

DMAn: 9,10-dimethylanthracene (E) and other components a) filler F-5: 75 parts by mass of spherical silica-titania having an average particle size of 0.2 μm, 10 parts by mass of D2.6E, and 15 parts by mass of 3G 0.1 part by mass of azobisisobutyronitrile is dissolved in a mixture of parts, and the organic-inorganic composite filler with an average particle size of 38 μm, which is pulverized after heat curing, F-6: amorphous silica with an average particle size of 3.6 μm, Zirconia b) Polymerization inhibitor • HQME: Hydroquinone monomethyl ether • BHT: 2,6-di-t-butyl-4-methylphenol In addition, the hardness and fluidity of the photocurable composite resin paste, polymerization shrinkage, and curing The surface glossiness of the body was measured by the following method.

(1) Paste was filled in a SUS nut-shaped mold having a composite resin (paste type) paste hardness φ8 mm and a depth of 3 mm, the surface was smoothed, and the paste temperature was maintained at 23 ° C. A plastic rod having a diameter of 5 mm was attached to a sun rheometer (manufactured by San Kagaku Co., Ltd.) as a pressure sensitive axis, and the maximum load when compressing and entering from the paste surface to a depth of 2 mm was defined as the paste hardness.

(2) Paste flowability of composite resin (flowable type) About 0.1 g of the paste-like composition was placed on a glass plate, and naturally developed at 37 ° C for 2 minutes while keeping the glass plate horizontal. The average value of the major axis and the minor axis of the paste-like composition at this time was defined as fluidity.

(3) Polymerization shrinkage ratio A SUS plunger having a diameter of 3 mm and a height of 7 mm was filled with a SUS plunger having a diameter of 3 mm and a height of 4 mm to make the hole height 3 mm. This was filled with a photopolymerizable dental composite resin, and pressed from above with a polypropylene film. A short needle that can be placed on a glass table with a dental irradiator (Tokuso Power Light, Tokuyama Dental Co., Ltd.) with the film side facing down, and the movement of a fine needle can be measured from above the SUS plunger. Was brought into contact. Polymerization and curing was performed with a dental irradiator, and the shrinkage [%] after 1 minute from the start of irradiation was calculated from the movement distance of the short needle in the vertical direction.

(4) Surface glossiness The paste was filled in a resin mold having a size of 1 cm × 1 cm × 2 mm, and polymerized and cured by a dental light irradiator. The flat surface of the cured body was polished with 1500-thick water-resistant abrasive paper, and then polished for 60 seconds under water injection using a dental abrasive (Soflex Superfine, 3M ESPE). Using a gloss meter (MODEL TC-108D, Tokyo Denshoku Co., Ltd.), the glossiness of the polished surface was measured when the glossiness of the standard black plate was 100.

Example 1
With respect to 100 parts by mass of a polymerizable monomer composed of D2.6E (70 parts by mass), 3G (20 parts by mass), and UDMA (10 parts by mass), 0.15 parts by mass of HQME as a polymerization inhibitor, and light As a polymerization initiator, 0.2 parts by mass of CQ, 0.35 parts by mass of DMBE, 0.35 parts by mass of MDA and 0.20 parts by mass of TCT are blended, and 1.0-1 of SA-1 is further added as a surfactant. After adding a mass part and stirring well and making it uniform, 200 mass parts of inorganic filler F-1 was mix | blended, and it mixed and stirred well with the agate mortar until it became uniform paste-form. Further, this was vacuum degassed to prepare a flowable type dental filling restorative paste.

Table 1 shows the results of measuring various physical properties of the obtained dental restoration material.
Examples 2-7, Comparative Examples 1-5
In Example 1, a paste was prepared in the same manner as in Example 1 except that the fillers and surfactants shown in Table 1 were used. Table 1 shows the results of measuring various physical properties of the obtained dental filling and restorative material.

Comparative Examples 1 to 4 are cases where surfactants were not used with the same composition of the filling and restorative materials as in Examples 1 to 4, respectively. A clear difference was observed in the fluidity of the paste, and in all of the examples, the fluidity was higher and the operability as a flowable type dental filling and restorative material was excellent. Comparative Example 5 is an example in which an amorphous filler having a large average particle size is used and blended in such an amount that the paste fluidity and the polymerization shrinkage rate are the same as those in Example 4 without using a surfactant. At this time, it was found that the surface gloss was remarkably lowered.
Example 8
With respect to 100 parts by mass of a polymerizable monomer composed of D2.6E (70 parts by mass), 3G (20 parts by mass), and UDMA (10 parts by mass), 0.15 parts by mass of HQME as a polymerization inhibitor, and light As a polymerization initiator, 0.2 parts by mass of CQ, 0.35 parts by mass of DMBE, 0.35 parts by mass of TEA and 0.20 parts by mass of TCT are blended, and 1.0-1 of SA-1 is further added as a surfactant. After adding mass parts and stirring well to make uniform, 67 parts by mass of inorganic filler F-1, 28 parts by mass of F-2, and 222 parts by mass of organic-inorganic composite filler F-5 are blended to form a uniform paste. The mixture was thoroughly mixed and stirred in an agate mortar. Further, this was vacuum degassed to prepare a flowable type dental filling restorative paste.

Table 2 shows the results of measuring various physical properties of the obtained dental filling and restorative material.
Example 9, Comparative Examples 6, 7
In Example 8, a paste was prepared in the same manner as in Example 8 except that the fillers and surfactants shown in Table 2 were used. Table 2 shows the results of measuring various physical properties of the obtained dental filling and restorative material.

Comparative Example 6 is an example in which the same composition as in Examples 8 and 9 was used but no surfactant was used. While the paste fluidity of Comparative Example 6 was small, the examples showed moderate fluidity.
Example 10
With respect to 100 parts by mass of a polymerizable monomer composed of GMA (60 parts by mass) and 3G (40 parts by mass), 0.15 parts by mass of HQME as a polymerization inhibitor, and 0.2 of CQ as a photopolymerization initiator. Parts by weight, 0.35 parts by weight of DMBE, 0.2 parts by weight of MDA and 0.20 parts by weight of TCT, and 1.0 parts by weight of SA-1 as a surfactant were added and stirred well to be homogeneous After that, 196 parts by mass of the inorganic filler F-4 and 294 parts by mass of the organic-inorganic composite filler F-5 were blended and mixed and stirred well in an agate mortar until a uniform paste was obtained. Further, this was vacuum degassed to prepare a paste-type dental filling and restorative paste.

Table 2 shows the results of measuring various physical properties of the obtained dental filling and restorative material.
Examples 11 and 12, Comparative Examples 8 to 10
In Example 10, a paste was prepared in the same manner as in Example 10 except that the fillers and surfactants shown in Table 3 were used. Table 3 shows the results of measuring various physical properties of the obtained dental filling and restorative material.

Comparative Example 8 is an example in which the surfactant was not used with the same composition as Example 10, and Comparative Example 9 was an example in which the surfactant was not used with the same composition as Examples 11 and 12. In these comparative examples, the paste hardness was higher than in the corresponding examples.
Example 13
As a photopolymerization initiator, 100 parts by weight of IMDPI, 0.6 parts by weight of CQ, 0.6 parts by weight of CQ, and DMAn0. 1 part by weight, 0.1 part by weight of BHT as a polymerization inhibitor, and 1.0 part by weight of SA-1 as a surfactant were added and stirred well to make an inorganic filler F-4. 182 parts by mass and 274 parts by mass of the organic-inorganic composite filler F-5 were blended and well mixed and stirred in an agate mortar until a uniform paste was obtained. Further, this was vacuum degassed to prepare a paste-type dental filling and restorative paste.

Table 4 shows the results of measuring various physical properties of the obtained dental filling and restorative material.
Example 14 and Comparative Example 11
In Example 13, a paste was prepared in the same manner as in Example 13 except that the filler and surfactant shown in Table 4 were used. Table 4 shows the results of measuring various physical properties of the obtained dental filling and restorative material.

Table 4 shows the results when a cationic polymerizable monomer was used as the polymerizable monomer (A). As in the case of using a radical polymerizable monomer, the effect of adding a surfactant was shown. Appeared.

Claims (3)

(A) 100 parts by mass of a polymerizable monomer, (B) 80 to 1000 parts by mass of an inorganic filler having an average particle size of 0.03 to 0.6 μm, (C) 0.5 to 5 parts by mass of a surfactant, and ( D) A dental filling and restorative material comprising 0.01 to 10 parts by mass of a polymerization initiator. (B) The dental filling / restoration material according to claim 1, wherein the inorganic filler having an average particle diameter of 0.03 to 0.6 μm is spherical. The dental filling / restoration material according to claim 1 or 2, wherein the component (C) is a nonionic surfactant or an anionic surfactant.