JP2011098944A - Packing/restoring material kit for dentistry - Google Patents

Abstract

In dental treatment, a pretreatment material and a filling restorative material can be cured by one-step light irradiation, and an adhesive strength between a cavity inner wall and a filling restorative material is excellent.
A filling restoration material containing an acid group-free radical polymerizable monomer, a filler and a photopolymerization initiator, and a pretreatment material containing an acid group-containing radical polymerizable monomer and water, At least one member selected from the filling restoration material and the pretreatment material contains a titanocene-based photopolymerization initiator. During dental treatment, the pretreatment material is applied to the cavity, and then the pretreatment material is applied. The filling restoration material is filled in the attached cavity, and then the filling restoration material is cured by irradiating visible light to the cavity portion filled with the filling restoration material and filling the cavity wall and the cavity. A dental filling / restoration kit characterized by adhering a restoration material.
[Selection figure] None

Description

    The present invention relates to a dental filling / restoration material kit.

  Conventionally, small defects (cavities) caused by dental caries or the like are filled with a metal material such as amalgam. However, in recent years, a filling restoration material called a composite resin containing an acrylic polymerizable monomer, an inorganic filler, and a polymerization initiator is preferably used because it can provide the same color tone as natural tooth color and is easy to operate. It has been. The filling restorative material can be easily deformed when the tooth shape is applied, but is preferably cured as soon as filling is completed. For this reason, recent filling / restoring materials contain a photopolymerization initiator and are cured using visible light that is harmless to a living body.

  However, the resin-based filling / restoring material itself does not have adhesiveness to teeth. For this reason, if the cavity of a tooth is filled with only a resin-based filling / restoring material, a gap may be generated between the filling / restoring material and the tooth. As a result, there is a high possibility that bacteria may enter from the gap, or the filling restoration material may fall off from the tooth.

  Therefore, a technique has been put into practical use in which a layer made of a pretreatment material containing a polymerizable monomer containing an acidic group as a main component is provided between a resin-based filling / restoring material and a tooth. The pretreatment material acts as a surface treatment agent for tooth enamel and dentin, and has an effect of increasing the adhesive force between the filling restorative material and the tooth. By interposing such a pretreatment material between the tooth and the resin-based filling / restoring material, the filling / restoring material and the tooth can be bonded without a gap. Recently, a pretreatment material that contains a photopolymerization initiator as in the case of a filling restoration material and is cured using visible light has been used.

  The operation of restoring a tooth is performed according to the following procedure. First, the tooth decay portion is cut to form a cavity. Next, a pretreatment material is applied to the cavity. Next, in order to cure the pretreatment material, visible light is irradiated to the portion where the pretreatment material is applied. And the filling restoration material is filled on the layer formed of the pretreatment material. Finally, in order to cure the filling / restoring material, the filling / restoring material is irradiated with visible light.

  In this photo-curing treatment, the adhesiveness between the cured filling restoration material and the tooth must be secured, but in addition to this, it is also necessary that the cured filling restoration material does not discolor from the viewpoint of aesthetics. It is. In order to suppress such discoloration, a dental adhesive composition containing an acidic group-containing radical polymerizable monomer, a titanocene compound, and water has been proposed (see, for example, Patent Document 1).

  Moreover, when performing the restoration | repair operation | work mentioned above using the dental adhesive composition etc. which are illustrated by patent document 1 etc., the timing of 2 times after application | coating of a pre-processing material and filling of a restoration restoration material is carried out. It is necessary to irradiate separately (2 step light irradiation). However, from the viewpoint of reducing the burden on the patient and simplifying the repair work, it is desirable to reduce the timing of irradiating visible light in a series of repair work. However, when the filling / restoring material is irradiated with visible light, shrinkage stress is generated as the filling / restoring material is polymerized. This shrinkage stress acts as a force for peeling off the bonded portion between the filling restorative material and the tooth. As a result, the adhesive strength between the filling restorative material and the tooth tends to be very small, or the problem of poor long-term adhesion durability tends to occur. And in a series of repair work, in the case of irradiation (one-step light irradiation) which is only after finishing a certain work, the timing of irradiating visible light is easily affected by the shrinkage stress accompanying the polymerization of the filling repair material, The problem described above tends to become more prominent.

  In order to solve the above-mentioned problem, a dental filling kit containing a polymerizable monomer having an acidic group, a polymerizable monomer having no acidic group, and a polymerization initiator in both the filling restorative material and the pretreatment material (For example, refer to Patent Document 2) and dental filling that accelerates the photopolymerization of the pretreatment material by adjusting the amount of the polymerization inhibitor or the photopolymerization initiator contained in the filling restoration material or the pretreatment material A repair kit has been proposed (see, for example, Patent Document 3).

JP 2007-14579 A (Claim 1, paragraph numbers 0007, 0053, etc.) JP 2006-131621 A (Claims) JP 2007-210944 A (Claims)

  In the dental filling kit described in Patent Document 2, the filling restoration material has a composition similar to that of the pretreatment material. For this reason, it is considered that the affinity of the adhesive interface between the pretreatment material and the filling / restoring material is increased, and peeling at the adhesive interface between the pretreatment material and the filling / restoring material can be suppressed. Moreover, in the dental filling / restoration kit described in Patent Document 3, when the pretreatment material applied to the tooth surface and the filling / restoration material filled on the layer made of this pretreatment material are simultaneously irradiated with light and cured. It is considered that peeling at the adhesive interface between the pretreatment material and the filling / restoration material can be suppressed since the photopolymerization of the pretreatment material layer is accelerated.

  In consideration of the mechanism described above, the techniques disclosed in Patent Documents 2 and 3 can secure sufficient adhesive strength simply by simultaneously polymerizing the pretreatment material and the filling / restoration material by one-step light irradiation. Conceivable. However, in practice, these conventional techniques do not provide sufficient adhesive strength.

  The present invention has been made in view of the above circumstances. In dental treatment, the pretreatment material and the filling restorative material can be cured by one-step light irradiation, and the adhesive strength between the cavity inner wall and the filling restorative material can be cured. Another object of the present invention is to provide an excellent dental filling / restoration kit.

The above-mentioned subject is achieved by the following present invention.
That is, the dental filling / restoration kit of the present invention comprises (A) a filling / restoring material containing (a) an acid group-free radical polymerizable monomer, (b) a filler, and (c) a photopolymerization initiator, and (d) (B) a pretreatment material containing (e) an acidic group-containing radical polymerizable monomer and (e) water, and at least one selected from (A) a filling restoration material and (B) a pretreatment material (C1) a titanocene-based photopolymerization initiator is contained in the member, and during dental treatment, (B) a pretreatment material is applied to the cavity, and then (B) in the cavity where the pretreatment material is applied. (A) Filling with the restoration material, and then irradiating the cavity portion filled with the (A) filling restoration material with visible light. (A) Curing the filling restoration material and filling the cavity wall and the cavity. The (A) filling restoration material is adhered.

  One embodiment of the dental filling / restoration kit of the present invention is that (a) 100 parts by mass of an acid group-free radical polymerizable monomer contains (a1) an acid group-free and water-soluble radical polymerizable monomer. It is preferably contained within the range of 3 to 30 parts by mass.

  In another embodiment of the dental filling / restoration kit of the present invention, (c1) the titanocene photopolymerization initiator is preferably contained in at least (B) the pretreatment material.

  A treatment method using the dental filling / restoration kit of the present invention comprises (A) a filling / restoring material containing (a) an acid group-free radical polymerizable monomer, (b) a filler, and (c) a photopolymerization initiator. (B) a pretreatment material containing (d) an acidic group-containing radical polymerizable monomer and (e) water, and selected from (A) a filling restoration material, and (B) a pretreatment material (C1) a pretreatment material application step of applying a pretreatment material to the cavity using a dental filling and repair kit containing a titanocene photopolymerization initiator, and a pretreatment material are applied to at least one member The filling restoration material filling process into the cavity and the filling restoration material filling step, and the filling restoration material is cured by irradiating visible light to the cavity portion filled with the filling restoration material and filled in the cavity wall and cavity Curing and bonding process for bonding the filling and restoration material in this order It is performed dental treatment by Rukoto.

  ADVANTAGE OF THE INVENTION According to this invention, the dental filling restoration kit which was excellent also in the adhesive strength of a cavity inner wall and a filling restoration material while being able to harden a pretreatment material and a filling restoration material by 1 step light irradiation at the time of dental treatment. Can be provided.

  The dental filling / restoration kit of the present embodiment includes (A) a filling restoration material (hereinafter sometimes referred to as “composite resin”) and (B) a pretreatment material (hereinafter sometimes referred to as “primer”). And have. Here, when performing dental treatment using the dental filling / restoration kit of the present embodiment, first, (B) a primer is applied to the cavity (pretreatment agent application step). Next, (B) the cavity coated with the primer is filled with (A) the composite resin (filling restoration material filling step), and then (A) the cavity filled with the composite resin is irradiated with visible light. As a result, (A) the composite resin is cured and the cavity wall and the (A) composite resin filled in the cavity are bonded (curing / bonding step). Then, the treatment is completed through these three steps.

  Thus, when performing dental treatment using the dental filling / restoration kit of the present embodiment, only one step of irradiating visible light to perform the curing / bonding step only after the filling / restoring material filling step is completed. Light irradiation is employed. For this reason, compared with the conventional dental filling restoration kit which should employ | adopt 2 step light irradiation which irradiates visible light in the timing after the primer application and the composite resin filling, the dental filling of this embodiment The repair kit can reduce the burden on the patient and simplify the repair work. Note that the one-step light irradiation performed only after the filling / restoring material filling process is completed may be performed only once, but for example, as necessary while confirming the degree of cure of the composite resin. In addition, light irradiation may be performed in two or more times.

  Moreover, in the dental filling / restoration kit of this embodiment, the composite resin contains (a) an acid group-free radical polymerizable monomer, (b) a filler, and (c) a photopolymerization initiator. d) An acidic group-containing radical polymerizable monomer and (e) water. Furthermore, at least one member selected from the composite resin and the primer contains (c1) a titanocene photopolymerization initiator.

  In the dental filling / restoration kit of this embodiment, a photopolymerization initiator is used as in the conventional dental filling / restoration kit. As the photopolymerization initiator, as described above, at least a titanocene photopolymerization initiator is used. Is always used. The reason is as follows.

  First, as a photopolymerization initiator used in a conventional dental filling / restoration kit, in order to avoid coloring caused by the photopolymerization initiator of a cured composite resin, from the viewpoint of ensuring aesthetics, it is generally visible light region. Among them, a compound having a maximum absorption wavelength in a relatively short wavelength region having a wavelength of around 400 nm or higher and lower than 500 nm is used.

  However, as a result of intensive studies by the present inventor, one-step light irradiation is performed only after the composite resin is filled in the cavity using the dental filling / restoration kit using the conventional photopolymerization initiator. When implemented, it was confirmed that the following problems occurred. That is, when the above-described one-step light irradiation is performed, the two-step light irradiation is performed in two steps after the primer has been applied to the cavity and after the composite resin has been filled into the cavity. Thus, it was confirmed that the hardened composite resin dropped out of the cavity and the gap was easily formed by peeling between the hardened composite resin and the inner wall of the cavity. When the hardened composite resin falls off, re-treatment is required. When a gap is formed between the composite resin and the cavity wall, bacteria enter the gap and caries is likely to occur again. Become. For this reason, generation | occurrence | production of the drop mentioned above and formation of a clearance gap need to be suppressed.

The reason why such dropouts and gaps are easily formed is as follows.
(1) In order to ensure aesthetics, the color tone of the composite resin should be a translucent color tone like the teeth.
(2) From said (1), the light transmittance with respect to visible light of a composite resin should become low.
(3) Thus, after applying the primer to the inner wall of the cavity, when the visible resin is irradiated with the composite resin filled in the cavity, the light is absorbed or scattered by the composite resin placed in the cavity. For this reason, as the thickness of the composite resin placed in the cavity increases, the light intensity that can reach the primer layer formed on the surface of the cavity inner wall tends to be insufficient.
(4) When the intensity of light reaching the primer layer is too weak, the primer is not sufficiently cured. For this reason, the adhesive strength between the dental material constituting the inner wall of the cavity and the composite resin becomes insufficient, and as a result, the above-mentioned dropping occurs or a gap is formed.

  On the other hand, the maximum absorption wavelength of the photopolymerization initiator used in the conventional dental filling / restoration kit is a comparatively short wavelength region (wavelength from near 400 nm to at most less than 500 nm) in visible light as described above. , Light of 500 nm or more is hardly absorbed and shows no activity. Thus, the light in the short wavelength region is more easily scattered than the light in the longer wavelength region. Therefore, in the case shown in (3) above, the light intensity effective for activating the photopolymerization initiator tends to be insufficient. Therefore, the present inventor is effective in activating the photopolymerization initiator and has sufficient light intensity that can reach the primer layer to cause dropping or formation of a gap. In order to suppress this, it was considered that it is extremely effective to use a photopolymerization initiator that absorbs light in a relatively long wavelength region having a wavelength of 500 nm or more.

  Here, as a photopolymerization initiator (including a system composed of a combination of two or more compounds) that absorbs light in a relatively long wavelength region having a wavelength of 500 nm or more, various substances can be selected from known photopolymerization initiators. Is considered available. For example, a photopolymerization initiator obtained by combining an electron acceptor such as triazine or an electron donor such as a borate compound with a sensitizing dye having absorption in the same region, or a sensitizing dye and an electron acceptor in the same molecule. A photoinitiator etc. are mentioned. However, as a result of intensive studies by the present inventors, the former photopolymerization initiator is an initiation mechanism that involves electron transfer between at least two molecules, and thus is easily affected by the pH of the reaction system. In addition, the absorption wavelength of the sensitizing dye changes depending on the pH of the reaction system. For this reason, the reproducibility and stability of the photopolymerization reaction are poor, and the practicality is lacking. Further, the latter photopolymerization initiator has a problem in terms of aesthetics because the color of the photopolymerization initiator remains after curing.

  Considering the above points, as a photopolymerization initiator, it is necessary to (a) be able to absorb light in a relatively long wavelength region having a wavelength of 500 nm or more in order to suppress the occurrence of dropout and formation of gaps. In consideration of practicality as a dental material, it is also necessary that (b) the photopolymerization reaction has excellent reproducibility and stability, and (c) has characteristics that can ensure aesthetics. Considering the above (a) to (c), it is considered necessary to use at least a titanocene photopolymerization initiator as the photopolymerization initiator.

  This titanocene-based photopolymerization initiator not only absorbs light in the wavelength range of 400 to 500 nm, like the photopolymerization initiators used for conventional dental materials, but also 500 nm or more, particularly around 500 to 530 nm. More preferably, light in a relatively long wavelength region of 510 to 520 nm can also be absorbed to initiate photopolymerization of the reaction system. For this reason, only after the completion of the filling / restoring material filling process, even if the one-step light irradiation for irradiating visible light to carry out the curing / adhesion process is adopted, the inner wall of the cavity and the composite resin filled in the cavity are used. Adhesive strength can be sufficiently secured. Therefore, it can suppress that the hardened composite resin falls out of the cavity, and that a gap is formed by peeling between the hardened composite resin and the inner wall of the cavity. In addition, the titanocene photopolymerization initiator is practical because it is excellent in reproducibility and stability of the photopolymerization reaction. Furthermore, since the titanocene photopolymerization initiator absorbs light and decomposes, the color peculiar to the photopolymerization initiator disappears. Therefore, in the dental filling / restoration kit of this embodiment, at least a titanocene photopolymerization initiator is used as the photopolymerization initiator.

  As described in the above items (3) and (4), as the thickness of the composite resin placed in the cavity increases, the intensity of light that can reach the primer layer formed on the surface of the cavity inner wall increases. Considering that in this case, dropout occurs or gaps are easily formed, the dental filling / restoration kit of this embodiment using a titanocene photopolymerization initiator is caused by severe caries or the like. It is particularly suitable to be used for repair treatment of formed deep cavities (specifically, cavities having a depth of 1.0 mm or more, more notably 1.5 mm or more).

  The reason is as follows. First, in a deep cavity, the composite resin placed in the cavity becomes thick. This makes it difficult for light of sufficient intensity to reach the primer layer formed on the cavity surface, and substantially absorbs only light in the conventional relatively short wavelength region (wavelength from near 400 nm to at most less than 500 nm). Incapable photopolymerization initiators cannot absorb light sufficiently and the primer layer is harder to cure. That is, when repairing a deep cavity, when using a conventional dental filling / restoration kit using a photopolymerization initiator that absorbs only light in the relatively short wavelength region, the occurrence of dropout, The formation of the gap is likely to be extremely remarkable. On the other hand, the dental filling / restoration kit of the present embodiment uses a titanocene photopolymerization initiator that absorbs light having a longer wavelength of 500 nm or longer and hardly scattered. For this reason, even if the composite resin placed in the cavity is thick, the titanocene photopolymerization initiator can absorb sufficient light necessary for the initiation of polymerization. Therefore, in the dental filling / restoration kit of this embodiment, even if the composite resin placed in the cavity is thick, it is relatively easy to suppress the occurrence of dropout and the formation of gaps.

  The titanocene-based photopolymerization initiator may be contained in at least one member selected from the composite resin and the primer, but is preferably contained in at least the primer. The reason for this is that the titanocene polymerization initiator is activated under acidic conditions and has a feature that the ability of initiating polymerization upon absorption of light is further enhanced. In addition, a titanocene polymerization initiator is used as a primer. This is because an acidic group-containing radical polymerizable monomer that realizes the acidic condition necessary for activation is contained. Therefore, in this case, particularly excellent adhesive strength can be obtained. In addition, the molecule | numerator which comprises the primer layer formed in the cavity inner wall, and the molecule | numerator which comprises the composite resin piled up in the cavity are mutually substance-diffusion and mixed in the interface of a primer layer and a composite resin. Therefore, even if the composite resin contains a titanocene polymerization initiator, the titanocene polymerization initiator near the primer layer side interface is mixed with the acidic group-containing radical polymerizable monomer in the primer layer. And can be activated. Therefore, even when a titanocene polymerization initiator is contained only on the composite resin side, sufficient adhesive strength can be ensured. Next, the detail of the various components which comprise a composite resin and a primer is demonstrated.

(A) Acidic group-free radically polymerizable monomer A radically polymerizable monomer that does not contain an acidic group increases the mechanical strength and water resistance of the cured product. Therefore, as the radical polymerizable monomer to be blended in the composite resin, those having no acidic group are used. Such an acid group-free radical polymerizable monomer is not particularly limited, and a known radical polymerizable monomer can be used. Also, the radically polymerizable unsaturated group is not particularly limited and may be any known group. Specific examples include (meth) acryloyl groups, (meth) acryloyloxy groups, (meth) acryloylamino groups, (meth) acryloyl group derivatives such as (meth) acryloylthio groups, vinyl groups, and styryl groups. Is done. Among these, from the viewpoint of polymerizability, a (meth) acryloyloxy group and a (meth) acryloylamino group are preferable, and a (meth) acryloyloxy group is more preferable. In this specification, “(meth) acryloyl” means both acryloyl and methacryloyl, and this means “meta” in the description of functional groups having other structures. It is.

  Specific examples of such (meth) acrylate polymerizable monomers having a (meth) acryloyloxy group include methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) ) Acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, allyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, 2- (meth) acryloxyethyl propionate, 2 -Water-insoluble (meth) acrylate monomers having one polymerizable unsaturated group such as methacryloxyethyl acetoacetate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl Mono (meta) Ak Water-soluble (meth) acrylate monomers such as rate, polyethylene glycol mono (meth) acrylate, ethoxylated undecenol (meth) acrylate, nonaethylene glycol di (meth) acrylate, decaethylene glycol di (meth) acrylate, Water-soluble di (meth) acrylate monomers such as dodecaethylene glycol di (meth) acrylate, tetradecaethylene glycol di (meth) acrylate, pentaerythritol di (meth) acrylate, ethylene glycol di (meth) acrylate , Diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol Di (meth) acrylate, neopentyl glycol di (meth) acrylate, 1,3-butanediol di (meth) acrylate, 1,4-butanediol di (meth) acrylate, 1.6-hexanediol di (meth) acrylate 1,9-nonanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, neopentyl glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolmethane tri (meth) acrylate, pentaerythritol Polymerizable unsaturation such as tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, UDMA Aliphatic (meth) acrylate monomers having multiple groups, 2,2-bis ((meth) acryloxyphenyl) propane, 2,2-bis [4- (2-hydroxy-3- (meth)] Acryloxypropoxy) phenyl] propane, 2,2-bis (4- (meth) acryloxyethoxyphenyl) propane, 2,2-bis (4- (meth) acryloxypolyethoxyphenyl) propane, 2,2-bis And aromatic (meth) acrylate monomers having a plurality of polymerizable unsaturated groups such as (4- (meth) acryloxypropoxyphenyl) propane.

  Among these (meth) acrylate monomers, those having two or more radically polymerizable unsaturated groups are preferable.

  On the other hand, it is preferable that a part of the radical polymerizable monomer not containing an acidic group contains a water-soluble radical polymerizable monomer. When a part of the acid group-free radical polymerizable monomer contained in the composite resin is made water-soluble, this water-soluble acid group-free radical polymerizable monomer and the acid group-containing radical contained in the primer The acidic group of the polymerizable monomer exhibits high affinity. For this reason, the affinity between the composite resin and the primer can be increased. Furthermore, when the composite resin contains only an acid group-free radically polymerizable monomer, the primer contains an acidic group-containing radically polymerizable monomer, so the pH of the composite resin is higher than the pH of the primer. Therefore, a pH gradient is generated between the composite resin and the primer. As a result, at the interface between the composite resin and the primer, movement of the radical polymerizable monomer to both occurs, and the two layers are fused. Therefore, not only the affinity between the composite resin and the primer is improved, but also when the titanocene polymerization initiator described later is added only to the composite resin, the acidic groups in the primer are obtained by the fusion of both layers. The titanocene polymerization initiator can be easily activated by the contained polymerizable monomer.

  Here, in this specification, “water-soluble” means that the solubility in water at 23 ° C. is 1 g / L or more. A more preferable solubility is 100 g / L or more. Examples of such an acid group-free and water-soluble radical polymerizable monomer include any water-soluble (meth) acrylate monomers among the acid group-free (meth) acrylate monomers. Can be used without restriction. Specifically, a (meth) acrylate monomer having a hydroxyl group such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate, polyethylene glycol di (meth) acrylate, methoxypolyethylene glycol methacrylate And methacrylate having an ethylene glycol chain in the molecule. These can be used alone or in admixture of two or more.

  Among the above-mentioned acidic group-free and water-soluble radical polymerizable monomers, it is preferable to use a polyfunctional radical polymerizable monomer. Specifically, polyfunctional radical polymerizable properties such as polyethylene glycol di (meth) acrylate rather than monofunctional radical polymerizable monomers such as 2-hydroxyethyl (meth) acrylate or 3-hydroxypropyl (meth) acrylate. It is preferable to use a monomer. By using a polyfunctional radically polymerizable monomer, the adhesive strength between the composite resin and the tooth, particularly the dentin can be improved via the primer.

  Examples of suitable non-acidic group-containing and water-soluble polyfunctional radical polymerizable monomers include polyethylene glycol dimethacrylate having a polymerization degree of 9 to 30 and polyethoxylated bisphenols having a total polymerization degree of polyethylene glycol moieties of 20 to 50. Methacrylic acid adducts of dimethacrylate, mono- or diethylene glycol diglycidyl ether, polyethylene glycol dimethacrylate and polyethoxylated bisphenol A dimethacrylate are more preferred, and polyethylene glycol dimethacrylate is most preferred.

  Further, the blending ratio of the above-mentioned acidic group-free and water-soluble radical polymerizable monomer in 100 parts by mass of the acidic group-free radical polymerizable monomer contained in the composite resin is not particularly limited, The range of 3-30 mass parts is preferable, and the range of 5-20 mass parts is more preferable. By setting the blending ratio in the range of 3 to 30 parts by mass, the adhesive strength of the composite resin to the dentin can be further improved through the primer. Therefore, it is possible to further effectively suppress the formation of a gap by preventing the cured composite resin from falling out of the cavity and preventing the cured composite resin from separating from the cavity inner wall. The specific reason why such an effect is obtained is as follows. When the mixing ratio of the above acidic group-free and water-soluble radical polymerizable monomer in 100 parts by mass of the acidic group-free radical polymerizable monomer is 3 parts by mass or more, the cavity is filled. The transfer of the titanocene photopolymerization initiator is more likely to occur between the composite resin and the primer layer formed on the inner surface of the cavity. For this reason, the adhesive strength between the cured composite resin and the cavity inner wall can be further increased. In addition to this, when the blending ratio is 30 parts by mass or less, the water absorption that causes a decrease in the adhesive strength can be lowered.

(B) Filler A filler is added to the composite resin in order to improve the strength of the composite resin and suppress shrinkage during polymerization. Further, the viscosity of the composite resin can be adjusted to a range suitable for the restoration work by adjusting the amount of filler added. The addition amount of the filler can be appropriately selected according to the above-described purpose, but is preferably in the range of 80 to 2000 parts by mass with respect to 100 parts by mass of the acidic group-free radical polymerizable monomer, The range of 500 parts by mass is more preferable, and the range of 120 to 230 parts by mass is most preferable. By making the addition amount of the filler 80 parts by mass or more, when the composite resin is cured, the strength of the cured product can be made more sufficient. Moreover, since it can suppress that the viscosity of a composite resin becomes high too much by making the addition amount of a filler into 2000 mass parts or less, the workability | operativity at the time of filling a composite resin in a cavity can be improved further.

  As the filler, at least one selected from an inorganic filler, an organic filler, and an inorganic-organic composite filler can be selected. Known organic fillers can be appropriately selected. For example, polymethyl (meth) acrylate, polyethyl (meth) acrylate, methyl (meth) acrylate / ethyl (meth) acrylate copolymer, methyl (meth) acrylate / butyl ( Non-crosslinkable polymer such as (meth) acrylate copolymer or methyl (meth) acrylate / styrene copolymer, methyl (meth) acrylate / ethylene glycol di (meth) acrylate copolymer, methyl (meth) acrylate / triethylene A (meth) acrylate polymer such as a glycol di (meth) acrylate copolymer or a copolymer of methyl (meth) acrylate and a butadiene monomer can be used. A mixture of two or more of these can also be used.

  As the kind of the inorganic filler, known ones can be appropriately selected. For example, periodic groups I, II, III, IV, transition metals or oxides thereof, halides, sulfates or mixtures thereof, or It can be selected from complex salts and the like.

  Specific examples of typical inorganic fillers include quartz, silica, alumina, silica titania, silica zirconia, lanthanum glass, barium glass, and strontium glass. Further, cation-eluting fillers such as hydroxides such as calcium hydroxide and strontium hydroxide, and oxides such as zinc oxide, silicate glass, and fluoroaluminosilicate glass are also preferable.

  Among the above-mentioned inorganic fillers, inorganic fillers composed of metal oxide particles such as silica, alumina or zirconia, or composite metal oxide particles such as silica-titania or silica-zirconia can be suitably used. Moreover, these can also be used in combination of 2 or more types.

  In addition, as the inorganic-organic composite filler, for example, a granular monomer can be used by adding a polymerizable monomer to the inorganic filler in advance, forming a paste, polymerizing, and then pulverizing. As such an organic-inorganic composite filler, for example, TMPT filler (filler pulverized after mixing and polymerizing trimethylolpropane methacrylate and silica filler) and the like can be used.

  The above inorganic filler or inorganic-organic composite filler can be treated with a surface treating agent typified by a silane coupling agent to improve the affinity and dispersibility for the polymerizable monomer contained in the composite resin, etc. Moreover, the mechanical strength and water resistance of the cured product obtained by curing the composite resin can be improved. The surface treatment agent and the surface treatment method are not particularly limited, and any known method can be employed without limitation. Examples of the silane coupling agent used for the surface treatment of the inorganic filler include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrichlorosilane, vinyltriethoxysilane, vinyltris (β -Methoxyethoxy) silane, [gamma] -methacryloyloxypropyltrimethoxysilane, [gamma] -chloropropyltrimethoxysilane, [gamma] -glycidoxypropyltrimethoxysilane, hexamethyldisilazane and the like are preferably used. In addition to the silane coupling agent, a titanate coupling agent, an aluminate coupling agent, a method using a zirco-aluminate coupling agent, or graft polymerization of the polymerizable monomer on the filler particle surface. Depending on the method, the surface treatment of the inorganic filler or the inorganic-organic composite filler can be performed.

  The refractive index of the filler described above is not particularly limited, but those having a refractive index in the range of 1.4 to 2.2 suitable for general dental use are preferably used. Further, the shape and particle size of the filler are not particularly limited and can be appropriately selected. However, the average particle size is usually preferably 0.001 to 100 μm, and more preferably 0.001 to 10 μm. Further, from the viewpoint of improving the surface smoothness of the cured product obtained by curing the composite resin, it is particularly preferable to use a spherical inorganic filler.

  In addition, a filler can also be added to a primer as needed. In this case, the adhesive strength can be further increased, and the strength of the primer layer can be further improved. In this case, it is preferable to use fluoroaluminosilicate glass as the filler. 0.5-30 mass parts is preferable with respect to 100 mass parts of all radical polymerizable monomers contained in a primer, and the compounding quantity of a filler is 1-30 mass parts.

(C) Photopolymerization initiator In the dental filling / restoration kit of this embodiment, it is necessary that a titanocene photopolymerization initiator is used as the photopolymerization initiator, but other than the titanocene system is used as necessary. A photopolymerization initiator (non-titanocene photopolymerization initiator) may be used in combination. The photopolymerization initiator must be contained in the composite resin regardless of whether it is titanocene or non-titanocene.
Hereinafter, (c1) a titanocene photopolymerization initiator and (c2) a non-titanocene photopolymerization initiator will be described separately. Also, amine compounds and photoacid generators will be described as representative substances that can be used in combination with these photopolymerization initiators as necessary.

(C1) Titanocene-based photopolymerization initiator The titanocene-based photopolymerization initiator is not particularly limited as long as it is a compound that can generate an active radical when irradiated with light, and a known compound can be used. JP-A-59-152396, JP-A-61-151197, JP-A-63-41483, JP-A-2-249, JP-A-2-291, JP-A-3-27393 Known compounds described in JP-A-3-12403 and JP-A-6-41170 can be selected and used. Especially, it is preferable to use the compound shown by following General formula (1) from a viewpoint from which high photosensitivity is acquired.
· General formula _{(1) Cp 2 Ti (IV} ) R 1 R 2
However, in the general formula (1), Ti (IV) is a tetravalent titanium atom, Cp is a cyclopentadienyl group, and R ¹ and R ² may be independently partially substituted. Good alkyl group, aryl group, chlorine atom or bromine atom.

  Specific examples of the titanocene compound include di-cyclopentadienyl-Ti-di-chloride, di-cyclopentadienyl-Ti-bis-phenyl, and di-cyclopentadienyl-Ti-bis-2,3. 4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti- Bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis- 2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl -T -Bis-2,3,5,6-tetrafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, bis (cyclopentadienyl ) -Bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium and the like. Among these, bis (cyclopentadienyl) -bis (2,6-difluoro-3- (pyr-1-yl) phenyl) titanium for reasons such as availability, high polymerization activity, and storage stability Is particularly preferred.

  These titanocene photopolymerization initiators are activated by the acid component as described above, thereby exhibiting photopolymerization ability. Not only when blended with a primer containing an acidic group-containing polymerizable monomer, but also when blended with a composite resin, the acidic group-containing polymerizable monomer in the primer at the contact portion of the composite resin and the primer or its unification portion It is activated by the body. The titanocene-based photopolymerization initiator is particularly preferably blended in at least the primer from the viewpoint that higher adhesive strength can be obtained. The titanocene photopolymerization initiator is most preferably blended only in the primer because there is little fear of discoloration of the cured product of the composite resin. When a titanocene polymerization initiator is blended in the primer, the blending amount of the titanocene polymerization initiator is in the range of 0.001 to 10 parts by mass with respect to 100 parts by mass of the total polymerizable monomer contained in the primer. The inside is preferable, and the range of 0.01 to 5 parts by mass is more preferable. Moreover, when a titanocene polymerization initiator is blended in the composite resin, the blending amount of the titanocene polymerization initiator is 0.001 to 10 parts with respect to 100 parts by mass of the total polymerizable monomer contained in the composite resin. The inside of the range of a mass part is preferable, and the inside of the range of 0.01-5 mass parts is more preferable.

(C2) Non-Titanocene Photopolymerization Initiator A non-titanocene photopolymerization initiator that can be used together with a titanocene photopolymerization initiator as needed is a compound that can generate an active radical when irradiated with light. Any known compound can be used without particular limitation. However, there is no particular limitation as long as it generates a radical capable of initiating polymerization by light irradiation. In particular, among visible light regions often used as an irradiation wavelength of a dental irradiator, a photopolymerization initiator that is particularly active for light in the wavelength region of 380 to 500 nm is preferable. Examples of such photodeposition initiators include α-ketocarbonyl compounds and acyl phosphine oxide compounds.

  Examples of the α-ketocarbonyl compound include α-diketone, α-ketoaldehyde, and α-ketocarboxylic acid ester. Specifically, diacetyl, 2,3-pentadione, 2,3-hexadione, benzyl, 4,4′-dimethoxybenzyl, 4,4′-diethoxybenzyl, 4,4′-oxybenzyl, 4,4 ′ Α-diketones such as dichlorobenzyl, 4,4′-nitrobenzyl, α-naphthyl, β-naphthyl, camphorquinone, camphorquinonesulfonic acid ester, camphorquinonecarboxylic acid ester or 2,2′-cyclohexanedione, methyl Examples include α-ketoaldehydes such as glioxal or phenylglyoxal, α-ketocarboxylic acid esters such as methyl pyruvate, ethyl benzoylformate, methyl phenylpyruvate or butyl phenylpyruvate.

Among these α-ketocarbonyl compounds, α-diketone is preferably used from the viewpoint of stability and the like, and camphorquinone is particularly preferable. Examples of the acylphosphine oxide compound include benzoyldimethoxyphosphine oxide, benzoylethoxyphenylphosphine oxide, benzoyldiphenylphosphine oxide, 2-methylbenzoyldiphenylphosphineoxy or 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2, 6-dimethoxybenzoyl) -2,4,4-trimethylpentylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like.

  Among the above-mentioned non-titanocene photopolymerization initiators, α-ketocarbonyl compounds are more preferable from the viewpoint that polymerization initiation is slower than that of titanocene photopolymerization initiators. In addition, the blending amount of the non-titanocene photopolymerization initiator is not particularly limited, but is preferably 0.001 to 10 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers contained in the composite resin, 0.01 to A range of 5 parts by mass is more preferable. Such a non-titanocene photopolymerization initiator may be added to the primer. Thus, also when making it mix | blend with a primer, the compounding quantity has the preferable inside of the range of 0.001-10 mass parts with respect to 100 mass parts of all the polymerizable monomers contained in a primer, 0.01-5 More preferably within the range of parts by mass. These non-titanocene photopolymerization initiators can be used in combination of two or more.

(Amine compound)
In order to improve the polymerization initiation effect of the photopolymerization initiator, particularly the non-titanocene photopolymerization initiator, or to promote the polymerization reaction of the reaction system, an amine compound may be used in combination. In particular, when an α-ketocarbonyl compound is used as a non-titanocene photopolymerization initiator, it is preferable to use a reducing compound such as an amine compound in combination in order to improve the polymerization initiation effect.

  As the amine compound, known amine compounds can be used, but tertiary amines are particularly preferably used. Specific examples of such tertiary amines include 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, p-dimethylaminobenzoic acid ethyl ester, p-dimethylaminobenzoic acid amyl ester, N, N-dimethylanthranilic acid methyl ester, N , N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethyla Nophenethyl alcohol, p-dimethylaminostilpene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tri Butylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl methacrylate N, N-diethylaminoethyl methacrylate or 2,2 ′-(n-butylimino) diethanol.

  Among these, the neutralization reaction with the acidic group of the acidic group-containing radical polymerizable monomer contained in the primer described later hardly occurs, and from the viewpoint of relatively low basicity, the corresponding ammonium ion in 25 ° C. water An amine compound having a pKa value of 9 or less is preferably used, and an amine compound having a pKa value of 7.0 to 0.5 is particularly preferably used. Such an amine compound having low basicity is generally an aromatic tertiary amine, and by using at least one of those exemplified above, the contact interface and contact between the primer and the composite resin described later are used. The initiating effect and the polymerization promoting effect of the photopolymerization initiator in both of the vicinity of the interface can be further enhanced. Moreover, when using in combination with the photo-acid generator mentioned later, it is preferable to use combining two types, an aliphatic tertiary amine and an aromatic tertiary amine. In this case, the composite resin can be cured by light irradiation for a shorter time. As a compounding quantity of these amine compounds, the range of 0.1-10 times of the photoinitiator to be used is preferable, and the range of 0.3-5 times is more preferable.

(Photoacid generator)
If necessary, a photoacid generator can be added to the composite resin together with the photopolymerization initiator. In this case, the polymerization activity of the photopolymerization initiator can be further increased. As the photoacid generator, those that generate Bronsted acid or Lewis acid by light irradiation are preferably used.

  Examples of such photoacid generators include halomethyl group-substituted s-triazine derivatives, diaryliodonium salt compounds, sulfonium salt compounds, and pyridinium salt compounds. Among these photoacid generators, halomethyl group-substituted s-triazine derivatives or diaryliodonium salt compounds are preferred.

  Examples of the halomethyl group-substituted s-triazine derivatives include 2,4,6-tris (trichloromethyl) -s-triazine, 2,4,6-tris (tribromomethyl) -s-triazine, 2-methyl- 4,6-bis (trichloromethyl) -s-triazine, 2-methyl-4,6-bis (tribromomethyl) -s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-methylthiophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- ( p-chlorophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (2,4-dichlorophenyl) -4,6-bis (trichloromethyl)- -Triazine, 2- (p-bromophenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (P-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2-n-propyl-4,6-bis (trichloromethyl) -s-triazine, 2- (α, α, β- Trichloroethyl) -4,6-bis (trichloromethyl) -s-triazine, 2-styryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxystyryl) -4,6-bis (Trichloromethyl) -s-triazine, 2- (o-methoxystyryl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-butoxystyryl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -s-triazine, 2- (3,4,5-trimethoxystyryl) -4,6 -Bis (trichloromethyl) -s-triazine and the like can be mentioned.

  Examples of the diaryliodonium salt compound include diphenyliodonium, bis (p-chlorophenyl) iodonium, ditolyliodonium, bis (p-tert-butylphenyl) iodonium, bis (m-nitrophenyl) iodonium, p-tert- Chloride, bromide, tetrafluoroborate, hexafluorophosphate, hexafluoroarsenate, hexabutylphenylphenyliodonium, methoxyphenylphenyliodonium, p-octyloxyphenylphenyliodonium, 4-isopropylphenyl-4-methylphenyliodonium, etc. Examples include fluoroantimonate, tetrakis (pentafluorophenyl) borate, trifluoromethanesulfonate, etc. Tetrafluoroborate in terms of, hexafluorophosphate, hexafluoroarsenate, hexafluoroantimonate, trifluoromethane sulfonate, tetrakis (pentafluorophenyl) borate salts are preferably used.

  You may use the above-mentioned photo-acid generator 1 type or in mixture of 2 or more types. The blending amount of these photoacid generators is not particularly limited as long as the effect is exhibited, but is not more than 0.1 parts by mass with respect to 100 parts by mass of the non-acid group-containing radical polymerizable monomer contained in the composite resin. 001 to 12 parts by mass is preferable, and 0.005 to 6 parts by mass is more preferable.

(D) Acid group-containing radical polymerizable monomer The acid group-containing radical polymerizable monomer is highly permeable to the tooth and has a decalcifying action, and has an adhesive force between the filling restorative material and the tooth. Since it has an enhancing effect, it is blended in the primer. Such an acidic group-containing radical polymerizable monomer is not particularly limited as long as it is a compound having at least one acidic group and one radical polymerizable unsaturated group in one molecule, and a known compound can be used. .

  Examples of the acidic group contained in the acidic group-containing radical polymerizable monomer include a carboxyl group, a sulfo group, a phosphone group, a phosphoric acid monoester group, and a phosphoric acid diester group. Among them, a carboxyl group, a phosphoric acid monoester group, or a phosphoric acid diester group is more preferable as the acidic group having high adhesiveness to the tooth. Furthermore, for the purpose of activating the movement of the material between the composite resin and the primer, in order to make the pH gradient between the composite resin and the primer more steep, the acidic group-containing radical polymerizable monomer contained in the primer The acidic group of the body is most preferably strongly acidic. As such a strongly acidic acidic group, a phosphoric acid monoester group or a phosphoric acid diester group is most preferable.

  Specific examples of the acidic group-containing radical polymerizable monomer include, for example, 2- (meth) acryloyloxyethyl hydrogen maleate, 2- (meth) acryloyloxyethyl hydrogen succinate, 2- (meth) Acroyloxyethyl hydrogen phthalate, 11- (meth) acryloyloxyethyl-1,1-undecanedicarboxylic acid, 2- (meth) acryloyloxyethyl-3′-methacryloyloxy-2 ′-(3,4 Carboxyl such as -dicarboxybenzoyloxy) propyl succinate, 4- (2- (meth) acryloyloxyethyl) trimellitate anhydride, N- (meth) acryloylglycine, N- (meth) acryloyl aspartic acid Acid acidic radical polymerizable monomers; 2- (meth) acryloyloxyethyl pheny Hydrogen phosphate, bis ((meth) acryloyloxyethyl) hydrogen phosphate, (meth) acryloyloxyethyl dihydrogen phosphate, 10- (meth) acryloyloxydecyl dihydrogen phosphate, 6- (meth) acryloyloxyhexyl Phosphoric acid group-containing radical polymerizable monomers such as dihydrogen phosphate; Phosphonic acid group-containing radical polymerizable monomers such as vinylphosphonic acid; Styrenesulfonic acid, 3-sulfopropane (meth) acrylate, Examples include radically polymerizable monomers containing sulfonic acid acidic groups such as 2- (meth) acrylamide-2-methylpropanesulfonic acid. Moreover, these acidic group-containing radically polymerizable monomers may be used in combination of two or more if necessary.

  In addition to the acidic group-containing radical polymerizable monomer, the primer may contain the acid group-free monomer described above. In this case, the blending ratio of the acidic group-containing radical polymerizable monomer in 100 parts by mass of the total radical polymerizable monomer contained in the primer is preferably 10 parts by mass or more, and more preferably 30 parts by mass or more. Here, as the acidic group-free polymerizable monomer, the above-mentioned acidic group-free and water-soluble radical polymerizable monomer, or acidic group-free and water-insoluble radical polymerizable monomer are used. be able to. In particular, it is preferable that the primer contains an acid group-free and water-soluble radical polymerizable monomer. In this case, it is possible to improve the penetrability of the primer into the tooth and the compatibility of the non-acidic group-free and water-insoluble radical polymerizable monomer with water.

  On the other hand, when an acid group-free and water-insoluble radical polymerizable monomer is contained in the primer, the strength of the cured primer layer can be improved. However, at the same time, it may cause phase separation between the non-acidic group-containing and water-insoluble radical polymerizable monomer and water, which may hinder the entry of the polymerization initiator from the composite resin. For this reason, the blending ratio of the acidic group-free and water-insoluble radical polymerizable monomer contained in the primer is preferably 5 parts by mass or less in 100 parts by mass of the total radical polymerizable monomer in the primer. When the blending ratio is more than 5 parts by mass, it is necessary to use an acid group-free and water-insoluble radical polymerizable monomer together with an acid group-free and water-soluble radical polymerizable monomer. preferable.

(E) Water The water contained in the primer has a function of assisting demineralization of the tooth by the acidic group-containing radical polymerizable monomer. The amount of water in the primer is preferably 5 to 150 parts by mass and more preferably 15 to 110 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers contained in the primer.

(Hydrophilic organic solvent)
Moreover, in order to improve the workability | operativity at the time of apply | coating a primer to a cavity inner wall, the primer may contain the hydrophilic organic solvent which has fluidity | liquidity. For example, a solvent such as acetone, ethanol or isopropyl alcohol may be included. In particular, from the viewpoint of easy drying treatment, as the hydrophilic organic solvent, a solvent having high volatility and low toxicity such as ethanol or isopropyl alcohol is preferable.

  The content of the hydrophilic organic solvent is preferably 20 to 400 parts by mass and more preferably 50 to 300 parts by mass with respect to 100 parts by mass of all radical polymerizable monomers contained in the primer.

(Other additives)
Various additives can be blended in the primer and composite resin constituting the dental filling / restoration kit of the present embodiment, if necessary. For example, a coloring material such as a pigment or a fluorescent pigment can be blended to match the color tone of a tooth or gum. Further, an ultraviolet absorber may be added to prevent discoloration with respect to ultraviolet rays. Furthermore, it is also preferable to add a polymerization inhibitor in order to improve storage stability. Moreover, you may add a stabilizer or a disinfectant.

(Dental treatment method)
When performing dental treatment using the dental filling / restoration kit of the present embodiment, the above-described pretreatment agent application step, filling / restoring material filling step, and curing / adhesion step are performed. Here, in the pretreatment agent application step, the method for applying the primer to the cavity is not particularly limited, but generally, an application method using a brush, a spatula, a brush, a roller, or the like, or an application method for spraying the cavity is adopted. be able to. Further, the primer may be applied in a plurality of times. In addition, when an etching agent is used separately, the primer can be applied after the etching agent is applied.

  After applying the primer to the cavity, it is preferable to perform a drying treatment in order to evaporate a solvent component such as water contained in the applied primer. As a drying method, for example, there are natural drying, heat drying, air drying, reduced pressure drying, or a combination of these drying methods. In consideration of drying in the oral cavity, an air gun that discharges dry air is used. It is preferable to blow dry.

  Next, a filling restoration material filling step is performed in which the composite resin is placed on the dried primer to fill the cavity. At this time, the filling method of the composite resin is not particularly limited, but in general, the composite resin is placed with a spatula or the like and arranged in the same shape as an actual tooth. Finally, by irradiating the cavity portion (filling restoration portion) filled with the composite resin with visible light with a dental light irradiator including light having a wavelength range of 500 nm or more, particularly 500 to 530 nm, the filling restoration portion is applied. Cure the existing composite resin. At this time, since the primer is also cured, the cavity wall and the composite resin filled in the cavity can be bonded. In addition, when a non-titanocene photopolymerization initiator is blended in the composite resin or primer, these are usually active by absorbing light in a relatively short wavelength region (wavelength near 400 nm to less than 500 nm) as described above. Therefore, the visible light irradiated by the dental light irradiator needs to include light in the short wavelength region.

(Package presentation)
In addition, the packaging form of the dental filling / restoration kit of the present embodiment is not particularly limited. However, since the operation is simpler, each is packaged in the same container, and 1 paste of the composite resin and 1 More preferably, it is packaged as a liquid primer.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated concretely, this invention is not restrict | limited to these Examples.

(1) Used compounds and their abbreviations [acid group-free radical polymerizable monomer]
“BisGMA”: 2,2′-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane “3G”: triethylene glycol dimethacrylate

[Acid-group-free and water-soluble radical polymerizable monomer]
“HEMA”: 2-hydroxyethyl methacrylate “14G”: polyethylene glycol (degree of polymerization 14) dimethacrylate (compound 1 shown below)

[Radical polymerizable monomer containing acidic group]
“PM”: Mixture “MDP” in which 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate are mixed at a mass ratio of 2: 1 “MDP”: 10-methacryloxydecyl dihydro Genfate

[Non-titanocene photopolymerization initiator]
“CQ”: camphorquinone “BTPO”: bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide

[Titanocene photopolymerization initiator]
“CPT”: Compound 2 shown below

[Tertiary amine]
“DMBE”: ethyl p-N, N-dimethylaminobenzoate

[Filler]
“F1”: spherical silica-zirconia (average particle size 0.4 μm) hydrophobized with γ-methacryloyloxypropyltrimethoxysilane, and spherical silica-titania (average particle size 0.08 μm) γ-methacryloyloxypropyl Mixture “F2” obtained by mixing with hydrophobized trimethoxysilane at a mass ratio of 70:30: Fumed silica (average particle size 0.02 μm) surface-treated with methyltrichlorosilane “MF”: Fluoro Aluminosilicate glass powder (Tokuso Ionomer, Tokuyama Co., Ltd.) pulverized to a mean particle size of 0.5 μm using a wet continuous ball mill (New My Mill, Mitsui Mining Co., Ltd.)

[Volatile water-soluble organic solvent]
IPA: isopropyl alcohol

[Polymerization inhibitor]
“HQME”: Hydroquinone monomethyl ether “BHT”: 2,6-di-t-butyl-p-cresol

(2) Method for measuring adhesion strength of 1.5 mm-thick composite resin Cattle were slaughtered, and the bovine front teeth were removed within 24 hours after slaughter. The extracted bovine anterior teeth were polished with # 600 emery paper under water injection, and two kinds of bovine anterior teeth samples were prepared by carving out the enamel and dentin planes so as to be parallel and flat to the lip surface. Next, each of these two kinds of bovine front teeth samples was dried by blowing compressed air on the cut surface for about 10 seconds. Next, a double-sided tape having a hole with a diameter of 3 mm is attached to this plane, and a paraffin wax having a hole with a thickness of 1.5 mm and a diameter of 8 mm is further attached to the center of the hole of the double-sided tape previously attached. A simulated cavity was formed by fixing the center of the paraffin wax hole together. A primer was applied to the simulated cavity and left for 20 seconds, and then dried by blowing compressed air for about 10 seconds. Furthermore, the composite resin is filled thereon, and visible light is irradiated for 30 seconds with a visible light irradiator (Tokuso Power Light, irradiation wavelength range of 380 to 530 nm, manufactured by Tokuyama Corporation). An adhesion test piece of 5 mm was produced.

  After immersing the above-mentioned adhesion test piece in water at 37 ° C. for 24 hours, using a universal testing machine (Autograph, manufactured by Shimadzu Corporation), pulling at a crosshead speed of 2 mm / min, the tooth and the composite resin Tensile bond strength was measured. The tensile bond strength between the tooth and the composite resin was measured for each of four test pieces for each example or each comparative example. The average value of the four times of tensile adhesive strength was used as the adhesive strength of the corresponding Example or Comparative Example.

(3) Color tone change before and after curing of composite resin In the method for measuring the adhesive strength of the 1.5 mm thick composite resin, the color tone is evaluated visually before and after the composite resin filled in the simulated cavity is irradiated with visible light and cured. did.

(4) Preparation of composite resin To 6.0 g of BisGMA, 4.0 g of 3G, 0.05 g of CQ, 0.10 g of DMBE, 0.01 g of HQME, and 0.003 g of BHT were added. The mixture was stirred until it became uniform to obtain a matrix. The obtained matrix was mixed with 16.3 g of F1 in an agate mortar and degassed under vacuum to obtain a photocurable composite resin CR1 having a filler filling rate of 61.7% by volume. Other composite resins (CR2 to CR9) were also produced in the same procedure as the composite resin CR1 except that the composition was as shown in Table 1.

(5) Preparation of primer Stir 5.0 g of PM, 5.0 g of HEMA, 0.1 g of CPT, 0.003 g of BHT, and 10.0 g of distilled water until uniform in the dark. P1 was obtained. Other primers (P2 to P11) were prepared in the same procedure as the primer P1 except that the composition was as shown in Table 2.

(Examples 1-18)
An adhesion test was performed by combining the composite resin and the primer so that at least one of the composite resin and the primer contained a titanocene photopolymerization initiator. In all cases, both enamel and dentin showed good adhesive strength. The results are shown in Table 3.

(Comparative Examples 1-7)
An adhesion test was performed by combining the composite resin and the primer so that neither the composite resin nor the primer contained a titanocene photopolymerization initiator. In all cases, both enamel and dentin showed low adhesive strength. The results are shown in Table 4.

Claims (3)

(A) an acid group-free radical polymerizable monomer, (b) a filler and (c) a photopolymerization initiator (A) a filling restoration material;
(D) an acid group-containing radical polymerizable monomer and (e) a pretreatment material containing water;
Have
(C1) a titanocene-based photopolymerization initiator is included in at least one member selected from (A) the filling restoration material and (B) the pretreatment material,
In the dental treatment, the (B) pretreatment material is applied to the cavity, and then the (B) filling restoration material is filled in the cavity where the (B) pretreatment material is applied. (A) The cavity part filled with the filling and repairing material is irradiated with visible light to cure the filling and repairing material (A) and bond the cavity wall and the filling and repairing material filled in the cavity (A). A dental filling / restoration kit. The dental filling and repair kit according to claim 1,
In (a) 100 parts by mass of the radical polymerizable monomer not containing an acidic group, (a1) the acidic group-free and water-soluble radical polymerizable monomer is contained within a range of 3 to 30 parts by mass. Characteristic dental filling and repair kit. The dental filling and repair kit according to claim 1 or 2,
The dental filling / restoration kit, wherein the (c1) titanocene photopolymerization initiator is contained in at least the pretreatment material (B).