JP6244207B2 - Dental adhesive composition - Google Patents

Description

  TECHNICAL FIELD The present invention relates to a dental composition used in the field of dentistry, a dental restoration material composed of a composite resin and the like, and a dental adhesive for adhering a tooth substance, and a dental adhesive composite resin.

  In the case of a tooth cavity damaged by caries or the like, if it is a relatively small cavity in the first mid-stage, restoration by a composite resin is performed from the viewpoint of aesthetics, simplicity of operation, and quickness. On the other hand, for repairing a relatively large cavity, a restoration using a prosthesis made of metal, ceramics, or dental resin is performed.

  Since these dental restorations such as composite resins and prostheses do not have adhesiveness to the tooth, an adhesive made of a polymerizable monomer composition is used to adhere to the tooth. . Thus, the polymerizable monomer used in such an adhesive is usually composed mainly of a methacrylate monomer, but its adhesive strength to the tooth is not sufficient. Therefore, for example, for bonding to a composite resin, it often does not have an adhesive strength enough to overcome internal stress generated upon curing, that is, tensile stress generated at the interface between the tooth substance and the composite resin. . Furthermore, the adhesive strength is often not sufficient to withstand the force applied by occlusion.

  Therefore, in order to improve the adhesive strength of these adhesives, the following pretreatment is performed on the tooth surface during use. That is, 1) Apply a pretreatment material for etching treatment on hard tooth (mainly enamel mainly composed of hydroxyapatite), and 2) As a penetration enhancer into the tooth called a primer The pretreatment material is applied.

  Under these circumstances, dental adhesives containing a polymerizable monomer having adhesiveness to the tooth have been developed for the purpose of higher adhesive strength and reduction of the complicated operations. That is, as at least a part of the polymerizable monomer component, a polymerizable monomer having an acidic group such as a phosphate group or a carboxylic acid group having a high affinity for a tooth (hydroxyapatite or collagen) ( It is an adhesive containing an acidic group-containing polymerizable monomer (see, for example, Patent Document 1 and Patent Document 2).

  In addition, it has been reported that phosphoric acid monoester is used as a polymerizable monomer containing an acidic group, and this is used in the form of a metal salt such as calcium to further improve the adhesive strength (patent) Reference 3). In addition, some adhesives and primers containing an acidic group-containing polymerizable monomer and water are known to further increase the adhesive strength by further adding a polyvalent metal ion-eluting filler. (For example, Patent Documents 4 to 8). Here, the polyvalent metal ion-eluting filler means a filler that elutes polyvalent metal ions such as alkaline earth metal ions and second and third element ions under an acidic solution such as fluoroaluminosilicate glass. . That is, in such an adhesive containing a polyvalent metal ion-eluting filler, an acidic group-containing polymerizable monomer, and water, the polyvalent metal ions are eluted from the polyvalent metal ion-eluting filler, and the acidic group-containing polymerization is performed. Since the ionic monomer forms a salt with the acidic group to form a dense ionic crosslink, the mechanical strength of the cured product is improved.

  In recent years, attempts have been made to incorporate Group 4 element compounds in place of the polyvalent metal ion-eluting fillers in order to develop and form such ion bridges (Patent Documents 9 and 10). That is, a Group 4 element ion is generated from a Group 4 element compound, which is a tetravalent ion, so that the ionic cross-links are more densely compared to alkaline earth metal ions and second and third element ions. Can be formed.

JP-A-52-113089 JP 58-21687 Japanese Patent Laid-Open No. 53-113843 JP-A-9-263604 Japanese Patent Laid-Open No. 10-236912 JP 2001-72523 A JP 2000-86421 A JP 2008-201726 A International Publication No. 2010/010901 Pamphlet JP 2013-189399 A

  An adhesive composition (adhesive or primer) containing an acidic group-containing polymerizable monomer has high adhesive strength, and when it contains water, it also has a sufficient decalcification function. Useful. However, as described above, since extremely strong adhesive strength is required between the tooth and the dental restoration, the adhesive strength is not yet sufficient, and further improvement is required.

  In this regard, the adhesive using the calcium salt of the above-mentioned acidic group-containing polymerizable monomer and the adhesive containing the polyvalent metal ion-eluting filler are useful because the adhesive strength is significantly improved. It was not yet satisfactory, and the adhesive was easily gelled and stored poorly when stored for a long period of time without being immediately cured. Therefore, in order to suppress gelation, when a polymerization inhibitor was blended with the adhesive, the adhesive strength decreased at a blending amount of a certain amount or more and still gelled easily at a blending amount of a certain amount or less.

  In a dental composition, a polymerization inhibitor may be blended for the purpose of preventing gelation based on polymerization of a polymerizable monomer during storage. In this case, when the amount of the polymerization inhibitor is increased, the storage stability is improved, but when cured at the time of use, the polymerization of the polymerizable monomer is inhibited, so that the strength and adhesive strength of the cured product tend to be inferior. That is, when a polymerization inhibitor is added to the dental adhesive composition, the storage stability is generally increased, but the adhesiveness is generally decreased. In consideration of such matters, generally, the amount of the polymerization inhibitor is often about 0.1 to 0.3 with respect to 100 parts by mass of the polymerizable monomer.

  On the other hand, the adhesive containing Group 4 element ions exhibits high adhesiveness. The reason why the adhesion strength is greatly increased by the incorporation of the Group 4 element ions in this way is that the acidic group of the acidic group-containing polymerizable monomer and the Group 4 element ions form a strong ionic bond. When a composition containing an ionic bond is polymerized and cured, in addition to the expression of the adhesive strength due to polymerization, the adhesive strength due to ionic crosslinking of the polymer chains generated by the polymerization of this ionic bond is synergistically combined to produce an adhesive strength. Is considered to be further improved.

  Therefore, the present inventors have examined in more detail an adhesive comprising an acidic group-containing polymerizable monomer and a Group 4 element ion. Then, the adhesive containing the acidic group-containing polymerizable monomer and the Group 4 element ion exhibits high adhesive strength as described above, but is not immediately subjected to curing and stored for a long period of time. In other words, it was found that gelation is easier than the adhesive using the calcium salt of the acidic group-containing polymerizable monomer and the adhesive containing the polyvalent metal ion-eluting filler. This is because group 4 element ions can bind to more ligands than alkaline earth metal ions and second and third element ions, and therefore, when the adhesive is stored, a slightly polymerizable group can be used. When the polymerization of the monomer occurs, it is expected that it develops into a dense cross-linked structure and gels, and the adhesive force decreases due to the gelation.

  As described above, a polymerizable monomer adhesive composition comprising an acidic group-containing polymerizable monomer is developed that does not cause gelation even when stored for a long period of time while maintaining its high adhesive strength. That was a big issue.

  The inventors of the present invention have made extensive studies to overcome the above technical problems. As a result, in a dental adhesive composition containing a polymerizable monomer containing at least a part of an acidic group-containing polymerizable monomer and a Group 4 element ion, it is relatively more specific than before. It has been found that by containing an amount of a polymerization inhibitor, gelation during storage can be prevented, and at the same time, high adhesive strength can be maintained and the above problems can be solved, and the present invention has been completed.

  Namely, (A) a polymerizable monomer comprising at least a part of an acidic group-containing polymerizable monomer, (B) a group 4 element ion, and (C) a dental adhesive comprising a polymerization inhibitor. In the composition, (A) 0.8 to 8 parts by mass of a polymerization inhibitor is contained with respect to 100 parts by mass of the polymerizable monomer (A) containing at least part of the acidic group-containing polymerizable monomer. A dental adhesive composition characterized by the above.

  The dental adhesive composition of the present invention has excellent adhesion to a tooth (regardless of dentin and enamel), and the tensile force generated at the interface between the dental restoration and the tooth. High adhesion strength can be obtained to resist stress and force applied by occlusion. Moreover, gelation hardly occurs even after long-term storage, and the high adhesive strength is well maintained even after storage.

  The dental adhesive composition of the present invention having such an excellent adhesive effect uses a dental adhesive or an adhesive that bonds a dental restoration (composite resin or prosthesis) and a tooth. It is useful as a so-called dental adhesive composite resin that directly adheres to a tooth at least.

  The dental adhesive composition of the present invention comprises (A) a polymerizable monomer comprising at least part of an acidic group-containing polymerizable monomer, (B) a group 4 element ion, and (C) a polymerization prohibition. Comprising an agent. Hereinafter, each of these components will be described sequentially.

[(A) polymerizable monomer]
In the present invention, a known organic compound having a polymerizable unsaturated group in the molecule is used without limitation as the polymerizable monomer. Among these, examples of the polymerizable unsaturated group present in the molecule include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. In particular, acryloyl group, methacryloyl group, acrylamide group and methacrylamide group are preferable from the viewpoint of curing speed, and acryloyl group and methacryloyl group are most preferable.

  In the present invention, an acidic group-containing polymerizable monomer is contained as at least a part of such a polymerizable monomer. As the acidic group of the acidic group-containing polymerizable monomer, known ones can be used, and examples thereof include a phosphoric acid group, a carboxylic acid group, and a sulfuric acid group. Among them, the phosphate group not only has a strong decalcification effect on the tooth, but also has a high intrinsic binding force with the tooth, and also has an excellent ability to form an ion bridge with a Group 4 element ion. It is preferable because the strength is increased. If a suitable example of such an acidic group-containing polymerizable monomer is shown,

Etc. However, in the above compounds, R ¹ represents a hydrogen atom or a methyl group. These compounds can be used alone or in admixture of two or more.

  Examples of other compounds that can be suitably used as acidic group-containing polymerizable monomers include bis (2-methacryloxy) phosphonic acid, bis (methacryloxypropyl) phosphinic acid, bis ( (Methacryloxybutyl) phosphinic acid and the like having a phosphonic acid group include 3-methacryloxypropylphosphonic acid, 2-methacryloxyethoxycarbonylmethylphosphonic acid, 4-methacryloxybutoxycarbonylmethylphosphonic acid, 6-methacryloxyhexyloxycarbonyl Examples of methylphosphonic acid, 2- (2-ethoxycarbonylallyloxy) ethylphosphonic acid and the like having a hydrogen phosphonic acid monoester group include 2-methacryloxyethylphosphonic acid mono (methacryloxyethyl). ) Esters, such as 2-methacryloxyethyl phosphonic acid monophenyl ester.

  The compounding amount of the acidic group-containing polymerizable monomer is not particularly limited, and the entire polymerizable monomer component may be composed only of the acidic group-containing polymerizable monomer. From the viewpoint of adjusting or improving the strength of the cured product, it is preferable to use in combination with a polymerizable monomer having no acidic group (hereinafter abbreviated as “non-acidic monomer”). Even when used in combination with a non-acidic monomer, the acidic group-containing polymerizable monomer is contained in an amount of 5% by mass or more in the total polymerizable monomer component because of its high adhesive strength to both enamel and dentin. Is more preferable, 5 to 80% by mass is more preferable, and 10 to 60% by mass is most preferable. If the blending amount of the acidic group-containing polymerizable monomer is small, the adhesive strength to enamel tends to decrease, and conversely if it is large, the adhesive strength to dentin tends to decrease.

  Specific examples of the non-acidic monomer include methyl (meth) acrylate (meaning methyl acrylate or methyl methacrylate; the same shall apply hereinafter), ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl. (Meth) acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, Mono (meth) acrylate monomers such as 2- (meth) acryloxyethyl acetyl acetate; ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (Meth) acrylate, nonaethylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, dipropylene glycol di (meth) acrylate, 2,2′-bis [4- (meth) acryloyloxyethoxyphenyl] propane, 2 , 2′-bis [4- (meth) acryloyloxyethoxyethoxyphenyl] propane, 2,2′-bis {4- [3- (meth) acryloyloxy-2-hydroxypropoxy] phenyl} propane, 1,4- Polyfunctional (meth) acrylate singles such as butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate, and epoxy (meth) acrylate To give a mass That.

  Furthermore, it is also possible to use polymerizable monomers other than (meth) acrylate monomers as non-acidic monomers. Examples of these other non-acidic monomers include fumaric acid ester compounds such as dimethyl fumarate, diethyl fumarate, diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, α- Examples include methylstyrene derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, and allyl diglycol carbonate.

  A non-acidic monomer can also be used individually or in mixture of 2 or more types. When a highly hydrophobic polymerizable monomer is used, an amphiphilic polymerizable monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate may be used. preferable. By using an amphiphilic polymerizable monomer, separation of water can be prevented and the uniformity of the composition can be improved. The blending amount of such amphiphilic polymerizable monomer is preferably 55 parts by mass or less, particularly 50 parts by mass or less in 100 parts by mass of the polymerizable monomer from the viewpoint of not increasing water absorption. More preferred.

[(B) Group 4 element ions]
The dental adhesive composition of the present invention contains (B) Group 4 element ions. (A) The polymerizable monomer comprising at least a part of the acidic group-containing polymerizable monomer coexists with the Group 4 element ion, and (C) a specific blending amount of the polymerization inhibitor described later. As a result, the adhesive strength is greatly improved, and even when stored for a long time, it is difficult to gel.

  (B) Specific examples of Group 4 element ions include titanium ions, zirconium ions, and hafnium ions. Of these, titanium ions are particularly preferred because of the excellent effect of improving the adhesive strength. These Group 4 element ions can be used in combination of two or more.

  The content of Group 4 element ions in the dental adhesive composition is preferably such that the molar ratio is 0.05 to 0.5 with respect to the acidic groups of the acidic group-containing polymerizable monomer, more preferably. Is an amount of 0.06 to 0.3. Here, when the content of the Group 4 element ion is 0.05 or more in terms of a molar ratio with respect to the acidic group of the acidic group-containing polymerizable monomer, the Group 4 element ion and the acidic group-containing polymerizable monomer are present. The crosslink density by the ionic bond with the acidic group of the monomer is increased, and the adhesiveness is improved. On the other hand, when the content of the Group 4 element ion is 0.5 or less, the Group 4 element ion is adjusted to an appropriate amount with respect to the acidic group-containing polymerizable monomer, and the adhesiveness is improved. When the content of the group 4 element ion exceeds 0.5, the group 4 element ion increases with respect to the acidic group-containing polymerizable monomer, and therefore, the ion bond is made to one group 4 element ion. The number of acidic group-containing polymerizable monomers decreases, and the adhesiveness tends to decrease as the crosslinking density decreases.

  The type and content of Group 4 element ions in the dental adhesive composition can be confirmed by measuring using an inductively coupled plasma (ICP) emission spectrometer after removing solid components. . Specifically, the adhesive composition is diluted with a water-soluble organic solvent to a concentration of 1% by mass, and the resulting diluted solution is filtered using a syringe filter or the like to remove solid components. Thereafter, the ion species and concentration of the obtained filtrate are measured with an ICP emission spectrometer, and the polyvalent metal ion species and amount in the adhesive composition are calculated. In addition, metal ion species other than polyvalent metal ions and their contents can also be measured by the same method.

In addition, the measurement of the type of acidic group in the dental adhesive composition is carried out by isolating the acidic group-containing polymerizable monomer from the composition by preparative high performance liquid chromatography, The molecular weight of the monomer is measured by mass spectrometry, and the molecular weight is determined by nuclear magnetic resonance spectroscopy (NMR) measurement to determine the structure. The chemical shift value can be determined by measuring NMR of a known compound under the same conditions (diluting solvent, concentration, temperature) and using it as a standard. In addition, the content of the acidic group-containing polymerizable monomer was determined by using the acidic group-containing polymerizable monomer isolated by preparative high-performance liquid chromatography to create a calibration curve with the above standard substance. It can be obtained by adding an internal standard substance to a part of the filtrate and measuring by high performance liquid chromatography. The adhesive composition of the present invention contains the above-mentioned specific amount of Group 4 element. In addition to ions, other metal ions may be contained. Examples of such other metal ions include monovalent and divalent metal ions such as alkali metal ions and alkaline earth metal ions, and further include aluminum (III), iron (III), ruthenium (III), and cobalt. And trivalent metal ions such as (III) and lanthanum (III). From the viewpoint of satisfactorily developing ion bridges by Group 4 element ions, the total ionic valence in the total amount of these other metal ions is 0.5 or less with respect to the total ionic valence of all the contained metal ions. More preferably, the ratio is 0.2 or less.

  As described above, in the adhesive composition, when the amount of metal ions including group 4 element ions increases, the acidic group of the acidic group-containing polymerizable monomer in the polymerizable monomer component is , It will be ionized and neutralized. Therefore, when “total valence of all metal ions” / “total valence of acid in the total amount of acidic group-containing polymerizable monomer” is 1 or more, the adhesive composition usually does not exhibit acidity. The adhesive composition does not have an etching function (dental demineralization function), and it is preferable to separately perform an etching operation on the dental substance. Therefore, in the present invention, when the “total ionic valence of all metal ions” is too large, the composition has a decalcification function, so that the acidity of the composition is maintained. It is preferable to contain an acidic substance.

  In this case, the acidity of the adhesive composition of the present invention may be such that the pH value measured by the following method is less than 4.8. That is, the acidity of the adhesive composition is determined by mixing the adhesive composition with ethanol at a concentration of 10% by mass and measuring the pH of the mixed solution. The pH can be measured by a conventionally known method. At 25 ° C., a pH electrode calibrated with a neutral phosphate pH standard solution (pH 6.86) and a phthalate pH standard solution (pH 4.01). The method of measuring with a pH meter using is simple and preferred. Ethanol used for dilution has a purity of 99.5% or more, and there is no particular problem if the pH value of the ethanol alone is 4.8 to 5.0 when measured by the method shown below. The adhesive composition preferably has a pH measured by this method in the range of 0.5 to 4.0, and in the range of 1.0 to 3.0, because of the decalcifying strength of the tooth. More preferably.

  In the adhesive composition of the present invention, the method for causing the Group 4 element ions to be present in the composition is not particularly limited, and when adjusting the adhesive composition, What is necessary is just to mix | blend or contact the said ion source of the said group 4 element ion, and to elute this group 4 element ion by the said quantity in a composition. Examples of the Group 4 element ion source include a Group 4 element simple substance, a Group 4 element ion-eluting filler, or a Group 4 element compound.

  Here, as the Group 4 element compound, a metal salt, a metal halide, or a metal alkoxide can be used. Metal salts include 1,3-diketone enol, citrate, tartrate, fluoride, malonate, glycolate, lactate, phthalate, isophthalate, terephthalate, acetate, Examples thereof include methoxyacetate, and examples of the metal halide include titanium fluoride, titanium chloride, zirconium fluoride, and hafnium fluoride. Examples of the metal alkoxide include titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide, zirconium methoxide, zirconium ethoxide, zirconium propoxide, zirconium isopropoxide, etc., and titanium methoxide, titanium Ethoxide, titanium propoxide, titanium isopropoiside and the like are particularly preferable. Among these Group 4 element compounds, lower alkoxides having 4 or less carbon atoms, more preferably 3 or less carbon atoms, elution of metal ions is fast and the by-product is alcohol, so that the adhesive strength is not affected and is easy to remove. Further, it is more preferable from the viewpoint of easy handling. Since some of these Group 4 element compounds have extremely low solubility, they may be used after confirming in advance by a preliminary experiment or the like.

  On the other hand, the Group 4 element ion-eluting filler is capable of eluting the Group 4 element ions in the dental adhesive composition. Usually, it is easy to elute when the dental adhesive composition is acidic. As the Group 4 element ion-eluting filler, known fillers can be used without limitation, but glass having a chain-like, layered, or network-like skeleton holding Group 4 element ions in the gap between the skeletons. Are preferably used. Specifically, examples of the glass having a chain-like, layer-like, or network-like skeleton include oxide glass and fluoride glass. Examples of the oxide glass include those made of titania silicate glass, borosilicate glass, soda lime glass, and the like, and examples of the fluoride glass include those made of titanium fluoride glass. In addition, the Group 4 element ion-eluting fillers made of these glasses, after eluting Group 4 element ions, filter out the precipitated particles with respect to aggregated particles and large particles. At least a part of the composition may be removed, but if it is left as it is in the dental adhesive composition as porous particles, it can contribute to the improvement of the strength of the cured product as a filler.

[(C) Polymerization inhibitor]
The dental adhesive composition of the present invention contains (C) a polymerization inhibitor. By blending a specific amount of the polymerization inhibitor, the dental adhesive composition exhibits high adhesiveness, and at the same time, gelation hardly occurs even when stored for a long period of time, and high storage stability is expressed. In the present invention, by including an acidic group-containing polymerizable monomer, a Group 4 element ion, a specific amount of a polymerization inhibitor, the reason for expressing high adhesive strength and high storage stability is not necessarily clear, Estimated as follows. That is, it is considered that, by blending a relatively large polymerization inhibitor as in the present invention, gelation is highly suppressed by long-term storage and high storage stability is expressed. Further, when the composition is polymerized and cured, a part of the composition becomes unpolymerized. On the other hand, an ionic conjugate formed by the acidic group-containing polymerizable monomer and the Group 4 element ion is polymerized. In order to form a highly crosslinked polymer, it is considered that high adhesive strength is developed. Moreover, it is thought that adhesive strength fall can also be prevented by suppressing gelation.

  In the present invention, a known polymerization inhibitor is used without limitation as the polymerization inhibitor. Of these, phenol-based polymerization inhibitors are preferred, and res-hindered phenols, semi-hindered phenols, and hindered phenols are preferably used.

  Resin hindered phenols have an excellent radical scavenging rate, but have the characteristic of easily releasing the trapped radicals. On the other hand, although hindered phenols have a low radical scavenging rate, they have the characteristic that they retain their captured radicals and are difficult to release. Semi-hindered phenols refer to intermediates between radical scavenging rate and radical retention.

  Resin hindered phenols include hydroquinone monomethyl ether, 4,4′-thiobis (3-methyl-6-tertiarybutyl) phenol (for example, Nocrack 300 from Ouchi Shinsei Chemical Co., Ltd.), 1,1,3- Tris- (2-methyl-4-hydroxy-5-tertiarybutylphenyl) butane (for example, Adeka Stub AO-30 from Adeka), 4,4′-butylidenebis (3-methyl-6-tertiarybutyl) phenol ( For example, Adeka Corporation's Adeka Stub AO-40) may be mentioned.

  Semihindered phenols include 3,9-bis [2- {3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] -2,4. -8,10-tetraoxaspiro [5,5] undecane (for example, Adeka Stub AO-80 from Adeka), ethylene bis (oxyethylene) bis [3- (5-tert-butyl-hydroxy-m-tolyl) Propionate] (for example, Irganox 245 from Ciba Specialty Chemicals), triethylene glycol bis [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate (for example, Adeka Stub AO-70 from Adeka) Is mentioned.

  Examples of hindered phenols include 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6-dicyclohexyl-4-methylphenol, 2,6-diisopropyl-4-ethylphenol, 2,6-di-tert-amyl-4-methylphenol, 2,6-di-tert-octyl-4-n-propylphenol, 2,6-dicyclohexyl-4 -N-octylphenol, 2-isopropyl-4-methyl-6-tert-butylphenol, 2-tert-butyl-2-ethyl-6-tert-octylphenol, 2-isobutyl-4-ethyl-6-tert-hexylphenol, 2-cyclohexyl-4-n-butyl-6-isopropylphenol, 1,1 1-tris (4-hydroxyphenyl) ethane, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, triethylene glycol-bis [3- (3-tert-butyl -5-methyl-4-hydroxyphenyl) propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], 2,2-thiodiethylene- Bis [3- (3,5-di-tert-butyl-4,4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-tert-butyl-4-hydroxy-hydrocinnamide) 1,3,5-tris (2,6-dimethyl-3-hydroxy-4-tert-butylbenzyl) isocyanurate, 1 3,5-tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris [(3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy Ethyl] isocyanurate, tris (4-tert-butyl-2,6-dimethyl-3-hydroxybenzyl) isocyanurate, 2,4-bis (n-octylthio) -6- (4-hydroxy-3,5-di) -Tert-butylanilino) -1,3,5-triazine, tetrakis [methylene (3,5-di-tert-butyl-4-hydroxy) hydrocinnamate] methane, bis [(3,3-bis (3-tert -Butyl-4-hydroxyphenyl) butyric acid) glycol ester, N, N'-bis [3- (3,5-di-tert- Butyl-4-hydroxyphenyl) propionyl] hydrazine, 2,2′-ogizamide bis [ethyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], bis [2-tert-butyl-4 -Methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl -4-hydroxybenzyl) benzene, 3,9-bis [1,1-dimethyl-2- {β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy} ethyl] -2,4, 8,10-tetraoxaspiro [5,5] undecane, 2,2-bis [4- (2- (3,5-di-tert-butyl-4-hydroxy) Nnamoyloxy)) ethoxyphenyl] propane, β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid alkyl ester, tetrakis- [methyl-3- (3,5-di-tert-butyl-4) -Hydroxyphenyl) propionate] methane, octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-tert- Butylphenyl) butane, thiodiethylene-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], ethylenebis (oxyethylene) bis [3- (5-tert-butyl-4- Hydroxy-m-tolyl) propionate], hexamethylenebis [3- (3,5-di- tert-butyl-4-hydroxyphenyl) propionate, triethylene glycol-bis-[-3- (3′-tert-butyl-4-hydroxy-5-methylphenyl)] propionate, 1,1,3-tris [2 -Methyl-4- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -5-tert-butylphenyl] butane.

The polymerization inhibitor may be used alone or in combination of two or more. When two or more types are combined, the combination of the hindered phenols and the hindered phenols is preferable because it prevents gelation and maintains high adhesive strength even after long-term storage. Among these, a combination of hydroquinone monomethyl ether and 2,6-di-tert-butyl-4-methylphenol is more preferable.
Although the reason why the combination of the hindered phenols with the hindered phenols is preferable is not clear, it is long because the radicals generated by the hindered phenols are captured instantly and then transferred to the hindered phenols. It is considered that gelation can be effectively prevented because radicals are stably captured over a period of time. That is, as in the present invention, gelation that tends to occur in the presence of an acidic group-containing polymerizable monomer and a Group 4 element can be considerably suppressed by blending a specific amount of a polymerization inhibitor, but still at a level that cannot be visually observed. Gelation, and a decrease in adhesive strength due to gelation, and as described above, by using a combination of specific types of polymerization inhibitors, gelation at an invisible level is effectively suppressed. It is presumed that the adhesive strength can be maintained high after long-term storage.

  The blending amount of the polymerization inhibitor is 0.8 to 8 parts by mass with respect to 100 parts by mass of the polymerizable monomer comprising (A) at least part of the acidic group-containing polymerizable monomer, and more. In order to make high storage stability and adhesive strength compatible, 1-4 mass parts is preferable. When the blending amount of the polymerization inhibitor is less than 0.8 part by mass, the storage stability is not satisfied, while when it exceeds 8 parts by mass, the curability of the composition is lowered and high adhesive strength cannot be obtained.

  Further, the blending ratio when two or more polymerization inhibitors are used is preferably such that the weight ratio of the hindered phenol to the hindered phenol is 1: 5 to 1: 100, and further higher storage stability and adhesive strength. Is more preferably 1:10 to 1:30.

[(D) Polymerization initiator]
The dental adhesive composition of the present invention contains (D) a polymerization initiator. A known polymerization initiator can be used as such a polymerization initiator. The polymerization initiator is classified into a chemical polymerization type and a photopolymerization type, and may be appropriately selected according to the purpose. It is also possible to use a dual cure type in which a photopolymerization initiator and a chemical polymerization initiator are used in combination, and polymerization can be initiated by either photopolymerization or chemical polymerization.

  Representative photopolymerization initiators include diacetyl, acetylbenzoyl, benzyl, 2,3-pentadione, 2,3-octadione, 4,4′-dimethoxybenzyl, 4,4′-oxybenzyl, camphorquinone, 9, Α-diketones such as 10-phenanthrenequinone and acenaphthenequinone, benzoin alkyl ethers such as benzoin methyl ether, benzoin ethyl ether and benzoin propyl ether, 2,4-diethoxythioxanthone and 2-chlorothioxan Thioxanthone derivatives such as Son, methylthioxanthone, benzophenone, benzophenone derivatives such as p, p'-dimethylaminobenzophenone, p, p'-methoxybenzophenone, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6 - Toxibenzoyl) -2,4,4-trimethylpentylphosphine oxide, acylphosphine oxide derivatives such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide, and aryl borate compounds / dyes / photoacid generators The system which becomes. Among these, an α-diketone photopolymerization initiator, an acylphosphine oxide photopolymerization initiator, and a photopolymerization initiator composed of a combination of an aryl borate compound / dye / photoacid generator are particularly preferable. is there.

  As the α-diketone, camphorquinone and benzyl are preferable. As the acylphosphine oxide, 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Trimethylpentylphosphine oxide and bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide are preferable. Although these α-diketones and acyl phosphine oxides exhibit photopolymerization activity alone, they are used in combination with amine compounds such as ethyl 4-dimethylaminobenzoate, lauryl 4-dimethylaminobenzoate, and dimethylaminoethyl (meth) acrylate. It is preferable to obtain higher polymerization activity. In addition, as a photopolymerization initiator of an aryl borate compound / dye / photoacid generator system, an aryl borate compound such as tetraphenyl boron sodium salt is used as a dye, and 3,3′-carbonylbis (7-diethylamino) coumarin is used as a dye. Substitution of halomethyl group such as 2,4,6-tris (trichloromethyl) -s-triazine, using a coumarin dye such as 3,3'-carbonylbis (4-cyano-7-diethylaminocoumarin) as a photoacid generator Those using s-triazine derivatives or diphenyliodonium salt compounds can be particularly preferably used.

  On the other hand, typical chemical polymerization initiators include combinations of organic peroxides and amines, organic peroxides, combinations of amines and sulfinates, combinations of acidic compounds and aryl borates, barbituric acid, alkyl Examples include chemical polymerization initiators such as borane.

  Examples of compounds suitable for use in the chemical polymerization initiator are as follows. Examples of the organic peroxides include t-butyl hydroperoxide, cumene hydroperoxide, di-t-butyl peroxide, dicumyl peroxide, Examples include acetyl peroxide, lauroyl peroxide, benzoyl peroxide and the like. These can be used alone or in combination of two or more.

  As the amines, secondary or tertiary amines are preferable, and specific examples thereof include N-methylaniline, N-methyl-p-toluidine and the like as secondary amines. 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-dimethylan Ranilic acid methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p-toluidine, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β-naphthylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N dimethylhexyl Amine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, 2,2 ′-(n-butylimino ) Examples include diethanol.

  Any aryl borate can be used as long as it has at least one boron-aryl bond in one molecule, but it has high storage stability, ease of handling, and availability. From the viewpoint of ease of use, aryl borates having four boron-aryl bonds in one molecule are most preferable. Specific examples of aryl borates having four boron-aryl bonds in one molecule include tetraphenyl boron, tetrakis (p-chlorophenyl) boron, tetrakis (p-fluorophenyl) boron, tetrakis (3,5-bistrifluoromethyl). ) Phenyl boron, tetrakis [3,5-bis (1,1,1,3,3,3-hexafluoro-2-methoxy-2-propyl) phenyl] boron, tetrakis (p-nitrophenyl) boron, tetrakis ( m-nitrophenyl) boron, tetrakis (p-butylphenyl) boron, tetrakis (m-butylphenyl) boron, tetrakis (p-butyloxyphenyl) boron, tetrakis (m-butyloxyphenyl) boron, tetrakis (p-octyl) Oxyphenyl) boron, tetrakis ( - it can be mentioned salts of boron compounds such as octyloxy phenyl) boron. As a cation forming a salt with a boron compound, a metal ion, a tertiary or quaternary ammonium ion, a quaternary pyridinium ion, a quaternary quinolinium ion, or a quaternary phosphonium ion may be used. it can.

  Among the above chemical polymerization initiators, a chemical polymerization initiator obtained by using a combination of an acidic compound and an aryl borate in combination with a + IV and / or + V vanadium compound is particularly suitable because of its high polymerization activity. Furthermore, the combined use of the above organic peroxide is most preferable because the polymerization activity can be further enhanced.

  Specific examples of the vanadium compound include divanadium tetraoxide (IV), vanadyl oxalate (IV), vanadyl sulfate (IV), oxobis (1-phenyl-1,3-butanedionate) vanadium (IV), bis (Maltrate) oxo vanadium (IV), vanadium pentoxide (V), sodium metavanadate (V), ammonium metavanadate (V) and the like can be mentioned.

  The (D) polymerization initiator of the present invention can be blended not only alone but also in combination of a plurality of types as required. These compounding amounts are preferably in the range of 0.01 to 10 parts by mass when the polymerizable monomer is 100 parts by mass. If the amount is less than 0.01 parts by mass, the curability of the adhesive tends to be reduced. Conversely, if the amount exceeds 10 parts by mass, the strength of the cured product of the adhesive tends to decrease. As for the said compounding quantity of a polymerization initiator, it is more preferable that it is the range of 0.1-8 mass parts.

〔water〕
Water may be mix | blended with the adhesive composition of this invention. By containing water, the affinity of the dental adhesive composition for the tooth substance is improved. Such water is generally removed by air blowing before the adhesive composition is cured when the adhesive composition of the present invention is applied to the tooth surface. 0.01-50 mass parts is preferable and, as for the compounding quantity of the water per mass part, 0.1-25 mass parts is more preferable.

[Volatile organic solvent]
A volatile organic solvent may be blended in the adhesive composition of the present invention. Here, as the volatile organic solvent, those which are volatile at room temperature and exhibit water solubility can be used. In addition, volatility means that the boiling point in 760 mmHg is 100 degrees C or less, and the vapor pressure in 20 degrees C is 1.0 KPa or more. The term “water-soluble” means that the solubility in water at 20 ° C. is 20 g / 100 ml or more, and it is preferably compatible with water at 20 ° C. in an arbitrary ratio.

  Examples of such volatile water-soluble organic solvents include methanol, ethanol, n-propanol, isopropyl alcohol, acetone, and methyl ethyl ketone. A plurality of these organic solvents can be mixed and used as necessary. In view of toxicity to the living body, ethanol, isopropyl alcohol and acetone are preferable.

  These volatile organic solvents are also removed by air blowing or the like after the adhesive composition of the present invention is applied to the tooth surface and before the adhesive composition is cured, like the water. .

  In this invention, the compounding quantity of a volatile organic solvent is the range of 2-400 mass parts normally with respect to 100 mass parts of (A) polymeric monomers, More preferably, it is 5-300 mass parts.

[Filler]
You may make the dental composition of this invention contain a filler as needed. Here, as the filler, conventionally known silica-based inorganic filler, organic filler, and inorganic-organic composite filler can be used without any limitation.

  Here, the silica-based inorganic filler refers to silica or composite oxide particles mainly composed of a metal oxide of Groups 2 to 14 of the periodic table that can be combined with silica. In the case of the composite oxide particles, the silica component is preferably contained at least 10 mol% or more, preferably 50 mol% or more.

  Specific examples of the silica-based inorganic filler include quartz, silica, silica-alumina, silica-titania, silica-zirconia, lanthanum glass, barium glass, and strontium glass. The silica may be wet silica, but is preferably dry silica called fumed silica. Moreover, a polyvalent metal ion-eluting filler such as fluoroaluminosilicate glass can also be suitably used. Among them, silica-zirconia, barium glass, etc. having X-ray contrast properties can be preferably used.

  The particle diameter and shape of these silica-based inorganic fillers are not particularly limited, and spherical or irregular particles having an average particle diameter of 0.01 μm to 100 μm, which are generally used as dental materials, are appropriately selected depending on the purpose. Use it. The method for producing the silica-based inorganic filler is not limited at all, and a spraying method, a sol-gel method, a flame melting method, and the like can be used. When applying the dental adhesive composition of this invention to a dental adhesive, the filler by a flame melting method is preferable. Moreover, when applying the dental adhesive composition of this invention to a dental adhesive composite resin, the filler by a sol gel method is preferable and a spherical filler is more preferable.

  As such a silica-based inorganic filler, those subjected to silane coupling treatment can be suitably used. Specific examples of silane coupling agents include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, vinyltrichlorosilane , Vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropyl Methyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyl Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, hexamethyldisilazane, 11-methacryloxy undecyl trimethoxysilane, 11-methacryloxy-undecyl methyl dimethoxy silane.

  Examples of the organic filler include polyalkyl methacrylate, methyl methacrylate-ethyl methacrylate copolymer, cross-linked polyalkyl methacrylate, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-butadiene- Examples thereof include particles made of an organic polymer such as a styrene copolymer, and polyalkyl methacrylate is particularly preferably used.

  Examples of the organic-inorganic composite filler include granular organic-inorganic composite fillers obtained by mixing these inorganic particles and a polymerizable monomer in advance, forming a paste, polymerizing, and pulverizing.

  The blending amount of these fillers when used for a dental adhesive is in the range of 2 to 100 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the (A) polymerizable monomer component. If the amount is less than 2 parts by mass, a sufficient strength improvement effect cannot be obtained, and if it exceeds 30 parts by mass, the viscosity increases, penetrability into the tooth is inhibited, and a sufficient effect for improving the adhesive strength of the tooth cannot be obtained.

  Moreover, the compounding quantity of the filler in case the adhesive composition of this invention is used as a dental adhesive composite resin is in the range of 100-2000 mass parts with respect to 100 mass parts of (A) polymerizable monomer component. is there. Here, the dental adhesive composite resin is a composite in which a polymerizable monomer composition for adhering to the above-mentioned tooth substance is contained in the composite resin and directly bonded to the tooth without using a bonding material. In this case, if the blending amount of the filler is less than 100 parts by weight, sufficient strength as a composite resin cannot be obtained.

  Furthermore, in the adhesive composition of the present invention, an organic thickening material such as a polymer compound such as polyvinyl pyrrolidone, carboxymethyl cellulose, polyvinyl alcohol, or the like is used as long as it does not deteriorate the performance of the adhesive composition of the present invention, if necessary. It is possible to add. Various additives such as ultraviolet absorbers, dyes, antistatic agents, pigments, and fragrances can be selected and used as necessary.

  When the usage method of the dental adhesive composition of the present invention is exemplified, when the use of the dental adhesive composition is a dental adhesive, the present invention is applied to a tooth structure that becomes an adherend from which a carious portion is removed. The adhesive composition was applied and allowed to stand for about 5 to 60 seconds, after which compressed air was lightly blown by air blow to volatilize the volatile components. Then, it may be polymerized and cured by irradiating visible light using a dental irradiator. The cured adhesive composition surface is further filled with a filling restoration material such as a composite resin using a filling device. The dental adhesive composition of the present invention can be used favorably as an adhesive that can provide a high adhesive force even when no pretreatment is required, as is apparent from the above method of use. It is also possible to use after performing the pre-treatment. Furthermore, when the use of the dental adhesive composition is a dental adhesive composite resin, the adhesive composition of the present invention is applied to the dentin that becomes an adherend from which the carious portion has been removed, for 5 to 60 seconds. After leaving to the extent, visible light may be irradiated and polymerized and cured using a dental irradiator.

  When the use of the dental adhesive composition is a dental adhesive, a preferred composition is (A) a polymerizable monomer comprising at least part of an acidic group-containing polymerizable monomer, and (B) No. 4 The composition contains a group element ion, (C) a polymerization inhibitor, (D) a polymerization initiator, water, a volatile organic solvent, and a filler. The blending ratio of each component is (B) Group 4 element ions of 0.1 to 100 parts by mass of polymerizable monomer comprising at least part of (A) acidic group-containing polymerizable monomer. 50 parts by mass, (C) 0.8 to 8 parts by mass of polymerization inhibitor, (D) 0.1 to 5 parts by mass of polymerization initiator, 1 to 30 parts by mass of water, and volatile organic It is suitable that it is 10-200 mass parts of solvent, and 5-50 mass parts of fillers.

  When the use of the dental adhesive composition is a dental adhesive composite resin, a preferred composition is (A) a polymerizable monomer comprising at least part of an acidic group-containing polymerizable monomer, (B) The composition contains a Group 4 element ion, (C) a polymerization inhibitor, (D) a polymerization initiator, and a filler. The blending ratio of each component is (B) Group 4 element ions of 0.1 to 100 parts by mass of polymerizable monomer comprising at least part of (A) acidic group-containing polymerizable monomer. 50 parts by mass, (C) 0.8 to 8 parts by mass of a polymerization inhibitor, (D) 0.01 to 5 parts by mass of a polymerization initiator, and 50 to 1000 parts by mass of a filler. is there.

Hereinafter, in order to specifically describe the present invention, examples and comparative examples will be described. However, the present invention is not limited to these examples. Abbreviations and abbreviations shown in the examples are as follows.

[Polymerizable monomer having acidic group]
SPM: mixture of 2-methacryloyloxyethyl dihydrogen phosphate and bis (2-methacryloyloxyethyl) hydrogen phosphate in a molar ratio of 1: 1 MDP: 10-methacryloyloxydecyl dihydrogen phosphate MHP: to 6-methacryloyloxy Xyl dihydrogen phosphate [Polymerizable monomer containing no acidic group]
BisGMA: 2,2-bis (4- (2-hydroxy-3-methacryloxypropoxy) phenyl) propane 3G: triethylene glycol dimethacrylate HEMA: 2-hydroxyethyl methacrylate [Group 4 element ion source]
Ti (O-iPr) ₄ : Titanium tetraisopropoxide W (O-iPr) ₄ : Tungsten (VI) tetraisopropoxide
[Ion sources other than Group 4 elements]
Al (O-iPr) ₃ : Aluminum triisopropoxide [Polymerization inhibitor]
BHT: 2,6-di-t-butyl-p-cresol HQME: hydroquinone monomethyl ether [polymerization initiator]
CQ: camphorquinone DMBE: ethyl p-N, N-dimethylaminobenzoate
[Volatile water-soluble organic solvent]
IPA: Isopropyl alcohol [Filler]
FS: Silica particles by flame melting method. Average primary particle size 7 nm, treated with dimethyldichlorosilane.
MSa: silica-titania spherical particles by sol-gel method, average primary particle size 0.07 μm. γ-methacryloyloxypropyltrimethoxysilane treated product.
MSb: silica-zirconia spherical particles by sol-gel method, average primary particle size 0.4 μm. γ-methacryloyloxypropyltrimethoxysilane treated product.
MS1: 1: 1 mixture of MSa and MSb

In the following examples and comparative examples, various measurements were performed by the following methods.
(1) Preparation method of adhesion test piece (a) Preparation method I of adhesion test piece (applicable when the dental adhesive composition is a dental adhesive)
Within 24 hours after slaughter, the front teeth of the cow were removed, and the enamel and dentin planes were cut out in parallel with the labial surface using # 600 emery paper in the water. Next, these surfaces were dried by blowing compressed air for about 10 seconds, and then a double-sided tape with a 3 mm diameter hole was fixed to either the enamel or dentin plane, and then the thickness was 0.5 mm. A paraffin wax having an 8 mm hole was fixed on the circular hole so as to be in the same center, thereby forming a simulated cavity. The one-part dental adhesive of the present invention is applied to the simulated cavity and left for 10 seconds, and then dried by spraying compressed air for about 10 seconds. If necessary (polymerization initiator for the used dental adhesive) Was irradiated with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) for 10 seconds. Furthermore, a dental composite resin (Esterite Σ, manufactured by Tokuyama Dental Co., Ltd.) was filled thereon, and irradiated with a visible light irradiator for 30 seconds to produce an adhesion test piece II.

(B) Preparation method II of adhesive test piece (applicable when the dental adhesive composition is a dental adhesive composite resin)
The dental adhesive composite resin of the present invention was filled in a simulated cavity formed by the same method as (a) Method I for preparing an adhesive test piece. If necessary (when the polymerization initiator used in the dental adhesive is a photoinitiator), light is irradiated for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation) for adhesion Test piece IV was produced.

(2) Adhesion test method The test piece prepared by the above method is put in a thermal shock tester, immersed in a 4 ° C water bath for 1 minute, transferred to a 60 ° C water bath, immersed for 1 minute, and returned to the 4 ° C water bath again. The operation was repeated 6000 times.

  Then, a stainless steel attachment is bonded to the above test piece, and the tensile tester (Autograph, manufactured by Shimadzu Corporation) is used to pull at a crosshead speed of 2 mm / min. The tensile bond strength between the enamel or dentin and the composite resin is measured. It was measured. For each test, four tensile bond strengths were measured by the above method, and the average value was measured as the bond strength after the storage test to evaluate the storage stability.

(3) Gelation test method during storage The dental adhesive composition was stored in an incubator set at 45 degrees Celsius for 10 weeks, and the presence or absence of gelation was visually confirmed. In the evaluation results, “◯” was shown when gelation could not be confirmed, and “x” was shown when gelation could be confirmed.

Example 1
25 g SPM as a polymerizable monomer, 30 g BisGMA, 20 g 3G and 25 g HEMA, 5.8 g titanium tetraisopropoxide as a titanium ion source, 1.0 g BHT and 0.1 G as a polymerization inhibitor HQME, 2.0 g of CQ and 2.0 g of DMBE as a photopolymerization initiator, 70 g of IPA as a volatile organic solvent, and 10 g of FS as a filler were mixed and stirred until 10 g Distilled water was added and stirred and mixed until uniform again to obtain the dental adhesive of the present invention.

  About the obtained dental adhesive, the adhesive strength with respect to enamel and dentin was measured according to (1) production method of an adhesive test piece and (2) adhesion test method, and it was set as initial stage adhesive strength. Further, according to (3) gelation test method during storage, the presence or absence of gelation after storage at 45 degrees Celsius for 10 weeks was confirmed, and the adhesive strength of the dental adhesive after storage was measured in the same manner as in the initial stage. The composition of the dental adhesive is shown in Table 1, and the evaluation results are shown in Table 2.

Examples 2-12, Comparative Examples 1-4
According to the method of Example 1, dental adhesives having different compositions shown in Table 1 were prepared. According to (1) the method for preparing an adhesive test piece and (2) the adhesive test method, the adhesive strength to enamel and dentin was measured and used as the initial adhesive strength. Further, according to (3) gelation test method during storage, the presence or absence of gelation after storage at 45 degrees Celsius for 10 weeks was confirmed, and the adhesive strength of the dental adhesive after storage was measured in the same manner as in the initial stage. The composition of the adhesive is shown in Table 1, and the evaluation results are shown in Table 2.

  Examples 1-12 use the dental adhesive composition blended so that each component satisfies the constitution shown in the present invention, but in either case both enamel and dentin On the other hand, the initial adhesive strength was high, and gelation of the dental adhesive composition after the storage test was not observed. In addition, the adhesive strength after storage could be maintained well.

  On the other hand, Comparative Example 1 is a case where the blending amount of the polymerization inhibitor is less than the range of the present invention, and the initial adhesive strength was high for both enamel and dentin, but after the storage test. The dental adhesive composition was gelled, and the adhesive strength was significantly reduced. Comparative Example 2 was a case where the blending amount of the polymerization inhibitor was larger than the range of the present invention, and both the initial adhesive strength and the adhesive strength after the storage test showed low values. Comparative Examples 3 and 4 are cases where aluminum ions which are Group 3 element ions were blended, and both the initial adhesive strength and the adhesive strength after the storage test showed low values.

Example 13
25 g SPM as a polymerizable monomer, 40 g BisGMA and 35 g 3G, 5.8 g titanium isopropoxide as a titanium ion source, 1.0 g BHT and 0.1 G HQME as a polymerization inhibitor, photopolymerization Using 0.5 g of CQ and 0.5 g of DMBE as an initiator and 150 g of MS1 as a filler, these were stirred and mixed until uniform to obtain the dental adhesive composite resin of the present invention.

  About the obtained dental adhesive composite resin, the adhesive strength with respect to enamel and dentin was measured according to (1) the method of preparing an adhesive test piece and (2) the adhesive test method to obtain the initial adhesive strength. Further, according to (3) gelation test method during storage, the presence or absence of gelation after storage at 45 degrees Celsius for 10 weeks was confirmed, and the adhesive strength of the dental adhesive composite resin after storage was measured in the same manner as in the initial stage. The composition of the dental adhesive composite resin is shown in Table 3, and the evaluation results are shown in Table 4.

Examples 14 to 16, Comparative Examples 5 and 6
According to the method of Example 13, dental adhesive composite resins having different compositions shown in Table 1 were prepared. According to (1) the method for preparing an adhesive test piece and (2) the adhesive test method, the adhesive strength to enamel and dentin was measured and used as the initial adhesive strength. Further, according to (3) gelation test method during storage, the presence or absence of gelation after storage at 45 degrees Celsius for 10 weeks was confirmed, and the adhesive strength of the dental adhesive composite resin after storage was measured in the same manner as in the initial stage. The composition of the dental adhesive composite resin is shown in Table 3, and the evaluation results are shown in Table 4.

  Examples 13 to 16 are those using a dental adhesive composition formulated so that each component satisfies the constitution shown in the present invention. In any case, both enamel and dentin are used. On the other hand, the initial adhesive strength was high, and gelation of the dental adhesive composition after the storage test was not observed. In addition, the adhesive strength after storage could be maintained well.

  On the other hand, the comparative example 5 is a case where the aluminum ion which is a group 3 element ion is mix | blended, and the initial stage adhesive strength and the adhesive strength after a storage test showed a low value. Comparative Example 6 was a case where the blending amount of the polymerization inhibitor was outside the scope of the present invention, and the initial adhesive strength was high for both enamel and dentin, but the dental adhesion after the storage test. The adhesive composition was gelled and the adhesive strength was significantly reduced.

Claims (5)

(A) a polymerizable monomer comprising at least part of an acidic group-containing polymerizable monomer, (B) a Group 4 element ion, (C) a polymerization inhibitor, and (D) a polymerization initiator In the dental adhesive composition comprising: (A) 0.8 parts of (C) a polymerization inhibitor with respect to 100 parts by weight of the polymerizable monomer comprising at least part of the acidic group-containing polymerizable monomer. A dental adhesive composition containing ˜8 parts by mass. The dental adhesive composition according to claim 1, wherein the polymerization inhibitor (C) is a combination of a hindered phenol and a hindered phenol. (A) 1 to 4 parts by mass of (C) a polymerization inhibitor per 100 parts by mass of the polymerizable monomer comprising at least part of the acidic group-containing polymerizable monomer, The dental adhesive composition according to claim 2, wherein the weight ratio of the hindered phenol to the hindered phenol is 1: 7.5 to 1:75 . A dental adhesive comprising the dental adhesive composition according to any one of claims 1 to 3. A dental adhesive composite resin comprising the dental adhesive composition according to any one of claims 1 to 3.