JP2012020975A - Adhesive composition for dentin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a dental adhesive composition having excellent water resistance of a cured body, capable of showing continuously adhesion strength even when being preserved for a long period in a single liquid state, and maintaining the adhesion strength highly even after being used for adhesion.SOLUTION: The single liquid type adhesive composition for dentin contains: (A) an acid group-containing polymerizable monomer containing ≥95 mass% of a phosphonic acid group-containing polymerizable monomer, or a phosphinic acid group-containing polymerizable monomer; (B) polyvalent metal ion, preferably titanium ion; (C) water; and further preferably (E) a photopolymerization initiator.

Description

  The present invention relates to dental adhesiveness useful as a primer or adhesive for adhering dental restorations made of metals, organic polymers, ceramics, or composite materials thereof, and the tooth in the dental field. Relates to the composition.

  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, direct restoration by a composite resin is often performed from the viewpoint of aesthetics, simplicity of operation and quickness. On the other hand, a relatively large cavity is often repaired using a prosthesis made of metal, ceramics, or dental resin.

These dental restorations such as composite resins and prostheses basically have no adhesiveness to the tooth. Therefore, in order to adhere these to a tooth substance, the adhesive material which consists of a polymerizable monomer composition is used. Many adhesives are mainly composed of methacrylate monomers, and their adhesive strength to the tooth has not reached a satisfactory level. For example, in the case of adhesion of a composite resin, it often does not reach an adhesive strength that can overcome the internal stress generated upon curing of the composite resin, that is, the tensile stress generated at the interface between the tooth and the composite resin. Furthermore, the adhesive strength that can withstand this force is often not reached even with respect to the force applied by occlusion. Therefore, for the purpose of improving the adhesive strength of these adhesives, the following pretreatment is performed on the tooth surface at the time of use. That is,
1) Application of a pretreatment material for etching hard teeth (mainly enamel mainly composed of hydroxyapatite);
2) In order to promote the penetration of the adhesive into the tooth, a pretreatment material called a primer is applied.

  Under these circumstances, attempts have been made to include a polymerizable monomer having adhesiveness to the tooth in the dental adhesive for the purpose of reducing the complexity of the operation and higher adhesive strength to the tooth. . For example, a polymerizable monomer having an acidic group such as a phosphate ester group or a carboxylic acid group (hereinafter referred to as an acidic group-containing polymerizable monomer) is contained as at least a part of the polymerizable monomer component. Since these acidic groups have high affinity for the tooth substance (hydroxyapatite and collagen), this adhesive has succeeded in greatly improving the adhesive strength to the tooth substance ( Patent Document 1 and Patent Document 2).

  Also developed are those that further enhance their polymerization curability by incorporating a polyvalent metal ion-eluting filler into an adhesive or primer containing an acidic group-containing polymerizable monomer and water. (Patent Documents 3 and 4). Here, the polyvalent metal ion-eluting filler means a filler that elutes polyvalent metal ions in an acidic solution, and specifically corresponds to fluoroaluminosilicate glass or the like. As the eluted polyvalent metal ions, alkaline earth metals, aluminum and the like are suitable. The reason why the adhesive strength to the tooth is improved in the adhesive containing such a polyvalent metal ion-eluting filler is the polymerization of the polymerizable monomer containing the acidic group-containing polymerizable monomer when the adhesive is cured. At the same time, the polyvalent metal ions eluted from the polyvalent metal ion-eluting filler form an acid group and salt of the acidic group-containing polymerizable monomer, thereby causing ionic crosslinking, and the strength of the cured product Is believed to be enhanced.

  On the other hand, some adhesives have been developed which are made of an adhesive composition containing a phosphonic acid group-containing polymerizable monomer as an acidic group-containing polymerizable monomer (for example, Patent Document 5).

  Thus, the adhesive composition (adhesive or primer) containing an acidic group-containing polymerizable monomer provides a higher adhesive strength than those not containing the monomer, and further the action of the acidic group. Because it also has a decalcification function of the tooth, it is possible to simplify the bonding operation and is very useful. However, as described above, an extremely strong adhesive strength is required between the tooth substance and the dental restoration, so that the adhesive strength is still not sufficient, and a higher adhesiveness can be stably exhibited. It was necessary to improve it.

Under such a background, the present inventors use specific polyvalent metal ions, water, and acidic group-containing polymerizable monomers containing acidic groups derived from phosphoric acid, An adhesive composition mixed in one liquid at a mixing ratio was proposed (Patent Document 6). This adhesive composition is a one-part storage form as described above, and is formed by the development of ionic crosslinking between polyvalent metal ions and phosphate group-containing polymerizable monomers during the storage. The adhesion strength is remarkably increased and is excellent. Here, in this adhesive composition, as the acidic group-containing polymerizable monomer derived from phosphoric acid, in the examples, as the acidic group derived from the phosphoric acid, a phosphate ester group [group-O Only compounds having —P (═O) (OH) ₂ (dihydrogen phosphate monoester group), group (—O—) ₂ P (═O) OH (hydrogen phosphate diester)] are specifically used. Absent.

JP-A-52-113089 JP 58-21687 JP-A-9-263604 JP 2000-86421 A JP 2009-46397 A JP 2008-201726 A

  However, an adhesive composition using a compound having a phosphate ester group as an acidic group derived from the phosphoric acid is certainly excellent in adhesion to the tooth at the initial stage of mixing with the one liquid. Although exhibiting properties, the hydrolysis of the phosphate ester group gradually progressed over time due to the moisture present in the composition, and the adhesiveness slightly decreased.

  Furthermore, even after being cured, the resulting cured product has insufficient water resistance, and when exposed to a harsh environment such as the oral cavity for a long time, there is a problem that the adhesive strength further decreases. .

  Therefore, even if it is stored for a long time in a one-component state, the adhesive strength continues to be exhibited, the cured body has good water resistance, and the adhesive strength is highly maintainable after use for bonding. The development of was strongly sought.

  As a result of intensive studies to overcome the above technical problems, the present inventors solved the above problems by using a compound having a phosphonic acid group or a phosphinic acid group as an acidic group-containing polymerizable monomer. We have found out that the present invention has been completed.

According to the present invention,
(A) An acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer (B) polyvalent metal ion (C) water A one-pack type adhesive composition for a tooth is provided.

In the invention of the dental adhesive composition,
(1) The composition exhibits acidity (2) (B) the polyvalent metal ion has the following formula (1):
R _{P +} = TV _{P +} / TV _A (1)
(Wherein, TV _{P +} is the total valence of (B) polyvalent metal ions contained in the composition, and TV _A is (A) a phosphonic acid group-containing polymerizable monomer contained in the composition Or the total valence quantity (R _{P +} ) defined by the acidic group-containing polymerizable monomer comprising 95% by mass or more of the phosphinic acid group-containing polymerizable monomer) (3) (B) the polyvalent metal ion is a titanium ion (4) (B) the polyvalent metal ion is represented by formula (1) The total value-quantity ratio (R _{P +} ) defined is blended in the range of 0.2 to 0.6 (5) (D) Formulating an acidic group-free polymerizable monomer (6) ( E) It is suitable to contain a photoinitiator.

According to the present invention, (A) an acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphonic acid group-containing polymerizable monomer, or (C) water , (B _alk ) A method for producing a dental adhesive composition by mixing a polyvalent metal alkoxide, wherein (A) a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer is used. The adhesive for one-part type tooth, characterized in that an acidic group-containing polymerizable monomer comprising 95% by mass or more is previously mixed with (B _alk ) polyvalent metal alkoxide and then mixed with (C) water. There is provided a method for producing a sex composition.

  The adhesive composition for a tooth according to the present invention is compared with a conventional adhesive containing a phosphate group-containing polymerizable monomer and a polyvalent metal ion. Although it is not so outstanding as to exceed, it has excellent storage stability. Therefore, even if it is subjected to adhesion after storage for a long time, the obtained adhesive strength is maintained at a value close to the initial production value, and in terms of reliability in terms of stable tooth restoration, phosphate group-containing polymerizability It is superior to adhesives using monomers. Moreover, the obtained cured product is excellent in water resistance, and the high adhesive strength is highly maintained even when used for a long time in a harsh environment such as in the oral cavity.

The adhesive composition for a tooth according to the present invention comprises (A) a phosphonic acid group-containing polymerizable monomer or an acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphinic acid group-containing polymerizable monomer. Body, (B) polyvalent metal ion, and (C) water.
<(A) Acidic group-containing polymerizable monomer comprising 95% by mass or more of phosphonic acid group-containing polymerizable monomer or phosphinic acid group-containing polymerizable monomer>
The phosphonic acid group-containing polymerizable monomer used in the present invention contains at least one phosphonic acid group (—C—P (═O) (OH) ₂ ) group and polymerizable illegal group in each molecule. It is a compound that has each one. Similarly, the phosphinic acid group-containing polymerizable monomer contains at least one phosphinic acid group ((—C—) ₂ P (═O) OH) group and polymerizable illegal group in each molecule. It is a compound that has. In these acidic group-containing polymerizable monomers, examples of the polymerizable unsaturated group include acryloyl group, methacryloyl group, acrylamide group, methacrylamide group, vinyl group, allyl group, ethynyl group, and styryl group. Can do. 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.

  As these phosphonic acid group-containing polymerizable monomers and phosphinic acid group-containing polymerizable monomers, known ones can be used without any limitation, but as examples of compounds that can be suitably used, the polymerizable compounds represented by the following general formula Monomer.

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.

  The reason why the storage stability is improved by using a phosphonic acid group- or phosphinic acid group-containing polymerizable monomer in the dental adhesive composition of the present invention is presumed as follows. That is, as described above, the conventional phosphate ester group polymerizable monomer does not have sufficient hydrolysis resistance of the phosphate ester group portion. It is considered that decomposition occurs and breaks the ion bridge formed between the phosphate group-containing polymerizable monomer and the polyvalent metal ion. In addition, the phosphoric acid produced by the hydrolysis is considered to inhibit the development of further ionic crosslinking between the phosphate group-containing polymerizable monomer and the polyvalent metal ion.

  From these, the phosphoric acid ester group polymerizable monomer is not sufficient in storage stability. On the other hand, if a phosphonic acid group and phosphinic acid group-containing polymerizable monomer is used, P—O— Since the C bond is replaced with the P—C bond, the hydrolysis resistance of the acidic group moiety is greatly improved. For this reason, the use of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer increases the stability of ion crosslinking formed between these acidic groups and polyvalent metal ions. It is believed that the shelf life of the composition is extended.

  Moreover, since the hardened | cured material of the dental adhesive composition of this invention has long-term water resistance, it can hold | maintain the said outstanding adhesive strength for a long period also under severe conditions like an intraoral area. The reason is presumed as follows. That is, in the case where the unit derived from the acidic group-containing polymerizable monomer has the phosphate ester group, when the cured product is exposed to harsh conditions such as in the oral cavity for a long time, it is gradually gradually. However, if this acidic group is the phosphonic acid group or phosphinic acid group, such hydrolysis does not occur and the high adhesive strength described above is maintained well. Conceivable.

  In the adhesive composition for a tooth according to the present invention, (A) the acidic group-containing polymerizable monomer is 95% by mass of the phosphonic acid group-containing polymerizable monomer or the phosphinic acid group-containing polymerizable monomer. As described above, more preferably 97% by mass or more is allowed even if the polymerizable monomer containing another acidic group is contained in an amount of less than 5% by mass, more preferably less than 3% by mass. The That is, the effect excellent in storage stability is fully exhibited. As the acidic group possessed by such other acidic group-containing polymerizable monomer, a phosphate ester group (a dihydrogen phosphate monoester group or a hydrogen phosphate diester) is preferable. If the compound which can be utilized suitably as a polymerizable monomer containing such a phosphate ester group is illustrated, the polymerizable monomer shown by the following general formula will be mentioned.

In the above compounds, R1 represents a hydrogen atom or a methyl group. These compounds can be used alone or in admixture of two or more.

In addition, examples of other acidic group-containing polymerizable monomers include carboxyl groups (—COOH), sulfo groups (—SO ₃ H), phosphinico groups {═P (═O) OH}, and the like as acidic groups. Is done. Specific examples thereof include (meth) acrylic acid, N- (meth) acryloylglycine, N- (meth) acryloylaspartic acid, N- (meth) acryloyl-5-aminosalicylic acid, 2- (meth) acryloyloxyethyl. A polymerizable monomer having one carboxyl group in the molecule such as hydrogen succinate, 2- (meth) acryloyloxyethyl hydrogen phthalate; 11- (meth) acryloyloxyundecane-1,1-dicarboxylic acid, 10- (meth) acryloyloxydecane-1,1-dicarboxylic acid, 12- (meth) acryloyl oxide decane-1,1-dicarboxylic acid, 4- (meth) acryloyloxybutyl trimellitate, 4- (meth) acryloyl Oxyhexyl trimellitate, 4- (meth) acryloyl Polymers having a plurality of carboxyl groups in the molecule such as xyldecyl trimellitate; sulfo groups in the molecule such as 2- (meth) acrylamide-2-methylpropanesulfonic acid, p-vinylbenzenesulfonic acid and vinylsulfonic acid And other monomers.
<(B) Multivalent metal ion>
In the present invention, the above-mentioned (A) phosphonic acid group-containing polymerizable monomer or acidic group-containing polymerizable monomer containing 95% by mass or more of the phosphinic acid group-containing polymerizable monomer is (B) many. It is important to coexist with a valent metal ion. In the present invention, a polyvalent metal ion coexists with these acidic group-containing polymerizable monomers, so that a reinforced structure by ionic bond is sufficiently developed and high adhesive strength is developed over a long period of time. become.

  Here, the polyvalent metal ion is a divalent or higher-valent metal ion capable of ion-bonding with a phosphonic acid group or phosphinic acid group, and any polyvalent metal ion can be used as long as it can bond with these acidic groups. It may be. Specific examples include divalent metal ions such as magnesium, calcium, strontium, barium, zinc, copper (II) and tin (II), and trivalent metal ions include aluminum. , Gallium, indium, scandium, yttrium, lanthanum, cerium, praseodymium, promethium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, iron (III), actinium, and the like. Examples of tetravalent or higher-valent metal ions include titanium ions, zirconium ions, tungsten (IV) ions, and the like. Of these, from the viewpoint of adhesive strength, trivalent or higher ions are preferred. Among these, the use of tetravalent polyvalent metal ions is more preferable because the crosslink density of the cured product can be further increased and the water resistance of the cured product can be further improved. Furthermore, titanium ions are more effective.

The compounding amount of these polyvalent metal ions is not particularly limited, but the following formula (1):
R _{P +} = TV _{P +} / TV _A (1)
(Wherein TV _{P +} is the total valence of (B) polyvalent metal ions contained in the composition, and TV _A is (A) a phosphonic acid group-containing polymerizable monomer contained in the composition Or the total valence quantity ( _{RP +} ) defined by the acidic group-containing polymerizable monomer comprising 95% by mass or more of the phosphinic acid group-containing polymerizable monomer) Is preferably in the range of 0.1 to 1.5. When (RP ₊ is less than 0.1, deashing is performed, but sufficient adhesive strength cannot be obtained. On the other hand, even when this ratio is greater than 1.5, the adhesiveness is not sufficient, and the water resistance When the coexistence amount of polyvalent metal ions increases, most of the acidic groups in the phosphonic acid group- and phosphinic acid group-containing polymerizable monomer component are reduced. Therefore, when _{RP +} is 1 or more, the adhesive composition usually exhibits almost no acidity, and in this case, the adhesive composition has an etching function (dental release). As a result, the adhesive strength of the ash function is greatly reduced, however, those that form an art complex such as titanium ions have an RP ₊ of 1 when such polyvalent metal ions are used. Above Since showing acidity, R P ₊ is never bonding strength even 1 or more is greatly reduced. However, by also increasing number that coexistence amount coming when an ionic bond in the polyvalent metal ions to form such art complexes From the viewpoint of lowering the crosslinking density, R _{P +} is preferably 1.5 or less, and from the viewpoint of sufficiently exerting the decalcification function of the tooth in the acidic group-containing polymerizable monomer, R _{P +} is 0.2 to 0.9 is more preferable, and 0.2 to 0.6 is most preferable.

In addition, in the formula showing the total quantity-quantity ratio (R _{P +} ), acidic group-containing polymerization comprising 95% by mass or more of a phosphonic acid group or phosphinic acid group-containing polymerizable monomer contained in the adhesive composition. The total valence quantity (TV _A ) of acidic groups possessed by the functional monomer is represented by the following formula (1a):
TV _A = ΣP _k × A _k (1a)
(In the formula, k is 1, 2, 3,..., N, n is the number of acidic group-containing polymerizable monomers contained in the composition, and P _k is the composition. It is the number of moles of the acidic group-containing polymerizable monomer contained therein, and _Ak is the valence of the acidic group of the acidic group-containing polymerizable monomer.

For example, in the case of a polymerizable monomer having a dialkylphosphinic acid group such as bis [3- (meth) acryloyloxypropyl] phosphinic acid, the valence of the acidic group is monovalent. Moreover, if it is a polymerizable monomer which has monoalkyl phosphinic acid groups, such as 3- (meth) acryloyloxypropyl phosphonic acid, the valence of an acidic group is bivalent. Further, when the acidic group-containing polymerizable monomer contained in the composition is only one kind of dialkylphosphinic acid polymerizable monomer, the dialkylphosphinic acid polymerizable monomer is represented by the above formula. When the valence quantity calculated for is the total valence quantity (TV _A ) and the composition contains a plurality of acidic group-containing polymerizable monomers including the dialkylphosphinic acid polymerizable monomer. Calculates the valence quantity for each acidic group-containing polymerizable monomer, and the total value is the total valence quantity (TV _A ).

On the other hand, the total valence quantity (TV _{P +} ) of the polyvalent metal ions contained in the composition is
TV _{P +} = ΣI _k × B _k (1b)
(Wherein k is 1, 2, 3,..., N, n is the number of types of metal ions contained in the composition, and I _k is the number of each of the various ions contained in the composition. It is the number of moles of valent metal ions, and B _k is the valence of each polyvalent metal ion).

  The type and content of polyvalent metal ions present in the adhesive composition for tooth of the present invention are determined by measuring using an inductively coupled plasma (ICP) emission spectrometer after removing solid components. be able to. Specifically, the adhesive is diluted with a water-soluble organic solvent to a concentration of 1% by mass, and the obtained diluted solution is filtered using a syringe filter or the like to remove the solid component. Next, the ion species and ion concentration of the obtained filtrate are measured with an ICP emission spectrometer, and the polyvalent metal ion species and amount of the adhesive are calculated.

  In addition, the kind and content of the acidic group contained in the acidic group-containing polymerizable monomer in the adhesive composition for tooth are determined from each acidic group-containing polymerizable single component in the composition by preparative high performance liquid chromatography. The body is isolated, the molecular weight of each acidic group-containing polymerizable monomer is measured by mass spectrometry, and the structure is determined by nuclear magnetic resonance spectroscopy (NMR). Calculations can be made.

For example, by measuring ³¹ P NMR, a dialkyl phosphinate group can be identified from the chemical shift value. That is, a known compound having a dialkyl phosphinate group, specifically, dimethylphosphinic acid is used as a standard substance, and ³¹ P-NMR is measured for these standard substances under the same conditions (diluting solvent, concentration, temperature). The chemical shift value can be determined by comparing the ³¹ P-NMR measured for the adhesive composition. In addition, methylphosphonic acid is used as a standard substance of a polymerizable monomer having a phosphonic acid monoalkyl group as an acidic group.

  The amount of the acidic group-containing polymerizable monomer in the composition was determined by preparing a calibration curve with a standard substance from each monomer isolated by preparative high performance liquid chromatography. It can be determined by adding an internal standard substance to the part and measuring by high performance liquid chromatography.

  Furthermore, as described above, the polyvalent metal ion is more preferably a trivalent or higher metal ion, particularly a tetravalent metal ion, and most preferably a titanium ion.

The total ionic quantity other than the tetravalent metal ions is preferably 50% or less, particularly 20% or less of the total valence quantity of the polyvalent metal ions contained in the composition. That is, the total valence ratio (R ₄₊ ) of tetravalent metal ions (particularly titanium ions) to polyvalent metal ions is represented by the following formula (2):
R ₄₊ = TV ₄₊ / TV _{P +} (2)
(Wherein, TV ₄₊ is the total quantity of tetravalent metal ions contained in the composition, and TV _{P +} is the total quantity of polyvalent metal ions contained in the composition as described above. The total value-quantity ratio (R ₄₊ ) is preferably in the range of 0.5 or more, particularly 0.8 or more.

In addition to the specific amount of polyvalent metal ions, the dental adhesive composition of the present invention may contain monovalent metal ions as long as the effects of the present invention are not significantly impaired. good. The total valence of these monovalent metal ions is the total valence of all metal ions contained in the composition (the sum of the total valence of polyvalent metal ions and the total valence of monovalent metal ions). The ratio is preferably 50% or less, particularly 30% or less. That is, the total valence quantity ratio (R ₁₊ ) of monovalent metal ions to all metal ions is expressed by the following formula (3):
R ₁₊ = TV ₁₊ / TV _T ... (3)
( _Wherein TV ₁₊ is the total valence of monovalent metal ions contained in the composition, and TV _T is the total valence of all metal ions contained in the composition). However, the total value-to-quantity ratio (R ₁₊ ) is preferably in the range of 0.5 or less, particularly 0.3 or less. When a large amount of monovalent metal ions coexist, the development of ionic bonds by polyvalent metal ions is impaired by the neutralization reaction between the monovalent metal ions and the acidic groups of the acidic group-containing polymerizable monomer. This is because there is a risk of losing.

  In the adhesive composition for a tooth according to the present invention, the method for containing a polyvalent metal ion in the system is not particularly limited. When preparing the adhesive composition for a tooth, What is necessary is just to mix | blend or contact the substance used as the ion source of the said polyvalent metal ion with a monomer component, and to elute this polyvalent metal ion by the said quantity in a system.

Examples of the polyvalent metal ion source compound include a polyvalent metal ion-eluting filler containing ions that elute the polyvalent metal ions. Examples of the polyvalent metal ion compound include metal salts, metal halides, and metal alkoxides. 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, zirconium fluoride, and hafnium fluoride. As the metal alkoxide, (B _alk ) polyvalent metal alkoxide is particularly preferable, and examples thereof include titanium methoxide, titanium ethoxide, titanium propoxide, titanium isopropoxide and the like. Among these compounds, lower polyvalent metal alkoxides having 4 or less carbon atoms have a fast elution of metal ions, and since the by-product is alcohol, the adhesive strength is not affected and the removal of the by-product is easy. Is more preferable because of its ease. In addition, since some of these polyvalent metal ion compounds have remarkably low solubility, it is preferable to use them after confirming in advance by a preliminary experiment or the like.

  In addition, as a polyvalent metal ion source compound, a simple substance of titanium and its oxide are often insoluble in a polymerizable monomer or an organic solvent, and generally correspond almost even in the presence of water. Since it does not elute metal ions, it is usually difficult to use as a polyvalent metal ion source. In general, strong acid salts tend to be difficult to exchange salts with weak acids. Therefore, when using a phosphonic acid group-containing polymerizable monomer, the pKa value based on the first dissociation of the phosphonic acid, or when using a phosphinic acid group-containing polymerizable monomer, the pKa value of the phosphinic acid An acid having a small pKa value, that is, a metal salt of a stronger acid than phosphonic acid or phosphinic acid is preferable as a source of polyvalent metal ions because the ionic bond between the released polyvalent metal ions and these acid groups does not occur sufficiently. Absent. In addition to the above phosphonic acid group-containing polymerizable monomer and phosphinic acid group-containing polymerizable monomer as the acidic group-containing polymerizable monomer, the other acidic group-containing polymerizable monomer When the pKa value of the acidic group possessed by the phosphonic acid is larger than the pKa value based on the first dissociation of the phosphonic acid or the pKa value of phosphinic acid, the polyvalent metal ion source has such other acidic group-containing polymerizable properties. It is a more preferable embodiment to avoid a metal salt of an acid having a pKa value smaller than that of the acidic group of the monomer.

From the viewpoint of ease of production, the adhesive composition for tooth according to the present invention is preferably produced using (B _alk ) polyvalent metal alkoxide as the polyvalent metal ion source. That is, after mixing the phosphonic acid group-containing polymerizable monomer or the acidic group-containing polymerizable monomer containing 95% by mass or more of the phosphinic acid group-containing polymerizable monomer with the polyvalent metal alkoxide first. And mix with water. When a polymerizable monomer other than the acidic group-containing polymerizable monomer is blended, the other polymerizable monomer is first mixed with the acidic group-containing polymerizable monomer and then multivalent. Mix with metal alkoxide and then with water. Alternatively, the acidic group-containing polymerizable monomer and the polyvalent metal alkoxide are first mixed and then finally mixed into the mixture mixed with water.

Mixing of the acidic group-containing polymerizable monomer and the polyvalent metal ion compound needs to be performed in the absence of water. When these are mixed in the presence of water, the polyvalent metal ions usually precipitate as solid oxides, and it becomes impossible to form an ionic bond with an acidic group. That is, when an acidic group-containing polymerizable monomer and a polyvalent metal ion compound are mixed in the presence of water, desired adhesive strength cannot be obtained immediately after the composition is prepared. Therefore, it is necessary to mix water after mixing the acidic group-containing polymerizable monomer and the polyvalent metal ion compound in advance and forming a sufficient ionic bond therebetween.
<(C) Water>
In the present invention, (C) water has a function as a solvent for uniformly dispersing various components, and at the same time, demineralization of teeth, (A) an acidic group-containing polymerizable monomer, and (B) Necessary for promoting ionic bonds with polyvalent metal ions. As the water, distilled water or deionized water that does not substantially contain impurities harmful to storage stability and medical components is preferably used. These waters are usually removed during the polymerization reaction because they are dried by air blow after the sufficient demineralization applied to the teeth during the use of the adhesive composition.

The blending amount of water is preferably 10 to 120 parts by mass, particularly 50 to 100 parts by mass with respect to 100 parts by mass of the (A) acidic group-containing polymerizable monomer component. If the amount of water is less than this range, tooth decalcification and ionic bonds are not sufficient, and high adhesive strength is difficult to obtain. Also, if it is used in a larger amount than the above range, the removability by air blow after applying this adhesive composition to the tooth surface will be reduced, and a lot of water will remain on the tooth surface, and sufficient adhesive strength Cannot be obtained.
<(D) Acidic group-free polymerizable monomer>
The dental adhesive composition of the present invention contains 95% by mass or more of the above-mentioned (A) phosphonic acid group-containing polymerizable monomer or phosphinic acid group-containing polymerizable monomer as a polymerizable monomer component. In addition to the acidic group-containing polymerizable monomer of (D), an acidic group-free polymerizable monomer may be blended. These acidic group-free polymerizable monomers can be used in various ways depending on the purpose such as adjusting the strength of the adhesive interface and the permeability of the pretreatment material to the tooth, and obtaining better adhesive strength to the tooth. Use different ones properly. From the viewpoint of the strength and water resistance of the cured product, use a combination of a highly hydrophobic bifunctional polymerizable monomer and an amphiphilic polymerizable monomer from the viewpoint of penetrating the adhesive component into the tooth. It is preferable.

  As the non-acidic group-containing polymerizable monomer that can be used in the present invention, known monomers can be used without any limitation, and specific examples of a compound having at least one polymerizable unsaturated group in the molecule are shown below. Methyl (meth) acrylate, ethyl (meth) acrylate, glycidyl (meth) acrylate, 2-cyanomethyl (meth) acrylate, benzyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, allyl (meth) acrylate, 2-hydroxyethyl Mono (meth) acrylate monomers such as (meth) acrylate, glycidyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, glyceryl mono (meth) acrylate, 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-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, urethane (meth) acrylate Polyfunctional epoxy (meth) acrylate (meth) acrylate monomer and the like.

  Furthermore, it is also possible to mix and polymerize a polymerizable monomer other than the (meth) acrylate monomer as the acidic group-free polymerizable monomer. Examples of these other polymerizable monomers include fumaric acid ester compounds such as dimethyl fumarate, diethyl fumarate and diphenyl fumarate; styrene such as styrene, divinylbenzene, α-methylstyrene, α-methylstyrene dimer, α-methylstyrene derivatives; allyl compounds such as diallyl phthalate, diallyl terephthalate, diallyl carbonate, allyl diglycol carbonate and the like. These polymerizable monomers can be used alone or in admixture of two or more.

  In addition, when a highly hydrophobic polymerizable monomer is used, an amphiphilic monomer such as 2-hydroxyethyl (meth) acrylate or 2-hydroxypropyl (meth) acrylate is used to separate water. It is preferable in terms of adhesive strength to prevent the above and to have a uniform composition.

The blending amount of such an acidic group-free polymerizable monomer is an acid comprising 95% by mass or more of the above-mentioned (A) phosphonic acid group-containing polymerizable monomer or phosphinic acid group-containing polymerizable monomer. 500 parts by mass or less, more preferably 350 parts by mass or less, based on 100 parts by mass of the group-containing polymerizable monomer component (A) phosphonic acid group-containing polymerizable monomer or phosphinic acid group-containing polymerization From the viewpoint of sufficiently exhibiting the blending effect of the acidic group-containing polymerizable monomer comprising 95% by mass or more of the polymerizable monomer.
<(E) Photopolymerization initiator>
An effective amount of a polymerization initiator may be added to the dental adhesive composition of the present invention, and is particularly necessary when used as the dental adhesive. Such a polymerization initiator is preferably a photopolymerization initiator because it can be polymerized and cured at an arbitrary timing. As photopolymerization initiators, α-diketones such as camphorquinone, benzyl, α-naphthyl, acetonaphthene, naphthoquinone, 1,4-phenanthrenequinone, 3,4-phenanthrenequinone, 9,10-phenanthrenequinone; 2,4 -Thioxanthones such as diethylthioxanthone; 2-benzyl-dimethylamino-1- (4-morpholinophenyl) -butanone-1, 2-benzyl-diethylamino-1- (4-morpholinophenyl) -butanone-1, 2 -Benzyl-dimethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-diethylamino-1- (4-morpholinophenyl) -propanone-1,2-benzyl-dimethylamino-1- ( 4-morpholinophenyl) -pentanone-1,2-benzyl-die Α-aminoacetophenones such as tilamino-1- (4-morpholinophenyl) -pentanone; 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,6-dimethoxybenzoyl) -2,4,4- Acylphosphine oxide derivatives such as trimethylpentylphosphine oxide are preferably used.

  Examples of the photopolymerization accelerator that can be used in combination with the photopolymerization initiator include N, N-dimethylaniline, N, N-diethylaniline, N, N-di-n-butylaniline, and N, N-di. Benzylaniline, 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-dimethylanthranic acid Methyl ester, N, N-dihydroxyethylaniline, N, N-dihydroxyethyl-p- Louisin, p-dimethylaminophenethyl alcohol, p-dimethylaminostilbene, N, N-dimethyl-3,5-xylidine, 4-dimethylaminopyridine, N, N-dimethyl-α-naphthylamine, N, N-dimethyl-β -Naphtylamine, tributylamine, tripropylamine, triethylamine, N-methyldiethanolamine, N-ethyldiethanolamine, N, N-dimethylhexylamine, N, N-dimethyldodecylamine, N, N-dimethylstearylamine, N, N- Tertiary amines such as dimethylaminoethyl acrylate, N, N-dimethylaminoethyl methacrylate, 2,2 ′-(n-butylimino) diethanol; 5-butyl barbituric acid, 1-benzyl-5-phenylbarbituric acid Barbi tools such as S; dodecyl mercaptan, and pentaerythritol tetrakis (thioglycolate) mercapto compounds, and the like.

  The blending amount of the photopolymerization initiator is such that (A) the phosphonic acid group-containing polymerizable monomer or the phosphonic acid group-containing polymerizable monomer is 95% by mass or more of the acidic group-containing polymerizable monomer. It is 0.01-10 mass parts with respect to 100 mass parts of components, More preferably, it is 0.1-5 mass parts. Furthermore, for the purpose of further increasing the polymerization initiation activity, an electron acceptor such as an iodonium salt, trihalomethyl-substituted S-triazine, or phenanthylsulfonium salt compound may be added in addition to the above polymerization initiator and polymerization accelerator.

  The adhesive composition for dentine of the present invention may further contain a filler. Preferred examples of the filler include inorganic fillers such as silica, zirconia, titania, silica / zirconia, and silica / titania. These inorganic fillers can be hydrophobized with a surface treatment agent typified by a silane coupling agent, thereby improving compatibility with the polymerizable monomer and improving mechanical strength and water resistance. The hydrophobization method may be carried out by a known method. Examples of the silane coupling agent include methyltrimethoxysilane, methyltriethoxysilane, methyltrichlorosilane, dimethyldichlorosilane, trimethylchlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane. , Vinyltrichlorosilane, vinyltriacetoxysilane, vinyltris (β-methoxyethoxy) silane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltris (β-methoxyethoxy) silane, γ-chloropropyltrimethoxysilane, γ-chloropropylmethyldimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) Trimethoxysilane, N- phenyl--γ- aminopropyltrimethoxysilane, etc. hexamethyldisilazane is preferably used. The blending amount of the inorganic filler is (A) an acidic group-containing polymerizable monomer component 100 comprising 95% by mass or more of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer. It is the range of 2-400 mass parts with respect to a mass part, More preferably, it is 5-100 mass parts.

  A volatile organic solvent may be further blended in the adhesive composition for tooth of the present invention. As the volatile organic solvent, those which are volatile at room temperature and water-soluble can be suitably used. The term “volatile” as used herein means that the boiling point at 760 mmHg is 100 ° C. or lower and the vapor pressure at 20 ° C. is 1.0 KPa or higher. 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, tertiary butanol, 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. The amount of these volatile organic solvents is not particularly limited, but (A) an acidic group containing 95% by mass or more of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer It is the range of 2-400 mass parts with respect to 100 mass parts of polymerizable monomer components, More preferably, it is 5-100 mass parts. These volatile organic solvents are also removed by air blowing before the adhesive is cured when the dental adhesive composition of the present invention is applied to the tooth surface, similarly to the water. Is.

  Furthermore, an organic thickener such as a polymer compound such as polyvinyl pyrrolidone, carboxymethyl cellulose, or polyvinyl alcohol is added to the adhesive of the present invention as needed, regardless of the application, as long as the performance is not deteriorated. It is possible. Various additives such as ultraviolet absorbers, dyes, antistatic agents, pigments, and fragrances can be selected and blended as necessary.

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.

(A) Phosphonic acid group-containing polymerizable monomer or phosphinic acid group-containing polymerizable monomer 6MHPA: 6- (meth) acryloyloxyhexylphosphonic acid 3MHPA: 3- (meth) acryloylpropylphosphonic acid B3MHPA: bis [3- (Meth) acryloyloxypropyl] phosphinic acid Other acidic group-containing polymerizable monomer MDP: 10-methacryloyloxydecyl dihydrogen phosphate Phenyl-P: 2-methacryloyloxyethylphenyl hydrogen phosphate PM1: 2-Methacryloyloxyethyl dihydrogen phosphate PM2: bis (2-methacryloyloxyethyl) hydrogen phosphate

(B) Multivalent metal ion Al (O-iPr) ₃ : Aluminum triisopropoxide Ca (O-iPr) ₂ : Calcium diisopropoxide Ti (O-iPr) ₄ : Titanium tetraisopropoxide

(D) Non-acidic group-containing polymerizable monomer Bis-GMA: 2,2′-bis [4- (2-hydroxy-3-methacryloxypropoxy) phenyl] propane D-2.6E: bisphenol A polyethoxymethacrylate HEMA: 2-hydroxyethyl methacrylate 3G: triethylene glycol dimethacrylate

(E) Photopolymerization initiator CQ: camphorquinone DMBE: ethyl p-N, N-dimethylaminobenzoate volatile organic solvent IPA: isopropyl alcohol inorganic filler F1: amorphous silica (methyltrimethyl) having a particle size of 0.02 μm Chlorosilane treated product)
F2: Spherical silica-zirconia (γ-methacryloyloxypropyltrimethoxysilane hydrophobized product) having a particle size of 0.4 μm and spherical silica-titania (γ-methacryloyloxypropyltrimethoxysilane hydrophobizing treatment) having a particle size of 0.08 μm And a mixture with a mass ratio of 70:30

In the following examples and comparative examples, various measurements were performed by the following methods.
(1) Measuring method of polyvalent metal ions After adjusting the adhesive composition of the present invention and stirring for 24 hours, 0.2 g was weighed into a 100 ml sample tube and diluted to 0.1% by mass using IPA. did. This liquid was filtered with a syringe filter, and the concentration of each metal ion (mmol / g) contained per 100 parts by mass of the polymerizable monomer was measured using ICP (inductively coupled plasma) emission spectrometry. . Each metal ion concentration was converted using a calibration curve obtained from a standard sample (1 ppm, 2.5 ppm, 6 ppm) of each ion.

(2) Measuring method of tooth adhesion a) Preparation method of adhesion test piece The bovine front teeth are removed within 24 hours after slaughter, and enamel and parallel to the lip surface with # 600 emery paper under running water. The dentin plane was cut out. 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. A dental adhesive is applied to the simulated cavity, left for 20 seconds, dried by blowing compressed air for about 10 seconds, and then lighted for 10 seconds with a dental visible light irradiator (Tokuso Power Light, manufactured by Tokuyama Corporation). Irradiated. Further, 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 prepare an adhesion test piece.
b) Adhesion test method The above-mentioned adhesion test piece was immersed in water at 37 ° C for 24 hours, and then pulled at a crosshead speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corporation). Tensile bond strength was measured. With respect to four test pieces per test, the tensile bond strength was measured by the above-described method, and the average value was used as the bond strength to enamel or dentin to evaluate the tooth adhesion.

(3) Storage stability evaluation method of adhesive material Adhesive strength using the adhesive composition of the present invention stored for 6 months in an incubator at 37 ° C after adjustment, using the same method as the above-described adhesive strength measurement method Was measured and compared with the adhesive strength before storage at 37 ° C.

(4) Long-term water resistance evaluation method After immersing the above-mentioned adhesion test piece in water at 37 ° C for 1 year, it was pulled at a crosshead speed of 2 mm / min using a tensile tester (Autograph, manufactured by Shimadzu Corp.) The tensile adhesive strength of the composite resin was measured. With respect to four test pieces per test, the tensile bond strength was measured by the above-described method, and the average value was used as the bond strength to enamel or dentin to evaluate the tooth adhesion.

Example 1
As a phosphonic acid group-containing polymerizable monomer, 10 g of 6MHPA, 1.5 g of Al (O-ipr) ₃ as a polyvalent metal ion source, 8 g of water, 0.4 g of CQ and 0 as a photopolymerization initiator .4 g of DMBE was weighed and mixed with stirring for 24 hours to obtain the dental adhesive of the present invention.

After measuring the amount of polyvalent metal ions for this adhesive, the adhesive strength to enamel and dentin was evaluated using this. The adhesive was tested for adhesion to enamel and dentin after storage for 6 months in a 37 ° C. incubator and after immersing the adhesive specimen in water at 37 ° C. for 1 year. The composition of the adhesive is shown in Table 1, and the evaluation results are shown in Table 2.
Examples 2-22
According to the method of Example 1, dental adhesives having different compositions shown in Table 1 were prepared.

About the obtained adhesive, after measuring the amount of polyvalent metal ions, the adhesive strength to enamel and dentin was evaluated using this. The adhesive was tested for adhesion to enamel and dentin after storage for 6 months in a 37 ° C. incubator and after immersing the adhesive specimen in water at 37 ° C. for 1 year. The composition of the adhesive is shown in Table 1, and the evaluation results are shown in Table 2.
Comparative Examples 1-10
In accordance with the method of Example 1, adhesives having different compositions shown in Table 3 were prepared.

  About the obtained adhesive, after measuring the amount of polyvalent metal ions, the adhesive strength to enamel and dentin was evaluated using this. The adhesive was tested for adhesion to enamel and dentin after storage for 6 months in a 37 ° C. incubator and after immersing the adhesive specimen in water at 37 ° C. for 1 year. The composition of the adhesive is shown in Table 3, and the evaluation results are shown in Table 4.

  In Examples 1 to 22, each component was formulated so as to satisfy the configuration shown in the present invention, and in any case, good adhesion strength to enamel and dentin was obtained. Even when stored in a 37 ° C. incubator for 6 months, and when the adhesion test piece is immersed in water at 37 ° C. for 1 year, the adhesive performance to the tooth is maintained, and good storage stability and water resistance It turns out that it has sex.

  On the other hand, Comparative Example 1 contains (A) a phosphonic acid group-containing polymerizable monomer or an acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphinic acid group-containing polymerizable monomer. In this case, the demineralization effect of the tooth due to the acidic monomer is not obtained at all, and ionic crosslinking does not occur. Therefore, the adhesiveness to the tooth is greatly reduced.

  Comparative Example 2 is a case containing no (B) polyvalent metal ion, which is a component of the present invention, but the effect of improving the adhesiveness by ionic crosslinking cannot be obtained, and the adhesiveness to the teeth is greatly reduced.

  Comparative Example 3 is a case where (C) water, which is a component of the present invention, is not included at all. However, not only the tooth decalcification effect is not obtained, but also multi-metal ions are not eluted, and thus the adhesiveness to the tooth. Is greatly reduced.

  Comparative Example 4 is a case in which the photopolymerization initiator (E), which is a component of the present invention, is not included at all.

  In Comparative Examples 5 to 9, instead of adding (A) a phosphonic acid group-containing polymerizable monomer or an acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphinic acid group-containing polymerizable monomer, In the case where other phosphate ester group-containing polymerizable monomers are blended, in any case, a good initial adhesive strength to enamel and dentin can be obtained, but an incubator at 37 ° C. After 6 months of storage, the adhesiveness of the tooth significantly decreased due to deterioration of the blended acid monomer. In addition, when the adhesion test piece is immersed in water at 37 ° C. for 1 year, the polymerized cured product obtained by adhering to the tooth has hydrophilicity, so that it deteriorates when immersed in water for a long period of time. Tooth adhesion decreased.

  Comparative Example 10 is a case where the phosphonic acid group-containing polymerizable monomer (A) component or the phosphinic acid group-containing polymerizable monomer is less than 95% by mass, but enamel and dentin On the other hand, although good initial adhesive strength can be obtained, after storage for 6 months in an incubator at 37 ° C., the adhesiveness of the tooth is greatly reduced due to deterioration of the incorporated acid monomer. Even when immersed in water for a year, the adhesiveness to the tooth decreased.

Claims (7)

(A) An acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer (B) polyvalent metal ion (C) water A one-pack type adhesive composition for dentine, comprising: The one-pack type adhesive composition for dentine according to claim 1, which exhibits acidity. (B) The polyvalent metal ion is represented by the following formula (1):
R _{P +} = TV _{P +} / TV _A (1)
(Wherein, TV _{P +} is the total valence of (B) polyvalent metal ions contained in the composition, and TV _A is (A) a phosphonic acid group-containing polymerizable monomer contained in the composition Or the total valence quantity (R _{P +} ) defined by the acidic group-containing polymerizable monomer comprising 95% by mass or more of the phosphinic acid group-containing polymerizable monomer) The one-pack type adhesive composition for a tooth according to claim 1 or 2, wherein the composition is blended in a range of 0.1 to 1.5. (B) The one-pack type adhesive composition for a tooth according to any one of claims 1 to 3, wherein the polyvalent metal ion is a titanium ion. Furthermore, (D) acidic group non-containing polymerizable monomer is mix | blended, The one-pack type adhesive composition for dentine as described in any one of Claims 1-4 characterized by the above-mentioned. Furthermore, (E) The photopolymerization initiator is contained, The one-pack type adhesive agent for dentine as described in any one of Claims 1-5 characterized by the above-mentioned. (A) An acidic group-containing polymerizable monomer comprising 95% by mass or more of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer (C) Water (B _alk ) polyvalent metal In the method for producing a dental adhesive composition by mixing an alkoxide, (A) an acid comprising 95% by mass or more of a phosphonic acid group-containing polymerizable monomer or a phosphinic acid group-containing polymerizable monomer The method for producing a dental adhesive, wherein the group-containing polymerizable monomer is preliminarily mixed with (B _alk ) multivalent metal alkoxide and then mixed with (C) water.